Rudina Bleta
email: rudina.bleta@univ-artois.fr

Benedetto Schiavo

Natale Corsaro

Paula Costa

Alberto Giaconia

Leonardo Interrante

Eric Monflier

Giuseppe Pipitone

Anne Ponchel

Salvatore Sau

Onofrio Scialdone

Sébastien Tilloy

Alessandro Galia
email: alessandro.galia@unipa.it

Robust Mesoporous CoMo/γ-Al2 O3 Catalysts from Cyclodextrin-Based Supramolecular Assemblies for Hydrothermal Processing of Microalgae: Effect of the Preparation Method

Keywords: heterogeneous catalysts, microalgae, hydrothermal liquefaction, cyclodextrin, biocrude

come

Introduction

The development of heterogeneously catalyzed processes for the conversion of biomass in aqueous phase is a challenge for biorefinery technologies, in concert with replacement of traditional fossil fuels feedstocks. [START_REF] Besson | Conversion of Biomass into Chemicals over Metal Catalysts[END_REF][START_REF] Lin | The critical role of heterogeneous catalysis in lignocellulosic biomass conversion[END_REF] Among biomass, microalgae have a significant potential as suitable renewable feedstock owing to their high production rate achievable in open ponds or photobioreactors and their interesting energy content related to the presence of lipids, in addition to proteins and carbohydrates. [START_REF] Wijffels | An outlook on microalgal biofuels[END_REF] One of the most promising conversion routes toward the processing of the entire algal feedstock is the hydrothermal liquefaction (HTL) which is carried out in water, under high temperature (250-550 °C) and high pressure (10-25 MPa) conditions [START_REF] Akhtar | A review on process conditions for optimum bio-oil yield in hydrothermal liquefaction of biomass[END_REF] producing biooil (or biocrude) as main product. [START_REF] Albrecht | Impact of heterotrophically stressed algae for biofuel production via hydrothermal liquefaction and catalytic hydrotreating in continuous-flow reactors[END_REF][START_REF] Arturi | Performance of hydrothermal liquefaction (HTL) of biomass by multivariate data analysis[END_REF][START_REF] Tian | Hydrothermal liquefaction for algal biorefinery: A critical review[END_REF][START_REF] López Barreiro | Hydrothermal liquefaction (HTL) of microalgae for biofuel production: State of the art review and future prospects[END_REF][START_REF] Biller | Hydrothermal processing of algal biomass for the production of biofuels and chemicals[END_REF] A key advantage of this process is that at near critical or supercritical conditions, water behaves as non-polar solvent due to the decreased value of the dielectric constant (ε), thus allowing ease solubilization of the biomass compounds. Moreover, as the ionic product of water (KW) increases with temperature, changing from 10 -14 to 10 -11 in the range of 25-350 °C, water behaves also as acid catalyst for hydrolysis reactions involving carbohydrates and lipids. [START_REF] Kruse | Water-A magic solvent for biomass conversion[END_REF] The biocrudes produced by HTL processes are generally more viscous and have higher oxygen contents than conventional crude oil. [START_REF] Elliott | Developments in direct thermochemical liquefaction of biomass: 1983-1990[END_REF] In order to meet the requirements of biofuel standards, biocrude must be upgraded by hydrodeoxygenation processes. [START_REF] Elliott | Historical developments in hydroprocessing bio-oils[END_REF] Therefore the development of hydrothermally stable catalysts that could be added during the HTL of microalgae to decrease the oxygen content of the obtained biocrude would be interesting.

The first extensive work on the catalytic HTL of microalgae Nannochloropsis at 350 °C was presented by Duan and Savage 13 who showed that the bio-oil yield could be increased by using both noble metals (Pd, Pt and Ru) supported on carbon (metal loading 5 wt%) and less expensive transition metals such as Ni, Co and Mo supported on alumina, silica or a zeolite. It was found that the utilization of a high amount of catalyst (50 wt% with respect to the dry and ash free algae) could increase the bio-oil yield, while decreasing its apparent viscosity. However, the structural transformations of the composite materials exposed to hydrothermal conditions were not evaluated. Pt and Pd addition was also confirmed to increase the bio-oil yield with Chlorella pyrenoidosa [START_REF] Yu | Nutrient flows and quality of bio-crude oil produced via catalytic hydrothermal liquefaction of low-lipid microalgae[END_REF] at lower temperatures (240 °C and 280 °C) when supported on Al2O3, while only Pt was effective with Chlorella vulgaris at 350 °C15 . Ni, Fe and Ce where also deposited on a high surface area zeolite (HZSM-5) and they were shown to increase the content of aromatics and alkanes and reduce oxygenated and nitrogenated compounds in the bio-oil obtained from HTL of the marine microalga Laminaria Japonica 16 or from Chlorella pyrenoidosa. [START_REF] Xu | Hydrothermal liquefaction of Chlorella pyrenoidosa for biooil production over Ce/HZSM-5[END_REF] Very recently, Egesa et al. [START_REF] Egesa | Multifunctional role of magnetic nanoparticles in efficient microalgae separation and catalytic hydrothermal liquefaction[END_REF] showed that ferrite magnetic nanoparticles doped with Zn and Mg could increase the biocrude yield in the liquefaction of Spirulina by 13.9%, while the percentages of heteroatom compounds, nitrogen and oxygen were significantly reduced. Moreover, the Zn-doped ferrite nanoparticles were easily recovered with a separation efficiency of 99% and recycled to further catalyze the HTL process. In another recent critical review, Galadima et al. [START_REF] Galadima | Hydrothermal liquefaction of algae and bio-oil upgrading into liquid fuels: Role of heterogeneous catalysts[END_REF] documented the use of different heterogeneous catalysts in the liquefaction of several algae species. An extensive overview of the literature was provided on the potential beneficial effects of these solids in both liquefaction and bio-oil upgrading.

On the other hand, Ravenelle et al., [START_REF] Ravenelle | Stability of Pt/γ-Al2O3 catalysts in model biomass solutions[END_REF][START_REF] Ravenelle | Structural changes of γ-Al2O3-supported catalysts in hot liquid water[END_REF] found that commercial γ-Al2O3-supported catalysts were more stable in biomass solutions than when they were in pure water at elevated temperature and pressure. This result was later explained by the stabilizing effect of polyols which form strongly bound multidentate alkoxy species on the γ-Al2O3 surface, stabilizing it against transformation to boehmite in hot water. [START_REF] Copeland | Surface interactions of C2 and C3 polyols with γ-Al2O3 and the role of coadsorbed water[END_REF] As stated by Weckhuysen et al. [START_REF] Jongerius | Stability of Pt/γ-Al2O3 catalysts in lignin and lignin model compound solutions under liquid phase reforming reaction conditions[END_REF] the stability of commercial Pt/γ-Al2O3 can also be affected by lignin-derived aromatic oxygenates which tend to adsorb on the support surface by coordinating via the oxygen functionalities, thus protecting the support against structural transformations under liquid phase reforming reaction conditions.

Although these studies have provided important insights into the stability of γ-Al2O3-supported catalysts in hot water, there are currently no investigations on how the preparation method may affect both the catalytic performance and the hydrothermal stability of these solids in the liquefaction of microalgae. A compromise between these two aspects must be found in order to maximize the recovery of microalgae energy and its densification and storage in the form of biooil.

Cyclodextrins (CDs) are water soluble cyclic oligosaccharides composed of n glucose units.

They possess a hydrophobic internal cavity and a hydrophilic exterior surface with a large number of hydroxyl groups. The most common cyclodextrins are α-CD, β-CD and γ-CD composed respectively of 6, 7 and 8 glucose units in the ring. Cyclodextrins demonstrate multifunctional properties such as the ability to form supramolecular adducts or host-guest inclusion complexes with a large number of molecules of appropriate size and shape. [START_REF] Szejtli | Introduction and general overview of cyclodextrin chemistry[END_REF][START_REF] Breslow | Biomimetic reactions catalyzed by cyclodextrins and their derivatives[END_REF] Moreover, these cyclic oligosaccharides have also the unusual ability to form supramolecular assemblies with a large variety of polymers and metal salts, and this property offers interesting possibilities for the preparation of metal-capped porous composites for applications in heterogeneous catalysis and photocatalysis. [START_REF] Bleta | Mesoporous RuO2/TiO2 composites prepared by cyclodextrin-assisted colloidal self-assembly: towards efficient catalysts for the hydrogenation of methyl oleate[END_REF][START_REF] Lannoy | Cyclodextrindirected synthesis of gold-modified TiO2 materials and evaluation of their photocatalytic activity in the removal of a pesticide from water: Effect of porosity and particle size[END_REF] In this work, we compare two different preparation methods to fabricate CoMo/γ-Al2O3 catalysts with suitable structural and textural characteristics and high chemical stability under hydrothermal conditions. The supramolecular assemblies formed between the randomly methylated-βcyclodextrin (RaMeβ-CD) and two block copolymers (Pluronic F127 and Tetronic T90R4) are used as template to prepare a highly porous γ-Al2O3 network over which uniform dispersion of the metal oxide nanoparticles can be achieved. The catalytic performance of these mesoporous solids is evaluated in the hydrothermal liquefaction of Nannochloropsis gaditana microalga. Biocrude oil is analyzed by elemental analysis and gas chromatography-mass spectrometry (GC-MS), while the gas phase composition is determined by GC. To the best of our knowledge, this is the first study reporting the effect of the preparation method on the catalytic performance of mesoporous CoMo/γ-Al2O3 for the hydrothermal liquefaction of microalgae. In addition, we investigate the chemical stability of these solids under hydrothermal conditions, in view of proposing guidelines that might be useful in practice for the selection of the appropriate catalyst for the HTL of microalgae or other biomass feedstocks. Ultrapure water HPLC grade was purchased from VWR International. Cyclohexane and acetone (analytical grade) were purchased from Sigma-Aldrich. Nitrogen and helium gas (99.999% purity) were obtained from Air Liquide. All chemicals were used as received, without further purification.

Experimental Section

Chemicals

Preparation of mesoporous γ-Al2O3 supports and CoMo/γ-Al2O3 catalysts

Mesoporous γ-Al2O3 supports were prepared using block copolymer/RaMeβ-CD supramolecular assemblies as template and boehmite (AlO(OH)) nanoparticles as building blocks.

