Palladium nanoparticles in polyols: synthesis, catalytic couplings and hydrogenations Isabelle Favier, † Daniel Pla, *, † and Montserrat Gómez *, † † Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), Université de Toulouse, CNRS, 118 route de Narbonne, 31062 Toulouse Cedex 9, France.

ABSTRACT: Alcohols, in particular polyols, are well-known for the synthesis of metal nanoparticles often acting as reducing agents, solvents, and stabilizers. Given not only their structural flexibility depending on the number of OH functions and their inherent H bonding interactions, but also the wide range of polyol molecular weights readily available, different physico-chemical properties (boiling point, polarity, viscosity) could be exploited towards the synthesis of well-defined nanomaterials. In particular, the relevance of the supramolecular structure of polyols has a fundamental impact on the formation of metal nanoparticles thereby favoring the dispersion of the nanoclusters. In the field of the metal-based nanocatalysis, palladium occupies a privileged position mainly due to its remarkable versatility in terms of reactivity representing a foremost tool in synthesis. In this review, we describe the controlled synthesis of Pd-based nanoparticles in polyol medium focusing on the progress in terms of tailoring size, morphology, structure, and surface state. Moreover, we discuss the use of 1. INTRODUCTION Certainly, palladium occupies a prominent place in catalysis for its efficiency in downstream wide-ranging processes (C-C and C-heteroatom bond formation reactions, hydrogenations, hydrodehalogenations, carbonylations, oxidations). 1,[START_REF] Tsuji | Palladium Reagents and Catalysts: New Perspectives for the 21st Century[END_REF] Specially, the relevance of palladium in catalysis has been recognized in 2010 by the Nobel Prize in Chemistry awarded to Richard F.

Heck, Ei-ichi Negishi, and Akira Suzuki for their original contributions in Pd-catalyzed crosscoupling reactions applied in organic synthesis of interest for both fundamental and applied purposes. [START_REF] Johansson Seechurn | Palladium-Catalyzed Cross-Coupling: A Historical Contextual Perspective to the 2010 Nobel Prize[END_REF] The ascertained versatility of palladium can be attributed to its ability to stabilize a large variety of matter states at different oxidations states, by appropriate tuning of conditions: organometallic complexes, nanoparticles, and extended surfaces, including polymetallic materials; furthermore, these different Pd-based species have proven their compatibility with different types of solids, permitting their immobilization and in consequence their recycling, aspect of foremost importance in the frame of developing sustainable industrial processes. [4][START_REF] Monguchi | Recent Development of Palladium-Supported Catalysts for Chemoselective Hydrogenation[END_REF][START_REF] Molnár | Efficient, Selective, and Recyclable Palladium Catalysts in Carbon-Carbon Coupling Reactions[END_REF] Concerning palladium nanoparticles, Bönnemann [START_REF] Bönnemann | Formation of Colloidal Transition Metals in Organic Phases and Their Application in Catalysis[END_REF] and Reetz [START_REF] Reetz | Propylene Carbonate Stabilized Nanostructured Palladium Clusters as Catalysts in Heck Reactions[END_REF] independently described the first syntheses of palladium nanocatalysts in conventional organic solvents prepared by bottom-up (palladium salt chemical reduction) and top-down (electrochemical process transforming palladium bulk into palladium nanoparticles), respectively, for applications in C-C crosscoupling reactions.

Focusing on nano-scale materials, metal nanoparticles (well-defined entities with dimensions in the range 1 -100 nm) have experienced a huge development over the last four decades due to their unique physical and chemical properties in comparison to materials belonging to higher or lower scales. This is in fact mainly thanks to the electronic and structural effects of nanomaterials, thus enabling a large panel of catalytic applications. [START_REF] Schmid | Nanoparticles: From Theory to Application[END_REF][START_REF] Serp | Nanomaterials in Catalysis[END_REF][11][START_REF] Adil | Biogenic Synthesis of Metallic Nanoparticles and Prospects Toward Green Chemistry[END_REF][START_REF] Ghosh Chaudhuri | Core/Shell Nanoparticles: Classes, Properties, Synthesis Mechanisms, Characterization, and Applications[END_REF] Although, metal nanoparticles have been applied for a long time in heterogeneous catalysis, contributing to important industrial developments mainly associated to oil sector, [START_REF] Zhou | Nanotechnology in Catalysis[END_REF] nanocatalysis has emerged at the end of 20 century, combining colloidal nanoparticles dispersed in a solvent and nano-entity engineering granting a control of size, shape, and surface state of the as-prepared objects. The advances towards the characterization and tailoring of nano-objects enable catalyst tuning and design at the nanometric scale. [15][START_REF]Metal Nanoclusters in Catalysis and Materials Science: The Issue of Size Control[END_REF][START_REF] Astruc | Nanoparticles and Catalysis[END_REF][START_REF] Heiz | [END_REF] In this frame, reproducible synthetic methodologies able to produce metal nanoparticles with a tight control of structure, morphology, composition, and surface state are crucial for their applications. The synthetic approaches towards metal nanoparticles are generally classified as physical (top-down) and chemical (bottom-up) methods. [START_REF] Torimoto | Top-down Synthesis Methods for Nanoscale Catalysts[END_REF][START_REF] Roucoux | Reduced Transition Metal Colloids: a Novel Family of Reusable Catalysts?[END_REF] The latter ones involve different types of solvents, from conventional (generally coming from fossil sources) to alternative ones (showing a lower environmental impact), such as water, [START_REF] Bulut | Aqueous-phase Hydrogenation of Alkenes and Arenes: The Growing Role of Nanoscale Catalysts[END_REF][START_REF] San | Synthesis of Alkanethiolate-capped Metal Nanoparticles Using Alkyl Thiosulfate Ligand Precursors: a Method to Generate Promising Reagents for Selective Catalysis[END_REF] ionic liquids, 23 scCO 2 , 24-26 polyols. [START_REF] Fiévet | The Polyol Process: a Unique Method for Easy Access to Metal Nanoparticles with Tailored Sizes, Shapes and Compositions[END_REF][START_REF] Favier | Metal-based Nanoparticles Dispersed in Glycerol: an Efficient Approach for Catalysis[END_REF][START_REF] Chahdoura | Glycerol as Suitable Solvent for the Synthesis of Metallic Species and Catalysis[END_REF] Usually, these greener solvents, in contrast to volatile organic compounds, can play several roles, such as stabilizer, reductant and/or liquid phase for trapping nanocatalysts thus facilitating their recycling. This is in particular the case of polyols. In 1989, thirty years ago, the polyol methodology was for the first time applied by Fiévet and co-workers with the aim of reducing metal salts in liquid polyols (mainly using ethylene glycol), to lead to the formation of well-defined metal-based nanoparticles; [START_REF] Fievet | Homogeneous and Heterogeneous Nucleations in the Polyol Process for the Preparation of Micron and Submicron Size Metal Particles[END_REF][START_REF] Fievet | Preparing Monodisperse Metal Powders in Micrometer and Submicrometer Sizes by the Polyol Process[END_REF] thus, the polyol acts as a polyfunctional component, i.e. solvent of the metal precursors (relative high dielectric constant), reducing agent (relative low reduction potentials) and in some cases stabilizer (mostly for higher polyols, such as polysaccharides, polyphenols… see section 2.3), preventing the agglomeration of the generated metal colloids. [START_REF] Fiévet | The Polyol Process: a Unique Method for Easy Access to Metal Nanoparticles with Tailored Sizes, Shapes and Compositions[END_REF][START_REF] Dong | Polyol Synthesis of Nanoparticles: Status and Options Regarding Metals, Oxides, Chalcogenides, and Non-metal Elements[END_REF] In addition, due to their polarity and high boiling points, polyols are suitable solvents to be applied in microwave-assisted synthesis of metal nanoparticles. [START_REF] Gabriel | Dielectric Parameters Relevant to Microwave Dielectric Heating[END_REF][START_REF] Zhu | Microwave-Assisted Preparation of Inorganic Nanostructures in Liquid Phase[END_REF][START_REF] Baghbanzadeh | Microwave-Assisted Synthesis of Colloidal Inorganic Nanocrystals[END_REF] The present review aims at describing both the synthesis of palladium nanoparticles in polyol medium, as well as their use as nanocatalysts in leveraging cross-couplings and hydrogenations, including polyol-modified supports for catalytic applications. The catalyst recycling is a crucial aspect both from an environmental point of view and industrial application purposes. Catalyst recyclability assessment requires studies leading to consistent high conversions and/or yields (no more than 1-2% decrease in at least 5-9 runs), or minimum total turnover numbers ca. 100,000. [START_REF] Molnár | Efficient, Selective, and Recyclable Palladium Catalysts in Carbon-Carbon Coupling Reactions[END_REF] Obviously, the recycling capability of a given catalyst is intimately related to the nature of the catalytically active species. Thus, kinetic studies, deactivation data, and catalyst characterization after catalytic reactions are necessary to conclude about the catalyst recyclability. [START_REF] Gladysz John | Recoverable Catalysts. Ultimate Goals, Criteria of Evaluation, and the Green Chemistry Interface[END_REF][START_REF] Gladysz | The Experimental Assay of Catalyst Recovery: General Concepts[END_REF][START_REF] Phan | On the Nature of the Active Species in Palladium Catalyzed Mizoroki-Heck and Suzuki-Miyaura Couplings -Homogeneous or Heterogeneous Catalysis, A Critical Review[END_REF] Taking into account this definition of catalyst recyclability, only those Pd-based systems meeting the aforementioned criteria will be considered as recyclable in the frame of this review.

Notably, this review pays special attention to characterization aspects and mechanistic insights. This contribution includes the works published until the end of February 2019. Electrocatalytic approaches are beyond the scope of this contribution.

Synthesis of palladium-based nanoparticles in polyol medium

In this part, we mainly focus on the contributions related to understanding the controlled synthesis of Pd-based NPs by the polyol approach, due to the impact that size and morphology produce on their properties and consequently in their applications; this discussion is presented by type of polyol, considering both mono and bimetallic Pd-based nanoparticles. This section focuses on the discussion of the synthesis of Pd-based nanoparticles by bottom-up methodologies under homogeneous conditions. Thus, the synthesis of supported nanoparticles has not been taken into consideration.

Palladium monometallic nanoparticles (PdNPs)

Ethylene glycol (EG) has been typically used in the polyol synthesis of metal nanoparticles. [START_REF] Dong | Polyol Synthesis of Nanoparticles: Status and Options Regarding Metals, Oxides, Chalcogenides, and Non-metal Elements[END_REF] In the case of palladium, PdNPs often exhibit single-crystal structures (cubes, bars, cuboctahedra), mainly due to the fast reduction in EG at relative high temperature. However, tuning the reaction conditions and/or using other polyols, the reaction kinetics evidently changes influencing both the type of seeds and their growth rate. In general, the shape of the NPs is mainly determined by growth rates of different nuclei facets. [START_REF] Xia | Shape-Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?[END_REF] It is important to highlight that polyols are predominantly not appropriate stabilizers, requiring the presence of capping agents in order to avoid the agglomeration of the nano-objects during their preparation. However, Arora and coworkers have prepared quasi-spherical PdNPs (ca. 6 nm) using palladium dichloride as precursor and EG acting as solvent, stabilizer and reducing agent; this approach has permitted to evidence the presence of monoalkoxides at the surface of isolated PdNPs by FTIR, TGA and AFM analyses. [START_REF] Arora | Evidence for Monoalkoxide Species on the Surface of Palladium Nanoparticles Synthesized in Ethylene Glycol[END_REF] In this section, we will particularly analyze the contributions exhibiting a control on the structure on the synthesized PdNPs. We firstly discuss the works related to EG and its diol derivatives [diethylene glycol (DEG), triethylene glycol (TrEG) and tetraethylene glycol (TEG)], followed by glycerol and other polyols.

Ethylene glycol and its diol derivatives

Reproducible methodologies leading to well-defined shape of nanoparticles is crucial for controlling their properties. In 2005, Xia and co-workers reported the first elucidation concerning the synthesis of uniform cuboctahedral PdNPs by a polyol methodology. [START_REF] Xiong | Understanding the Role of Oxidative Etching in the Polyol Synthesis of Pd Nanoparticles with Uniform Shape and Size[END_REF] They monitored the formation of PdNPs in EG at 110 °C in the presence of PVP using Na 2 [PdCl 4 ] as metal precursor; at 5 min, the reaction mixture was mainly constituted by cuboctahedra together with twinned particles (ca. 10%). The latter dissolved after 1 h reaction and the cuboctahedral PdNPs grew to 8 nm, reaching 10 nm after ca. 8 h of reaction, as evidenced by HRTEM analysis (Figure 1). Both chloride anions and O 2 were responsible for the oxidative etching of twinned NPs (under Ar, the twinned NPs remained stable over time) that only disappeared by exposing the sample to air. Thus, twinned NPs are more reactive due to the higher concentration of surface defects than cuboctahedra; in consequence, the presence of an oxidant in reaction medium provides a way to control the formation of PdNPs exhibiting a well-defined morphology. It is known that icosahedral structure is favored over both decahedral and cuboctahedral arrangements for small PdNPs [i.e. for total metal atoms less than 309]. [START_REF] Baletto | Structural Properties of Nanoclusters: Energetic, Thermodynamic, and Kinetic Effects[END_REF] In EG, PdNPs showing icosahedral structure (mean sizes from 5 to 35 nm) were prepared by adding HCl to slow the reaction rate. [START_REF] Lv | Controlled Synthesis of Nanosized Palladium Icosahedra and Their Catalytic Activity Towards Formic-Acid Oxidation[END_REF] Using DEG at 105 °C for the reduction of Na 2 [PdCl 4 ] in the presence of PVP, decahedral or icosahedral PdNPs were mainly obtained by adjusting the reaction medium through the presence of additives. [START_REF] Huang | Polyol Syntheses of Palladium Decahedra and Icosahedra as Pure Samples by Maneuvering the Reaction Kinetics with Additives[END_REF] The increase of acidity of the reaction medium by addition of HCl hampered the reduction of [PdCl 4 ] 2-anionic complex in both EG and DEG. In contrast, the addition of Na 2 SO 4 triggers an increase of reducing properties of DEG due to hydrogen bonds formed between SO 4 2-and the hydroxyl groups of DEG, favoring the oxidation of the polyol to the corresponding aldehyde, and then improving their reducing properties.

