Feng Niu

Mounib Bahri

Ovidiu Ersen

Zhen Yan

Bright T Kusema

Andrei Y Khodakov
email: andrei.khodakov@univ-lille.fr

Vitaly V Ordomsky
email: vitaly.ordomsky-ext@solvay.com

Multifaceted Role of Mobile Bismuth Promoter in Alcohol Amination over Cobalt Catalysts

Promotion with small amounts of different elements is an efficient strategy for the enhancement of the performance of many heterogeneous catalysts. Supported cobalt catalysts exhibit significant activity in the synthesis of primary amines via alcohol amination with ammonia, which is an economically efficient and environmentally friendly process. Insufficient selectivity to primary amines, low activity and fast cobalt catalyst deactivation remain serious issues restricting application of alcohol amination in the industry.

In this work, we have discovered the multifaceted role of the bismuth promoter, which is highly mobile under the reaction conditions, in 1-octanol amination over supported cobalt catalysts. First, the overall reaction rate was enhanced more than twice on the promotion with bismuth. Second, the selectivity to primary amine increased 6 times in the presence of Bi at high alcohol conversion. Finally, the bismuth promotion resulted in the extremely high stability of the cobalt catalyst.

Characterization by XRD, temperature programmed reduction, STEM, CO chemisorption, BET, TGA and FTIR has showed that the enhancement of the catalytic performance on the promotion with bismuth is due to better cobalt reducibility, easy removal of strongly adsorbed intermediates and products by the mobile promoter and steric hindrances for amine coupling reactions resulting in secondary and tertiary amines.

Introduction

Amines are important materials in chemical industry and life science [1]. Most aliphatic amines and their derivatives are essential intermediates for organic synthesis, which are widely used in the production of agrochemicals, pharmaceuticals, organic dyes, detergents, fabric softeners, surfactants, corrosion inhibitors, lubricants, polymers and so on [START_REF] Heilen | Ullmanns Encyclopedia of Industrial Chemistry[END_REF][START_REF] Wittcoff | Industrial Organic Chemicals[END_REF].

A number of routes for amines synthesis have been developed like Hofmann alkylation, Buchwald-Hartwig and Ullmann reactions, hydroamination, reduction of nitriles, and reductive amination [START_REF] Xu | [END_REF]5,6,7,8,[START_REF] Brown | The Organic Chemistry of Aliphatic Nitrogen Compounds[END_REF][START_REF] Zhou | [END_REF]11]. Most of currently available amine synthesis routes involve generation of by-side products harmful for environment and human health. Direct one-pot amination of alcohols with ammonia is a safe method of amine synthesis with the environmentally benign byproduct such as water. This route of amination corresponds to the most part of the principles of Green Chemistry like prevention, atom economy, safer chemicals, no solvents, catalysis, reduce derivatives etc.

The alcohol amination on different supported metallic catalysts, such as Ru [12],

Ni [13] and Co [14], under hydrogen can be achieved via so called hydrogen borrowing or hydrogen auto transfer methodology [15,16,17,18], which consists of dehydrogenation and hydrogenation processes. The one-pot alcohol amination generally consists of three consecutive steps: (i) dehydrogenation of an alcohol to a reactive aldehyde (or ketone); (ii) imine formation by coupling of a carbonyl compound with ammonia; (iii) amine formation by hydrogenation of the imine over the catalyst. During the whole process, water is the only by-product, which emphasizes the advantage of this environmental friendly route. The alcohol amination catalysts however, usually suffer from the low selectivity to primary amines [19].

Insufficient activity and fast catalyst deactivation significantly restrict application of the alcohol amination in the industry [20]. Hydrogen pressure during the amination reaction is essential to prevent catalyst deactivation. Amines in the hydrogen borrowing mechanism are produced by hydrogenation of imines. An increase in the selectivity to primary amine during alcohol amination in the presence of hydrogen can be due to the faster imine hydrogenation [21].

Our previous report indicates structure-insensitive character of amination reaction over ruthenium nanoparticles, but strong structure sensitivity of the primary amine coupling to secondary amine. The rate of primary amine coupling rapidly increases with the increase in the ruthenium particle size. A combination of structure insensitive alcohol amination and structure sensitive primary amine coupling results in a significant increase in the selectivity to primary amines with decrease in the size of metal nanoparticles [12].

Different approaches have been used to control the activity and selectivity in amination of alcohols. In our previous work [14], intentional deposition of polymeric carbonaceous species on the surface of Co/Al 2 O 3 catalysts was used to considerably improve the selectivity of primary amines in the gas and liquid-phase amination of aliphatic alcohols with NH 3 . The selectivity enhancement was attributed to the suppression of primary amine self-coupling because of hindering of secondary imine hydrogenation. Addition of secondary metals to the parent cobalt catalyst was shown to be an efficient way to enhance the reaction activity and selectivity. Fischer et al. [22] reported the catalytic synthesis of 1, 3-diaminopropane from 1, 3-propanediol and ammonia in a continuous fixed-bed reactor using unsupported Co-based catalysts.

Promotion of the unsupported cobalt catalyst with iron or lanthanum significantly improved the selectivity of 1,3-diaminopropane. The effect has been assigned to suppression of the transformation of active metastable β-cobalt phase to the thermodynamically more stable α-cobalt phase under reaction conditions, which improved the catalytic selectivity. Takanashi et al. investigated the synergetic effect between rhodium and indium for the amination of 1,2-propanediol [23]. The obvious catalytic rate promotion was mainly attributed to the electronic perturbation of Rh sites by indium that weakens the binding of ammonia. Wang et al. [24] combined DFT calculations, scaling relations, kinetic simulations and catalysis experiments to determine the key factors that govern the activity and selectivity of metal catalysts for the direct amination of alcohols with ammonia. They uncovered that addition of Ag or Ru into supported Co catalyst led to the most promising catalysts.

Traditionally metallic or non-metallic promoters are considered immobile on the catalyst surface and play a static role with local modification of the active sites [25,26,27]. Recently, we have discovered strong promoting effects of low melting point metal promoters such as Bi and Pb [28,29] in Fischer-Tropsch synthesis over Fe and Co catalysts. An exceptional increase in the reaction rate (up to 10 times), higher selectivity to light olefins (up to 60 %) and enhanced stability have been observed over Fe catalysts in high temperature Fischer-Tropsch synthesis. These effects have been assigned to a pseudo-liquid state of the promoters under the reaction conditions, their intensive migration, redox cycles during the reaction and close contact between metal and the promoters. We have also found that the presence of Bi promoter significantly improves stability of the cobalt and nickel catalysts in low temperature Fischer-Tropsch synthesis [29].

In this paper, we uncovered multiple effects of the bismuth promoter on the cobalt catalysts in the amination of alcohols. A significant increase in the activity, higher selectivity to primary amines and enhanced stability were observed (Figure 1).

Results and Discussion

Enhancement of catalytic performance on bismuth promotion

The Co/Al 2 O 3 catalysts with the Bi promoter content in the range from 0 to 5 wt% were prepared by impregnation with subsequent calcination and reduction at 450 o C.