Boehmite nanoparticles were synthesized in aqueous phase according to a previously reported solgel method. [START_REF] Yoldas | Alumina sol preparation from alkoxides[END_REF] Typically, in a dry 250 mL flask, 185 mL of hot distilled water (85 °C) was added fast to 25.3 g (0.1 mol) of ASB at a hydrolysis ratio of 100 (h = H2O/Al). After 15 min, the hydroxide precipitate was peptized by adding dropwise 0.474 mL (0.1 mol) of HNO3 ([HNO3]/[Al] = 0.07). The mixture was maintained under reflux at 85 °C for 24 h. The final product was a transparent suspension of boehmite nanoparticles (pH 4.4-4.8) with an aluminum concentration of 0.486 mol/L. 80 mL aliquots of the above colloidal solution were then mixed with a block copolymer solution (3 wt% Pluronic F127, EO/Al molar ratio = 1) and a RaMeβ-CD one (80 mg/mL RaMeβ-CD, RaMeβ-CD/Al molar ratio = 0.126). Hydrosols were maintained under stirring for 3 h, then allowed to equilibrate at 25 °C for additional 24 h. After drying at 60 °C, xerogels were calcined in air at 500 °C for 4 h with a heating ramp of 5 °C/min.

For the preparation of γ-Al2O3 supported bimetallic CoMo catalysts, two different synthetic procedures were used, i.e. the impregnation method and the direct incorporation (also referred to as one-pot colloidal approach). The appropriate amount of Co(NO3)2•6H2O and (NH4)6Mo7O24 4H2O was used in both preparation methods in order to obtain 0.6-1.2 wt% Co and 6.4-15.7 wt% Mo in the final catalysts.

In the first method, 500 mg of the calcined mesoporous γ-Al2O3 prepared using RaMeβ-CD/Pluronic F127 assemblies as template were impregnated at pH 5 first with a Mo/βCD aqueous solution, then with a Co/βCD one (total volume 5 mL, Mo(Co)/βCD molar ratio = 60). Suspensions were maintained under stirring at 75 °C until the water was completely evaporated, and then dried at 120 °C for 24 h. Two successive calcinations were performed at 500 °C for 2 h under air flow, the first one after molybdenum addition and the second one after cobalt addition. The catalysts prepared by impregnation are labelled CoMo1, CoMo2 and CoMo3. CoMo1 and CoMo2 contain identical loadings in active metals (i.e. 0.6 wt% Co and 6.4 wt% Mo), while higher metal loadings were used for the preparation of CoMo3 (i.e. 1.2 wt% Co and 15.7 wt% Mo). The difference between CoMo1 and CoMo2 resides in the order of introduction of Co(NO3)2•6H2O and (NH4)6Mo7O24 4H2O (see Table 1). In the second method, 20 mL aliquots of the boehmite sol were mixed with 20 mL aliquots of CoMo/RaMeβ-CD/F127 (CoMo4 and CoMo5) or CoMo/RaMeβ-CD/T90R4 (CoMo6) metallo-supramolecular assemblies (EO/Al = 1 and RaMeβ-CD/Al = 0.126).

The difference between CoMo4 and CoMo5 concerns the loadings in active elements (i.e. 0.6 wt% Co and 6.4 wt% Mo for CoMo4, and 1.2 wt% Co and 15.7 wt% Mo for CoMo5). On the other hand, CoMo5 and CoMo6 contain the same loadings in active elements (i.e. 1.2 wt% Co and 15.7 wt% Mo), but their difference resides on the polymer used as template in the preparation method. Thus, CoMo5 was prepared using Pluronic F127 as template, while CoMo6 was prepared using Tetronic 90R4 (see Table 1).

Hydrothermal conversion tests of microalgae and characterization of the products

A commercial AISI 316L Swagelok VCR male connector (1 inch nominal diameter), closed by two VCR caps with silver plated AISI 316L-stainless steel disposable gaskets, was used as reactor with a volume of 29.7 mL. One of the cap was equipped with a 1/16" male connector to couple the vessel to an expansion chamber through a 1/16" OD tube. This chamber with known volume (18 mL) was equipped with valves to purge, evacuate and isolate it from the reactor, and with a pressure transducer (Honeywell) for pressure measurement. The chamber was used as gas collection system (GCS) to collect and quantify the amount of gas phase in the reactor at the end of each test. The GCS was equipped with a gas sampling system closed by a rubber septum to collect the gas phase with a gas-tight syringe. The gas samples were analyzed by gas chromatography (GC) to determine the composition of the gas. In a typical experiment, 1 g of dry microalga and 8.9 g of HPLC grade water were loaded in the reactor, so that 30% of the reactor volume was filled with an aqueous biomass slurry 10 wt%. The prepared catalysts were added in 80 mg amount. Then the reactor was manually closed without sealing it, and purged with nitrogen at 0.2-0.3 MPa in order to remove the air. Nitrogen was introduced in the reactor from the GCS which was purged as well. After 5 min flushing, the reactor was sealed and the two connected systems (reactor and GCS) were further purged with nitrogen performing 5 cycles of pressurization at 1.6 MPa and pressure release up to 0.25 MPa. At the end of this procedure the systems were left with a residual nitrogen atmosphere at 0.25 MPa and disconnected form the GCS. The gas phase remained in the GCS was sampled and analyzed by GC to control that oxygen had been effectively removed by this procedure.

The reactor was then inserted in a modified GC oven HP G1540A apparatus whose temperature is electronically controlled. The oven temperature was initially set at 30 °C for 10 minutes to equilibrate the reactor then the temperature of the oven was set to 449 °C and, after 18.3 minutes, the set point was changed to 377 °C and kept at this value for the selected reaction time (15 min). This temperature profile of the oven corresponded to an increase of the temperature inside the reactor with a heating rate of about 19 °C/min up to the reaction temperature of 375 °C, which was then hold for the desired reaction time. After 15 min, the reactor was quickly cooled down by immersion in water at ambient temperature to stop the chemical evolution of the system, then the reactor was left for one hour in vertical position for gravity separation of the products inside. Then the reactor was reconnected with the GCS with the reactor valve still closed. The GCS assembly was evacuated through vacuum/purge outlet shown in Figure 1, and the gas phase inside the reactor was expanded in the GSC by opening the reactor valve. The pressure value of the expanded gas was measured and used to calculate the amount of gas phase using the ideal gas law. To perform analysis of the composition of the gas, the GCS valve (Figure 1) was closed, and the reactor was disconnected from the GCS. At least, four gas samples were collected with a syringe through the rubber septum of the GCS and injected into the GC for the analysis of the composition.

After the disconnection from the GCS, the reactor was opened and the liquid and solid products were collected and separated. First the aqueous phase was poured from the reactor into a vacuum filtering system equipped with 47 mm diameter nylon membrane filter (Alltech) with 0.2 μm average pore size. The bio-crude was too viscous to flow out of the vessel and it was recovered by three consecutive extractions with 15 mL of cyclohexane; the organic liquid solution was vacuum filtered through the nylon membrane with the same features previously reported. A fourth extraction with solvent was performed by sonicating the reactor for ten minutes. The filtered cyclohexane with the extracted bio-oil contained also some entrained water which separated by gravity in the bottom of the flask. The cyclohexane solution with the extracted bio-oil was transferred into a 100 mL pre-weighted flask, while residual water (mixed with the remaining small amount of the cyclohexane-solution) was transferred in a centrifugation glass tube.

Figure 1. Scheme of the experimental apparatus. After the reaction and the cooling, the reactor is connected to the gas collection system (GCS) assembly through the connection indicated by "A".

All the operations performed with the cyclohexane, except for the centrifugation, were then repeated by using acetone as solvent to extract the residual bio-oil and complete its recovery from the vessel. The organic-aqueous mixture contained in the centrifugation glass tube was centrifuged at 3000 rpm for 10 minutes, after this time the two phases were well separated. The aqueous phase was recovered with a syringe and added to the main aqueous phase previously collected by filtration procedure and stored into a pre-weighted 10 mL vial, while the organic phase was merged with the biocrude-cyclohexane solution. The water-soluble products were determined after drying the content of the 10 mL vial at 60 °C overnight. The solid products were determined after drying the filter with the remaining solid residue cake at 105 °C. The drying time ranged between 4 and 8 hours. Drying was considered complete when the mass of the filter with solid residue reached a stable value in two consecutive determinations. Both cyclohexane and acetone used to solubilize the biocrude oil were removed by evaporation under reduced pressure in a BUCHI RII rotavapor.

The evaporation of the solvent was continued at room temperature under fume hood and was considered as completed when the flask reached constant weight (± 0.5 mg). The mass yield of each phase was evaluated with respect to the initial mass of dry microalgae (dry biomass basis).

Selected tests were repeated three-four times to check reproducibility. The bio-oil yield was obtained with a standard deviation lower than ± 2 %.

Hydrothermal test for the catalyst stability

Catalysts were exposed to the same operative conditions used to convert the microalgae (i.e. 375 °C for 15 min), but without the presence of biomass inside the reactor. In this case, a stainless steel cylinder was put inside the reactor to host the catalyst and to facilitate its recovery at the end of the test. After the test, the cylinder was placed in a stove at 60 °C for 12 h to remove the water, and then the treated catalyst was recovered and analyzed.