The same group has quantitatively studied the correlation between reduction rates of the metal precursor and structure for different diols (EG, DEG and TrEG). [START_REF] Wang | Use of Reduction Rate as a Quantitative Knob for Controlling the Twin Structure and Shape of Palladium Nanocrystals[END_REF] Thus, combining the data obtained at different temperatures (ranging from 60 to 140 ºC) for the three polyols, they concluded that for low initial reaction rate (ca. 10 -8 Ms -1 ), a stacking-fault-lined structure was privileged, while at high rates (ca. higher than 10 -4 Ms -1 ), single-crystals were mainly formed; twinned icosahedra were selectively formed in the narrow range of 8.7 x 10 -6 to 4.0 x 10 -7 Ms -1 (Figure 2). Reaction times for truncated octahedra (or icosahedra), and nanoplates syntheses were 3 h and 30 h, respectively. [START_REF] Wang | Use of Reduction Rate as a Quantitative Knob for Controlling the Twin Structure and Shape of Palladium Nanocrystals[END_REF] However, the authors did not report under which atmosphere the reactions were conducted. Reprinted with permission from reference. [START_REF] Wang | Use of Reduction Rate as a Quantitative Knob for Controlling the Twin Structure and Shape of Palladium Nanocrystals[END_REF] Copyright (2015) American Chemical Society.

Teranishi and co-workers, following a similar protocol described by Xia in EG, [START_REF] Xiong | Understanding the Role of Oxidative Etching in the Polyol Synthesis of Pd Nanoparticles with Uniform Shape and Size[END_REF] but under slow reaction conditions, could control the selective formation of icosahedral PdNPs. [START_REF] Li | Controllable Polyol Synthesis of Uniform Palladium Icosahedra: Effect of Twinned Structure on Deformation of Crystalline Lattices[END_REF] They studied the influence of the reaction temperature, ranging from 100 °C to 150 °C in air. At high temperature (150 °C), small (mean size in the range 2-6 nm) and spherical NPs were obtained; however, from 140 °C to 100 °C only icosahedra were formed with sizes from 15 to 42 nm (Figure 3). The as-prepared icosahedral NPs were stable in air for months. By PXRD, they could prove the high density of twin boundaries and sharp edges on the surface of icosahedral PdNPs.

Under harsher conditions (160 °C) and in the presence of small amounts of silver nitrate, Na 2 [PdCl 4 ] was reduced in EG with PVP to form PdNPs of ca. 10 nm of mean diameter, showing different shapes. [START_REF] Long | Controlled Synthesis and Properties of Palladium Nanoparticles[END_REF][START_REF] Long | Chemical Synthesis and Characterization of Palladium Nanoparticles[END_REF] Despite the authors do not explicitly comment on the reaction atmosphere used to carry out the syntheses, their protocols seem to be in air. [START_REF] Long | Controlled Synthesis and Properties of Palladium Nanoparticles[END_REF][START_REF] Long | Chemical Synthesis and Characterization of Palladium Nanoparticles[END_REF] For noble metals, microwave-assisted heating can induce faster nucleation processes than conventional activation, leading to reproducible synthesis and controlled structures in air. [START_REF] Dahal | Beneficial Effects of Microwave-Assisted Heating versus Conventional Heating in Noble Metal Nanoparticle Synthesis[END_REF] Notably, the authors report that the working temperature of 150 ºC could be quickly achieved by preheating the samples below the temperature of nucleation (76 ºC) before applying a high power pulse to reach the desired temperature for controlled nucleation within seconds. [START_REF] Dahal | Beneficial Effects of Microwave-Assisted Heating versus Conventional Heating in Noble Metal Nanoparticle Synthesis[END_REF] In particular, for Pd, small cuboctahedra could be exclusively obtained in contrast to conventional heating, resulting in a range of sizes and morphologies. Moreover, under microwave irradiation, a mixture of nanocubes and nanorods was observed in the synthesis of PdNPs from H 2 [PdCl 4 ] in TEG in the presence of PVP and CTAB as surfactant. [START_REF] Yu | Microwave-assisted Synthesis of Palladium Nanocubes and Nanobars[END_REF] Despite the authors do not report if the synthesis was performed under a controlled atmosphere or in air using a modified domestic microwave oven operating at 900 W, the in situ formed [PdBr 4 ] 2-anions (chloride exchange by bromide present in CTAB) could be slowly reduced; it is important to note that under similar conditions but using EG instead of TEG, only spherical NPs were obtained. This behavior can be explained because TEG is a milder reducing agent showing higher viscosity in comparison with EG; these conditions can slow down both the nucleation and growth rate of PdNPs favoring the formation of large nanocubes (ca. 24 nm) with the presence of nanorods. Following a similar methodology, Gao and co-workers managed to synthesize selectively nanorods in EG; SQUID measurements evidenced the ferromagnetic properties of the as-prepared Pd nanorods, at room and lower temperatures (reaction atmosphere not described in the synthetic protocol). [START_REF] Xiao | Shape-Controlled Synthesis of Palladium Nanorods and Their Magnetic Properties[END_REF] As discussed above, different polygonal PdNPs structures can be formed in EG at 85 ºC in air, using PVP as stabilizer, due to its selective adsorption on {111} and {100} facets. [START_REF] Xiong | Kinetically Controlled Synthesis of Triangular and Hexagonal Nanoplates of Palladium and Their SPR/SERS Properties[END_REF] With the aim of obtaining anisotropic structures, a mixture of two surfactants, PVP and CTAB, was necessary, by optimization of the appropriate PVP/CTAB ratio and the addition of Fe(III) salts in acid medium (Figure 4). {111} facets, respectively. Reprinted with permission from reference 55 . Copyright (2005) American Chemical Society.

Harada and Cong have recently described the synthesis of PdNPs by a MW-assisted polyol methodology, using EG or Gly as polyol, under continuous flow regime at 471 K (for EG) and 523 K (for glycerol) for about 10 min. (Figure 5). [START_REF] Harada | Microwave-Assisted Polyol Synthesis of Polymer-Protected Monometallic Nanoparticles Prepared in Batch and Continuous-Flow Processing[END_REF] A comparative study using both continuous flow-type and batch-type reactors for the synthesis of PdNPs (and also Rh, Ru and Pt NPs) in EG and Gly has proven the feasibility of the scale-up MNPs synthesis under flow conditions, as evidenced by TEM and EXAFS analyses of the structures obtained with both types of reactors.

However, the authors do not describe the reaction atmosphere employed in their synthetic protocol. Sonochemical synthesis of noble metal nanoparticles have attracted the attention of researchers, mainly due to the high temperatures (thousands of degrees) and high pressures (hundreds of atmospheres) generated inside the collapsing cavitation bubbles [for the pioneering work of synthesis of PdNPs in water by ultrasound activation see ref. [START_REF] Okitsu | Sonochemical Preparation of Ultrafine Palladium Particles[END_REF] ]. Rehspringer and co-workers have studied the synthesis of PdNPs from Pd(NO 3 ) 2 in water using EG as reductant and PVP as capping agent. [START_REF] Nemamcha | Synthesis of Palladium Nanoparticles by Sonochemical Reduction of Palladium(II) Nitrate in Aqueous Solution[END_REF] They obtained spherical NPs with small sizes (from 3.5 to 5.5 nm), depending on the Pd(II)/PVP molar ratio: the ratio increase (from 0.13 x 10 -3 to 0.53 x 10 -3 ) led to a slight mean diameter increase together with a decrease in number of NPs; for the highest Pd(II) content (more than 2.5 x 10 -3 mol), aggregates of small NPs were observed.

Alternatively, Lamaty et al. have described in situ formation of spherical PdNPs of 7±1, 9±2 and 10±3 nm for catalytic Heck reactions (see section 4.4.) using 5 mol% Pd(OAc) 2 , NaHCO 2 (0.2 equiv.) as reducing agent in PEG1100, PEG2000 and PEG3400, respectively, under ball-milling (30 Hz) conditions and in the absence of phosphine ligands, respectively. [START_REF] Declerck | Poly(ethylene glycol) as Reaction Medium for Mild Mizoroki-Heck Reaction in a Ball-mill[END_REF] Notably, in the absence of aryl halide and acrylate substrates, the reaction led to agglomeration.

Glycerol and other polyols

Coming from biomass and also obtained as the main coproduct (ca. 10 wt%) in the biodiesel production by transesterification of vegetable oils, glycerol has caused a great interest in its applications, due to both economic and environmental standpoints. [START_REF] Pagliaro | The Future of Glycerol[END_REF] Its low-cost, non-toxicity, high boiling point (290 °C), negligible vapor pressure (< 1 mmHg at 293 K), high solubilizing ability for organic and inorganic compounds (dielectric constant: 44.38 at 25 °C; dipole moment: 2.68 D at 30-50°C), and low miscibility with other organic solvents such as ethers and alkanes, [START_REF] García | Quantitative Structure-property Relationships Prediction of Some Physico-chemical Properties of Glycerol Based Solvents[END_REF] constitute outstanding properties towards its use as solvent for applications in synthesis and catalysis. [START_REF] Favier | Metal-based Nanoparticles Dispersed in Glycerol: an Efficient Approach for Catalysis[END_REF][START_REF] Chahdoura | Glycerol as Suitable Solvent for the Synthesis of Metallic Species and Catalysis[END_REF][START_REF] Corma | Chemical Routes for the Transformation of Biomass into Chemicals[END_REF][START_REF] Gu | Glycerol as a Sustainable Solvent for Green Chemistry[END_REF][START_REF] Díaz-Álvarez | Glycerol and Derived Solvents: New Sustainable Reaction Media for Organic Synthesis[END_REF] 6). [START_REF] Lee | Glycerol-mediated Synthesis of Pd Nanostructures with Dominant {111} Facets for Enhanced Electrocatalytic Activity[END_REF] This anisotropic growth was also observed by Grace and Pandian applying microwave activation instead of conventional heating up to 290 ºC. [START_REF] Nirmala Grace | One pot Synthesis of Polymer Protected Pt, Pd, Ag and Ru Nanoparticles and Nanoprisms under Reflux and Microwave Mode of Heating in Glycerol -a Comparative Study[END_REF] Neither of these two references describe the use of inert atmosphere to carry out the syntheses. Varma and co-workers reported the effect of stabilizers such as PVP, CTAB and SDS on the shape and dispersion of noble metal NPs synthesis (Au, Pt, Pd) under MW irradiation at 100 ºC (unspecified reaction atmosphere). [START_REF] Kou | Green Synthesis of Noble Nanometals (Au, Pt, Pd) Using Glycerol under Microwave Irradiation Conditions[END_REF] For Pd, in the absence of any stabilizer, PdNPs of ca. 10 nm were obtained, without observing any variation in the presence of SDS. However, the addition of PVP or CTAB led to smaller and better dispersed PdNPs, although in CTAB the PdNPs tended to aggregate (Figure 7). Adapetd with permission from reference. [START_REF] Kou | Green Synthesis of Noble Nanometals (Au, Pt, Pd) Using Glycerol under Microwave Irradiation Conditions[END_REF] Copyright (2013) American Chemical Society.

Based on the idea of Ratna, [START_REF] Puvvada | Synthesis of Palladium Metal Nanoparticles in the Bicontinuous Cubic Phase of Glycerol Monooleate[END_REF] O'Sullivan and co-workers developed liposomal nanoreactors for the preparation of PdNPs in glycerol and Ar gas bubbling at 25 ºC. [START_REF] Clergeaud | Liposomal Nanoreactors for the Synthesis of Monodisperse Palladium Nanoparticles Using Glycerol[END_REF] For that purpose, PdNPs were prepared by encapsulation of Na 2 [PdCl 4 ] with glycerol in nanosized liposomes, which were generated from zwitterionic or charged lipids (Figure 8). Small (ca. American Chemical Society.