They were used for the synthesis of primary 1-octylamine directly from 1-octanol and ammonia in the presence of hydrogen in a batch reactor. Note that no 1-octanol conversion was observed in a blank experiment without catalyst addition.

Direct liquid phase amination of alcohol with ammonia over supported cobalt catalyst follows the hydrogen borrowing mechanism (Figure 2). Generally, the rate determining step is catalytic dehydrogenation of alcohol to corresponding aldehyde [30,31,32]. Condensation of octanal with ammonia is a fast non-catalytic reaction leading to formation of hemiaminal followed by elimination of water to produce primary imines [33]. Finally, hydrogenation of imines leads to the formation of primary amines. The selectivity to primary amines sharply decreases at high conversion, because of self-coupling of primary amine to secondary and tertiary amines.

The catalytic performance data for liquid phase amination of 1-octanol over the catalysts before and after Bi addition to Co are displayed in Figure 3a and 1-octylamine at the conversion of 20 %. As the conversion increases to nearly 100 %, the selectivity to 1-octylamine dramatically decreases to 11 %, which is similar to the reported results in both gas phase and liquid phase amination of alcohols due to the self-coupling of primary amines to secondary and tertiary amines (Figure 2) [16].

Surprisingly, the bismuth promotion of cobalt catalysts produces a strong effect on the selectivity especially at high 1-octanol conversion. The selectivity to 1-octylamine gradually increases (at the same 1-octanol conversion) as Bi loading content increases.

The optimal selectivity at higher conversion over Co5.0Bi/Al 2 O 3 catalyst increases to 66 %, which is 6 times higher than that of freshly activated Co/Al 2 O 3 . Thus, the selectivity to primary 1-octylamine during liquid phase amination of 1-octanol can be controlled by adjusting the Bi content.

The catalytic stability data for liquid phase amination of Scherrer equation using X-ray line broadening method was around 10 nm for the fresh non-promoted and Bi promoted Co catalysts as well as for the one after amination reaction (Table 1). The particle sizes measured by XRD were consistent with STEM results calculated from particle size distribution (Figure 6, Figure S2). Therefore, no obvious modification of Co particle size and distribution occur after the Bi promotion.

Ex-situ XPS analyses of Co1.0Bi/Al 2 O 3 before and after reduction and amination have provided further information about the bismuth and cobalt phases (Figure S3, SI). The Co 2p binding energies, spin-orbital splitting and low intense shake-up satellite structure indicate [34,35]

Mechanism of bismuth promotion

Catalyst characterization was indicative of the appearance of new low temperature peaks in the TPR profiles (Figure 5) related to easily reducible cobalt species and decrease in the fraction of barely reducible mixed cobalt alumina species after the promotion with bismuth. Thus, the increase in the amination rate could be at least partially attributed to the reducibility enhancement.

Numerous previous kinetic studies [30,31,32] suggest that dehydrogenation of alcohol is the rate limiting step for amination reaction over metal catalysts [38] (Figure 2). To investigate the effect of Bi over this step, liquid phase dehydrogenation of 2-octanol to 2-octanone was tested over activated Co/Al 2 O 3 and bimetallic CoxBi/Al 2 O 3 catalysts. As shown in Figure 7, the conversion was only 2.8 % for freshly activated Co catalyst [39]. The conversion of alcohol increased to 16 % after addition of promoter, which corresponds to thermodynamic equilibrium. The conversion gradually decreases from 16 % to 1 % when Bi loading content increases from 0.5 to 5 wt%, which is consistent with the activity enhancement effect for 1-octanol amination. Thus, this experiment confirms that the limiting step of amination over metal catalysts such as alcohol dehydrogenation (Figure 2) is enhanced over the Bi-promoted Co catalysts. Higher Bi content suppresses the activity in both dehydrogenation and amination reaction.

It is known that carbonyl compound produced on the alcohol dehydrogenation can poison cobalt active surface and result in the significant decrease in the catalytic activity [ 40 ]. Thus, possible explanation of the enhancement of alcohol dehydrogenation step in the presence of Bi could be continuous regeneration of the surface of Co by the removal of adsorbed amines, alcohol and aldehydes. In order to prove this assumption, amination of 1-octanol was performed after preliminary poisoning of Co/Al 2 O 3 by CO adsorption. The activity of freshly activated non-promoted cobalt catalysts sharply decreased after CO poisoning, while there was no effect of carbon monoxide pre-adsorption on the Bi-promoted Co catalyst (Figure S5, SI). Increase in the activity could be explained by easy carbon monoxide removal by the mobile Bi promoter. The observed phenomenon is similar to our earlier findings [29]. Indeed, the temperature of 1-octanol amination is higher than the bismuth Tammann temperature.

It is widely accepted that secondary and tertiary amines can form accordingly to two mechanisms: amination of remaining 1-octanol with 1-octylamine or self-coupling reaction of 1-octylamine through condensation of primary amines with corresponding imines. Amination of 1-octanol with 1-octylamain can be observed at low or medium conversions, while 1-octylamine self-coupling reaction seems to be the main reason for selectivity loss at high 1-octanol conversion (Figure 2). To investigate the effect of Bi addition on the selectivity enhancement during liquid phase amination, 1-octylamine coupling to dioctylamine and trioctylamine was conducted at relatively low 1-octylamine conversion (< 10%). Figure 8 shows the distribution of 1-octylamine converted products over freshly activated Co/Al 2 O 3 and Bi-promoted catalysts. The main products of 1-octylamine coupling were secondary imines and amines. The selectivity to secondary imine increases and the selectivity to secondary amine decreases with increase in the Bi content in the catalyst.

The calculated TOF for 1-octylamine self-coupling reaction gradually decreased from 365 to 148 h -1 after Bi promotion (Table S2, SI). The TOF numbers for 1-octanol amination for all the catalysts were about 210 h -1 . Thus, the ratio of TOF the key role of poisoning in deactivation of the catalyst (Figure 4). Note that no noticeable deactivation was observed for the Bi-promoted catalysts after 3 consecutive reaction cycles. The presence of Bi on the surface of the catalyst seems to reduce deposition of carbon species due to higher mobility and continuous removal of these species by Bi.

Conclusion

The promotion of alumina supported cobalt catalysts with bismuth results in multiple effects on the catalyst structure and performance in alcohol amination. First, the promotion with bismuth results in weakening cobalt-alumina interaction and lower fraction of barely reducible cobalt aluminates. The increase in the amination activity in the presence of Bi is also due the promotion of dehydrogenation reaction by desorption of adsorbed poisoning species. Second, the increase in the selectivity to primary amine after the Bi addition is a result of suppression of 1-octylamine self-coupling reaction by hindering of bulky secondary imine hydrogenation.