Analytical methods

Dynamic light scattering (DLS) measurements were carried out on a Malvern Zeta Nanosizer at a scattering angle (θ) of 173° (backscattering detection). The instrument was equipped with a 4 mW He-Ne laser operating at 633 nm. The temperature was varied between 25 and 50 °C and controlled to within  0.1°C. Samples were analyzed immediately after preparation or two months later. Diffuse Reflectance (DR) UV-visible spectra were collected on solid catalysts using a Perkin Elmer (Lambda 19) spectrophotometer equipped with an integrating sphere. Samples were placed in quartz cells and BaSO4 was used as the reference. For the aqueous CoMo solutions, UV-Visible measurements were performed using the same apparatus in normal mode. X-ray powder diffraction patterns were recorded on a Siemens D5000 X-ray diffractometer in a Bragg-Brentano configuration operating with a Cu Kα radiation (λ = 1.5406 Å). Scans were run between 10-30° and 50-70° 2θ with a step size of 0.05° and a scan speed of 3 s. Nitrogen adsorption-desorption isotherms were collected at -196 °C using an adsorption analyzer Micromeritics Tristar 3020. Prior to analysis, 100-200 mg samples were outgassed at 320 °C overnight to remove the species adsorbed on the surface. From N2-adsorption isotherms, specific surface areas were determined using the BET method [START_REF] Brunauer | Adsorption of gases in multimolecular layers[END_REF] and pore size distributions were calculated using the BJH (Barrett, Joyner and Halenda) method. [START_REF] Barrett | The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms[END_REF] Hydrogen temperature programmed reduction (H2-TPR) measurements were carried out on a Micromeritics AutoChem 2920 chemisorption analyzer. Typically, 30-40 mg of calcined sample was introduced in a U-tube quartz reactor and outgassed under argon flow at 120 °C for at least 2 h. Then, a mixture of 5% H2/Ar (v/v) was introduced into the sample reactor at a flow rate of 10 mL/min. The sample was heated at 1000 °C with a ramp of 10 °C/min and maintained at that temperature for 30 minutes. The H2 consumption during the reduction process was recorded using a thermal conductivity detector (TCD). The composition of the gas obtained in the experiments of HTL of microalgae was determined using a GC Agilent 7890B equipped with a Carboxen® 1000 60-80 mesh packed column from Supelco. Samples of 250 µL were injected through injector used in splitless mode and heated at 120 °C. A TCD detector was used with temperature at 275 °C. The oven was kept isothermal at 35 °C for 5 minutes, then it was heated up to 225 °C with an heating rate of 20 °C/min and kept isothermal for other 40 min. Helium (99.999% purity) was used as carrier gas with a flow rate of 30 mL/min. Elemental analyses were performed using a Thermo Finnigan -CE Instruments Flash EA 1112 analyzer and according to ISO 16948:2015 procedure "Solid biofuels -Determination of total content of carbon, hydrogen and nitrogen". HHV of the obtained biocrude was calculated from the elemental analysis, according to the Boie's formula 31 : HHV (MJ/kg) = 0.3517C + 1.1626H -0.111O + 0.1047S were C, H, O, S are the weight percentages of the element in the sample. The Boie's formula was also used for the estimation of the energy content of the algae, which resulted equal to 20 MJ/kg. This value was confirmed also by measurements performed with a bomb calorimeter (Parr, model 6200). The biocrude samples were also analyzed by GC-MS with the following procedure: around 20 mg were placed into a glass vial and 1.5 mL of acetone (Fluka, chromatography grade) were added. The solution was centrifuged (2000 rpm), and 50 μL were taken and diluted up to 1 mL with dichloromethane (Fluka, chromatography grade). An Agilent 7890 GC was used equipped with MS quadrupole 5973N and CP-Sil 8CB column (0.25mm x 30 m x 0.25 µm). Helium (99.9999% purity) was used as carrier gas with 1 mL/min flow rate. The oven temperature program was 70 °C for 7 min, 70-280 °C ramp at 10 °C/min, 280 °C for 10 min. Temperatures of injector and of the interface GC-MS were 280 °C and 250 °C respectively. The MS detector was used in TIC modality (30-300 m/z); in order to obtain qualitative information, a NIST008 MS library was used for the spectra identification. The chromatography standards for the six quantified fatty acids (FAs), were purchased as follows: stearic acid (C18:0, ≥ 98.5%) by Sigma-Aldrich, oleic (C18:1, ≥99.0%) and linoleic (C18:2, ≥95%) acids by Alfa Aesar, palmitic (C16:0, ≥99%) acid by Sigma Aldrich, palmitoleic (C16:1, ≥99%) acid by Scbt, myristic (C14:0, ≥98%) acid by Scharlau. The quantitative analysis was performed in SIM modality, selecting three representative m/z peaks for each FA.

Results and discussion

Preparation and characterization of solid CoMo/γ-Al2O3 catalysts Two different approaches for the aqueous phase synthesis of mesoporous CoMo/γ-Al2O3 catalysts are compared. In a first approach, called "impregnation", a nanostructured γ-Al2O3 material is first prepared using the supramolecular assemblies formed between the randomly methylated β-cyclodextrin (RaMeβ-CD) and the Pluronic F127 as soft template, and sol-gel boehmite (AlO(OH)) nanoparticles as building blocks. After thermal treatment at 500 °C, the porous support is impregnated with an aqueous solution of Co and Mo in presence of the native β-CD. Here, the RaMeβ-CD acts as pore expander allowing for tailoring the pore size of γ-Al2O3, [START_REF] Bleta | Coassembly of block copolymer and randomly methylated β-cyclodextrin: from swollen micelles to mesoporous alumina with tunable pore size[END_REF][START_REF] Bleta | Investigating the effect of randomly methylated β-cyclodextrin/block copolymer molar ratio on the template-directed preparation of mesoporous alumina with tailored porosity[END_REF] while the native β-CD acts as dispersing agent, providing uniform distribution of active elements over the porous support [START_REF] Jean-Marie | β-Cyclodextrin for design of alumina supported cobalt catalysts efficient in Fischer-Tropsch synthesis[END_REF] (Figure 2 A). In a second approach, referred to as "one-pot", Co and Mo are encapsulated directly into the supramolecular assemblies formed between the RaMeβ-CD and a block copolymer (Pluronic F127 or Tetronic T90R4) around which boehmite colloids self-assemble (Figure 2 B). Here, the metallo-supramolecular assemblies play a dual role; they increase the pore size and surface area of the alumina support and, simultaneously, promote uniform dispersion of metal oxide nanoparticles within the solid matrix. In both approaches, a thermal treatment is performed at 500 °C to remove the CD-based assemblies leaving behind Co and Mo oxide nanoparticles deposited onto the pores (impregnation method) or incorporated into the alumina framework (one-pot approach). agent and B) one-pot colloidal approach using the metallo-supramolecular assemblies as template.

Before preparing the supported catalysts, the interactions between metal salts and supramolecular assemblies were studied using UV-visible spectroscopy. The pH of all solutions was maintained fixed at 5. interact with heptamolybdate anions (Mo7O24 6-) yielding bimetallic CoMo complexes. These results are in agreement with those reported by Weckhuysen et al. [START_REF] Bergwerff | On the interaction between Co-and Mocomplexes in impregnation solutions used for the preparation of Al2O3-supported HDS catalysts: A combined Raman/UV-vis-NIR spectroscopy study[END_REF] who proposed on the basis of Raman and UV-vis-NIR spectroscopy a molecular structure for the CoMo complex, similar to that of Fe-and Mn-heptamolybdates 36 in which Co(II) cations are coordinated to Mo7O24 6-anions via one or two oxygens, as shown in Figure 3 A (inset). Interestingly, pronounced changes in the band position and intensity of diluted CoMo solutions (4 mM Co and 56 mM Mo) were observed upon addition of RaMeβ-CD-F127 and RaMeβ-CD-T90R4 assemblies indicating changes in the electronic environment of the CoMo complex (Figure 3 B). Thus, the disappearance of the band at 516.5 nm coincides with the appearance of new absorption bands at 569.2 and 567.7 nm resulting from the formation of new metallo-supramolecular assemblies. These bands are somewhat flattened for CoMo-RaMeβ-CD-F127 mixtures and rather intense for CoMo-T90R4 and CoMo-RaMeβ-CD-T90R4 ones, consistent with the dark brown color of these latter. Such particular behavior of Tetronic-based assemblies may be explained by the establishment of electrostatic interactions between the negatively charged [Co2Mo7O24] 2-complex and the positively charged amino groups of the T90R4 block copolymer at pH 5. Indeed, the presence of two tertiary amine groups in the center of the poloxamine confers to this molecule a pH sensitive behavior. [START_REF] Alvarez-Lorenzo | Tetronic micellization, gelation and drug solubilization: Influence of pH and ionic strength[END_REF] The two pKa values of Tetronic T90R4 are reported to be 4.34 and 8.15, as determined by potentiometric titration. [START_REF] Larrañeta | Phase behavior of reverse poloxamers and poloxamines in water[END_REF] Thus, below pH 4.34, the ethylene diamine is diprotonated, while at pH values between 4.34 and 8.15, as is the case here, the monoprotonated form is predominant. In contrast to Pluronic, which does not contain any pH-sensitive moieties in its structure, the protonated amino groups in Tetronic must provide stronger metal-template interactions.

Remarkably, because of these interactions, the stability of metallo-supramolecular assemblies was greatly affected. Thus, visual inspection of two-months aged template-free CoMo solutions revealed formation of a suspension of solid particles which precipitated over time as a hydrated solid (Figure 4 Micelles start forming at 30 °C with an RH of 22.3 nm, while a small amount of residual nonassembled species still exists in solution (RH = 2.4 nm). Between 30 and 50 °C, micelles remain stables, although a slight shift of the intensity distribution towards lower sizes (from 24 to 18 nm) is observed due to dehydration of the hydrophobic core. [START_REF] Basak | Encapsulation of hydrophobic drugs in Pluronic F127 micelles: Effects of drug hydrophobicity, solution temperature, and pH[END_REF] No phase separation occurs in this temperature range. On the other hand, for CoMo-RaMeβ-CD-T90R4 assemblies (4 mM Co and 56 mM Mo, 0.7%T90R4 and 1.3% RaMeβ-CD), unimers are the only scattering species at 25 °C with an apparent hydrodynamic radius of 2.2 nm, consistent with the value reported in literature for T90R4 (Figure 4 D). [START_REF] Larrañeta | Phase behavior of reverse poloxamers and poloxamines in water[END_REF] Aging the solutions at room temperature for two months and increasing the temperature to 30 °C provokes a broadening of size distributions, indicating the beginning of the agglomeration process. At 40 °C, micelles are the main scattering species (RH = 6.2 nm), while at higher temperatures the solution becomes turbid and RH abruptly shifts to higher sizes indicating the beginning of phase separation, in agreement with SANS and DSC data reported by Plestil et al. Taken together, these results evidence that specific interactions exist in aqueous solution between the [Co2Mo7O24] 2-complex and the supramolecular template, avoiding irreversible precipitation and yielding stable metallo-supramolecular assemblies. Such interactions are expected to impact the dispersion of Co and Mo oxide nanoparticles over the alumina support and this must have direct consequence on the stability and catalytic activity of CoMo/γ-Al2O3 materials.

To assess the validity of this statement, six CoMo/γ-Al2O3 catalysts were prepared using the two-steps impregnation method and the one-pot colloidal approach. Details about the preparation methods and the composition of each catalyst are given in Table 1. a Mo/-Al2O3 has been prepared by incorporating Mo into the RaMeβ-CD-F127-AlO(OH) assemblies followed by drying and calcination at 500°C. b Nanostructured -Al2O3 has been prepared using the RaMeβ-CD-F127 assemblies as soft template and sol-gel AlO(OH) nanoparticles as building blocks. The material has been calcined at 500 °C.