In our group, we were interested in the synthesis of metal-based NPs for applications in catalysis (couplings, hydrogenations, hydrodehalogenations, carbonylations… including tandem processes), in neat glycerol under base-free conditions, using molecular hydrogen as reducing agent, with the aim of avoiding any transformation of the solvent during the synthesis; besides palladium, NiNPs, [START_REF] Reina | Stable Zero-Valent Nickel Nanoparticles in Glycerol: Synthesis and Applications in Selective Hydrogenations[END_REF] Cu 2 O NPs, [START_REF] Chahdoura | Copper(I) Oxide Nanoparticles in Glycerol: A Convenient Catalyst for Cross-Coupling and Azide-Alkyne Cycloaddition Processes[END_REF] and CuNPs [START_REF] Dang-Bao | Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst[END_REF] were also prepared following this strategy at 100 ºC, 100 ºC and 120 ºC, respectively. Concerning monometallic PdNPs, we synthesized a number of nano-materials differing in the nature of the stabilizer. Thus, PdNPs were prepared from Pd salts and organometallic precursors, namely, Pd(OAc) 2 , [PdCl 2 (COD)], [Pd(ma)(nbd)], and hydrogen pressure using different types of stabilizers (top). TEM images recorded in glycerol for some of these PdNPs (bottom). [START_REF] Reina | Stable Zero-Valent Nickel Nanoparticles in Glycerol: Synthesis and Applications in Selective Hydrogenations[END_REF][START_REF] Chahdoura | Palladium Nanoparticles in Glycerol: A Versatile Catalytic System for C-X Bond Formation and Hydrogenation Processes[END_REF][START_REF] Chahdoura | Palladium Nanoparticles Stabilised by PTA Derivatives in Glycerol: Synthesis and Catalysis in a Green Wet Phase[END_REF] The as-prepared PdNPs were analyzed by (HR)TEM showing the formation of highly dispersed small nanoparticles; EDS analyses evidenced the presence of the corresponding stabilizer on the isolated nanoparticles. With the aim of checking the coordination of TPPTS at the metallic surface in glycerol, the synthesis and 31 P NMR monitoring of TPPTS-stabilized PdNPs was carried out at NMR tube scale (Figure 10). In the absence of molecular hydrogen, the reaction between Pd(OAc) 2 and TPPTS at 60 °C in glycerol afforded the formation of palladium phosphine complexes (signals in the range 22-35 ppm). After adding H 2 (3 bar), phosphorus signals almost disappeared due to the formation of PdNPs. [START_REF] Favier | A New and Specific Mode of Stabilization of Metallic Nanoparticles[END_REF][START_REF] Kohlmann | NMR Diffusion, Relaxation, and Spectroscopic Studies of Water Soluble, Monolayer-Protected Gold Nanoclusters[END_REF] Given the high affinity of sulphur compounds for late transition metal surfaces, dodecanethiol was then added to the mixture and TPPTS could be quantitatively released from the surface as detected by [START_REF] Fievet | Preparing Monodisperse Metal Powders in Micrometer and Submicrometer Sizes by the Polyol Process[END_REF] P NMR. 77 With the aim of modifying the coordination mode of the ligand at the metal surface, cinchonabased alkaloids were also used as stabilizers (Figure 9). [START_REF] Reina | Palladium Nanoparticles Stabilised by Cinchona-based Alkaloids in Glycerol: Efficient Catalysts for Surface Assisted Processes[END_REF] In contrast to the strong interactions between P-donor ligands and metal surface, [START_REF] Raluy | P-Stereogenic Phosphines for the Stabilisation of Metal Nanoparticles. A Surface State Study[END_REF] mainly by -dative Pd-P bonds, cinchona ligands can interact with the surface through both N-quinoline  bonding or by  interaction with the quinoline aromatic ring. [START_REF] Ferri | An in Situ Attenuated Total Reflection Infrared Study of a Chiral Catalytic Solid-Liquid Interface: Cinchonidine Adsorption on Pt[END_REF][START_REF] Kraynov | Determination of Geometric Orientation of Adsorbed Cinchonidine on Pt and Fe and Quiphos on Pt Nanoclusters via DRIFTS[END_REF] Using quinidine as stabilizer, small (1.4 ± 0.3 nm) and welldispersed PdNPs were obtained; PXRD and HR-TEM analyses evidenced the formation of fcc PdNPs. XPS spectra in glycerol confirmed the exclusive presence of Pd(0); curiously, in the nitrogen region, two signals were observed, in contrast to one signal observed for PdNPs at solid state (isolated by centrifugation) and for the free ligand. This behavior could be explained because two types of quinidine molecules are present in glycerol solution, those adsorbed at the metal surface and those solvated by glycerol as evidenced by 15 N HMBC NMR experiments.

For a summary of monometallic Pd-based NPs synthetic conditions and characterization outcomes, see Table S1 in the Supporting Information.

Palladium bimetallic nanoparticles

Bimetallic nanoparticles represent a noteworthy type of nanomaterials due to their unique physico-chemical properties in relation to their corresponding monometallic counterparts. These distinctive features are mainly due to their composition and structure, causing specific electronic effects and in particular singular catalytic behavior, which is distinguished by the synergy between both metals. [START_REF] Singh | Synergistic Catalysis over Bimetallic Alloy Nanoparticles[END_REF][START_REF] Peng | Segregation in Bimetallic Nanoparticles[END_REF][START_REF] Notar Francesco | Synergy in the Catalytic Activity of Bimetallic Nanoparticles and New Synthetic Methods for the Preparation of Fine Chemicals[END_REF] Furthermore, the miscibility of the metals constituting Pd-based

BMNPs is a relevant parameter with a direct impact on their structure. [START_REF] Massalski | Binary Alloy Phase Diagrams[END_REF][START_REF] Fang | The Maximum Solid Solubility of the Transition Metals in Palladium[END_REF] The use of alternative solvents for the synthesis of BMNPs is especially attractive in order to control the reduction rate of the metal precursors with the consequent impact on nucleation, growth, shape and structure of the polymetallic nanoparticles. [START_REF] Dang-Bao | Bimetallic Nanoparticles in Alternative Solvents for Catalytic Purposes[END_REF] After the pioneering work of Silvert et al. concerning the synthesis of PdAg nanoalloys by polyol methodology using EG as solvent, [START_REF] Silvert | Synthesis and Characterization of Nanoscale Ag-Pd Alloy Particles[END_REF] a plethora of contributions of palladium bimetallic nanoparticles (BMNPs) have been described in the literature, mostly containing noble metals, such as gold, platinum and ruthenium, but also BMNPs including first-row transition metals, such as iron, cobalt, nickel and copper. Here, we describe the main works reported in the literature in relation to controlled syntheses affording well-defined PdM nanoparticles (where M is a metal other than Pd) using polyols as solvents, including their characterization and mechanistic approaches; in the main part of these contributions, the polyol acts also as reducing agent. Most works concern AuPd and PdPt nanoparticles mainly showing both core-shell and alloy structures. In the most cases, the BMNPs are prepared under batch conditions by successive or simultaneous reduction of the corresponding metal salts. Depending on reaction conditions, simultaneous co-reduction of the metal precursors can lead to core-shell structures and sequential addition of precursors can give alloys. Other BMNPs arrangements have been also observed, such as cluster-in-cluster. The composition and distribution of the elements in the nanoparticles is often assessed by scanning transmission electron microscopy combined with X-ray energy dispersive spectroscopy (STEM-EDS), together with data from other techniques such as PXRD, cyclic voltammetry, including theoretical calculations.

2.2.1. Palladium bimetallic nanoparticles containing 4d and 5d transition metals.

Gold

Gedanken and Harpeness reported the first synthesis of Au(core)Pd(shell) nanoparticles by coreduction of metal salts in EG under microwave conditions. [START_REF] Harpeness | Microwave Synthesis of Core-Shell Gold/Palladium Bimetallic Nanoparticles[END_REF] Thermodynamically, the reduction of Au(III) ions is favored in relation to Pd(II) ions [the reduction potential of Au(III) is more positive than that of Pd(II)] and additionally, the reduction of [AuCl 4 ] -species is faster than [PdCl 4 ] 2-ions, favoring the formation of Au clusters which act as seeds for the growth of the Pd layer; this behavior was also observed using glycerol as solvent. [START_REF] Patel | Synthesis of Au, Au/Ag, Au/Pt and Au/Pd Nanoparticles Using the Microwave-polyol Method[END_REF] From these results, the plausible catalytic role of the initial AuNPs for the reduction of Pd(II) ions cannot be ruled out.

Actually, Yang and co-workers have proved that the gold-based seeds promote the reduction of Pd(II) species leading to the formation of Au(core)-Pd(shell) BMNPs under smooth reduction conditions. [START_REF] Chen | Gold-catalyzed Formation of Core-shell Goldpalladium Nanoparticles with Palladium Shells up to Three Atomic Layers[END_REF] José-Yacamán and co-workers prepared AuPd nanoparticles by sequential reduction of Pd(II) followed by Au(III) ions in EG and in the presence of PVP under conventional heating. [START_REF] Ferrer | Three-Layer Core/Shell Structure in Au-Pd Bimetallic Nanoparticles[END_REF] The as-prepared BMNPs showed a complex structure above a critical size (ca. larger than 5 nm), which led to three-layer nanoparticles. As evidenced by STEM-EDS line scanning analyses, the core is constituted by an alloy, surrounded by an Au-rich layer and followed by a Pd-rich external layer (Figure 11). Studies of phase diagrams at nanoscale indicate that these diagrams become more complex as the size is diminished. 94 Rosales and co-workers prepared AuPd alloys (Au and Pd are miscible) by successive addition of metal precursor in EG using PVP as capping agent under conventional thermal activation, exhibiting different compositions (AuPd, Au 3 Pd, AuPd 3 ). [START_REF] Mejía-Rosales | On the Structure of Au/Pd Bimetallic Nanoparticles[END_REF] In this work, which combines experimental and theoretical approaches, it was proven that the different nano-alloys showed a rough surface with several types of surface defects (kinks, edges, vacancies), with a truncated octahedron morphology; this behavior is in contrast to monometallic nanoparticles for which icosahedra with defect-free surfaces were obtained, structures corresponding to low energy shapes as proven by the authors by theoretical calculations (molecular dynamics cooling process methodology).

Silver

Kim et al. described for the first time AgPd nanoalloys synthesized by a polyol approach for hydrogen permeation purposes. [START_REF] Kim | Polyol Synthesis of Pd/Ag Alloy Nanocrystalline[END_REF] They were prepared by co-reduction of the corresponding metal salts (Pd(NO 3 ) 2 and AgNO 3 ) in EG at 190 °C, in the absence of any other stabilizer, leading to the formation of aggregates. Powder XRD analyses evidenced the presence of cubic small crystallites with a lattice parameter (a = 3.942 Å), between that of Pd (3.889 Å) and Ag (4.085 Å), indicating the formation of an alloy. STEM coupled with EDS line-scanning analyses showed the alloy arrangement and the Ag:Pd ratio of ca. 1:3, in agreement with the ratio used in the synthesis. The addition of stabilizers leads to well-dispersed alloyed AgPd NPs; therefore, well-defined AgPd NPs were obtained by sequential addition of both metals in DEG using hexadecylamine, [START_REF] Adekoya | Polyol Mediated Hexadecylamine Capped Silver Allied Nanobimetallic Particles and Their Fluxional Properties[END_REF] as well as in EG using PVP as capping agent. [START_REF] Santoveña | Characterization Microstructural and Electrochemical of AgPd Alloy Bimetallic Nanoparticles[END_REF] In this latter case, spherical AgPd NPs were observed by HAADF-STEM analysis (mean diameter ca. 9.1 nm); EDS mappings evidenced the formation of alloys (Figure 12).

Platinum

Jurczakowski and co-workers prepared PdPt nanoparticles in neat EG by co-reduction of PdCl and K 2 PtCl 4 in the absence of any other reagent, leading to nanoparticles highly aggregated as proven by TEM analyses. [START_REF] Januszewska | Spontaneous Chemical Ordering in Bimetallic Nanoparticles[END_REF] These materials were used to study the spontaneous segregation of PdPt nanoalloys, mainly evidenced by the enhanced hydrogen solubility under ambient conditions together with XPS studies, proving a higher segregation trend than their bulk counterparts. These experimental results confirm the theoretical DFT studies reported by Barcaro et al. concerning the multi-shell segregation of PdPt nano-alloys. 100 In agreement with both experimental and theoretical approaches, the works described below in relation to the synthesis and characterization of well-defined PdPt nanoparticles in polyol media correspond to segregate phases (core-shell, cluster-in-cluster).

The synthesis of Pt(core)Pd(shell) nanoparticles has been mostly reported in the literature by applying the polyol methodology, according to a sequential addition of metal precursors.

Moreover, the presence of small amounts of silver salt is required, which acts as a structuremodifying agent of the Pt nanocluster seeds as proven by Viet Long, Nogami and co-workers; 101- 103 in general, silver is not detected in the final product, probably due to its precipitation or removal during the purification process. Following this strategy, José-Yacamán and co-workers have reported a deep characterization of Pt(core)Pd(shell) nanoparticles prepared in EG and using PVP as stabilizer. 104 This time, they could observe a small amount of silver in the core.

The nanoparticles obtained have cuboctahedral-octahedral and cuboctahedral-truncated tetrahedral core-shell morphology. Authors could confirm the presence of Pt core and Pd shell by HAADF-STEM images, STEM-EDS line scans and elemental maps of isolated nanoparticles (Figure 13). Pd(core)Pt(shell) nanoparticles (mean size 6.5 ± 0.6 nm) have also been prepared using flow processes under microwave irradiation, in a sequential addition of metal precursors in EG or Gly and using PVP as stabilizer; 105 EDS analysis evidenced the formation of a shell thickness of ca.

0.25 nm around the Pd core, which corresponds to one atomic layer of Pt. Harada and coworkers prepared PdPt nanoparticles showing a cluster-in-cluster structure, as proven by HRTEM, EDS and EXAFS, under both batch and continuous flow conditions. 106 These arrangements were observed in both synthetic approaches under single-mode microwave irradiation, in EG or Gly and in the presence of PVP. However, under flow conditions and in contrast to batch ones, BMNPs were better dispersed showing smaller mean size, in particular using EG as solvent.

Ruthenium

Ru(core)Pd(shell) nanoparticles have been prepared in EG using PVP as stabilizer applying a sequential procedure, where firstly a Ru core nanocluster was generated from reduction of RuCl 3 and then the palladium precursor was added forming a Pd layer around the former Ru nanoparticles. 107 The as-prepared BMNPs showed a cylinder-like shape with a high density of terrace and kinks defects in the surface (Figure 14). These Ru(core)Pd(shell) nanoparticles were then treated with a solution of H 2 PtCl 6 in EG; the surface defects of the RuPd nanoparticles were nucleation centers for promoting the growth of Pt clusters (Figure 14c). SAXS spectra corroborated the structure of the trimetallic Pt/Ru(core)Pd(shell) nanoparticles. DFT calculations found that electrons are injected to Pt nanoclusters from the core-shell, electrons localized at the near Fermi level of the nanoparticles. The size-controlled synthesis of alloy RuPd nanoparticles is particularly challenging taking into account that palladium and ruthenium are immiscible at atomic level in the bulk state. Kusada and co-workers have prepared alloyed Pd x Ru 1-x (x = 0.1, 0.3, 0.5, 0.7, 0.9) nanoparticles in TrEG by co-reduction of Ru(III) and Pd(II) salts in the presence of PVP that consisted of both fcc and hcp structures, coexisting both phases in an individual nanoparticle (Figure 15). 108 These nanomaterials exhibited higher catalytic behavior in the CO oxidation than the monometallic ruthenium nanoparticles. This type of nanoalloys has been also applied in the electrooxidation of formic acid and methanol. 109,110 As known, the control of structure and morphology of metal-based nanoparticles is crucial for establishing structure-property relationships. Therefore, it is essential to optimize all the parameters involved in the synthesis and to determine the corresponding kinetic profiles. The reduction rate of metal precursors helps to understand the mechanism involved in the formation of nanostructures. However the precursor conversion is rarely quantified, due to the difficulties to separate the formed nanoparticles from the unreacted starting material (see section 2.1.1.). [START_REF] Wang | Use of Reduction Rate as a Quantitative Knob for Controlling the Twin Structure and Shape of Palladium Nanocrystals[END_REF] With the aim of monitoring the synthesis of PdRu nano-alloys, Asano and co-workers have used a microflow reactor in order to achieve both rapid heating and a controlled short residence time. 111 Working under semi-batch conditions, samples could be collected from the reactant solution at different times and analyzed by STEM-EDS and ICP-AES (local and bulk analysis technique, respectively). This monitoring revealed a slower reducing time for Ru(III) than for Pd(II); as the reaction time increases, PdRu nanoparticles become more homogeneous in atomic composition and their mean size increase. This latter fact indicates that particle growth is more dominant than nucleation, which only seems to proceed at the beginning of the injection. In addition, the change in the atomic distribution of the Ru on the time is probably related to an intraparticle solid state diffusion. When metal precursors were added in a sequential way, the resulting BMNPs were not alloyed as evidenced by XRD.