Furthermore, the high stability of Bi promoted Co catalyst has been attributed to the easy removal of strongly adsorbed carbon species from the catalyst surface by mobile bismuth species. The promotion of alumina supported cobalt catalyst with bismuth results in a novel versatile bimetallic CoxBi/Al 2 O 3 catalyst with high activity, selectivity and stability for liquid phase amination of alcohols with ammonia.

Methods

Reagents

All the commercial reagents were used without any purification

Characterization

The ex situ XRD patterns were measured by an X-ray diffractometer (D5000, Siemens) using Cu Kα radiation (λ = 0.15418 nm). The scans were recorded in 2θ Ex situ Fourier transform-infrared (FT-IR) measurement of fresh and used catalysts was carried out on a Perkin-Elmer 1720 spectrometer using an Attenuated Total Reflectance (ATR) detector.

Ex situ X-ray photoelectron spectrometry (XPS) was carried out using a PHI 5000 Versa Probe X-ray photoelectron spectrometer with Al Kα radiation. C 1s (284.6

eV) was used to calibrate the peak position.

  For the Co0.5Bi/Al 2 O 3 catalyst, the catalytic conversion and reaction rate were ~2.3 times higher than those of fresh catalyst without Bi promotion (81 % and 0.105mol octanol •g Co -1 •h -1versus 38 % and 0.046 mol octanol •g Co -1 •h -1 respectively). This indicates that Bi addition to the cobalt catalysts largely increases the amination activity. As the Bi loading content increased from 0.5 to 5 wt%, the 1-octanol conversion gradually decreased from 81 % to 14.4 %. Higher Bi loading leads to lower reaction rate probably because of the decrease in the amount of accessible Co atoms for the catalytic reaction. For comparison, a pure Bi/Al 2 O 3 catalyst was also tested and showed a low conversion of 4.5 %. This reveals that Co metal is the main active phase for 1-octanol amination in the non-promoted and bismuth promoted cobalt catalysts. It is interesting to note that a mechanical mixture of Co/Al 2 O 3 and Bi/Al 2 O 3 exhibited 61% conversion, which is much higher in comparison with Co/Al 2 O 3 . In the mechanical mixture, because of spatial separation, no interaction between cobalt and bismuth species could be expected. Bismuth has a low melting temperature (271 °C).It can be therefore, in the liquid state during catalyst activation, which was conducted at 450 °C. Alcohol amination was performed over the cobalt catalyst at the temperature higher than the Tammann temperature of metallic bismuth. This suggests that some bismuth mobility can take place even during the reaction at 180 °C. Higher reaction rate observed over the mechanical mixture of alumina supported cobalt and bismuth catalysts proves high mobility of metallic Bi on the surface of Co under reaction conditions. The selectivity-conversion curves for amination of 1-octanol over Co catalysts before and after the Bi promotion with different loading content are shown in Figure 3b. Different 1-octanol conversions were obtained by varying the reaction time from 0 h to 48 h. The freshly activated sample Co/Al 2 O 3 displays 90 % selectivity to

  the presence of Co 3 O 4 phase in Co/Al 2 O 3 and Co1.0Bi/Al 2 O 3 . Bi 4f XPS suggests the presence of Bi in the form of Bi 2 O 3 in the catalysts (Figure S3b, SI). It is interesting to note that after the amination reaction, the peak shifts to lower binding energy, which can be explained by strong interaction of Bi with Co with partial reduction of Bi oxide. The localization of Bi promoter for the Co1.0Bi/Al 2 O 3 catalyst after pretreatment was further investigated using HAADF-STEM and corresponding EDX mapping. As shown in Figure 6, the Bi promoted Co catalyst exhibits a broad size distribution of agglomerated Co nanoparticles in the range of 5 to 20 nm (Figure S2, SI). The EDX mapping graph in Figure 6a clearly shows that Bi is localized in the close proximity to Co nanoparticles. The localization of Bi and Co can be observed by HR STEM analysis (Figure S4, SI). The prepared catalyst contains Bi oxide particles distributed over Co 3 O 4 nanoparticles. Reduction of the catalyst leads to sintering of Bi to large particles, however, after the amination reaction Bi forms a 2-3 nm layer over Co surface (Figure S4, SI).The high mobility of Bi has been also confirmed by EDX analysis of mechanical mixture before and after catalysis. Localization of Bi and Co is different for the mechanical mixture before reaction (Figure6). Catalyst activation and catalytic reaction induce migration of liquid Bi to the surface of Co nanoparticles according to EDX mapping (Figure6).The reducibility ofCo before and after Bi promotion was investigated by H 2 -TPR technique. As shown in Figure 5b, the TPR profile of oxidized Co/Al 2 O 3 depicts two hydrogen consumption peaks at 335 and 622 o C. The first peak at 335 o C corresponds to the reduction process of Co 3 O 4 → CoO → Co, while the broad reduction peak at 622 o C mostly due to the reduction of Co-Al mixed oxide phases [36, 37]. After Bi promotion, the CoxBi/Al 2 O 3 catalysts exhibit extra hydrogen consumption peaks at 270-310 o C, which corresponds to the reduction of Bi 2 O 3 and Co 3 O 4 in proximity to Bi 2 O 3 . At the same time, the Co 3 O 4 reduction peak shifts to higher temperatures in comparison with non-promoted catalyst (from 335 to ~350 °C) with increase in the Bi content. The peak shift can be explained by more difficult cobalt reducibility in the presence of bismuth. Interestingly, the broad reduction peak at 622 °C corresponding to the formation of barely reducible cobalt-alumina mixed oxides observed in Co/Al 2 O 3 disappears for all CoBi/Al 2 O 3 catalysts. This could indicate weakening interactions between cobalt species and alumna support and a smaller fraction of barely reducibly cobalt aluminate in the Bi-promoted catalysts.Cobalt metal dispersion and surface area were evaluated using CO adsorption in a pulse mode after in-situ reduction for all samples. Note that there was no CO adsorption on activated Bi/Al 2 O 3 . The freshly reduced Co/Al 2 O 3 catalyst shows relatively low carbon monoxide adsorption (1.14 mmol CO/mmol Co). The CO adsorption over the bismuth promoted catalysts gradually decreased from 1.14 to 0.18 mmol CO/mmol Co caused by increasing Bi content. The variation of CO adsorption as a function of Bi content was consistent with the observed decrease in the catalytic activity (Figure2).