Figure 5 shows the Diffuse Reflectance (DR) UV-visible spectra of the catalysts prepared by impregnation (A, B) and colloidal approach (C, D). For all catalysts, the ligand-to-metal charge transfer (LMCT) O 2- Mo 6+ band can be observed in the 200-320 nm region (Figure 5 A,C). This band is comprised of two main peaks at 220-240 nm and 260-320 nm belonging to tetrahedron coordination Mo(Td) and low polymeric octahedral coordination Mo(Oh) species respectively. [START_REF] Ramirez | Effect of boron addition on the activity and selectivity of hydrotreating CoMo/Al2O3 catalysts[END_REF][START_REF] Weber | Effect of local structure on the UV-visible absorption edges of molybdenum oxide clusters and supported molybdenum oxides[END_REF] For the same CoMo loading (0.6% Co and 6.4% Mo), the absorption band of Mo(Td) species is better-defined for the one-pot catalyst (CoMo4) compared to impregnated ones (CoMo1 and CoMo2). This suggests that at low CoMo concentrations, RaMeβ-CD-F127 assemblies promote formation of tetrahedral molybdenum species at the expense of octahedral ones, similarly to what has been observed previously with beta-FDU12/γ-Al2O3 composites upon addition of EDTA. [START_REF] Wang | Effect of promoters on the HDS activity of alumina-supported Co-Mo sulfide catalysts[END_REF][START_REF] Du | Synthesis of a novel micro/mesoporous composite material Beta-FDU-12 and its hydro-upgrading performance for FCC gasoline[END_REF] Note that the way of introduction of Co and Mo does not affect the spectral profiles which indicate very similar proportion of Mo(Td) and Mo(Oh) (see CoMo1 vs. CoMo2). On the other hand, the proportion of octahedral coordinated polymolybdate species increases with increasing the loadings in active elements (see CoMo3, CoMo5 and CoMo6). More important differences on the spectral profiles were observed in the visible range (Figure 5 B, D). Thus, the three successive bands noticed at 540, 580 and 627 nm for all catalysts are ascribed to tetrahedron coordinated divalent Co species incorporated into the alumina framework as cobalt aluminate ( 4 A2 (F)  4 T1 (P) transition, CoAl2O4, spinel). [START_REF] Ramirez | Characterization and catalytic activity of CoMo HDS catalysts supported on alumina-MCM-41[END_REF] Interestingly, for the same loading in active elements (0.6% Co and 6.4% Mo), these bands were better defined for the catalyst prepared by the one-pot approach (CoMo4) compared to those prepared by impregnation (CoMo1 and CoMo2). Moreover, further increase in the intensity of these bands was observed for higher loadings in active elements (1.2% Co and 15.7% Mo). Accordingly, this means that the one-pot colloidal approach facilitates the diffusion of Co 2+ ions into the tetrahedral sites of γ-Al2O3 lattice, thus promoting the formation of spinel cobalt aluminate. Actually, this triple band corresponds to a Jahn-Teller distortion of the tetrahedral structure which is also responsible for the blue coloration of CoAl2O4, also known as Thenard's blue. [START_REF] Zheng | Synthesis and characterization of blue TiO2/CoAl2O4 complex pigments good colour and enhanced near-infrared reflectance properties[END_REF][47][START_REF] Wang | Fabrication of blue-colored zirconia ceramics via heterogeneous nucleation method[END_REF][START_REF] Rangappa | Transparent CoAl2O4 hybrid nano pigment by organic ligand-assisted supercritical water[END_REF] Except for CoMo3, no other obvious signals could be observed for the other catalysts. This means that Co and Mo oxide particles may be either amorphous or composed of very small crystallites. Conversely, from the XRD pattern of CoMo3, it can be seen that in addition to the diffraction peaks of MoO3 phase (JCPDS card No 09-0209), other strong signals appear corresponding to the Al2(MoO4)3 phase (JCPDS card No 84-1652). This is an indication that surface MoO3 nanoclusters interact with γ-Al2O3 support and transform into Al2(MoO4)3 which is a stable thermodynamic phase formed during the thermal treatment. Note that for all catalysts, the diffraction peaks of crystalline Co3O4 or CoO are not observed in the XRD patterns, indicating that these oxides do not form on the γ-Al2O3 surface. [START_REF] Vakrosa | CoMo/Al2O3-SiO2 catalysts prepared by co-equilibrium deposition filtration: characterization and catalytic behavior for the hydrodesulphurization of thiophene[END_REF][START_REF] Arnoldy | Temperature-programmed reduction of CoOAI2O3 catalysts[END_REF] Instead, they tend to transform into CoAl2O4, in agreement with UV-vis data. Nevertheless, from the XRD patterns, it is difficult to distinguish CoAl2O4 from γ-Al2O3 because these two phases crystallize both in a cubic spinel structure and have very similar lattice parameters. [START_REF] Tielens | Periodic DFT study of the structural and electronic properties of bulk CoAl2O4 spinel[END_REF] The reducibility behavior of these materials was investigated using H2-temperature programmed reduction (H2-TPR) measurements (Figure 7). For all catalysts, the peaks at 335 and 600 °C, characteristics of the reduction of cobalt oxides (Co3O4 and CoO respectively) [START_REF] Liu | Synthesis and hydrodesulfurization performance of hierarchical mesopores alumina[END_REF] were not observed in TPR profiles, in agreement with XRD data. The catalysts prepared by impregnation present three peaks ascribed to the reduction of Co and Mo species in a three steps process: first, the partial reduction of amorphous, highly defective, multi-layered oxides octahedral Mo 6+ species (peak at 540-560 °C), [START_REF] Arnoldy | Temperature-programmed reduction of CoO/MoO3/Al2O3 catalysts[END_REF][START_REF] Rajagopal | Silica-alumina-supported acidic molybdenum catalysts-TPR and XRD characterization[END_REF][START_REF] Qu | TPR, and TEM studies of the interaction of NiMo with alumina and silica-alumina supports[END_REF] then the reduction of surface Al2(MoO4)3 [START_REF] Chen | Improved alkene selectivity in carbon monoxide hydrogenation over silica supported cobalt-molybdenum catalyst[END_REF][START_REF] Rodriguez | Reaction of H2 and H2S with CoMoO4 and NiMoO4: TPR, XANES, time-resolved XRD, and molecular-orbital studies[END_REF] and MoO3 crystallites (peaks at c.a. 670-690 °C), [START_REF] Vakrosa | CoMo/Al2O3-SiO2 catalysts prepared by co-equilibrium deposition filtration: characterization and catalytic behavior for the hydrodesulphurization of thiophene[END_REF][START_REF] Rajagopal | Silica-alumina-supported acidic molybdenum catalysts-TPR and XRD characterization[END_REF][START_REF] Qu | TPR, and TEM studies of the interaction of NiMo with alumina and silica-alumina supports[END_REF] and finally the deep reduction of all Co and Mo species incorporated into the alumina framework, including the highly dispersed tetrahedral (monomer) Mo 4+ oxospecies [START_REF] Vakrosa | CoMo/Al2O3-SiO2 catalysts prepared by co-equilibrium deposition filtration: characterization and catalytic behavior for the hydrodesulphurization of thiophene[END_REF][START_REF] Arnoldy | Temperature-programmed reduction of CoO/MoO3/Al2O3 catalysts[END_REF][START_REF] Rajagopal | Silica-alumina-supported acidic molybdenum catalysts-TPR and XRD characterization[END_REF] and more stable CoAl2O4 and MoAl2O4 species (peaks at 940-960 °C) in strong interaction with the support. By contrast, the catalysts prepared by one-pot colloidal approach present only two peaks at 540-560 °C and 940-960 °C indicating that the reduction of Co and Mo species is now performed in a two-steps process. The absence of additional reduction peaks at 670-690 °C suggests stronger interactions between the active elements and the γ-Al2O3 surface, thus hindering the formation of MoO3 and Al2(MoO4)3 crystallites on the support surface. [START_REF] Vakrosa | CoMo/Al2O3-SiO2 catalysts prepared by co-equilibrium deposition filtration: characterization and catalytic behavior for the hydrodesulphurization of thiophene[END_REF][START_REF] Lopez Cordero | Temperature-programmed reduction and zeta potential studies of the structure of Mo/O3Al2O3 and Mo/O3SiO2 catalysts effect of the impregnation pH and molybdenum loading[END_REF] Note that among the catalyst prepared by one-pot approach, CoMo6 displays the highest Mo 6+ reduction temperature (562 °C) resulting from stronger metal-support interactions. The impact of the metallo-supramolecular assemblies on the textural characteristics of the catalysts was evaluated by N2-adsorption analysis. Figure 8 depicts the adsorption isotherms and corresponding pore size distributions (inset) for the catalysts prepared by impregnation (Figure 8 A) and one-pot approach (Figure 8 B). All catalysts display type-IV isotherms which are characteristic of mesoporous materials. Note that the highest specific surface areas (410-440 m 2 g -1 ) are obtained for the catalysts prepared by one-pot approach (Table 2). Moreover, whatever the preparation method, for low CoMo loadings (0.6% Co and 6.4% Mo), the pore size is not significantly altered compared to the support alone (γ-Al2O3 prepared without CoMo has a pore diameter of 15.5 nm). This means that the active elements are either dispersed as small particles or incorporated into the walls of alumina. On the other hand, for higher loadings in active elements (1.2% Co and 15.7% Mo), the pore size of the impregnated catalyst (CoMo3) abruptly decreases to 4.8 nm as a result of the filling of pores. a BET specific surface area determined in the relative pressure range 0.1-0.25, b PV = cumulative pore volume (BJH), c PS = pore size calculated from BJH method.

Hydrothermal stability of supported catalysts

It is well-known that γ-Al2O3 is thermodynamically unstable under harsh hydrothermal conditions. [START_REF] Macdonald | The thermodynamics of the aluminium-water system at elevated temperatures[END_REF] At 150 °C or above, γ-Al2O3 transforms into hydrated boehmite (AlO(OH)) which is more stable than both gibbsite (Al(OH)3) and γ-Al2O3 in hot water. This transformation usually results in a drastic reduction of surface area of the material [START_REF] Ravenelle | Effects of metal precursors on the stability and observed reactivity of Pt/γ-Al2O3 catalysts in aqueous phase reactions[END_REF] and complete loss of Lewis acidity, [START_REF] Ravenelle | Structural changes of γ-Al2O3-supported catalysts in hot liquid water[END_REF] which in turn provokes sintering of metal nanoparticles deposited on the support surface. [START_REF] Ravenelle | Structural changes of γ-Al2O3-supported catalysts in hot liquid water[END_REF][START_REF] Luo | Glycerol aqueous phase reforming for hydrogen generation over Pt catalyst-Effect of catalyst composition and reaction conditions[END_REF][START_REF] Ketchie | In-situ X-ray absorption spectroscopy of supported Ru catalysts in the aqueous phase[END_REF] The supported catalysts were exposed under the same operative hydrothermal conditions adopted to perform the liquefaction of microalgae (375 °C for 15 minutes under autogenic pressure). All catalysts underwent changes in their crystalline structure due to partial or total rehydration of the γ-Al2O3 surface and transformation to its hydrated form, boehmite, as deducible from XRD characterization (Figure 9). Thus, for CoMo1 and CoMo2 catalysts, only the sharp reflexions of AlO(OH) (JCPDS card No 21-1307) are observed indicating total alumina-to-boehmite phase transformation, while a higher resistance to rehydration is noticed for all one-pot catalysts. Moreover, in the case of CoMo3, although the major diffraction peaks of Al2(MoO4)3 disappeared, the stability of γ-Al2O3 support was not much affected by the hydrothermal conditions.