Bismuth

Interestingly, Bi 2 Pd cube-shaped nanoparticles, with diameters from 40 to 60 nm, were prepared in neat TEG using NaBH 4 as reducing agent, showing -Bi 2 Pd structure as evidenced by powder X-ray diffraction. 112 Moreover, the microwave-assisted polyol methodology was applied in the preparation of nanosized ternary Pd 3 Bi 2 X 2 (X = S, Se) phases (ca. 50 nm), using EG as solvent;

microwave irradiation favors the dissolution of reagents, in particular in this case, elemental selenium. for FePd NPs of different compositions: FePd analyses showed the presence of NiO phase. STEM-EDS analyses proved the presence of both metals in the anisotropic BMNPs randomly distributed. As observed in previous works, [START_REF] Xiong | Understanding the Role of Oxidative Etching in the Polyol Synthesis of Pd Nanoparticles with Uniform Shape and Size[END_REF] the presence of bromide anions was able to favor the reduction of metal salts, the use of a milder reducing agent and relative low temperatures permit to privilege the growth of NPs over some facets; in this work, for TTAB/total metal molar ratio lower than 50/1, (100) and (110) facets were favored, thus leading to cubic and rod-like bimetallic nanoparticles (Figure 17). For a summary of polymetallic Pd-based NPs synthetic conditions and characterization outcomes, see Table S2 in the Supporting Information.

Hydroxyl compounds from natural sources

The synthesis of metal nanoparticles by chemical bottom-up methodologies involves multiparameter protocols; the kind of metal precursor (salts or well-defined organometallic compounds), solvent, reducing agent and stabilizer are particularly crucial in order to produce nanomaterials with well-defined morphology, structure and surface state, features undoubtedly related to their distinctive physicochemical properties. [START_REF] Schmid | Nanoparticles: From Theory to Application[END_REF][START_REF] Adil | Biogenic Synthesis of Metallic Nanoparticles and Prospects Toward Green Chemistry[END_REF] In the last years, a special emphasis has been devoted to develop environmentally friendly procedures, mainly using polyfunctional reagents coming from natural sources. [127][128][129] In the biogenic synthesis of metal nanoparticles, the use of extracts from plants has experienced a significant growth due to the chemical reduction properties shown by polyphenols, alkaloids, polysaccharides and terpenoids among others, commonly present in their composition; they can also act as stabilizers using in general water as solvent. [START_REF] Adil | Biogenic Synthesis of Metallic Nanoparticles and Prospects Toward Green Chemistry[END_REF] Most of the reported methods consist in the direct use of extracts from different plants coming from diverse parts (leaves, roots, flowers, fruits), but often without identification of the molecules responsible of the nanoparticles formation. [START_REF] Adil | Biogenic Synthesis of Metallic Nanoparticles and Prospects Toward Green Chemistry[END_REF] These works were initially focused on silver and gold, 130,131 but in the last ten years some contributions concerning palladium, both mono and bimetallic Pd-based nanoparticles and supported counterparts has been published. 132,133 In the present review, we highlight the contributions focusing on characterization and PdNPs formation mechanisms using plant extracts.

One of the first reports concerning the synthesis of PdNPs using natural extracts was reported by

Varma and co-workers in 2008, using coffee and tea extracts. 134 For the different brands of tea and coffee used, PdNPs were formed in aqueous solution from PdCl 2 in the presence of the corresponding natural extract at room temperature, obtaining spherical particles from ca. 5 to 40 nm (Figure 19). The extracts are mainly constituted by caffeine and polyphenols. The reduction potential of caffeine is 0.3 V vs SCE which is enough to reduce Pd(II) salts (Pd(II) reduction potential is 0.915 V vs SCE); polyphenols and oxidized caffeine are proposed as capping agents avoiding the agglomeration of particles. Analogously, other authors have applied a similar procedure using other types of extracts.

Therefore, Philip and co-workers prepared spherical and small nanoparticles (mean size in the range 2.5-4.5 nm) from extracts of Anacardium occidentale leaves; authors stated that the water soluble polyols act as reducing agents of Pd(II) ions. 135 Li and co-workers also obtained regular and small spherical nanoparticles (mean size in the range 3.2-6.0 depending on Pd(II) ions concentration) using Cinnamomum camphora extract leaves, proving that polyols are the responsible of the metallic ions, favoring the stabilization of PdNPs. 136 Bigger nanoparticles (mean size ca. 20-25 nm) were obtained from Pulicaria glutinosa extracts; 137 authors proved that the plant extract not only acts as bioreducing agent but also as capping agent as evidenced by FTIR spectroscopy. More recently, Kim and co-workers have reported the synthesis of PdNPs using fruit juices, leading to spherical PdNPs exhibiting uniform size distributions (between 2-25 nm depending on the juice type); 138 they have proved that sugars and polyols present in the juices are in a first time reducing agents, and inhibiting the agglomeration of nuclei in a last stage; the as-prepared PdNPs showed size-dependent SERS activities with applications in ultrasensitive detection of organic molecules. Cynarine, a hydroxycinnamic acid extracted form artichoke leaves, 139 Charanthus roseus leaf extract where eight metabolites were identified by GC-MS, 140 and Terminalia chebula aqueous extract where polyphenols act as reducing agents and their oxidized forms as stabilizers 141 led to the formation of bigger PdNPs (ca. from 25 to 100 nm) in the presence of anisotropic particles. 141 It is important to highlight that the biosynthesis of metalbased nanoparticles is also an efficient approach to prepare bimetallic nanoparticles. In this frame, Li and co-workers have reported the preparation of alloyed PdAu nanoparticles, synthesized from Cacumen platycladi leaf extract, exhibiting a mean size of 7.4 nm. 142

Pd-based nanocatalysts applied in hydrogenations

Organic synthesis involving the activation of small nonreactive molecules, such as H 2 , N 2 , NH 3 , H 2 O, and CO 2 by transition metal catalysts or by enzymes represents an attractive approach for industrial purposes in terms of high atom-efficiency. As an example, catalytic hydrogenation remains the main reaction for the reduction of unsaturated bonds. [143][144][145][146] Current researches in this field tackle the improvement of H 2 production processes, together with the enhancement of catalyst performance and reaction medium optimization towards greener and safer hydrogenation protocols.

To override both the dependence on fossil fuels and diminish CO 2 emissions associated to classical H 2 production processes, alternatives consisting in its generation from NH 3 , 147 biomass resources, 148 water splitting 149 or hydrogen transfer reactions are actively sought. 150 Concerning the choice of solvent used for hydrogenation applications, alternatives to classical organic solvents are actively pursued due to the risks associated to their high flammability, toxicity and volatility properties. 151 The solvent plays key roles in hydrogenation reactions: First, due to the interactions with the substrate (polarity, solubility, mass transfer) [152][153][154] or/and with the catalyst; 155,156 but also due to the solubility of H 2 gas in the medium. 157 The H 2 solubility in alcohol clearly increases with temperature and pressure and also with the number of carbon atoms; the solubility of H 2 is higher in mono-alcohols than in diols (e.g. Henry's constant diminishes from 20000 in 1,2-ethanediol to 4000 bar -1 in ethanol at 50 °C). 158 The O 2 solubility follows a similar trend. 159

The quest for hydrogenation catalysts exhibiting enhanced selectivity and reactivity is an active research field for Pd, Ru, Rh, and Ir transition metal complexes. 160 Nanocatalysis in particular offers privileged means towards hydrogenation processes, given the extended surface area ratios. 161,162 Pd NPs, for instance, show high reactivity towards H 2 activation 163-166 as palladium is known to adsorb up to 900 times its own volume. 167,168 Thus, the (chemo)-selectivity of these nanomaterials towards hydrogenation is highly controlled by surface interactions with the modifiers/stabilizers, the substrates or even the supports. 169,170 In this section, we describe the use of palladium nanoparticles as hydrogenation catalysts in polyols. A few reports concerning bimetallic Pd based NPs have been described for hydrogenations in EG. In this context, bimetallic PdNi NPs were active in the hydrogenation of nitrobenzene under smooth conditions (30 °C and atmospheric pressure of H 2 ). 121 Moreover, PdCo NPs were efficient catalysts for both hydrogenation and oxidation of C=C bonds. Nearambient pressure XPS spectra (NAPXPS) revealed that Co(0) and Co(III) sites are the responsible of the hydrogenation and oxidation of styrene, respectively; this dual catalytic behavior was attributed to the intrinsic electronic modifications between the two metals during the catalytic processes. 120 Hitherto, mostly hydrogenations conducted in PEG and glycerol have been reported in the literature.

Hydrogenation reactions catalyzed by PdNPs in PEG

Polyethylene glycols (PEG) are interesting for catalysis because they are soluble in polar and non-polar solvents and insoluble in aliphatic hydrocarbons. 171 They are inexpensive and less hazardous than other organic solvents. Additionally, PEG are stable under ambient conditions due to their negligible vapor pressure and do not release volatile organic compounds. The applications of PEG in hydrogenations involve three aspects: i) phase transfer catalysts, 172 ii) supported catalysts, 173 and iii) solvents. 174,175 In relation to the solubility of H 2 , for example for PEG400 is higher compared to an ionic liquid such as 1-ethyl-3-methylimidazolium tetrafluoroborate. 176 Based on the work of Zhang and coworkers, 177 PdNPs were prepared in PEG from decomposition of Pd(OAc) 2 by polyol methodology at 90 °C for 2 h. 178 It was observed that for a same concentration in precursor and the same mass of PEG, the size of the PdNPs increases with the molecular weight of polymer (PdNPs of 3-5 nm mean diameter for PEG800 and PEG1000;

7-9 nm for PEG2000 and 19-23 nm for PEG4000). These as-prepared PdNPs were tested for the hydrogenation of cyclohexene as benchmark reaction (with a substrate/Pd ratio of 5500:1 at 70°C). With PEG4000 the viscosity of the polymer is too high triggering a low conversion of cyclohexene; PdNPs obtained in this solvent were larger than the previously described under similar conditions 177,179 Among these catalysts, PdNPs stabilized by PEG2000 showed the highest activity and was used to run the hydrogenations of differently substituted alkenes (Scheme 1). The authors explained that small particles are not the most active due to the smaller distance between the polymer and the metallic surface which disfavors the mass transfer. These catalysts are highly active; with PdPEG1000-NPs and PdPEG2000-NPs, 60 and 55 min respectively were needed to reach full conversion of cyclohexene, in comparison to Pd/C which required higher pressure of H 2 (40 bar instead of 10 bar for PEG1000 and PEG2000).

Scheme 1. Pd-catalyzed hydrogenation of different alkenes catalyzed by PdNPs in PEG2000. 178 In the field of biodiesel development, there is an increasing interest in Z-mono-unsaturated compounds instead of poly-unsaturated ones while avoiding side Z/E olefin isomerization in order to improve the cold-flow properties as fuels. In this context, Later on, the same authors have adapted the experimental conditions to the partial hydrogenation of sunflower oil derived fatty acid methyl esters (FAME). 180 The best conditions were the following ones: FAME/Pd = 2000, 80 °C, 20 bar H 2 , and 1500 rpm stirring speed. This methodology permitted to obtain full conversion of methyl linoleate with a high selectivity towards methyl oleate (85%), while minimizing the total reduction towards stearic acid (only 7%). This catalyst was reused up to 5 times without loss of activity nor selectivity.

The Wang group developed a thermoregulated PEG biphasic system, where PEG was used as stabilizer of PdNPs and also as a catalytic biphasic system with a toluene/heptane mixture. When the solution was heated at 70 °C, the system became monophasic and when cooled, the organic compounds could be easily separated from the PEG-Pd catalytic phase. 181 PdNPs stabilized by PEG4000 were in situ formed in this mixture of solvent of PEG4000/toluene/heptane = 2/3/1 using Pd(OAc) 2 as precursor for the hydrogenation of 1,5-cyclooctadiene (1,5-COD). The asprepared PdNPs exhibited a mean diameter size of 3.1 ± 0.8 nm. The best conditions to get high conversion in 1,5-COD and high selectivity in cyclooctene are presented in Scheme 3.

Scheme

3.

Hydrogenation of 1,5-cyclooctadiene catalyzed by PdNPs in PEG4000/toluene/heptane biphasic system. 181 Later, the same authors used hydrated Na 2 [PdCl 4 ] as metallic precursor for the analogous synthesis of thermoregulated PdNPs in a PEG4000/toluene/heptane biphasic system. The asprepared catalyst featuring nanoparticles of a smaller size (1.9 ± 0.5 nm) than the ones obtained previously from Pd(OAc) 2 were applied for the hydrogenation of cinnamaldehyde (Scheme 4). 182 This catalytic biphasic phase was recycled up to eight times without loss of activity; nor PdNPs size changes were evidenced by TEM, nor Pd leaching in the organic fractions, which were analyzed by ICP-AES.