( 1 -

 1 octylamine coupling)/TOF (1-octanol amination) is about 2.5 times higher for non-promoted Co catalyst in comparison with Co5.0Bi/Al 2 O 3 . This result demonstrates that the reaction rate of 1-octylamine self-coupling over Bi promoted surface Co sites was much lower than that of 1-octanol amination to 1-octylamine resulting. Consequently, the selectivity to primary amine has increased. Steric hindrance during hydrogenation of secondary imine induced by Bi on the surface of Co results in suppression of hydrogenation of bulky secondary imine with shift of the reaction selectivity to primary amine. The similar effect has been observed during amination of alcohols over Co nanoparticles after their pretreatment with alcohol resulting in carbon deposition.[14].Usually, Co based catalysts can be easily deactivated by surface residuals as well as being oxidized to Co oxides during catalytic reactions[41,42,43]. The presence of Bi had significant effect on the enhancement of the stability of Co catalyst during amination reaction (Figure3). TGA (FigureS6, SI) and FTIR (Figure S7, SI) techniques were used to investigate both fresh and Bi promoted Co catalysts before and after the amination test. TG analysis exhibits a total weight loss of about 8 wt% for Co/Al 2 O 3 catalyst after reaction and nearly half of that for Bi promoted Co catalyst (~4 wt%). Analysis of FTIR spectra indicates the presence of carbonaceous species with C-H stretching vibrations at 2965 and 2910 cm -1 in -CH 3 and -CH 2 groups, respectively in the spectra of both non-promoted and Bi-promoted catalysts. The C-N stretching vibration of aliphatic amines is observed by the band at 1250 cm -1 . Thus, deposition of amines and their derivatives over Co metal surface could deactivate the supported Co catalyst. Regeneration of the catalyst by calcination and reduction results in increase of the catalytic activity of Co/Al 2 O 3 to the initial level indicating on

range from 10 o

 10 to 80 o using a step size of 0.02 o and a step time of 5 s. The catalysts for measurement were all in oxide state without reduction in hydrogen. The average Co 3 O 4 was calculated by Scherrer equation using X-ray line broadening method, which could be used for calculation of metallic cobalt size by the formula: d (Co 0 ) = 0.75 d (Co 3 O 4 ). Hydrogen temperature-programmed reduction (H 2 -TPR) was performed using a Micromeritics AutoChem II 2920 V3 0.2 apparatus equipped with a thermal conductivity detector (TCD) using ~60 mg sample. The thermal profiles were measured from room temperature to 800 o C with a temperature ramp of 5 o C•min -1 under a 5 v/v% H 2 /Ar flow [10 mL(STP)/min]. Scanning transmission electron microscopy (STEM) characterization in the high-angle annular dark-field (HAADF) mode was performed using a Cs-corrected JEOL JEM-2100F microscope operated at 200 keV with an EDX mapping detector from JEOL Silicon Drift Detector (DrySD60GV: sensor size 60 mm 2 ). The Agilent 720-ES ICP-OES combined with a Vulcan 42S robot was used for determining the metal loading in the catalyst before and after amination reaction. BET specific surface areas and pore size were measured from the N 2 adsorption-desorption isotherms at 77 K on an automated gas sorption analyzer Micromeritics ASAP 2010. Thermogravimetric analysis (TGA) of fresh and used catalysts was carried out using Mettler Toledo SMP/PF7458/MET/600W instrument under air flow [10 mL(STP)/min] in the temperature range of 20-900 o C using a heating rate of 5 o C•min -1 .

with 1 mL 1 -

 1 octylamine, 20 mg of catalysts, and nominal 1-octylamine/NH 3 /H 2 molar ratio was kept at 1/4.5/0.85. The reaction was performed at 180 o C for 0-4 h. No solvent was either used during the self-coupling reaction. For dehydrogenation reaction, conditions were as follows: 2-octanol 50 mg, toluene 1 g in the presence of catalyst 50 mg. The reaction was performed at 140 o C for 15 h.

Figure 3

 3 Figure 3 Catalytic conversion modification by Bi promotion (a) and selectivity-conversion curves (b) for liquid phase amination of 1-octanol over activated Co/Al 2 O 3 and bimetallic CoxBi/Al 2 O 3 catalysts (1-octanol, 0.84 g; molar ratio of 1-octanol/NH 3 /H 2 = 1/4.5/0.85; P H2 = 3 bar; catalyst amount, 100 mg; reaction temperature, 180 o C; time, 0-48 h; no solvent used).

Figure 4

 4 Figure 4 Catalytic reusability and stability for liquid phase amination of 1-octanol over activated Co/Al 2 O 3 and Co1.0Bi/Al 2 O 3 catalysts (1-octanol, 0.84 g; molar ratio of 1-octanol/NH 3 /H 2 = 1/4.5/0.85; P H2 = 3 bar; catalyst amount, 100 mg; reaction temperature, 180 o C; time, 5 h; no solvent used; reactivation condition: 400 o C calcination under air followed by H 2 activation at 450 o C).

Figure 5

 5 Figure 5 XRD patterns (a) and H 2 -TPR profiles (b) of oxidized Co/Al 2 O 3 , Bi/Al 2 O 3 and bimetallic CoxBi/Al 2 O 3 catalysts.

Figure 6 Figure 7

 67 Figure 6 HAADF-STEM images and EDX mapping of Co and Bi of reduced Co1.0Bi/Al 2 O 3 catalyst and mechanical mixture Co/Al 2 O 3 +Bi/Al 2 O 3 before and after reaction of amination

Figure 8

 8 Figure 8 Model reaction of 1-octylamine transformation over activated Co/Al 2 O 3 and bimetallic CoxBi/Al 2 O 3 catalysts at a conversion of < 10% (1-octylamine, 1 mL; catalyst amount, 20 mg; molar ratio of 1-octanol/NH 3 /H 2 = 1/4.5/0.85; P H2 = 3 bar; reaction temperature, 180 o C; time, 0-4 h; no solvent used).

  After 3 catalytic amination cycles, for the freshly activated Co/Al 2 O 3 catalyst, 1-octanol conversion sharply drops from 36 % to 8 %. Interestingly, for the Bi-promoted Co catalyst, conversion decreased only very slightly, which indicates higher stability and reusability. ICP analysis suggests that no leaching of Bi has been observed after 3 cycles (TableS1, SI). Thus, the Bi promoter has positive effects on overall activity, selectivity to primary amines and stability of the Co based catalysts in the 1-octanol amination.

	Catalyst characterization
	N

1-octanol over freshly activated Co/Al 2 O 3 and Bi-promoted Co1.0Bi/Al 2 O 3 are shown in Figure 4. 2 adsorption-desorption and BET results show similar surface area and pore size for the calcined Co/Al 2 O 3 and CoxBi/Al 2 O 3 catalysts (Table

1

). Figure

5a

displays the XRD patterns of all samples. The calcined Co/Al 2 O 3 and Bi/Al 2 O 3 catalysts exhibit the presence of Co 3 O 4 and Bi 2 O 3 phases, respectively. For the Bi promoted Co catalysts, XRD peaks corresponding to the Bi 2 O 3 phase gradually appear as the loading content of Bi increased from 0.5 wt% to 5.0 wt% and reached highest intensity for Co5.0Bi/Al 2 O 3 . The average particle size of Co 3 O 4 calculated by

Preparation of supported Co and bimetallic CoBi catalysts

  Co/Al 2 O 3 , Bi/Al 2 O 3 and CoxBi/Al 2 O 3 catalysts were prepared through incipient wetness impregnation and co-impregnation (IWI) of γ-Al 2 O 3 using an aqueous solutions of cobalt nitrate hexahydrate [Co(NO 3 ) 2 •6H 2 O] and bismuth(III) nitrate pentahydrate [Bi(NO 3 ) 3 •5H 2 O], where x represents the weight percentage of Bi (x = 0.5, 1.0, 2.0, and 5.0). The weight percentage of Co for all the samples was kept 10 wt%. The impregnated samples were dried in an oven at 80 o C for overnight and calcined in air with a heating ramp of 2 o C•min -1 from 25 o C to 500 o C to get the oxidized catalysts. All the catalysts were activated under a pure H 2 flow at 450 o C for 2 h before each amination test. The Co/Al 2 O 3 and Co1.0Bi/Al 2 O 3 catalysts after amination test were labeled as Co/Al 2 O 3 -AA and Co1.0Bi/Al 2 O 3 -AA, respectively. To evaluate the level of deactivation resistance for fresh and Bi promoted Co catalysts, the Co/Al 2 O 3 and Co1.0Bi/Al 2 O 3 catalysts were poisoned by CO chemisorption using CO pulses on the Micromeritics AutoChem instrument before amination test.