It has been established by both adsorption micro-calorimetry experiments and thermodynamic

calculations, combined with DFT models, [START_REF] Mchale | Surface energies and thermodynamic phase stability in nanocrystalline aluminas[END_REF] that γ-Al2O3 easily transforms in hot water into hydrated boehmite due to the negative free energy of this reaction. Indeed, the free energy of transformation of pure γ-Al2O3 to boehmite has been calculated to be -42.8 kJ mol -1 with H2O (gas) and -34.3 kJ mol -1 with H2O (liquid) which makes this transformation thermodynamically favorable. 65 Under hydrothermal conditions, it is therefore difficult to obtain exactly the same structure as the fresh catalyst because of the energetic instability of bare γ-Al2O3. Nevertheless, the transformation kinetics can be considerably slowed down by introducing doping elements. For instance, the adsorption micro-calorimetry experiments as a function of hydroxyl coverage have shown that the adsorption enthalpy of Zr-doped γ-Al2O3 is less negative than that of bare γ-Al2O3 (-130 kJ mol -1 vs. -38 kJ mol -1 for 5 OH nm -2 coverage), while no significant change was observed in the presence of Mg (-110 kJ mol -1 for 5 OH nm -2 coverage). [START_REF] Castro | Surface energy and thermodynamic stability of γ-alumina: Effect of dopants and water[END_REF] Moreover, the enthalpies of alumina-to-boehmite transformation became less exothermic with increasing the dopant loading, indicating a lowering of the surface energy of γ-Al2O3 by the zirconium additive.

In agreement with these studies, our results show that when cobalt and molybdenum are used as dopants, the hydrothermal stability of γ-Al2O3 can be significantly enhanced. More importantly, the way how Co and Mo are introduced into the γ-Al2O3 framework appears to have a strong impact on the catalyst stability. Thus, for low metal loadings, the XRD data indicate that while the catalysts prepared by impregnation are totally transformed into boehmite, the catalysts prepared by the one-pot approach exhibit only marginal changes in their crystalline structure indicating a high resistance against hydrolysis. Further evidence for such difference in the hydrothermal stability was provided by N2-adsorption analysis. The adsorption isotherms and pore size distributions are compared in Figure 10. Clearly, the isotherms present different shapes depending on the catalyst loading and the preparation method. CoMo1 and CoMo2 show a type IV isotherm with a type H3 hysteresis loop characteristics of materials with large slit-shape mesopores and macropores. [START_REF] Sing | Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity[END_REF] The pore size distribution dramatically broadens compared to non-treated catalysts (Figure 8) and shifts to higher sizes indicating a structural collapse. Consequently, the specific surface area drops from 360-370 to 20-50 m 2 /g, representing an average loss of 86-96 % relative to the initial value (Table 3).

Conversely, all one-pot catalysts present a type H1 hysteresis loop with a well-defined plateau at high relative pressures and a narrow pore size distribution indicating that the mesoscopic order is now preserved. The reduction of pore sizes from 11-13 to 4-6 nm points however towards a densification of the catalyst network. Moreover, the loss in surface areas is much slower than for impregnated catalysts (SBET drops from 410-440 to 280-290 m 2 /g representing an average loss of 33-35%). This is an indication that the one-pot catalysts prepared with low CoMo loadings undergo slower deactivation compared to the impregnated catalysts prepared with the same CoMo loadings.

Most probably, cobalt-and molybdenum-aluminates, which make-up the majority of the former catalysts, are able to create a physical barrier towards water, thus opposing alumina-to-boehmite phase transformation. On the other hand, for CoMo3 prepared with high CoMo loadings, the loss in surface area was found to be less severe (only 7%) compared to the analogous one-pot catalysts (CoMo5 and CoMo6). Similar stabilizing effect against transformation of γ-Al2O3 to boehmite in hot liquid water was recently observed in the presence of biomass-derived compounds, such as two-or three-carbon polyols, as well as lignin, which showed the ability to adsorb over γ-Al2O3 support [START_REF] Copeland | Surface interactions of C2 and C3 polyols with γ-Al2O3 and the role of coadsorbed water[END_REF] or Pt/γ-Al2O3 catalysts. [START_REF] Ravenelle | Stability of Pt/γ-Al2O3 catalysts in model biomass solutions[END_REF][START_REF] Jongerius | Stability of Pt/γ-Al2O3 catalysts in lignin and lignin model compound solutions under liquid phase reforming reaction conditions[END_REF] Indeed, the multidentate interactions established between lignin and γ-Al2O3 via the oxygen functionalities were shown to prevent formation of boehmite phase and sintering of the supported Pt nanoparticles. [START_REF] Jongerius | Stability of Pt/γ-Al2O3 catalysts in lignin and lignin model compound solutions under liquid phase reforming reaction conditions[END_REF] Based on the above results, the proposed mechanism through which metal oxide nanoparticles are supposed to interact with the nanostructured γ-Al2O3 support prepared from RaMeβ-CD-based assemblies is illustrated in Figure 11. When cobalt and molybdenum species are dispersed at low concentration over the γ-Al2O3 support by impregnation, small and well-dispersed metal oxide nanoparticles form on the support surface without affecting significantly its structural and textural properties but, with a failure to stabilize the support against hydrolysis in hot water. Increasing the metal loading promotes partial diffusion of metal oxide nanoparticles into the walls of alumina, and leads to formation of surface Al2(MoO4)3 and MoO3 crystallites. High Co and Mo ladings are necessary to ensure diffusion of these species into the alumina framework and stabilize the material under hydrothermal conditions.

On the other hand, the incorporation of [Co2Mo7O24] 2-complex directly within the supramolecular template promotes diffusion of the active elements into the walls of γ-Al2O3, even at low CoMo loadings, thus leading to small and well-dispersed metal oxide nanoparticles and hydrothermally stable catalysts. Such diffusion of Co and Mo into the pores of the support occurs during the crystallographic conversion of boehmite into γ-Al2O3 at 500 °C. Table 3. Textural characteristics of mesoporous CoMo/γ-Al2O3 catalysts after exposure in hydrothermal environment at 375°C for 15 minutes.

Sample

SBET a (m 2 g -1 ) PV b (cm 3 g -1 ) PS c (nm) SBET loss (%) a BET specific surface area determined in the relative pressure range 0.1-0.25, b PV = cumulative pore volume (BJH), c PS = pore size calculated from BJH method.

The crystalline structure of boehmite is planar and built-up of oriented sheets of octahedral (Oh) aluminum units connected via hydrogen bonds, [START_REF] Bleta | Rheological behaviour and spectroscopic investigations of cerium-modified AlO(OH) colloidal suspensions[END_REF] while the crystalline lattice of γ-Al2O3 is cubic spinel and built-up of close-packed stacked oxygen layers where Al 3+ ions occupy both the octahedral (Oh) and the tetrahedral (Td) sites and where some lattice sites remain empty in order to satisfy the stoichiometry of γ-Al2O3. The thermal transformation of nanocrystalline boehmite into γ-Al2O3 has previously been modelled by a four steps reaction mechanism [START_REF] Krokidis | Theoretical study of the dehydration process of boehmite to γ-alumina[END_REF][START_REF] Alphonse | Structure and thermal behavior of nanocrystalline boehmite[END_REF] involving (i) the removal of physisorbed water located in the interlayer space, (ii) the removal of chemisorbed water, (iii) the structural collapse of boehmite, and (iv) the transfer of first aluminum species from octahedral to tetrahedral sites. Surface hydroxyl groups have been shown to condensate first, followed by bulk hydroxyls, before complete transformation to γ-Al2O3 with an equilibrium structure containing about 25-31% of tetrahedral aluminum sites. A DFT study [START_REF] Raybaud | Morphology and surface properties of boehmite (γ-AlOOH): a density functional theory study[END_REF] has shown that the basal (010) faces of AlO(OH), which have the lowest interfacial tension, tend to attain the highest development. This explains the low thickness of AlO(OH) nanoparticles (~ 3 nm) and the fibber-like structure of the resulting γ-Al2O3 material. [START_REF] Bleta | An efficient route to aqueous phase synthesis of nanocrystalline γ-Al2O3 with high porosity: from stable boehmite colloids to large pore mesoporous alumina[END_REF] When the supramolecular assemblies formed between the block copolymer and the RaMeβ-CD are introduced into the boehmite sol, they interact weakly, through hydrogen bonding, with the basal surface hydroxyl groups. [START_REF] Bleta | Coassembly of block copolymer and randomly methylated β-cyclodextrin: from swollen micelles to mesoporous alumina with tunable pore size[END_REF] Moreover, as cobalt and molybdenum species are encapsulated directly into these assemblies, the template removal during calcination at 500 °C should facilitate incorporation of these ions into the Td and Oh sites of the cubic spinel structure. Consequently, in addition to their important role in enhancing the porosity and surface area of the support, the supramolecular assemblies may also facilitate incorporation of cobalt and molybdenum within the alumina framework during the crystallographic conversion of boehmite, thus resulting in stabilization against hydrolysis.

Cobalt ions, with lower cationic charge, should diffuse preferentially into the tetrahedral sites.

Indeed, the presence of the triple absorption band in the 540-630 nm region (Figure 5 B, D), as well as the blue color of these catalysts, are typical of Co 2+ in a tetrahedral environment. Actually, the formation of cobalt aluminates results from the lattice matching between γ-Al2O3 and CoAl2O4, [START_REF] Dandapat | Host-mediated synthesis of cobalt aluminate/γ-alumina nanoflakes: a dispersible composite pigment with high catalytic activities[END_REF] both of which adopt a cubic spinel structure with the same space group (Fd3m) and have very similar lattice constant values (i.e. 7.9 Å for γ-Al2O3 74 and 8.1 Å for CoAl2O4 [START_REF] Tielens | Periodic DFT study of the structural and electronic properties of bulk CoAl2O4 spinel[END_REF] ). On the other hand, molybdenum ions, with higher cationic charge, are forced to enter preferentially into the octahedral sites, although a small portion of tetrahedral molybdenum species is also detected in the UV spectra (Figure 5 A,C). The proportion of tetrahedral and octahedral coordinated polymolybdate species appears, however, to be dependent on the concentration in active elements; the octahedral environment being favored for the highest Mo loadings. Notably, CoMo3 prepared with the highest metal loadings, displayed only marginal loss in surface area and negligible hydrolysis to boehmite. Such a particular behavior of this catalyst may be explained by the distribution of the active elements between the interior and the exterior surface of the porous support, thus hindering the interactions of water molecules with both the surface and bulk hydroxyl groups of alumina, thus preserving the support from hydrolysis.