Scheme 4. Hydrogenation of cinnamaldehyde catalyzed by PdPEG4000/toluene/heptane in biphasic conditions. 182 The use of stabilizers in combination with PEG leads to tailor-made PdNPs active nanocatalysts. 183 Based on a work described by Huang and coworkers in ionic liquids, 184 phenanthroline was used to stabilize PdNPs in PEG and used as catalyst for the hydrogenation of a series of aliphatic alicyclic and aromatic olefins (Scheme 5). The experimental conditions were optimized by using cyclohexene as substrate and varying different parameters such as temperature, amounts of Pd, PEG and stabilizer, the nature of palladium precursor [Pd(OAc) 2 , PdCl 2 , Pd(acac) 2 , (acac = acetylacetonate)], the nature of the metal (acetates of Cu, Ni, Co and Zn), and the stabilizer (phenanthroline, PVP, 1-hexadecylaniline). In this study, authors postulated that the molecular weight of PEG had no noticeable influence on the activity of the catalyst, but no experimental data is reported in the paper to support this conclusion. It was proved that phenanthroline prevents the agglomeration of PdNPs (mean size in the range 2-6 nm determined by TEM), giving more active PdNPs catalysts compared to the non-stabilized ones in PEG (mean size in the range 500-1000 nm determined by TEM); but what is noteworthy to mention is that the recyclability of the catalyst was not affected by the absence of phenanthroline and the activity increased after the first run (84% conversion of cyclohexene for the first run and 100% for the second one, maintaining a full conversion up to the sixth run). That point was ascribed by the authors to the fact that the palladium precatalyst was not fully converted after the first run towards the formation of nanoclusters. The two other stabilizers (PVP and 1hexadecylaniline) gave the same catalytic behavior than phenanthroline under the same conditions. Notably, the metal leaching promoted by phenanthroline has not been studied (no experimental data is reported); thereby the contribution of homogeneous catalytic regime cannot be excluded.

Hydrogenation reactions catalyzed by PdNPS in glycerol

Glycerol presents many advantages, namely, it is nontoxic and biodegradable, it can be produced from renewable sources, and it is able to dissolve many organic compounds. Many organic syntheses have been described thus far in glycerol. 185,186 In our research team (see section 2.1.2), we developed an efficient catalytic system composed of PdNPs dispersed in neat glycerol and stabilized by TPPTS. [START_REF] Chahdoura | Palladium Nanoparticles in Glycerol: A Versatile Catalytic System for C-X Bond Formation and Hydrogenation Processes[END_REF] In the absence of TPPTS, PdNPs agglomerated and precipitated in glycerol. These nanoparticles were prepared under H 2 in glycerol as solvent, without observing any hydrogenolysis of the solvent. The best active catalytic system was obtained starting from Pd(OAc) 2 using 1 equiv. of TPPTS giving nanoparticles with a mean diameter size of 4.1 ± 1.4 nm. This catalyst was highly active for the hydrogenation of alkenes, alkynes, and nitro compounds (Scheme 6). 74 Scheme 6. Hydrogenation of styrene derivatives, alkynes and nitro compounds catalyzed by PdTPPTS NPs in glycerol. [START_REF] Chahdoura | Palladium Nanoparticles in Glycerol: A Versatile Catalytic System for C-X Bond Formation and Hydrogenation Processes[END_REF] This catalytic colloidal solution of PdTPPTS NPs in glycerol was also applied in sequential coupling/hydrogenation processes (Scheme 7). [START_REF] Chahdoura | Palladium Nanoparticles in Glycerol: A Versatile Catalytic System for C-X Bond Formation and Hydrogenation Processes[END_REF] hydrogenation of E-4-phenylbut-3-en-2-one and was recycled up to ten times without loss of activity (Scheme 9). Notably, the size of the PdPTA NPs was smaller after the tenth run, which could be explained due to an inter-particle reorganization under the catalytic conditions in glycerol.

Scheme 9.

Hydrogenation of E-4-phenylbut-3-en-2-one and coumarin catalyzed by PdPTA NPs in glycerol. [START_REF] Chahdoura | Palladium Nanoparticles Stabilised by PTA Derivatives in Glycerol: Synthesis and Catalysis in a Green Wet Phase[END_REF] Furthermore, PdPTA nanocatalyst was also applied towards the reduction of 4nitroacetophenone into 4-aminoacetophenone, however further ketone group reduction to 4ethylaniline was also observed (Scheme 10). 76

Scheme 10. Hydrogenation of 4-nitroacetophenone catalyzed by PdPTA NPs in glycerol. [START_REF] Chahdoura | Palladium Nanoparticles Stabilised by PTA Derivatives in Glycerol: Synthesis and Catalysis in a Green Wet Phase[END_REF] This catalyst was also active in sequential C-C coupling/hydrogenation processes for the synthesis of 4-phenylaniline, affording exclusively this product in 54% yield (Scheme 11). 76

Scheme 11. Sequential Coupling/hydrogenation catalyzed by PdPTA NPs in glycerol. [START_REF] Chahdoura | Palladium Nanoparticles Stabilised by PTA Derivatives in Glycerol: Synthesis and Catalysis in a Green Wet Phase[END_REF] More recently cinchona based alkaloids were also used as PdNPs stabilizers in glycerol. [START_REF] Reina | Palladium Nanoparticles Stabilised by Cinchona-based Alkaloids in Glycerol: Efficient Catalysts for Surface Assisted Processes[END_REF] The best active catalytic system was obtained starting from Pd(OAc) 2 (among [PdCl 2 (COD)] and [Pd 2 (dba) 3 ]) using 1 equiv. of quinidine (among cinchonidine, cinchonine, quinine and quinidine). Quinidine leads to a better dispersion of the particles according to the TEM images with a mean diameter size of 1.4 ± 0.3 nm. Notably, Pd-cinchona based NPs are more active for the hydrogenation of E-4-phenylbut-3-en-2-one compared to the previously described PdTPPTS NPs (Scheme 12).

Scheme 12.

Hydrogenation of E-4-phenylbut-3-en-2-one catalyzed by PdNPs in glycerol. [START_REF] Reina | Palladium Nanoparticles Stabilised by Cinchona-based Alkaloids in Glycerol: Efficient Catalysts for Surface Assisted Processes[END_REF] The PdNPs stabilized by quinidine were applied in the hydrogenation reaction of various alkenes and alkynes (Scheme 13). [START_REF] Reina | Palladium Nanoparticles Stabilised by Cinchona-based Alkaloids in Glycerol: Efficient Catalysts for Surface Assisted Processes[END_REF] It is noteworthy to mention that in the case of 1-dodecene, only 1% of isomerization product was detected for 99% conversion into dodecane.

Scheme 13. Hydrogenation of different alkenes and alkynes catalyzed by PdNPs stabilized by quinidine in glycerol. [START_REF] Reina | Palladium Nanoparticles Stabilised by Cinchona-based Alkaloids in Glycerol: Efficient Catalysts for Surface Assisted Processes[END_REF] More interestingly the as-prepared PdQN NPs were also applied towards catalytic syntheses of secondary and tertiary amines from carbonyl and amine reagents, as well as in the synthesis of N-substituted anilines from nitrobenzene and aldehydes by one-pot reductive amination; in addition, PdQN NPs were efficient catalysts for hydrodebromination reactions (Scheme 14). Bimetallic nanoparticles also have been synthetized in alternative solvents for catalytic proposes as hydrogenation reactions. [START_REF] Dang-Bao | Bimetallic Nanoparticles in Alternative Solvents for Catalytic Purposes[END_REF]190 They represent an attractive catalytic system thanks to the synergistic effects between both metal partners; the addition of a "guest" to a "host" metal in a same entity could modify its electronic properties (by charge transfer, orbital hybridization…) and/or structure (alloy, core shell...). 191 In our group, PdCu BMNPs were prepared in glycerol under H 2 pressure (as for the Pd NPs previously described) via two main strategies: co-and sequential reduction. 126 Pd(OAc) 2 and Cu-TMEDA, [[Cu( 2 -N,N,N',N'-TMEDA)(-OH)] 2 Cl 2 , TMEDA = tetramethylethylenediamine] were used as metal precursor and PVP (Mw = 10000 g/mol) was used as stabilizer. Under these conditions, only co-reduction processes permitted to obtain BMNPs (see section 2.2.2). The as-prepared BMNPs were tested in the catalytic semihydrogenation of alkynes (Table 1). a Reaction conditions: 1 mmol of diphenylacetylene or phenylacetylene in the catalytic solution, 0.5 mol% total palladium (or copper), 1 bar of H 2 at 80 ºC for 2 h. b Determined by GC-MS using decane as internal standard. c Data using a substrate:palladium ratio of 1000.

With the aim of studying reactivity-structure relationships, the as-prepared BMNPs were tested in the semihydrogenation of phenylacetylene and diphenylacetylene. A similar catalytic behavior was observed for both substrates (Table 1). Actually, PdCu nanoalloys (obtained for Pd:Cu molar ratio = 1:2) and cluster-in-cluster structure (obtained for Pd:Cu molar ratio = 1:1) gave exclusively the formation of the corresponding alkene (entries 4-5 and 9-10, Table 1), in contrast to the behavior observed for an equimolar mixture of individually prepared monometallic nanoparticles, i.e. PdNPs and CuNPs, mainly obtaining the full hydrogenated alkanes (entries 3 and 8, Table 1). Using low load of palladium (substrate:palladium ratio = 1000), monometallic

PdNPs catalyzed the semihydrogenantion of diphenylacetylene favoring in this case the formation of Z-stilbene (entry 1). These results proved that even though very small amount of palladium is present on the surface of MNPs, the semihydrogenation reaction of alkynes is possible, in agreement with the behavior observed using PdCu BMNPs. applications in many other disciplines, such as material science, biomedicine, and electronics. 1,[192][193][194] Transition metals are among the most versatile elements for enabling these coupling reactions by providing energetically affordable reaction pathways. 195,196 Nanocatalysis permits to envisage novel avenues towards substrate activation by a combination of both homogeneous and heterogeneous reaction manifolds. [197][198][199][200] Among transition metals, Pd exhibits a prevalent role notably due to its catalytic activity towards C-C cross-coupling reactions and related transformations. [START_REF] Johansson Seechurn | Palladium-Catalyzed Cross-Coupling: A Historical Contextual Perspective to the 2010 Nobel Prize[END_REF]198,[201][202][203][204] Pioneering studies by Beletskaya, 205 Reetz 206 and de Vries 207

showed that Pd nanoparticles can activate aryl halide substrates (iodides and, in some cases, bromides) at ppm concentrations, enabling C(sp 2 )-C(sp 2 ) cross-coupling reactions (Heck and Suzuki-Miyaura) at catalyst turnover numbers as high as 540,000. Furthermore, the increasing of the catalyst turnover with the decreasing Pd/substrate ratios suggested that a homogeneous mechanism by metal leaching could be operative for the Heck reaction. [208][209][210] These very low catalyst loadings have enabled a direct entry towards nanoparticle-leveraged sustainable approaches 199,211,212 via immobilization on solid supports 213 or biomass-derived solvents as liquid phases. 214 Astruc and co-workers have recently showed that PdNPs supported on supramolecular dendrimeric assemblies featuring tri(ethylene glycol) tethers exhibit high catalytic activities and turnover numbers at low catalytic loadings (0.01 mol%) for Suzuki-Miyaura reactions. 210,215 From a mechanistic point of view, many efforts have been addressed with the aim of elucidating the nature of the active palladium species involved in C-C couplings: homogeneous (reagents interact with one active site) or heterogeneous (reagents interact with neighboring sites), based on the modern definition proposed by Schwartz 216 surpassing the classical definition based on the catalyst solubility. Studies for distinguishing the catalyst nature include kinetics, poison experiments (Hg, CS 2 …), polymer test, hot filtration, catalyst characterization after catalysis. [START_REF] Phan | On the Nature of the Active Species in Palladium Catalyzed Mizoroki-Heck and Suzuki-Miyaura Couplings -Homogeneous or Heterogeneous Catalysis, A Critical Review[END_REF]217,218 Several reports on the utilization of polyol medium both as reducing agent of metal precursor, as well as matrixes for nanoparticle immobilization have been described in the literature. 219 The low cost, nontoxicity and eco-friendliness of most polyols (glycerol, PEG) makes them solvents of choice for a number of catalyzed reactions, with significant advantages over ionic liquids and perfluorinated solvents. 220 Moreover, the polarity of polyol media has non-negligible effects in facilitating catalytic activity. 172 In particular, polysaccharides are adequate polyol materials exhibiting high stability and recyclability for catalysis. 221,222 This section intends to give an overview and critical summary of research achievements in the use of both polyol medium and polyols embedded into polymeric matrixes in coupling reactions.

Dimerization of alkynes.

Pd-catalyzed dimerization of terminal alkynes provides a straightforward method for the synthesis of 1,4-disubstituted enynes. 223 However, very few reports in polyol leveraged nanocatalytic systems have been reported thus far. For instance, Firouzabadi, Iranpoor and coworkers have reported the dimerization reaction of phenylacetylene in air under ligand-and amine-free conditions using PEG400 as solvent at 100 °C to furnish the homo-coupled E-enyne product in 70% isolated yield (Scheme 17). The reaction proceeds in air with high regio-and stereoselectivity. 224 Further mechanistic studies for this transformation are required to identify the active catalytic species and the catalytic regime.

Scheme 17. Pd-catalyzed dimerization of phenylacetylene. 224

C(sp)-C(sp 2 ) Sonogashira cross-coupling

The Sonogashira coupling is a Pd-catalyzed cross-coupling reaction that forms a new C-C bond between a terminal alkyne and an sp 2 -carbon halide (most notably, aryl or vinyl). 225 This reaction was initially reported with a Cu(I) co-catalyst in the presence of a base under anaerobic and anhydrous conditions, but other methods have been later reported to overcome these limitations.