	. Commercial
	γ-Al 2 O 3 (SASOL, PURALOX SCCa-5/170, D50: 50μm-100μm) was used as a
	catalytic support. Cobalt(II) nitrate hexahydrate (Co(NO 3 ) 2 •6H 2 O, >99%) and
	bismuth(III) nitrate pentahydrate (Bi(NO 3 ) 3 •5H 2 O, >98%) supplied by Sigma-Aldrich,
	were used as impregnation precursors for synthesis of metallic and bimetallic active
	phases loaded on the support. 1-Octanol (C 8 H 18 O, >99.5%), 1-octylamine
	(C 8 H 19 N, >99.5%), di-1-octylamine (C 16 H 35 N, >99.5%), tri-1-octylamine
	(C 24 H 51 N, >99.5%), 2-octanol (C 8 H 18 O, >99.5%), 2-octanone (C 8 H 16 O, 98%), toluene
	(C 7 H 8 , >99.5%), biphenyl (C 12 H 10 ), 1-pentanol (C 5 H 12 O, >99.5%), benzyl alcohol
	(C 7 H 8 O, >99%), furfuryl alcohol (C 5 H 6 O 2 , >99%), supplied by Sigma-Aldrich, were
	used as reactants and standards for GC calibration. Hydrogen and ammonia supplied
	by Air Liquide were used in the catalytic amination test.

Table 1

 1 Physical properties of supported fresh and Bi promoted cobalt catalysts The average particle size of Co 3 O 4 is calculated by Scherrer equation using X-ray line broadening method; e Determined from the molar volume correction of size using d (Co) = 0.75 d (Co 3 O 4 ); f Determined from randomly selected particles in HAADF-STEM; g The total H 2 consumption from H 2 -TPR analysis;

	Catalyst	S BET (m 2 /g) a	V tot (cm 3 /g) b	D meso (nm) c	Particle size (nm) d Co 3 O 4 d e TEM d Co d Co f	Total H 2 consumption (mmol/g) g	Metallic surface area (m 2 /g) h	Co (CO) / Co (%) h
	Co/Al 2 O 3	120.72	0.39	10.55	13.2	9.9	10.0	0.87	7.73	1.14
	Co0.5Bi/Al 2 O 3	121.32	0.40	10.61	13.9	10.4	10.2	1.43	5.6	0.83
	Co1.0Bi/Al 2 O 3	122.23	0.42	10.82	12.8	9.6	10.8	1.5	4.5	0.67
	Co2.0Bi/Al 2 O 3	119.04	0.39	10.85	13.0	9.8	10.3	1.3	3.1	0.46
	Co5.0Bi/Al 2 O 3	120.66	0.38	10.28	14.1	10.6	10.5	1.52	1.2	0.18
	Bi/Al 2 O 3	124.06	0.41	10.45	-	-	-	0.67	-	-

a BET surface area measured by N 2 adsorption-desorption; b Pore volume of pores; c Pore diameter in mesoporous region; d h Obtained from CO chemisorption measurement.

Acknowledgment

The authors thank Solvay for financial support of this work. Chevreul Institute (FR 2638), Ministère de l'Enseignement Supérieur, de la Recherche et de l'Innovation, Hauts-de-France Region and FEDER are acknowledged for supporting and funding partially this work.

Data availability

All data are available from the authors upon reasonable request.

Catalytic amination tests

The catalytic performance of the prepared freshly activated and Bi promoted Co catalysts was evaluated in the liquid-phase amination of 1-octanol with NH 3 , which was carried out in a 30-mL stainless steel autoclave geared with a pressure gauge and a safety rupture disk. In a typical experiment, the autoclave reactor was charged with 0.84 g of 1-octanol and catalyst (~100 mg). No solvent was used in the test. Then, the reactor was sealed and evacuated by applying vacuum followed by charging NH 3 (~7 bar) and H 2 (~3 bar) into the reactor as reported earlier to keep catalyst in reduced form and fast catalyst deactivation by adsorbed amines [38]. Finally, the reactor was placed on a hot plate equipped with a magnetic stirrer (500 rpm) at 180 o C for 0-48 h.

The nominal 1-octanol/NH 3 /H 2 molar ratio in the reactor was kept at 1/4.5/0.85. After the amination reaction, the reactor was cooled down to room temperature, and the mixture was filtrated and analyzed on an Agilent 7890 GC equipped with a HP-5 capillary column using biphenyl as the internal standard for calculation of conversion and selectivity. For catalytic stability test, after each amination reaction, the used catalyst was washed with ethanol and water and separated by centrifugation for several times and dried at 80 o C under vacuum for 10 h for retest. After 3 cycles, the used catalysts were calcined at 400 o C under air to remove surface cokes followed by hydrogenation at 450 o C for further amination test.

Catalytic model reactions

The liquid-phase self-coupling of 1-octylamine and dehydrogenation of 2-octanol over the freshly activated and Bi promoted Co catalysts were conducted in

Supporting Information

Catalytic reaction rate, TGA, FTIR, STEM, XPS, HRTEM, ICP-OES and TOF values.


1

The Palawan Epics Festschrift in honor of William Henry Scott 2001

Nicole Revel

In my last meeting with Dr. William Henry Scott in 1993, we talked about the need to preserve oral epics in the Philippines. I have myself been trying since 1992 to help in epic retrieval in this country, with the support of the French government, after my proposal to UNESCO was accepted in 1990. The international seminar, "Epics along the Silk Roads" (maritime and terrestrial), undertaken as part of the "The Integral Study of Silk Roads, Road of Dialogue," a program of the World Decade for Cultural Development (1988)(1989)(1990)(1991)(1992)(1993)(1994)(1995)(1996)(1997)(1998) has continued up to this day in various countries and particularly here in the Philippines. Dr. Scott expressed regret about this vanishing tradition not only among the Tagalogs, but also among the Visayans, the epics of which Father Alcina made mention in his sixteenth-century chronicles. I have sought to help reverse or at least halt this trend. Dr. Scott guided me toward northern Luzon, but insisted on my recording the living tradition of this literary genre in Mindanao, Tawi-Tawi, and Sulu.