Previous studies have shown that cobalt aluminates can be highly active toward the oxidation of CO [START_REF] Thormählen | The influence of CO2, C3H6, NO, H2, H2O or SO2 on the low-temperature oxidation of CO on a cobalt-aluminate spinel catalyst (Co1.66Al1.34O4)[END_REF] and the decomposition of H2O2 at room temperature. [START_REF] Dandapat | Host-mediated synthesis of cobalt aluminate/γ-alumina nanoflakes: a dispersible composite pigment with high catalytic activities[END_REF] However, to our knowledge, no detailed investigation of the structure-property relationships in supported bimetallic CoMo/γ-Al2O3 catalysts for the liquefaction of microalgae has been performed to date. As reported in many articles, the structural and textural characteristics of the heterogeneous catalysts, as well as the distribution of the active elements, may have a great impact on both the diffusion of the reactants and the products yields. [START_REF] Budroni | Pd nanoparticles embedded in sponge-like porous silica as a Suzuki-Miyaura catalyst: Similarities and differences with homogeneous catalysts[END_REF][START_REF] Garcia-Martinez | Incorporation of Pd nanoparticles in mesostructured silica[END_REF][START_REF] Linares | Incorporation of chemical functionalities in the framework of mesoporous silica[END_REF] In what follows, we discuss how the preparation method may affect the catalytic performances of mesoporous CoMo/γ-Al2O3 catalysts in the hydrothermal liquefaction of microalgae.

Catalytic performances

The six prepared catalysts were tested in the hydrothermal liquefaction of microalga Nannochloropsis gaditana whose proximate and ultimate analyses are reported in Table 4. HTL tests were performed at 375 °C. The reaction time was fixed at 15 min in order to limit loss of biocrude due to follow-up reactions, such as cracking and repolymerization, which would otherwise enhance gas and char formation. [START_REF] Zhou | Hydrothermal liquefaction of macroalgae Enteromorpha prolifera to bio-oil[END_REF] Thus, as pointed out by Alba et al. 80 , when working near the critical point of water (i.e. 374°C), short reaction times appear to be more convenient for a maximum oil production. The reactor was unstirred that is a frequent choice to study the effect of catalysts in the HTL of microalgae in batch reactors. This means that bio-constituents of the solid biomass, i.e. proteins, polysaccharides, triglycerides, are first hydrolyzed by hot water. The heterogeneous catalyst will work on the products of aforementioned decomposition reactions dissolved in the fluid phase. It must be considered that reactions were performed at near critical conditions in which small temperature gradient can activate significant natural convection inside the reactor. For this reason, even if the reactor was not stirred, mass transfer was not only diffusional but also promoted by convection. [START_REF] Johnson | Critical phenomena in hydrothermal systems: state, thermodynamic, electrostatic, and transport properties of H2O in the critical region[END_REF] The results of HTL tests performed with the six catalysts are reported in Figure 12 together with the results of an experiment without added catalyst. All catalysts prepared by impregnation method (CoMo1, CoMo2 and CoMo3) gave biocrude yields close to that obtained in the absence of added catalyst. This could be due to the limited hydrothermal stability that these catalytic systems showed in hydrothermal environment. On the other hand, among the three catalysts prepared by the one-pot colloidal approach (CoMo4, CoMo5 and CoMo6), the one with lower metal loading (CoMo4, with 0.6 wt% Co and 6.4 wt% Mo) exhibited a marginal effect on the biocrude yield, while the two other catalysts with 1.2 wt% Co and 15.2 wt% Mo (CoMo5 and CoMo6) allowed for increasing the biocrude mass yield by about 3.9-4.6%, that is a statistical significant modification with respect to the catalyst-free test (i.e. 15% higher). The catalysts prepared with the highest Co and Mo loadings by the one-pot colloidal route were the most effective in enhancing this figure of merit. Interestingly, impregnated catalyst with the same metal loadings, (CoMo3), did not induce an analogous gain in biocrude production, even if the hydrothermal stability of this catalyst was found to be quite good with respect to the other impregnated catalysts with lower metal loading (Table 3). For this catalyst, the diffraction peaks of Al2(MoO4)3 and MoO3 were clearly detectable, indicating formation of large Al2(MoO4)3 and MoO3 crystallites (see Figure 11).

The catalysts prepared by the one-pot colloidal approach were the focus of the following examination because they were stable under hydrothermal conditions and gave the highest biocrude yields. The elemental composition of biocrude oil obtained with those catalysts, as well as that of non-catalytic test are reported in Table 5. Overall, the catalysts did not cause any change in the biocrude higher heating values (HHV), even at the highest metal loading, but a clear increase in the oil yield was observed. The bio-oil produced under the adopted operating conditions has a high energy density with HHV up to 37 MJ/kg. The total amount of the recovered products accounted for 75% of the initial biomass in all experiments. The obtained yields of gas and solid residue are in the range usually reported in literature for HTL of microalgae at temperature of 350-375 °C. [START_REF] Valdez | Characterization of product fractions from hydrothermal liquefaction of Nannochloropsis sp. and the influence of solvents[END_REF]83,[START_REF] Neveux | Biocrude yield and productivity from the hydrothermal liquefaction of marine and freshwater green macroalgae[END_REF] The gas phase composition was similar in the absence and in the presence of all tested catalysts. It was mainly constituted of CO2 (90 mol%), CO (about 5 mol%) and few volumetric percentages of H2 and CH4, C2H4 and C2H6, in agreement with literature. [START_REF] Chen | Distributions of organic compounds to the products from hydrothermal liquefaction of microalgae[END_REF] For what concern the yield in aqueous products, it was found in the range 10-13 wt% that is lower than that reported in the literature for HTL of similar microalgae. [START_REF] López Barreiro | Assessing microalgae biorefinery routes for the production of biofuels via hydrothermal liquefaction[END_REF] Some authors calculated the aqueous phase yield both as complement to 100 wt% of the quantified gas, bio-oil and solid residue fractions, and after the solvent removal from the aqueous phase through stripping with N2 for 6 h. [START_REF] Valdez | Hydrothermal liquefaction of Nannochloropsis sp.: Systematic study of process variables and analysis of the product fractions[END_REF] They found a big difference between the two estimations and ascribed it to the presence of water-soluble high volatile organic compounds which were removed during the solvent stripping.

Analogous considerations were reported by Zhou et al. [START_REF] Zhou | Hydrothermal liquefaction of macroalgae Enteromorpha prolifera to bio-oil[END_REF] , who estimated the water-soluble products after evaporation of water from the aqueous fraction at 65 °C for 12 h. Thus, it seems probable that the missing aliquot to close the mass balance in the product distribution of Figure 12 could be similarly explained as loss of volatile organic compounds during the aqueous phase collection via vacuum filtration and during the evaporation of water at 60 °C overnight. Figure 13 shows the comparison of quantitative GC-MS analyses of biocrude obtained with the two best catalysts which gave the highest yield in bio-oil, i.e. CoMo5 and CoMo6, compared to the test without catalyst. Six C14-C18 fatty acids (FAs) were detected and quantified using standards. They are generated by the triglyceride hydrolysis, which is a fast chemical step in the presence of hot water at operation temperature adopted in the study. [START_REF] Alenezi | Continuous flow hydrolysis of sunflower oil for biodiesel. Energy Part A Recover[END_REF] Fatty acids could transform into hydrocarbons via hydrodeoxygenation (HDO) or hydrodecarboxylation (HDC) processes, forming water or CO2, respectively, [START_REF] Galadima | Zeolite catalysts in upgrading of bioethanol to fuels range hydrocarbons: A review[END_REF] both of these processes reducing the oxygen content in the bio-oil. In comparison with conventional fossil fuels, bio-oil contains much higher oxygen contents, which dramatically decrease its heating value and may cause other undesirable effects, such as high viscosity, instability and corrosion. Removal of oxygen is therefore critical for bio-oil upgrading. In the presence of the two catalysts, a reduction of the amount of detected fatty acids was observed with respect to the bio-oil obtained with the thermal test, indicating an improvement in the oxygen removal activity. In particular, the cumulative amount of detected FAs was lower with CoMo6 in comparison with CoMo5 indicating higher activity of this catalyst for in-situ partial upgrading of the obtained bio-oil.

Quite interestingly, the ratio between the cumulative area of peaks assigned to hydrocarbons and that of fatty acids increased in the order CoMo6>CoMo5>no catalyst (Table 6), which could be another indication of a better capability of higher loading catalyst prepared by one-pot approach to remove oxygen from biocrude.

×

This parameter indicates how the process is effective in concentrating the energy content of the initial biomass feedstock in the obtained bio-oil. As both the yield and the HHV of the bio-oil are taken into account, this parameter highlights the role of the catalyst in orienting the process toward the formation of more energetic compounds in the obtained bio-oil. We found that the catalyst obtained through the one-pot colloidal approach at high active metals loadings could yield an energy recovery of 63-64% that is much higher than that obtained from HTL processes performed in the absence of catalyst.

Nevertheless, it is important to emphasize that the hydrothermal liquefaction of microalga is still in a developing stage and further process improvement is needed for increasing biocrude oil yield and quality. Moreover, the separation of the catalyst from the solid residues (typically ashes) and its reusability are still important factors that need to be evaluated in the microalga biorefinery processes. Another important aspect is the experimental set-up which should also be modified to protect the catalyst from fouling and be sure that there is a good contact with the organic molecules and the aqueous phase. This study must be performed with a modified experimental set-up to decouple the effect of the phase behavior of the reaction system from the catalytic effects. Indeed, at reaction conditions, different phases are generated inside an unstirred reactor, i.e. an oil-rich phase with suspended solid at the bottom, a water-rich phase with suspended solids in the middle and a gas-phase at the top. We think that experimental outcomes are dependent not only on the catalyst nature but also on the relative amounts of aforementioned phases and on their contact with the catalyst. To remove these sources of uncertainty, we are currently working on changing the batch reaction system in a two-step continuous process in which the first one is a thermally activated HTL in a well-stirred CSTR connected in sequence with a fixed bed reactor loaded with the catalyst in which the biocrude-rich phase is up-graded.

Conclusions

In this work, two experimental procedures for cyclodextrin-assisted synthesis of CoMo-based catalysts for HTL of microalgae were proposed and compared. Catalysts were extensively characterized by different techniques such as diffuse reflectance UV-visible spectroscopy, X-ray diffraction, N2-adsorption-desorption and H2-temperature programmed reduction. Results showed that both methods allow preparation of mesoporous structures with high surface area (300-450 m 2 /g). Catalysts prepared by the one-pot colloidal approach exhibited high stability, even at low metal loadings, after exposure to hydrothermal environment. Differently, the stability of catalysts prepared by impregnation was affected by the metal loading. Catalyst characterizations suggested that this behavior could be attributed to a better dispersion and incorporation of the active catalytic species into the alumina support framework. In particular, the incorporation of tetrahedral coordinated divalent Co species (cobalt aluminate phase CoAl2O4, spinel) was found to occur more effectively for catalysts prepared via the one-pot method. Results of microalgae HTL tests showed that impregnated catalysts had almost no effect on the performances of the process in comparison with the catalyst-free test. Interesting results were obtained with the two catalysts prepared by the one-pot approach with the highest Co and Mo loadings. Thus, the combination of higher yield and higher heating value (HHV) of the obtained biocrude led to a 13% enhancement of the biomass energy recovery (ER) into the biocrude with respect to the catalyst-free test. Moreover, the nature of the block copolymer used during the CoMo/γ-Al2O3 preparation was also found to affect the catalyst performance. Thus, the ability of pH-sensitive Tetronic T90R4 to interact through its positively charged amino groups with the negatively charged [Co2Mo7O24] 2-complex was beneficial in the oxygen removal efficiency from biocrude. The proposed one-pot cyclodextrinassisted approach presented in this study gave promising results toward the preparation of hydrothermally stable catalytic systems and can be used to prepare many other composites of technological importance.