For the Cu-free version in particular, the activation of the terminal alkyne derivative is achieved by formation of Pd(II) monoacetylide and Pd(II) bisacetylide complexes in the presence of base, which are competent species to undergo the corresponding transmetallation under mild reaction conditions. The proposed catalytic cycle encompasses an oxidative addition of the aryl halide to the zero-valent Pd catalyst, generating a Pd(II) complex which is involved in the transmetallation step with the Pd(II) bisacetylide complex, followed by reductive elimination to deliver the disubstituted alkyne product and the regeneration of the zero-valent Pd species completing the catalytic cycle (Figure 20). 226 Homogeneous catalysts were first described as active catalytic species for this transformation. In 2006, Corma, García and co-workers described the use of a covalently immobilized oxime carbapalladacycle on PEG (averaged Mw 6000 Da) as a reusable catalytic system for a copperfree Sonogashira couplings (up to 10 recyclings). 219 Despite the stability of the anchored molecular catalyst on heating over extended periods in PEG, it decomposed during catalysis to form palladium nanoparticles which were active towards copper-free Sonogashira couplings and enabled catalyst recycling up to 10 times with no significant decrease in activity. 219 The authors highlight that the reactants employed during catalysis can have an impact in the size of the in situ formed nanoparticles, which can lead to broad particle size distribution. However, the most active in situ formed nanocatalytic systems were those featuring average particle size of 6 ± 2 nm. 219 Another highly activity heterogenized Cu-free catalytic system with agarose as support for the Sonogashira reaction with low catalyst loading (0.5 mol%) has been recently described by

Firouzabadi, Iranpoor and co-workers. 227 Despite the fact that the authors describe a stabilizerfree catalytic system for this cross-coupling reaction of various aryl halides with phenyl acetylene in PEG400, the effect of the polyol polymeric support, namely agarose as stabilizer for the palladium nanoparticles is not negligible (Scheme 18). 227 The same authors have also reported a similar strategy for the use of edible gelatin as both reducing agent of Pd(II) salt precursors and support for PdNPs exhibiting high activity towards amine-free catalyzed Sonogashira reaction. Thus, (hetero)aryl halides or even β-bromo styrene reacted with phenylacetylene at 100 °C in PEG400 medium under Ar to yield the desired crosscoupling products in high selectivity and moderate to high yields (Scheme 19). 224

Scheme 19. Amine-free Sonogashira reaction in PEG medium. 224 Moreover, EG has also been used as reducing and dispersing agent for the preparation of highly efficient Sonogashira nanocatalysts based on PdCo BMNPs grafted on three-dimensional graphene nanocomposites by Dabiri and co-workers. Progress on the classical fluoride-assisted Pd-catalyzed C(sp/sp 2 /sp 3 )-C(sp 2 ) Hiyama crosscoupling 229 has yielded safe alternatives that preclude the risks associated to the handling of fluoride. 230,231 The key step of this reaction involves the formation of a pentavalent silicon species that is capable to undergo transmetalation with the Pd center. In the classical version, the formation of such species was driven via the formation of pentacoordinated fluorosilanes due the high affinity of F and Si, but organosilanols either in the presence of Brønsted bases or as their silanolate salts are also competent species to undergo transmetalation (Figure 21). 232 The postulated Hiyama-Denmark cross-coupling reaction mechanism was believed to operate under homogenous regime; however, Nájera and co-workers identified the decomposition of Pd(OAc) 2 or even 4-hydroxyacetophenone oxime-derived palladacycles towards the formation of PdNPs at catalyst loadings up to 0.01 mol% when tetrabutylammonium bromide was used as stabilizer. 233 Nanoparticles can act as homogeneous catalysts (reservoirs of active molecular species), surface reactivity, or a combination both processes.

For instance, Sarkar and co-workers have described the synthesis of PdNPs using a tungsten carbene complex as reducing agent and PEG6000 as capping agent in water. 234 The as-prepared nanocatalysts (average particle size 9.70 nm) catalyzed the Hiyama-Denmark cross-coupling reaction with low catalyst loadings (1 mol %) in air (Scheme 20). 234

Scheme 20. PdNPs leveraged Hiyama cross-coupling of arylsiloxanes with aryl bromides. 234 Recent studies on the Hiyama-Denmark cross-coupling leveraged by preformed PdNPs in glycerol medium shed light on the key role of different additives; not only to ensure the kinetic stabilization of the colloidal catalyst systems, but also the coordination mode between these additives and the metal surface modifying the reaction manifold. 235 Thus, our group has described a highly active preformed Pd nanocatalyst system featuring small PdNPs (mean diameter 1.8 ± 0.4 nm) using TPPTS in glycerol. 235 TPPTS favors the leaching and further stabilization of Pd(II) molecular complexes thanks to the strong P-Pd bond. 235 The as-prepared catalytic system exhibited substrate-dependent chemoselectivity towards the expected Hiyama- The Heck-Mizoroki cross-coupling reaction was the first example of a Pd catalyzed C(sp 2 )-C(sp 2 ) bond-forming reaction between aryl or vinyl halides and olefins. 237,238 The initially proposed Pd(0)/Pd(II) catalytic cycle under homogeneous conditions encompasses the oxidative addition an aryl or vinyl halide to a zero-valent Pd center to generate an electrophilic Pd(II)

species that can coordinate with an olefin via a π interaction, followed by alkene insertion in the Pd-C(sp 2 ) bond via a syn addition step. The generated intermediate undergoes then a β-hydride elimination to deliver the C(sp 2 )-C(sp 2 ) cross-coupling product and the residual hydrido(halo)palladium(II) complex regenerates the initial Pd(0) by reductive elimination. In the course of the reaction, the base is stoichiometrically consumed (Figure 22).

However, the formation of nanoparticles in Heck-Mizoroki cross coupling reactions has been evidenced in many literature reports most of them under ligand-free conditions. 209 Palladium is known to give unstable and polydisperse solutions in the absence of polymers or amphiphilic stabilizers encompassing catalyst deactivation and precipitation of Pd black aggregates. 209,239 The obtention of monodispersed systems is thus highly envisaged for enhancing the catalyst activity. In this context, the use of polyol medium in combination with palladium salts or organometallic complexes leads to the formation of zero-valent Pd nanoparticles both under classical thermal treatment and ball-milling conditions. [START_REF] Declerck | Poly(ethylene glycol) as Reaction Medium for Mild Mizoroki-Heck Reaction in a Ball-mill[END_REF]221,240 Lamaty at al. have reported a phosphine-free Mizoroki-Heck reaction using ball-milling in PEGs and methyl ethers derivatives of different molecular weights, obtaining good to excellent yields of cross-coupling products. [START_REF] Declerck | Poly(ethylene glycol) as Reaction Medium for Mild Mizoroki-Heck Reaction in a Ball-mill[END_REF] Notably, this activation technique allowed the formation of PdNPs of 4 ± 2 nm (average diameter size) from Pd(OAc) 2 in the time course of the reaction when sodium formate was used (as characterized by TEM analysis of the reaction crudes). [START_REF] Declerck | Poly(ethylene glycol) as Reaction Medium for Mild Mizoroki-Heck Reaction in a Ball-mill[END_REF] Another example of Heck-Mizoroki cross-coupling reaction catalyzed by PdNPs supported on optically-active polymeric supports has been described by Frey and co-workers 240 The authors described the encapsulation of PdNPs of 1-5 nm average sizes from PdCl A key elementary step of this transformation has been classically described as an oxidative addition of an aryl halide to a zero-valent Pd center taking place under a homogenous regime.

However, Razler and co-workers identified the formation of in situ-generated 15 ± 5 nm PdNPs from Pd(OAc) 2 after only 1 min of reaction in PEG media by TEM analysis. 244 Thus, the impact of the in situ formed nanoparticles on the operating catalytic cycles needed further studies. Corma, García and co-workers reported that small size nanoparticles have a key role in facilitating the oxidative addition involving the formation of aryl Pd(II) intermediates, 219 but the nanocatalysts regimes, i.e. reservoirs of molecular species or surface heterogeneous-like catalysts remain still not clear. Catalyst heterogenization on inorganic supports (SiO 2 , Al 2 O 3 , zeolites) or organic polymers has received an increasing interest in the scientific community, with special emphasis on entrapped nanoparticles in polymeric matrixes. 197,245 Furthermore, Pd nanocatalysis enables one-pot, two-step processes to transform aryl and benzyl halides into unsymmetrical biaryls and diarylmethanes via sequential borylation-Suzuki-Miyaura coupling as reported by Sarkar and co-workers. 246 The authors described the synthesis of nanoparticles of 6 nm average diameter size by thermal treatment at 70 ºC of K 2 [PdCl 4 ] in PEG for 15 min. The preformed nanoparticles catalyzed the synthesis of aryl/benzyl boronates from their chloro and bromo precursors (in low catalyst loadings 2-3 mol%). 246 This example highlights the fact that planar trigonal B centers preclude the in situ transmetallation of the boronate ester products formed in moderate to good yields (50-78%) using KOAc as mild base.

However, the addition of CsF in combination with the aryl halide of choice to the reaction medium enabled the Suzuki-Miyaura cross coupling reaction manifold. In particular, the high affinity of fluoride and boron might trigger the formation of the corresponding ate complex, leading to the pyramidalization of boron. The boron center is then poised to undergo transmetallation with Pd, which is the elementary step needed for the Suzuki-Miyaura crosscoupling reaction manifold. This sequential strategy with a preformed Pd nanocatalyst was applied in one-pot towards the synthesis of both unsymmetrically and symmetrically substituted bis-aryls and diarylmethanes (55-75% isolated yields). 246 The efficiency of similar phosphine-free Suzuki-Miyaura cross-coupling of (hetero)aryl bromides with (hetero)arylboronic acids has been carried out at preparative scale in PEG medium allowing the isolation of the desired bis-aryl products in good to excellent yields after an aqueous workup. 244 Moreover, the advantages of glycerol for the immobilization of the Pd nanocatalysts in liquid phases has been extensively studied in our group. Controlled syntheses in glycerol of preformed nanoparticles were carried out starting from metal salts or organometallic complexes under H 2 pressure (1 to 3 bar) with different stabilizers P-and N-containing stabilizers, such as TPPTS 187

or cinchona-based alkaloids (cinchonidine, quinidine). 187,235 The as-prepared zero-valent homogeneously dispersed PdNPs exhibited spherical morphology and mean diameters in the range of 1.4-2.1 nm, as determined by TEM analyses. The kinetically stabilized colloidal solutions with TPPTS showed excellent catalytic properties towards facilitating cross-coupling reactions and prolonged activity upon recycling preserving its selectivity. [START_REF] Chahdoura | Palladium Nanoparticles in Glycerol: A Versatile Catalytic System for C-X Bond Formation and Hydrogenation Processes[END_REF]187,235 The literature reports on ligand-free Suzuki-Miyaura cross-coupling reactions under aerobic conditions attire great attention, as the presence of O 2 has thus far been deleterious towards the cross-coupling reaction. For instance, Liu and co-workers report ligand-free in situ generated nanocatalysts to work under aerobic conditions in PEG400 at room temperature for the coupling of aryl chlorides and boronic acids. 247 The in situ generated nanoparticles of 1.5 nm in average diameter size were more active than preformed ones. This can be explained by Ostwald ripening or agglomeration under the reported ligand-free conditions. 247 Despite the authors do not comment on the solubility of O 2 gas in PEG400 used as solvent for this transformation, this might be a key parameter to preclude competing side reactions such as the homo-coupling of boronic acid derivatives. Indeed, Moreno-Mañas and co-workers 248 and Amatore, Jutand and collaborators 249 reported the key role of O 2 in the formation of palladium (II) peroxo species capable of undergoing two successive transmetallation events with boronic acid derivatives to generate the corresponding homo-coupling products in a competitive fashion to the analogous transmetallation to a Pd(II) center generated by the oxidative addition of an aryl halide to Pd(0) in the classical Suzuki-Miyaura cross-coupling reaction (Figure 23). Progress on the mechanistic insight of this elementary step has revealed that pre-transmetallation complexes containing Pd-O-B linkages are kinetically competent species poised for transmetallation. 250,251 Despite the 0.5 equiv. excess of boronic acid derivatives used by the authors compared to aryl halides, the role of the ionic liquid polymer in precluding the homo-coupling reaction manifold merits further studies. Nájera and co-workers have recently described the use of a mixture of glycerol and urea for the preparation of carbon quantum dots (CQD) on magnetite composites which were used as supports for the immobilization of PdNPs (Pd@CQD@Fe 3 O 4 , Scheme 24). 254 The as-prepared catalytic composites catalyzed the Suzuki-Miyaura cross coupling reaction of aryl bromides and boronic acids at low catalyst loadings (0.3 mol% Pd), exhibiting uniform particles of 15-20 nm in size, but Pd species could not be distinguished from the magnetite cores. 254 TEM analysis of the magnetically recycled catalyst after ten runs showed that the structure of the composite was preserved; leaching of Pd and Fe after ten runs was 16 and 0.2%, respectively; which could explain the small decrease in yield observed for the reaction of 4-iodoanisole with phenylboronic after to 10 catalytic runs. 254

Scheme 24. Palladium supported on glycerol-derived carbon quantum dots and magnetite composites. Reproduced with permission from John Wiley and Sons, 254 license number 4558650798931.

Bathula and co-workers employed Pd nanocatalysts from fenugreek tea for the Suzuki-Miyaura cross-coupling reaction between bromobenzene and phenyl boronic acid at a low catalyst loading (0.5 mol% Pd) in a solvent mixture of polyethylene glycols and water, affording the corresponding 1,1'-biphenyl in 96% yield. 255 Many literature reports on the Suzuki-Miyaura cross-coupling feature benchmark reactions between aryl halides (mostly bromide and iodide) and phenyl boronic acid or its ester derivatives to give the symmetric 1,1'-biphenyl product.

Despite its large utilization, these benchmark substrates are not well suited to study the crosscoupling reaction as competing homo-coupling reaction manifolds could also be operative and lead to the same product. Thus, building blocks with different substitution patterns should be employed for accurate studies of C-C cross-coupling reaction and parent homo-coupling reactions.