As my monographic work since 1970 has focused upon the Palawan people, he asked me with keen interest about the content of the long chanted narratives I was able to record among the highlanders of the southern part of the island by the same name. As a historian, Dr. Scott worked not only on archives but also on oral traditions, with an acute sense for material culture and was never neglectful of any of the details prized by ethnographers.

The ancient aural and oral memory of the national communities of the Nusantara archipelagoes is a treasure as yet largely not taken into consideration by historians. However, should they accept the specificity of such documents and treat them with the necessary intellectual attitude and care that their very nature demands, historians would discover unheard of wealth, in more ways than one.

Dr. Scott and I also discussed the core of an epic, where always present are the two major narrative ganglia, namely, an initiation-quest and the conflict-or warrelated to it.

Through his many questions he stimulated my own queries regarding his then recently published work, Slavery in the Spanish Philippines (1991). He spoke about "Weapons and War," now chapter 8 in his posthumously published volume, Barangay: Sixteenth-Century Philippine Culture and Society (1994). In this book, Palawan is not taken into consideration; hence there remains an unsated curiosity about an island to be explored in its past and present. This essay aims to answer some of the questions that were of interest to Dr. Scott as a historian, an ethnographer, and an anthropologist.

Although originating in pure orality, epics sometimes have ancient links with writing in continental and island Southeast Asia. In the course of space and time, xylographs, etched lontars, as well as the manuscripts of scribes and poets, have mingled with the voices of the rhapsodies in a multitude of written forms. These media have engendered a "mixed" orality, an orality coexisting with writing, but only partially influenced by this. 1

On the other hand, in the process of communication and transmission, societies with an oral tradition rely upon hearing, memory, and the voice. In these aural/oral situations, memory sets into motion complex cognitive devices, stimulating associative networks and allowing the mind and body of the bard to gain mastery of the long sung narratives and to bring them to the level of perfection that we come to know when performed.

Oral epics in the Philippines, as in other countries of South Asia and Southeast Asia, convey a history of manners and customs. They exemplify kinship systems and social organizations, religious practices, customary law, material cultures, and trade between exogenous and endogenous groups. Rather than a history of events, they illustrate a history of tradition in its holistic sense.

Epics are a focal point in the quest for ancient roots and cultural identity, for they always convey an ideological content in a poetic form within a particular sociocultural context.

The Palawan and Their Culture

In the southern highlands of Palawan, "la isla de la Paragua," lives a society of blowgun hunters and swidden agriculturists. Surrounded by lush vegetation of thousands of species and a peculiar fauna-both fauna and flora are akin to those in Borneo and Luzon-the people live in an intense relationship with nature. They call themselves "Palawan," which is also the island's name. The Palawan are distinct from the Tagbanuwa and the Batak, the two other autochthonous groups on this island.

In order to ensure their survival and to live harmoniously in this world, the Palawan have elaborated and have tried to maintain a respectful and fundamental relationship with nature based on the notion of gift and return gift, a relationship of "exchange." A moral code of nonexcess is highly valued. It is a pragmatic, rather than an "ecological," attitude that links life and death; preying and disease; the "true human beings," taw banar-such as you and me-and the "other beings," the Säqitän or Länggam (see [START_REF] Maceda | Philippines. Musique des hautesterres palawan[END_REF].

The Palawan's material culture is based on wood, bamboo, rattan (architecture, tools, and basketry), while manufactured goods are acquired from seafaring people by trading with Islamized groups and Chinese merchants. Betel boxes, trays, and gongs of brass, swords, together with jars, celadons, and Chinese plates make up the pusakaq, the "heirloom" of a group of siblings.

The highlanders' daily life and ritual life are linked to these objects. They convey a very peculiar human "seal," an identity likewise manifest in the epic songs through poetic formula: "material motives," distinguished from "social motives," are present in these long sung narratives.

Through formulaic poetry Palawan epics chant about landscapes, waterways (rivers, seas, and waterfalls), trees, birds, and mountains, natural phenomena, celestial bodies; men's activities, festivities, and conflicts-namely, rice wine and honey-wine-drinking ceremonies, blood pacts, gong music, shamanic voyages, faraway travels, marriages and wars; invisible beings ("Good-doers"/"Evil-doers"), their mythical features and actions, supernatural events and deities; beauty in lines, shapes, ornaments, soundscapes, and music. All these motifs are present so that tableaux of nature and of institutional life, frescoes of mores, a testimony to a cosmogony, a lifestyle, an ethic, an aesthetic, and a world view proper to highland culture develop.

In this excerpt from Mämiminbin, a maritime landscape is evoked after a narration of the hero's ordeal through the Hell of Amaranthus. It describes Mämiminbin's voyage to another world and his arrival at the abode of the Lady of Fishes, a rock in the middle of the sea:

And as for him, as soon as he leaves, what do you think? His body is as powerful as the whirring of sparrows' wings. Before you can chew a quid, he has already arrived at the Hell of the Amaranthus Lady.

It invades the sky. There is not even the space for a single strand of hair, absolutely none, and he is there. He doesn't hesitate for a second and soars through like a speeding bird. And he is already on the other side. But when he thinks of his lady, he cannot get her out of his mind . . . And he says, "If I live here, I will see my lady again." What happens to him, according to the story? He went farther and farther away. Before you can chew a quid he is flying over the Sea of Mats. It is like settling sago, without the faintest breeze.

And he says, "If I choose this place to live, I will see my lady again. I will go far enough so that she will be torn from my thoughts." What happens to him, according to the story? As soon as he throws himself towards this space, he has not even chewed a quid when he sees in the middle of the sea a rock rising halfway up in the middle space. And he lands on it like a bird.

And he says, "It is here that my place will be." When he scans the horizon, the landscape is open and looks like the circle of a bracelet, the story says.

And for him, he is already sitting cross-legged on the top of the rock. He is already chewing a quid.

And as for her, the Lady of the Fishes is sewing one of her dresses and when she looks at him, he is like the midday sun that has just landed on the jetty of her house. 2

Kinship and Marriage

Major significant matters are sung in an epic, tultul: the relationship among kin and affines in a bilateral society with an uxorilocal rule of residence (that is, the man lives with his wife's family), a sexual division of work, and an ethics of "equal sharing," bagi, and "mutual help," tabang, within the hamlet, rurungan; the respect paid to elders; the absence of a political organization. In spite of a certain dissymmetry, an acephalous society, regulated by the constant reiteration through subtle jural discussion, bisara-of the Adat, the customary law, a code of rights and duties teaching politeness and good behavior as well as rhetorics, burak ät bäräs, "flowers of speech," the refined manner of "speaking and thinking."

The Quest for a Wife

A Palawan epic sings a constant, recurrent theme, namely, marriage, or rather the quest for a wife and the many deeds and ordeals that necessarily accompany this quest and have to be overcome by the hero for the fulfillment of his manhood, his personal happiness and that of his group. The multifarious facets of the Law, Saraq, in relation to marriage are depicted in the many epics I was able to record and listen to. Each one illustrates a "case" concerning marriage.