  Both the linear poloxamer Pluronic F127 with a chemical formula PEO106PPO70PEO106 [PEO = poly(ethylene oxide) and PPO = poly(propylene oxide)] (Mw 12500 g/mol) and the star-shaped poloxamine Tetronic T90R4 (ethylenediamine tetrakis (ethoxylate-block-propoxylate) tetrol) with a chemical formula (PPO19PEO16)2NCH2CH2N(PPO19PEO16)2 (Mw 7200 g/mol) were purchased from Sigma Aldrich. Randomly methylated β-cyclodextrin (denoted RaMeβ-CD, average degree of molar substitution (DS) of 1.8 and average Mw 1310 g/mol) and native β-cyclodextrin (denoted β-CD, average Mw 1135 g/mol) were gifts from Wacker Chemie GmbH and Roquette Frères respectively. Aluminum tri-sec-butoxide, Al[OCH(CH3)C2H5]3 (referred to as ASB, Mw 246.32 g/mol), (HNO3, 68 wt%), cobalt (II) nitrate hexahydrate Co(NO3)2•6H2O (Mw 291.03 g/mol) and ammonium heptamolybdate tetrahydrate (NH4)6Mo7O24 4H2O (Mw 1235.86 g/mol) were procured from Sigma-Aldrich. The microalga Nannochloropsis gaditana was purchased from Algaspring in powder form. The proximate analysis of the used microalgae batch was provided by the supplier.

Figure 2 .

 2 Figure 2. Schematic illustration for the preparation of -Al2O3 supported CoMo catalysts: A) two-

Figure 3 A

 3 Figure 3 A shows the UV-visible spectra recorded on mixtures prepared with 0.02 M Co (II) and

4 (

 4 A). Mixtures prepared with higher Mo loadings precipitated faster than those prepared with lower Mo loadings. Examination of the precipitate by X-ray diffraction revealed the formation Mo8O24.8)(O2)1.2(H2O)2(H2O)4 (JCPDS card No 88-1326) and the triclinic (NH4)2Mo4O13 (JCPDS card No 80-0756) phases (Figure 4 B). In a marked contrast with the template-free CoMo solution, CoMo-RaMeβ-CD-F127 and CoMo-RaMeβ-CD-T90R4 mixtures were homogenous and stable for several months.

Figure 3 .

 3 Figure 3. UV-vis spectra of: (A) CoMo aqueous solutions prepared with 0.02M Co and increasing

40

 40

Figure 4 .

 4 Figure 4. (A) Visual aspect of template-free CoMo solution (25 mM Co and 335 mM Mo) before

Figure 5 .

 5 Figure 5. UV-vis diffuse reflectance spectra of CoMo/-Al2O3 catalysts prepared by impregnation

Figure 6 .

 6 Figure 6. XRD patterns of CoMo/-Al2O3 catalysts prepared by impregnation (A, B): CoMo1 (a),

Figure 7 .

 7 Figure 7. H2-TPR profiles of CoMo/-Al2O3 catalysts prepared by impregnation (A): CoMo1 (a),

Figure 8 .

 8 Figure 8. Evolution of the adsorption-isotherms and pore size distributions (inset) for CoMo/-

  Conversely, the pore size of the one-pot catalysts (CoMo5 and CoMo6) prepared with the same loadings remains almost unchanged, indicating the presence of open pores > 11 nm.

Figure 9 .

 9 Figure 9. XRD patterns of CoMo/-Al2O3 catalysts prepared by impregnation (A): CoMo1 (a),

Figure 10 .

 10 Figure 10. N2-adsorption isotherms and corresponding pore size distributions (inset) of CoMo/-

69

 69

Figure 11 .

 11 Figure 11. Proposed formation mechanism of mesoporous CoMo/-Al2O3 catalysts prepared via

Figure 12 .

 12 Figure 12. Product distribution for the catalytic HTL of the microalga Nannochloropsis gaditana,

Figure 13 .

 13 Figure 13. Quantification via GC-MS of six common fatty acids in algal biomass, present in the

Table 1 .

 1 Mesoporous CoMo/γ-Al2O3 catalysts prepared by two different methods.

	Catalyst	Preparation method	Introduction of Co(NO3)2•6H2O and (NH4)6Mo7O24 4H2O	Co (wt%)	Mo (wt%)
	CoMo1		Only one impregnation of Mo/-Al2O3 a with Co+CD	0.6	6.4
	CoMo2	Impregnation method	Two successive impregnations of -Al2O3 b : first Mo+CD, then Co+CD	0.6	6.4
	CoMo3		Two successive impregnations of -Al2O3: first Mo+CD, then Co+CD	1.2	15.7
	CoMo4		Simultaneous introduction of Co an Mo in RaMeCD-F127-AlO(OH) assemblies	0.6	6.4
	CoMo5	One-pot colloidal approach	Simultaneous introduction of Co an Mo in RaMeCD-F127-AlO(OH) assemblies	1.2	15.7
	CoMo6		Simultaneous introduction of Co an Mo in RaMeCD-T90R4-AlO(OH) assemblies	1.2	15.7

Table 2 .

 2 Textural characteristics of CoMo/γ-Al2O3 catalysts after thermal treatment at 500 °C.

	Sample	Co(wt%)	Mo(wt%)	SBET a (m 2 g -1 )	PV b (cm 3 g -1 )	PS c (nm)
			Impregnation method
	CoMo1	0.6	6.4	418	1.10	15.0
	CoMo2	0.6	6.4	373	1.29	16.1
	CoMo3	1.2	15.7	306	0.35	4.8
			One-pot colloidal approach
	CoMo4	0.6	6.4	437	1.17	13.9
	CoMo5	1.2	15.7	411	1.08	4.3 and 16.5
	CoMo6	1.2	15.7	429	1.36	15.2

Table 4 .

 4 Proximate and ultimate analyses of the Nannochloropsis gaditana microalga adopted for HTL tests; the composition values are weight percentages referred to the dry microalga mass.

		Proteins		Lipids		Carbohydrates	Ashes
		38.0		24.1		10.7			27.2
	C	H	N	S	O a	H/C molar	O/C molar	N/C molar	HHV (MJ/kg)
	42.1	6.2	5.7	0.4	18.4	1.77	0.33	0.12	20.0
	a calculated by difference

Table 5 .

 5 Ultimate analysis of the biocrude obtained with HTL of Nannochloropsis gaditana at 375 °C, 15 min in the presence of catalysts prepared by the one-pot colloidal approach.

	Cat.	C (wt%)	H (wt%)	N (wt%)	S (wt%)	O a (wt%)	H/C molar	O/C molar	N/C molar	HHV (MJ/kg)	Yieldoil b (wt%)	ER% (%)
	none	74.9 10.1 3.6	0.3	11.0 1.62 0.11 0.04 37.0	30.2	55.6
	CoMo4	73.5 10.0 3.0	0.3	13.2 1.63 0.13 0.03 36.1	30.4	54.7
	CoMo5	73.0 10.7 3.0	0.3	13.0 1.76 0.13 0.04 36.7	34.8	63.7
	CoMo6	74.6 10.1 3.6	0.3	11.4 1.62 0.11 0.04 36.7	34.1	62.5

a calculated by difference; b yield calculated with respect to dry algae (dry basis)

Table 6 .

 6 Ratio between cumulative Area percent of the peaks assigned to hydrocarbons (A) and to fatty acids (B), respectively.In Table5is shown the Energy Recovery (ER) obtained in the experiments, defined by the following equations90 :

	Cat

Acknowledgements

The financial support of MIUR under project PRIN 2010-2011 2010H7PXLC_005 and of European Commission under project STAGE-STE FP7 Cooperation 609837 is gratefully acknowledged. The European Regional Development Fund (ERDF), the Conseil Regional du Haut de France, the CNRS and the Ministère de l'Education Nationale de l'Enseignement Supérieur et de la Recherche are acknowledged for funding of the X-ray diffractometer.

Conflicts of interest

There are no conflicts to declare.

AUTHOR INFORMATION

Corresponding Authors: *E-mail: rudina.bleta@univ-artois.fr *E-mail: alessandro.galia@unipa.it


M Cárdenas-Barrantes
email: manuel-antonio.cardenas-barrantes@umontpellier.fr

J Barés

M Renouf

E Azéma

Mixtures of soft and rigid grains: an experimental approach

Keywords: Granular matter, Soft granular compaction, High deformation

Dans bien des cas, les milieux granulaires sont composés de grains avec des propriétés mécaniques très différentes. Nous étudions expérimentalement la compaction de systèmes bidisperses 2D constitués de particules molles et rigides, et analysons également l'évolution de leurs principaux observables macroscopiques tout au long de la compaction. L'analyse est faite depuis l'état lâche jusqu'à des densités très élevées, bien au-delà du blocage, en suivant les modifications à l'échelle locale pour chaque particule du système. Nous exposons les principales caractéristiques du comportement de ces systèmes dans chacune des différentes phases (lâche, bloquée et dense) et leur variations à la traversée des zones de transition. Cette étude constitue la première étape vers une meilleure compréhension du comportement mécanique des matériaux granulaires polydisperses en termes de rhéologie des grains.

Introduction

Homogeneous assemblies of soft granular media are involved in a wide variety of natural and industrial processes, such as biological tissues composed of soft cells [START_REF] Mauer | low-Induced Transitions of Red Blood Cell Shapes under Shear[END_REF], suspensions [START_REF] Stannarius | Packing and flow profiles of soft grains in 3D silos reconstructed with X-ray computed tomography[END_REF], clayey materials [START_REF] Ilieş | Soil improvement with polyetylene waste materials in order to improve mechanical parameters[END_REF][START_REF] Rúa | Modeling the mechanical behavior of a kaolin ceramic paste owing to the variation in the particle size[END_REF], and any sintered material [START_REF] Kawakita | Some considerations on powder compression equations[END_REF][START_REF] Kim | Compaction equations for strain hardening porous materials[END_REF]. However, it has been shown that the mixture of materials with different elastic properties, such as soft and rigid particles, gives rise to new and fascinating mechanical effects. These outcomes include better stress relaxation [START_REF] Khatami | The arching effect in rubber-sand mixtures[END_REF], foundation damping [START_REF] Indraratna | Use of geogrids and recycled rubber in railroad infrastructure for enhanced performance[END_REF][START_REF] Khatami | The arching effect in rubber-sand mixtures[END_REF], and seismic isolation [START_REF] Senetakis | Dynamic properties of dry sand/rubber (SRM) and gravel/rubber (GRM) mixtures in a wide range of shearing strain amplitudes[END_REF][START_REF] Tsang | Seismic isolation by rubber-soil mixtures for developing countries[END_REF]. All without compromising the macroscopic mechanical stability of the material. The amount of stiff or soft particles that are added to these composite materials is generally chosen in an empiric manner, therefore, a more precise study of these composites for their optimization is necessary.