The Pd(0)-catalyzed C-C cross-coupling reactions described by Moumen and Ouaskit used PdNPs immobilized in an aqueous emulsion of copolymers containing poly(vinyl acetate-vinyl versatate) and EG. Their liquid-phase immobilized catalytic system exhibited excellent chemoselectivity and high conversions towards Suzuki, Heck and Sonogashira reactions at catalyst loadings ranging from 1 to 2 mol% Pd. 256 As described by Zhang and co-workers, the immobilization of PdNPs into micellar triazolecontaining dendrimers featuring polyethylene glycol spacers has proven an excellent strategy towards catalyst heterogenization for the Suzuki-Miyaura reaction in water (Scheme 25). 257 The mild reaction conditions required to work with this catalytic system such as room temperature, low catalyst loadings (0.5% or less), combined to the ease of catalyst recovery after each reaction cycle, and the negligible activity decrease towards catalyst recycling and reuse enable sustainable applications. 257

Scheme 25. Heterogenized PdNPs on triazole-containing cross-linked polyol micelles.

Reproduced with permission from John Wiley and Sons, 257 license number 4558650609114.

Other types of polymeric matrixes containing cross-linked triarylphosphine moieties, imidazolium ionic liquids and polyethylene glycol have been prepared by Doherty, Knight and co-workers for the immobilization of highly dispersed PdNPs of <2.5 nm in average diameter size (Figure 25). 258 A turnover frequency of 16300 h -1 at room temperature is one of the highest for Pd nanocatalyzed Suzuki-Miyaura cross-coupling of 4-bromoacetophenone and phenylboronic to date at catalyst loading as low as 0.05 mol% Pd. 258 Carbon-supported PdNPs (2.0-2.5 nm average mean size) have been prepared by decomposition of Pd 2 (dba) 3 under H 2 atmosphere in the presence of spherical mesoporous carbon beads (average particle sizes ranging in the 0.5-1.0 mm range) by García-Suárez and Philippot. 259 The nanocatalysts exhibited excellent activities at catalyst loadings ranging from 0.4 to 1. encompassing one oxidative addition of an aryl halide to a Pd(0) metal center which delivers an arylpalladium (II) species. 265 Although, the following elementary step involving the activation of a second molecule of aryl halide, leading to the formation of diarylpalladium (II) species with a concomitant loss of the halide salt, seems rather unrealistic for these reviewers. 265 Our group has recently described a highly selective nanocatalyst for C-C homo-coupling reactions prepared from Pd(OAc) 2 and cinchona-based alkaloids (quinidine and cinchonidine) under H 2 (3 bar) in neat glycerol. 235 The metal surface and stabilizer coordination mode via π-π interactions is key for promoting this catalytic pathway. The mechanistic studies derived from this study with an analogous preformed zero-valent Pd nanocatalysts stabilized with PVP in neat glycerol led to the identification of a surface-mediated radical manifold based on single-electron transfer processes (Figure 26), with the experimental identification of the aryl bromide radical anion by electron paramagnetic resonance (EPR). Thus, aryl bromides homocouplings proceeded efficiently to produce the corresponding bis-aryls in moderate to excellent yields and using relatively low catalyst loadings (1 mol% Pd). 266 The as-prepared nanocatalysts from different Pd salt precursors were quite sensitive towards surface poisoning by halides, notably iodide hampered the reactivity. The halide/Pd ratio was determined by X-ray fluorescence analysis. 266 This work sheds light on the crucial role of Pd(0) nanocatalyst surfaces towards enabling the activation of aryl halides involving the Fermi level electrons. Besides, a surface dehydrogenative coupling of organosilanes leveraged by PdNPs for the formation of Si-N bond has recently been described by Wang and co-workers This nanocatalytic system outsmarts existing catalysts in terms of durability characteristics and higher level of efficiency. In a broader context, these results illustrate powerful nanocatalytic approaches to maximize the performance of palladium catalysis in the quest of green and sustainable processes required for future industrial applications.

Conclusions and Outlook

In this review, we highlight the paramount relevance of polyols in the synthesis of metal-based nanoparticles, in particular through the palladium case; in most reported examples, the reactions are carried out in the presence of water, but also in neat polyol. One of the unrivalled advantages of polyols, and alcohols in general, is their versatility, working as multi-task reaction components, i.e. reductant of metallic precursors, solvent, and sometimes even as stabilizer. But this latter function towards precluding MNPs agglomeration is mainly reserved to polyol derivatives, such as those polyols containing ethers handles in one or several hydroxyl groups of the polyol, especially the ones featuring long carbon chains. Furthermore, polyols promote the dispersion of the formed MNPs mainly due to their hydrogen-bonded supramolecular structure.

Polyols have been classically used for the synthesis of high electronegativity metals (such as Ag, Au, Pd, Pt…), mainly due to the ease of reduction of these metals. Notwithstanding, polyols are appropriate solvents for 3d transition metals in combination with stronger reducing agents for the synthesis of zero-valent MNPs given the relative low solubility of molecular oxygen in polyol media, avoiding in this case the formation of products coming from the oxidation of the corresponding polyols (aldehydes, ketones). More recently, polyols coming from plant extracts have attracted the attention of some groups for the preparation of well-defined nanoparticles; at present, the main concern is the control of the surface state of these as-prepared nanoparticles, highly dependent on the nature of these bio-polyols as raw materials. In this review, we focus on palladium given its versatility in catalysis towards streamlined organic synthesis, mainly couplings and hydrogenations processes, among others. In addition, its efficiency is proven at angstrom (homogeneous), micrometer (heterogeneous), and nanometer (homogeneous -reservoir of complexes-or heterogeneous -surface reactivity-) scales, being palladium able to stabilize different types of structures with an impact towards reactivity. Due to its robustness, palladium can undergo different type of activation modes (classical heating, microwaves irradiation, ultrasounds). Polyols together with stabilizers, often polymers such as PVP but also ligands such as phosphines, thiols or aromatic nitrogen-based stabilizers, are able to control the size and shape at the nanometric level, with a great potential for applications. Furthermore, PdNPs can be prepared under batch and continuous-flow conditions; this latter approach is in particular important from a mechanistic point of view, permitting the monitoring of PdNPs synthesis, and then the study of the kinetics for the different synthetic steps (reduction of metal precursor, nucleation, growth), which can be crucial for the synthesis of bimetallic nanoparticles. As can be ascertained from this contribution, the methods for preparing PdNPs and in general metal-based nanoparticles using polyols as solvents are largely applied for bottom-up methods, namely decomposition/reduction of metallic precursors to generate in situ "naked" metal atoms that quickly form nuclei, which produce nano-objects under appropriate and well-controlled conditions (temperature, pressure, concentration, stabilizer...). However, top-down methods other than electrochemical approaches are rarely described in the literature. Recently, Staszek and coworkers have reported the synthesis of noble metal nanoparticles (Ag, Au, Pd, Pt) by sputtering metal atoms in anhydrous glycerol. 267 The main concern is related to the vapor pressure of polyols, because sputter technique works under high vacuum (< 10 -7 mmHg). However, this limitation can be overcome for high molecular weight polyols. This methodology leads to the synthesis of mono-or polymetallic nanocatalysts precluding the oxidation of the polyol, being an attractive approach for applications; currently, its main restraint is associated to the limited development of sputtering techniques using liquids as substrates.

Figure 1 .

 1 Figure 1. Left: TEM images prepared in EG at 110 °C in air at different times: 5 min (A); 3 h

Figure 2 .

 2 Figure 2. Schematic plot indicating the relative distribution of the twin structure of Pd

Figure 3 .

 3 Figure 3. TEM micrographs of PdNPs synthesized at different temperatures: a) 150 °C, b) 140

Figure 4 .

 4 Figure 4. Electron microscopy characterization of Pd triangular nanoplates prepared at 85 °C in

Figure 5 .

 5 Figure 5. Illustration of the continuous-flow reactor system for the production of metal

Figure 6 .

 6 Figure 6. (a) FE-TEM and (b-c) HR-TEM micrographs of PdNPs synthesized in glycerol acting

Figure 7 .

 7 Figure 7. (a) SEM micrograph of PdNPs at 2 min. (b) SEM micrograph of PdNPs at 30 min. (c)

  2 nm) and well-dispersed PdNPs were obtained with 1,2-dioleoyl-sn-glycero-3-phosphor-rac-(1-glycerol) (DOPG), derived from glycerol. Raman spectra evidenced the presence of both glycerol and phospholipid in the composition of PdNPs, taking advantage of their surface-enhanced Raman scattering (SERS) properties.[START_REF] Chen | Synthesis of Palladium Nanoparticles and Their Applications for Surface-Enhanced Raman Scattering and Electrocatalysis[END_REF]

Figure 8 .

 8 Figure 8. Structure of lipids employed for the nanoreactor study: 1,2-dipalmitoyl-sn-glycero-3-

Figure 9 .

 9 Figure 9. Synthesis of PdNPs in neat glycerol from Pd(II) and Pd(0) precursors under molecular

Figure 10 .

 10 Figure 10. 31 P NMR monitoring of the formation of PdNPs stabilized by TPPTS in glycerol under 3 bar H 2 . 31 P NMR spectra (121 MHz, 298 K) starting from Pd(OAc) 2 and TPPTS in 0.7

Figure 11 .

 11 Figure 11. Quantitative STEM-EDS line scanning analyses for AuPd BMNPs prepared in glycerol. Reprinted with permission from reference 93 . Copyright (2007) American Chemical

Figure 12 .

 12 Figure 12. a) HAADF-STEM image of the AgPd BMNPs and its corresponding size distribution

Figure 13 .

 13 Figure 13. Top: STEM and EDS line scan analyses for Pt(core)Pd(shell) nanoparticles: (a)

Figure 14 .

 14 Figure 14. HRTEM micrographs of (a) Pd, (b) Ru(core)Pd(shell), and (c) Pt/Ru(core)Pd(shell) nanoparticles. Reprinted with permission from Royal Society of Chemistry, 107 license number

Figure 15 .

 15 Figure 15. Left: (a) HAADF-STEM image, (b) Pd-L STEM-EDX map and (c) Ru-L STEM-

  113

2. 2 . 2 .

 22 Palladium bimetallic nanoparticles containing 3d transition metals.IronBased on the methodology described bySun et al. for the synthesis of FePt nanoparticles,114 Ohta and co-workers prepared FePd NPs by simultaneous reduction of Pd(acac) 2 (acac = acetylacetonate anion) and thermal decomposition of Fe(CO) 5 in 1,2-hexadecanediol at high temperature (280-300 °C), in the presence of tributylphosphine and adamatanecarboxylic acid or oleic acid as stabilizer; this methodology led to the formation of spherical NPs showing a narrow size distribution (mean diameter: 11 ± 2 nm). 115 XRD analysis evidenced a disordered cubic structure and the shift observed of the (111) peak pointed to the formation of FePd alloy. By modifying the mixture of stabilizers, it was possible to tune the growth of NPs and thus to obtain larger nanoparticles exhibiting interesting magnetic properties; in this case, a segregation of phases cannot be excluded.Watanabe et al. prepared FePd NPs in a similar way; the as-prepared FePd NPs were isolated by centrifugation; the XRD analysis showed a disordered fcc (facecentered cubic) structure. Then, these FePd NPs were treated at 600 °C under vacuum, leading to a structural change, from fcc to L1 0 -ordered fct (face-centered tetragonal) structure after the annealing process. 116 L1 0 FePd NPs exhibited a higher coercive force than fcc FePd NPs isolated after reaction (2040 Oe and 630 Oe, respectively). This change of structure has been also observed when FePd NPs prepared by a polyol process were further transformed in bulk magnets by spark plasma sintering.117 The chemical composition of FePd NPs can strongly impact on the magnetic properties. It has been proved that the presence of interstitial carbon atoms on FePd NPs, coming from the co-solvent used (ether derivatives, such as dioctylether and diphenylether), prevents the structural change from disordered fcc to L1 0 -ordered fct: 117 high content of interstitial carbon hinders the diffusion of Fe and Pd atoms, and then the structural change is prevented. Lezama and co-workers have also studied the impact of the chemical synthesis on the magnetic properties of FePd NPs.118 They prepared FePd NPs using benzyl ether or toluene as solvent and 1,2-hexadecanediol as reducing agent, in the presence of a mixture of stabilizers (oleic acid and oleylamine, sometimes also adding dodecanethiol). Depending on the relative Fe/Pd ratio of precursors, different compositions were obtained[FePd 3.4 (A), FePd 3.2 (B), FePd 5 (C), FePd 1.4 (D), FePd 4 (E), and FePd 1.6 (F)], showing spherical nanoparticles from 5.0 to 8.3 nm (TEM data). Magnetization measurements evidenced a superparamagnetic behavior in agreement with the absence of hysteresis at room temperature (Figure16); from electron magnetic resonance data, it is observed that for higher iron contents (more than 16%) the plausible Pd magnetic polarization is practically inexistent. Zero-valent iron state is highly sensitive to oxidation, and FePd NPs can be easily oxidized. Actually, FePd(core)-iron oxide(shell) NPs have been obtained, showing enhanced magnetic properties and increased thermal and chemical stability of NPs in relation to oxide-free FePd nanomaterials.119

Figure 16 .

 16 Figure 16. Magnetization vs magnetic field curves measured at 5 K (a) and room temperature (b)

Figure 17 .

 17 Figure 17. TEM images for NiPd BMNPs with the corresponding shape distribution graphs as a

Figure 18 .

 18 Figure 18. Synthesis of PdCu BMNPs in neat glycerol from Pd(II) and Cu(II) precursors under

Figure 19 .

 19 Figure 19. TEM images of PdNPs synthesized using (a) Sanka coffee, (b) Bigelow tea, (c)

Scheme 5 .

 5 Scheme 5. Hydrogenation of different alkenes containing aliphatic, alicyclic and aromatic groups catalyzed by phenanthroline-stabilized PdNPs in PEG400. 183

4 .

 4 Pd-based nanoparticle leveraged coupling reactions. Catalysis offers a plethora of new tools not only to activate chemical bonds, but also to introduce new chemical functions in a tailored fashion. The selective formation of new C-C, C-N, C-O, C-S or C-P bonds through catalyzed processes represents unrivalled means in synthesis with

Figure 20 .