The epic Durus-Mata, for instance, teaches that to be an orphan is an unbearable situation. Marriage involves the joining of two families, thus making it difficult for an orphan to obtain a wife. Hence, in this story, the hero is treated as an adopted child by two cousins.

Further it teaches that to be a man, an adult, is to have and maintain solidarity among siblings; to be a hunter in quest of food, and more particularly of game, to complement the staple food with good viands, in accordance with the sexual division of work; to fight and be a brave warrior in conflicts; to be modest, when referring to one's deeds and achievements. Then, and only then, is one eligible for marriage.

Käswakan illustrates the case of a man marrying a girl child he has raised till puberty, and teaches that, in order to get a wife, a hunter must be mature and responsible and must avoid telling lies.

In this epic the custom of taking a second wife, duwäy is exemplified: If a man has a first wife, puqun, he must clarify with her the terms and arrangements for taking a second wife. The two women involved have to come to an agreement. Marriage, therefore, becomes an agreement among three persons who have to live in intimate harmony. The pact of brotherhood, pägtipusäd, and respect for the elder person act as constraints for maintaining balance in the relationship.

This epic, which tells of two fictive brothers marrying two fictive sisters, advises marrying someone of equal status-that is, of "same wealth," saliq-saliq artaq, and of "same power," saliq-saliq käsäg.

The epic, Mämiminbin illustrates sambiq, an ideal affinity link between a brother and a sister marrying a sister and a brother, or an alliance between two groups of siblings, where two men "exchange" their sisters, saliq-saliq pägtipusäd. The solidarity of siblings is therefore reinforced by the link of marriage. In this relationship of exchange there is an equal balance, and the price for the bride, ungsud, is no longer necessary. Instead there is a "reciprocal adherence," an equal one, saliqsaliq nämikit, that replaces it.

The epic also emphasizes the prohibition of incest, sumbang, in this particular case between a brother and a sister, which threatens the balance in the whole of nature and of the social world.

In Tyäw it is the stealing of a wife, agäw, that is depicted and denounced: marriage must be between single persons. Tyäw also stipulates that in order to neutralize the conflict between rival men, the pänglimaq can decide to seal a pact of brotherhood, mägtipusäd, between them through a rice-wine drinking ceremony. It is necessary to reestablish the Adat ät mämikit and to help them to live peacefully among the same group of neighbors.

Kudaman and Datuq ät Pänärängsangan, "Sunset Datuq" are two long sung narratives of a man's successive quests for several wives. Each epic is sung for seven nights. The marriage to the first wife, puqun, followed by the quest for and marriage to a second wife, thereby leading to bigamy, then polygamy-preferably sororal polygamy-are the situations that give rise to the social motives exemplified in these two Palawan epics. As a limitation on his rights, a man cannot divorce his first wife to marry a duwäy, but he has the right to abandon and divorce a duwäy. The ideal relationship between wives is to behave like sisters, or indeed to be real sisters.

Sunset Datuq describes in a very subtle way women's psychological reactions to polygamy, seldom practiced today, but nevertheless still in the minds of the Palawan.

Chewing a Quid and Romance

In Mämiminbin one also finds an illustration of how a man and a woman can show their mutual attraction to each other by the offering of betel and the chewing of a quid together: "Little Sister, I don't need to tell you to offer a quid to the friend. According to our custom, it is wrong to be slow to offer it." "I tell you, you might be making a little mistake towards Labit. Quick! Offer him the betel box!" "Even if you had not whispered a word to me, Elder Brother," she says, "I would have thought of it." And she takes her betel box, cuts the areca nut into slices, and fills the box. The nuts are already finely peeled and the betel leaves cut into quarters.

"Sir, here is my betel box in case you would like to chew a quid. But I only offer it to you. Perhaps you do not want to chew, since my quids might be bitter."

And when she puts her box down, it throws itself like a child at the visitor.

And the box goes straight to him, jumps into his lap, and opens itself. "Lady Friend, I offer the quids to you, and what I will say is not meant to offend, but if you already have a supply from your trip, do please, chew them. Perhaps you cannot chew mine." "Really, Lady Friend, it is not necessary that I chew. I still have my supply." And he adds, "It is not very kind if I do not take a quid." And you wonder, why is it like this? And when he takes seven slices and puts them in his mouth, how exquisite these quids are! What does he put in his mouth? Her scent follows his hand.

The flowers of any tree that he could choose cannot compare with the fragrance of the young maiden! And he says, "I am really moved by this lady. She is obviously quite remarkable in this world!"

Warfare, Trade, and Piracy

An epic also-and necessarily so-sings of crisis in the world. In Palawan epics the hero undergoes several ordeals before succeeding in his quest. Hence the basic theme of warfare and open conflict takes place.

Among the Palawan, the conflict can arise between neighbors, as in Mämiminbin, between neighboring groups, but most of the time between an autochthonous group and an outside group: seafaring people, rich merchants, armed and violent pirates-all are alien and often referred to as Ilanän (Ilanun) or Bängigi (Balangingi, Balingigi) as in Kudaman, Binyag bäkäq Käqislam-islaman, "Binyag and the Muslims." The epics illustrate, with extraordinary humor, a radical opposition between the two identities, the two moral codes.

The social equilibrium desired and which is achieved through marriage within an endogenous group, according to Palawan Adat, is always threatened by these maritime outsiders, these exogenous groups who adhere to a different set of values at the social, political, and religious levels and who follow a different moral code. A similar characterization is applied to new Christian settlers today.

For the Palawan, violence and war are an offense against Ämpuq, the Lord-Master. The main objective is to vanquish the enemy with a magic spell, batyaq; to avoid engaging in the fight, nonaggressive tactics are chosen and highly valorized. And in order to behave with absolute selfcontrol, one uses an art of dodging, tangkis, which involves various motions of the body, calm speech, and the mastery of various rhetorical devices, namely, inversions, baliwät, and politeness, päribasa, a complex set of good manners and seemliness.

Weaponry

Indicative of the presence in Palawan epics of fighting and conflict with neighboring groups, raids, and piracy, is the material culture-weapons and magic spells evoked in the sung narratives.

At least four varieties of spears, budyak, are referred to, namely: ligid, or awakawak, an oval-leaf-shaped blade; linyasan with three levels of symmetrical hooks; surayan with a mobile head; and kalawit, a javelin with a detachable head. These weapons were also used to hunt wild boar and other game. The ax (kapa), an adze (wasäy), the blowgun (sapukan), and poisoned arrows (basläy), are exclusive to hunting and work, and are never used in face-to-face combat.

The most intimate bladed weapon is the buladäw "dagger," often wielded by women. For men, there are various kinds of swords: barung, bälansyung, gayang, katariq, or the Malay kris. For protection, the round wooden shield, taming kalasaq, and various amulets, käpandayan ät pämumunuq, are hidden in one's turban to lessen the impact of the enemy's sharp sword, mainly the heavy kampilan, on one's head. All of these weapons have a handle wrapped in a fibrous material.