The effect of adding soft particles to rigid ones must be understood from the particles and contact scale, looking at how each particle deforms and what their contribution is to the whole system as a bulk. Experimentally, the measurement of local mechanical properties is a great challenge and even more in this case where the particles exceed the limit of the small deformation regime, which most measurement methods take as a basis [START_REF] Abed-Zadeh | Enlightening force chains: a review of photoelasticimetry in granular matter[END_REF]. In this study, we use a recently developed experimental method that employs Digital Image Correlation methods coupled with very accurate imaging. This permits to measure these large deformations at the particle scale relying on the resolution of the imaging [START_REF] Vu | Soft-grain compression : Beyond the jamming point[END_REF].

The communication is structured as follows. In Section 2, we briefly describe the experimental approach followed during the compaction and also the image analysis procedure. In Section 3, we present the main results of this study. Here we differentiate the macro-mechanical and micro-mechanical aspects of the compaction. Finally, conclusions are presented in Section 4.

Experimental set up and image processing

The experiment consists of a bidimensional piston of initial dimension (270 × 202) mm 2 which compresses oedometrically a bidisperse assembly of rigid and soft cylinders randomly placed on top of a flatbed scanner. The loading piston is composed of a stepper motor rotating a screw that moves the edge of the piston in the inward direction and two force sensors (Figure 1.(a)). The force is measured with a frequency of 100 Hz, and the pressure P is directly computed (P = σ yy by convention). The compressed cylinders are made of hyperelastic silicone and rigid PVC with Young's moduli E = 0.7 MPa and 1.2 GPa, respectively. PVC and Silicone cylinders both have a size bidispersity with diameters of 20 mm and 30 mm and a height of 15 mm. In both cases the Poisson ratio is close to 0.5. For each loading step, the piston moves by 0.5 mm steps with a speed of 2 mm/min to assure being in the quasistatic regime. Then, the system is imaged from below with a resolution of 2400 dpi (10.6 µm/px). For each experiment, about N = 100 particles are used keeping the ratio between rigid and soft particles κ = N soft /N constant. This ratio is equally spread among soft and rigid particles and varies in the set κ ∈ [0.2, 0.5, 0.8, 1.0]. To avoid basal friction, the scanner glass is coated with oil which also lubricates the contacts between particles, making them virtually frictionless. The bottom of each particle is painted with thin metallic glitter, which creates a random pattern with a correlation length of approximately 50 µm [START_REF] Vu | Soft-grain compression : Beyond the jamming point[END_REF]. Figure 1.(c) shows the evolution of the measured force as a function of the global strain ε for different mixture ratios.

For each experiment, a set of about 90 pictures shows the evolution of the compaction. These pictures are post-processed with a DIC algorithm modified from [START_REF]Python codes to post-process experimental images (particle tracking, DIC, fields computation[END_REF][START_REF] Vu | Soft-grain compression : Beyond the jamming point[END_REF][START_REF] Vu | Numerical simulations of the compaction of assemblies of rubberlike particles: A quantitative comparison with experiments[END_REF]. First, each particle center is detected on the initial undeformed image and then tracked from one image to the next one getting their solid-rigid motion. Second, for the soft particles, the displacement field for each particle i at each step n is obtained (u(x, y) n i ). The deformation gradient tensor is then computed: F = ∇u + I, with I the second-order identity tensor. Then, From F the right Cauchy-Green strain tensor field, C = F T F, and the von Mises strain, C, are deduced. For the rigid particles, the local stresses are too low to induce any significant deformation of the PVC, so we assume that they do not deform. Finally, contacts between particles are measured from the proximity of the boundaries and the von Mises strain. 3 Results and discussions

Macromechanical aspects

Figure 2 shows the evolution of the main macroscopic quantities of the system. On one side, we show the packing fraction, ϕ, defined as the ratio between the particles and the particles' container volume, as a function of the applied pressure directly calculated from the measured force. On the other side, the coordination number, Z, quantifying the average number of neighbors per particle, is shown as a function of the packing fraction. The previous quantities are presented relatively to the packing fraction ϕ 0 and coordination number Z 0 at the jammed state. We have selected the jamming transition point where the system can support a non-negligible load, P c = 1 kPa in our case. At this fixed point P c , ϕ 0 takes the values (0.83, 0.83, 0.81, 0.78), and Z 0 takes the values (3.31, 3.50, 3.25, 3.30) for the mixture ratios (0.2, 0.5, 0.8, 1.0), respectively.

In Fig. 2(a), the packing fraction evolves with the same general trend regardless of κ. It first increases with P from ϕ 0 and then tends asymptotically to a maximum packing fraction ϕ max , which clearly depends on κ. Together with the evolution of the compaction, Fig. 2(a) also shows a previously developed micromechanical model, based on the evolution of the stress tensor and without ad-hoc parameters, to describe the evolution [START_REF] Cárdenas-Barrantes | Compaction of mixtures of rigid and highly deformable particles: A micromechanical model[END_REF]. This model gets excellent predictions for the different values of κ, except for κ = 0.2 for which minor discrepancies are observed, even if the general tendency is reproduced. In this latter case, we can invoke finite size-effect and sharp particle rearrangements due to the small number of soft grains.

In Fig. 2(b), as has been systematically reported in the literature, Z increases following a power-law, Z -Z 0 = ξ(ϕϕ 0 ) α , with α ∼ 0.5 and ξ a structural parameter fully defined as P → ∞. Both ϕ and Z reach a maximum value ϕ max and Z max , respectively. This relation was observed both numerically Figure 2: (a) Evolution of the global stress applied to the system, P , as a functions of ϕ-ϕ 0 for different mixture ratio κ. Plain curves correspond to the micro-mechanical model presented in [START_REF] Cárdenas-Barrantes | Compaction of mixtures of rigid and highly deformable particles: A micromechanical model[END_REF] (b) Evolution of the excess coordination number, Z -Z 0 , with Z 0 ≈ 3.8, as a function of the excess packing fraction, ϕϕ 0 for different mixtures ratios κ. The solid line is the power-law relation Z -Z 0 = ξ(ϕϕ 0 ) α , with α = (0.7 ± 0.15) and its uncertainty value taken from the numerical regression. and experimentally for many granular assemblies like foams, emulsions, and rubber-like particles [START_REF] Forterre | Granular media: between fluid and solid[END_REF][START_REF] Katgert | Jamming and geometry of two-dimensional foams[END_REF][START_REF] Vu | Soft-grain compression : Beyond the jamming point[END_REF]. All the curves collapse fairly well on the power-law relation. Although the exponent α is slightly overestimated, within the error bars, we are in the same domain of α ≈ 0.5. This large error bar is mainly due to the smallness of the system.

Microstructural aspects

It is then possible to relate the strain inside the particles to macroscopic observables. Under the small deformation assumption the infinitesimal strain tensor, ε, is related to the Cauchy-Green strain tensor by ε = 1/2(C -I). In a compressed bulk material, this strain tensor and the global stress and strain are linearly related. Since deep in the jammed state, the material has a density close to the bulk, one can wonder if this relation is still observed.

As seen in Fig. 3(a) and (b), when the system is compressed, the mean von Mises strain ⟨C⟩ inside soft particles decreases from 1 while the pressure and the packing fraction increase. At low compaction level, for ⟨C⟩ > C c ≈ 0.991, it decreases linearly with the packing fraction regardless of the mixture ratio, ⟨C⟩ ∼ ϕϕ 0 . For a higher level of compression, it leaves this linear regime decreasing more rapidly for higher values of κ. It is worth noting that in the linear regime, all curves collapse in a single one regardless of the mixture ratio. On the contrary, at a high compression level, for ⟨C⟩ < C c , the mean von Mises strain decreases linearly with the global pressure except for some noise due to the particle rearrangements, ⟨C⟩ ∼ P . For low deformation levels, all curves collapse on a parabolic curve. In the first regime (⟨C⟩ > C c ), the linearity is reminiscent of the one observed between the global strain scale and the packing fraction, being still in a rigid regime. In the second regime (⟨C⟩ > C c ), the linearity between the local strain and the global stress suggests that the material behaves like a bulk. This is consistent with the material's low porosity. It is also consistent with the fact that, at large compression levels, the pressure decreases faster with the strain for lower mixture ratio: the material gets stiffer for lower κ. On the contrary, in small compression levels, linear relations collapse and do not significantly depend on the mixture ratio.

Conclusions

We analyzed experimentally the oedometric compaction of granular assemblies composed of mixtures of both rigid and soft cylindrical particles. First, these experimental results validate a previously developed compaction model for the case of the oedometric compaction of a quasi-two-dimensional system. Second, we confirmed the power-law tendency for the excess coordination number as a function of the excess packing fraction. However, the exponent is slightly overestimated from the one reported in the literature, which is mainly due to the small size of the system. Finally, we found that the average strain inside soft particles evolves linearly with the packing fraction, while in the case of high loading levels, it scales with the global pressure applied to the system. This evidences two distinct regimes separated by a critical value independent of κ.

  Fig. 1.(b) shows the von Mises strain field toghether with the scan of a granular sample with κ = 0.5.

Figure 1 :

 1 Figure 1: (a) Experimental set-up. (b). Composite view of measured fields. All rigid particles are colored in blue. Raw image, in gray level, is shown on the left, particle boundaries are in red. Von Mises strain field is shown on the right with a color scale going from dark red (low value) to yellow (high value). Contacts are shown in white. (c) Evolution of the measured force, F , as a function of the global strain, ε, for different values of mixture κ.

Figure 3 :

 3 Figure 3: (a),(b): Evolution of the global stress, P , and of the excess of packing fraction ϕϕ 0 , as a function of the average value of the von Mises strain, ⟨C⟩ in soft particles, for different κ values. In (a) and (b) the straight black dashed lines display linear regimes. The vertical gray line and the shaded area shows the critical strain C c = 0.991 ± 1.2 × 10 -3 and its errorbar, respectively. It splits the space horizontally between large and small particles' deformation regimes.