 20 Figure 20. Proposed mechanism for the Cu-free Sonogashira cross-coupling reaction based on

Scheme 18 .

 18 Scheme 18. Sonogashira reaction of aryl halides with phenyl acetylene catalyzed by agarose

  228

4. 3 .

 3 C(sp 2 )-C(sp 2 ) Hiyama-Denmark cross-coupling

Figure 21 .

 21 Figure 21. Pd-catalyzed Hiyama-Denmark reaction mechanism based on molecular palladium

Scheme 21 .

 21 Scheme 21. PdNPs catalyzed Hiyama cross-coupling reaction of aryltrialkoxysilanes and benzyl halides.236

Figure 22 .

 22 Figure 22. Classical Pd-catalyzed Heck-Mizoroki reaction mechanism based on molecular

Scheme 22 .Scheme 23 .

 2223 Scheme 22. Synthesis of Pd supported nanocatalysts on a porous PVPy monolith. Reprinted with permission from Elsevier, 241 license number 4558310654891.

Figure 23 .Figure 24 .

 2324 Figure 23. Competing cross-coupling vs homo-coupling manifolds catalyzed by molecular

Figure 25 .

 25 Figure 25. Pd nanoparticle-supported on polymeric matrixes featuring cross-linked

  Scheme 26. Pd-catalyzed carbonylative Suzuki reactions of aryl iodides and arylboronic acids.264

4. 7 .

 7 C(sp 2 )-C(sp 2 ) Ullmann-type homo-coupling.Beyond the aerobic homo-coupling reaction of boronic acid derivatives via the formation of palladium (II) peroxo species under homogenous conditions (Figure23), nanocatalysts generated in polyol media show enhanced surface-like reactivity which confers them unique potential towards homo-coupling reactions. Thus, PdNPs of 4 ± 1 nm average size synthesized from H 2 [PdCl 4 ] reduction with PEG in the presence of a polyethylene imine polymer (Mw = 25000) under sonication at room temperature showed almost quantitative conversion of aryl bromides and high yields towards the synthesis of symmetric bis-aryls via homo-coupling reaction at 90 ºC in a solvent mixture of EG -ethanol (1:2) at a catalyst loading below 1 mol% Pd. 265 Different mechanistic approaches have been proposed for the synthesis of bis-aryls by homo-coupling reaction. For instance, Mandal and co-workers reported a homogeneous catalytic cycle

Figure 26 . 4 mol%

 264 Figure 26. Proposed radical homo-coupling reaction mechanism promoted by PdNPs involving neighboring metal centers. 266

  ABBREVIATIONS

  3.2 (B), FePd 5 (C), FePd 1.4 (D), FePd 4 (E), and FePd 1.6 (F). Reprinted with permission from Springer Nature, 118 license number 4558861174833. Co(shell) nanoparticles with different compositions (Pd 1 Co 2 , Pd 1 Co 1 , Pd 2 Co 1 ) were prepared by a sequential methodology, starting by the reduction of Pd(acac) 2 in EG in the presence of PVP at 120 °C; after 30 min, Co(acac) 2 was added and the temperature increased at 180 °C with a rapid injection of NaOH for accelerating the reduction of Co(II) ions. OAc) 2 and NiSO 4 salts in EG in the presence of PVP at 198 °C under basic conditions.121 The resulting colloidal solutions were stable for months, without any sign of agglomeration probably due to the efficient stabilization of PVP and keeping the BMNPs surface state thanks to the reductive medium (EG). They obtained BMNPs over an entire composition range in agreement with the continuous fcc solid solution formed by the bulk metals. of the cubic parameter). PXRD, XPS, XANES, and EXAFS analyses proved both metals are in the zero-valence state and that they formed random alloys. Based on this work, Yao and co-workers have prepared NiPd nanoalloys studying in particular their magnetic properties.122 For nickel rich BMNPs, both the saturation magnetization (Ms) and

	Cobalt
	Pd(core)coercive force (Hc) increased: for Ni/Pd molar ratio from 3:7 to 7:3, Ms varied from 7.8 to 41.3 emu/g and Hc from 1.2 to 2.2 kOe. The high heat-generation capabilities of these nanoalloys
	offer alternative means to conventional heating, thanks to the high specific power absorption
	rates.

120

The former PdNPs showing a high density of states helps to reduce Co(II) to Co(0). PXRD analysis mainly showed the presence of Pd fcc and Co fcc structures, together with Co(OH) 2 phase. TEM combined with EDS analyses evidenced the formation of spherical NPs of 7-10 nm of mean diameter (4-6 nm for inner core and 2-6 nm corresponding to outer shell thickness) with the same composition than that used in the synthesis of these BMNPs.

Nickel

In 1999, Toshima and co-workers reported the synthesis of NiPd BMNPs by co-reduction of Pd(86 TEM analyses showed the formation of well-dispersed small spherical BMNPs (from 1.5 to 2.3 nm, with standard deviations in the range 0.27-0.37 nm) and HRTEM analyses pointed to the formation of nanoalloys (determination Kuhn and co-workers have prepared shape-controlled NiPd BMNPs, leading to the formation of nanocubes and nanorods by an adapted polyol methodology.

123

NiPd nano-objects were prepared by simultaneous reduction of metal precursors (i.e. Ni(acac) 2 and (NH 4 ) 2 [PdCl 4 ]) in 1,5pentanediol in the presence of PVP and trimethyl(tetradecyl)ammonium bromide (TTAB) as capping agents, at different temperatures (in the range 140-160 °C). Depending on the temperature and TTAB/total metal molar ratio, TEM analyses evidenced the formation of different shape compositions (F). The optimized conditions to mainly obtain nanocubes and nanorods was at 160 °C TTAB/total metal molar ratio of 30/1. At high temperature (180 °C) and high TTAB/total metal molar ratio (50/1), no control of the shapes was observed. PXRD

  Liu et al. described the use of PdNPs with a mean diameter size of 4.0 nm. As observed by UV-vis during the formation of the PdNPs using PEGs of different molecular weights, high Mw PEGs are better reducing agents; low molecular weights of PEGs can stabilize better Pd(II) complexes hindering the reduction to

	PdNPs in PEG with different molecular weights (Mw = 400, 600, 1000, 2000, and 4000) as catalysts in order to reduce methyl linoleate into (Z)-methyl oleate while minimizing shown in Scheme 2. Despite that substrate hydrogenation was faster with PEG-400 and 1000, the yield of methyl oleate was better when PEG-600, 2000, and 4000 were used. PEG2000 and PEG4000 were finally chosen for this study due to the instability of PdNPs generated in PEG600 isomerization towards (E)-methyl elaidate. Pd(0). Upon optimization of the experimental parameters, the best conditions were the ones by formation of a precipitate.

179

The best catalyst was prepared from Pd(OAc) 2 in PEG4000, at 75 °C for 2 h, which solidified upon cooling down to room temperature, leading to Scheme 2. Pd-catalyzed hydrogenation of different alkenes catalyzed by PdPEG4000-NPs.

179

  [START_REF] Reina | Palladium Nanoparticles Stabilised by Cinchona-based Alkaloids in Glycerol: Efficient Catalysts for Surface Assisted Processes[END_REF]

Scheme 15 .

 15 Hydrogenation of alkenes and alkynes catalyzed by PdNPs stabilized by choline derivative in glycerol.

188

This catalytic system is even more interesting towards the hydrogenation of the carbonyl groups which can be reduced under relatively smooth conditions (Scheme 16). 188 Scheme 16. Hydrogenation of nitro and carbonyl groups catalyzed by PdIL NPs in glycerol.

188

Table 1 .

 1 Semihydrogenation of diphenylacetylene and phenylacetylene catalyzed by PdCuBMNPs.

	Entry	Catalyst			Conv. (%) b	Entry	Catalyst	Conv. (%) b
		(Pd:Cu BMNPs)	ratio	for	(alkene:alkane) b		(Pd:Cu ratio for BMNPs)	(alkene:alkane) b
	1	PdNPs			100 (0:100)	6	PdNPs	100 (0:100)
					98 (80:20) c
	2	CuNPs			0	7	CuNPs	0
	3	PdNPs + CuNPs		100 (0:100)	8	PdNPs + CuNPs	100 (17:83)
	4	PdCu BMNPs (1:2)		37 (100:0)	9	PdCu BMNPs (1:2)	56 (100:0)
	5	PdCu BMNPs (1:1)		59 (100:0)	10	PdCu BMNPs (1:1)	84 (100:0)

  The as-prepared material catalyzed Suzuki Miyaura cross-coupling reactions of aryl halides and phenylboronic acid in PEG in high efficiency at 1.8 mol% Pd the synthesis of arylketone derivatives.263 In particular, Han and co-workers have described a highly selective carbonylative reaction using in situ generated PdNPs (of 2.6 nm in average particle size) by decomposition of Pd(OAc) 2 in PEG.264 This nanocatalytic system converted electron-donating or electron-withdrawing aryl iodides with arylboronic acids into the corresponding diaryl ketones at 2 mol% Pd catalyst loading, room temperature and under ambient pressure of CO employing pivalic acid as an additive to effectively suppress the corresponding Suzuki-Miyaura coupling (Scheme 26) at gram-scale. According to the authors, this transformation operates under a homogeneous regime as determined by the total inhibition of the reaction in the presence of equimolar amounts of CS 2 and negative Hg poisoning tests.

	5 mol% Pd
	towards Suzuki-Miyaura cross-coupling in PEG/water mixtures under conventional heating
	without any loss of activity up to 10 recyclings.
	Furthermore, Nikoorazm and co-workers reported a grafted palladium S-benzylisothiourea
	complex on MCM-41 (Pd-SBT@MCM-41) reduced with NaBH 4 to generate PdNPs of 4 ± 1 nm
	in average diameter.

264

Scheme 26. Pd-catalyzed carbonylative Suzuki reactions of aryl iodides and arylboronic acids.

References

Acknowledgments

Abbreviations

ACKNOWLEDGMENTS

Financial support from the Centre National de la Recherche Scientifique (CNRS) and the University of Toulouse 3 -Paul Sabatier are gratefully acknowledged.

Scheme 7. Sequential Coupling/hydrogenation processes catalyzed by PdTPPTS NPs in glycerol. [START_REF] Chahdoura | Palladium Nanoparticles in Glycerol: A Versatile Catalytic System for C-X Bond Formation and Hydrogenation Processes[END_REF] Furthermore, the as-prepared catalytic systems were also active towards coupling/cyclization/hydrogenation tandem reactions for the synthesis of phthalimides, 1-benzyl-1, 3-dihydroisobenzofuran and 3-(4-substitued-benzyl)isoindoin-1-one derivatives in high yields (>90%, Scheme 8). 187

Scheme 8. Sequential coupling/cyclisation/hydrogenation processes catalyzed PdTPPTS NPs in glycerol. 187 An analogous nanocatalyst generated from [PdCl 2 (COD)] as metal precursor and stabilized with benzyl substituted 1,3,5-triaza-7-phosphoadamantane (PTA, Pd/L ratio = 1:1) in glycerol furnished PdNPs with a mean diameter of 3.2 ± 0.8 nm. [START_REF] Chahdoura | Palladium Nanoparticles Stabilised by PTA Derivatives in Glycerol: Synthesis and Catalysis in a Green Wet Phase[END_REF] This catalyst was tested for the Scheme 14. Hydrogenation processes catalyzed by PdQN NPs in glycerol. [START_REF] Reina | Palladium Nanoparticles Stabilised by Cinchona-based Alkaloids in Glycerol: Efficient Catalysts for Surface Assisted Processes[END_REF] Choline based ionic liquids in neat glycerol were also used as stabilizers for PdNPs in glycerol. 188 Nanocatalysts were synthesized from [PdCl 2 (COD)] as Pd precursor and choline Ntosylalaninate as stabilizer with a ratio Pd/IL (1:17) under Ar atmosphere at 80 °C overnight, leading to nanoparticle mean diameter sizes of 1.7 ± 0.6 nm. Notably, the water present in the medium triggered the reduction of Pd(II) to Pd(0) NPs, as previously observed in the literature. 189 Contrarily to the PdQN NPs, the hydrogenation of monoalkenes (as 1-dodecene)

with PdIL NPs leads to the formation of a high quantity of isomerization products. Although, the hydrogenation was complete and selective for conjugated systems. Thus, the more hindered substrate 1,2,3,4,5-pentamethylcyclopentadiene was selectively reduced into the cyclopentene derivative under 20 bar of H 2 pressure (Scheme 15). catalyst loading. Catalyst recovery was easily performed by centrifugation and it remained active up to six consecutive runs without loss in activity. 260 An heterogenization method described by Naghipour and co-workers consists of a pyridinecarboxaldehyde-derivatized magnetite-containing chitosan as support for Pd nanocatalysts. The as-prepared catalytic material featuring crystallites of 31 nm average size (as determined by PXRD) was highly efficient towards Suzuki-Miyaura cross-coupling (at 1 mol% Pd catalyst loading) and it was magnetically-recovered with no significant losses in catalytic activity up to 5 runs. 261 In terms of substrate scope, aryl halides were efficiently coupled to phenylboronic acid using K 2 CO 3 in PEG to yield the corresponding unsymmetrical bis-aryls in 40-99% yields. 261 An alternative Pd nanoparticle immobilization strategy using a polyol-containing co-polymer of styrene and 3-(2,3-dihydroxypropyl)-1-vinylimidazolium chloride as support have been reported

by Song and co-workers. 262 The as-prepared material of co-polymer dispersed nanoparticles (4 nm average size) catalyzed Suzuki-Miyaura cross-coupling with particularly low catalyst loadings (0.05 mol% Pd) in water-ethanol solvent mixtures at mild temperature (70 ºC). Despite the authors highlighted in several occasions that this Pd(0)-catalyzed cross-coupling reaction is run under air atmosphere, they do not further comment on potentially competing homo-coupling reaction manifolds such as the O 2 -mediated homo-coupling reaction of boronic acids.