On the side of the Ilanän (or Ilanun), gimpul and the large kampilan are added to a similar array of swords and kris, including firearms, such as guns and rifles, timbak and baril; brass cannons rantakaq. Mention of all these enables us to approximate the period referred to in a particular epic. Ilanän people also wore brass helmets and armors, pälang ät badyuq tumbaga, turbans made of cloth with brass.

In this excerpt from Kudaman the raiders use rifles, but this does not give us an indication of the actual time when the epic was originally composed, only the time the epic in its present form refers to, since a later singer of tales may have made some revisions and recontextualized the narrative: "Towards me enemies are coming," says Kudaman. "By making rice beer I did not intend to provoke trouble around the jar. . . ."

Instantly the ladies sharpen their daggers and hold them in their hands. . . . And the Ilanän are coming from the sea closer and closer. . . . As they fire their guns all at once, the leaves of the trees seem sparse and the bullets dense.

"Cousins, let us see how our cousin-wives look! If I win the fight, I shall capture their wives and bring them back here."

When Kudaman hears their rifles, they sound like tirabun grasses crackling ceaselessly. The earth is shaking, they arrive in multitude. Ilanän and their people are already in the surroundings of the house. They keep on flowing in. . . . "Why this tremendous roar, could you tell us?" "For sure we come for a quick visit. Here we are to fight!" The story says they brought their rifles. "Come down, Cousin! Let us compare our magic powers!" At this very moment Kudaman's house is blown up. Ilanän's house is of firestone but seems of wax.

Here is a war lasting for seven years. . . . When he looks towards his elder brother his tongue surrounds his head in a turbanlike manner. . . . And his turban is made of iron, the story says.

The Feared Ilanän

The epics Kudaman and Sunset Datuq clearly call to mind raids of pirates coming from the south and Palawan women taken into slavery, uripän. 3

In chant 2 (of seven chants during seven nights), Kudaman is threatened with the abduction of his four wives: "In my opinion, Elder Brother, if you go alone, by yourself you will be hit by the bullets of Ilanän people," says Kudaman.

The Ilanän are so many that the water of the sea can no longer dance.

"Our cousin and his people are not coming with good intentions and their only purpose is to capture my wives."

As for the Ilanän, they keep coming closer and closer over the sea.

As they fire all their guns, the leaves of the trees seem scarce, such is the multitude of their bullets. . . . "My wife," says Kudaman, "you already know what your duty is towards your sisters." "As for me, I shall not be possessive facing them. You will give away to them whatever they want to take."

As for Kudaman, he keeps on chewing a quid of areca in betel leaf. . . . "My wives, they are coming closer, do not make any sound." Kudaman says, "My wife, as you are my first wife, you shall be the one to talk." Tuwang Putliq says, "My husband, even if you do not say a word, I know already." She brings closer to her the small dagger, buladäw.

These are ways of life that people, such as James Brooke from Sarawak and his associates, set out to destroy in the nineteenth century.

It is interesting to listen to testimonies of old people-men and women-and their memories of their Palawan forefathers, for they refer to experiences of life in the early part of this century. Their stories are corroborated by reports of the British press and those of ship captains in the middle-and late-nineteenth century. They describe battles with the most daring and dreaded of all, the fearful Ilanun and Balanini of Sulu and Mindanao, whose ferocity and brutality made "lanun" the only word equivalent to piracy in the Malay language. (Tate 1988, 25) This is complemented by the long sung narratives observed as a convergence of events and acts of warfare, trade, and raids not only by Sulu Sea pirates but also Bornean pirates, namely, the Iranun pirates of Malubu Bay, south of Balabac Strait; the Iban of Sarawak, the Malay pirates who lurked in the many islands of the Riau Archipelago, south of Singapore as well as the Chinese pirates better equipped in ships and weapons, moving to the South China Sea from northern coasts, from Fukien, Hong Kong, and Kwangtung.

Enemies of the European traders these people were. They were also, by any Western definition, pirates. They attacked vessels of commerce, killed and plundered. But for these local inhabitants, piracy was a traditional profession. . . . Piracy was a legitimate way of making a living, of survival. . . . Tate 1988, 25) in his Descriptive Dictionary observed: "The receivers of the stolen goods, at least the shares in the booty, have been many of the native princes, who, far from thinking piracy any discredit, have looked on its gains as a fair and regular branch of their income."

As Crawfurd (in

The regularity of these Ilanun and Balanini (or Balangingi, Bälangingi) sweeps led the British in Singapore to refer to August until October as the "Lanun season," when these raiders would attack in time with the southwest monsoon, the habagat.

The average galley in a Lanun fleet varied from 40 to 100 tons and carried forty to sixty men. By the early nineteenth century the korakora, a traditional fighting craft of the Moluccan and Sulu islands and outrigger vessel of 15 meters paddled by more than a hundred men, had evolved into a vessel with broader hull and able to accommodate a double bank: one bank of oarsmen standing, and the other sitting. (see Tate 1988, 27) John White, a lieutenant of the U.S. Navy, gave us a very vivid account of an attack on his ship by pirates off Banka, on 24 May 1819, by three vessels of this type, one larger than the others and propelled by seventy-four oars; the other two . . . about one-quarter part less, giving them in the aggregate one hundred and eighty-five oars. . . . They approached with a great appearance of resolution till nearly within range of our guns, when they began to slacken and kept aloof, probably for the purpose of reconnoitering. (Tate 1988, 28) White describes the pirates' response to having been fired at from his ship:

Immediately, as if electrified by this salute, every oar was set briskly to work, and they made directly for us, with every appearance of determined courage, tossing up the water with their oars, which moved without the least [ir]regularity, and assumed the appearance of the legs of a centipede in rapid motion" (Tate 1988, 28) In 1852, a British ship, the Royalist, was engaged in the survey of the island of Palawan and its topography. In charge of the mission, Commander Bate reported that they reached the areas of the Spanish port of Tai-Tai in the north, on their way to Pancol at a distance of about twenty miles: At 5:00 P.M. we found the village in a state of excitement from a report brought by one of their own boats, that seven large pirate prahus were in the neighborhood. (Tate 1988, 35) After two days and one night of fruitless search, the report continues:

The pirate fleet, now left in our rear, was estimated to consist of 400 men disposed in eight prahus, a force sufficient to devastate any portion of country in this neighborhood, and consign its inhabitants to hopeless slavery. . . . I know, both on the east and the west coasts of Palawan, the people are kept in constant dread of them. . . . On our visit to Paloan Bay, Mindoro Island, in December last [1851], the inhabitants informed us that seven prahus, each containing 50 men, suddenly appeared in the bay, ransacked the village, carried off five women and two children, murdering . . . one man and wounding two others, because they resisted the capture of their families. (Tate 1988, 35) The Ilanun took their name from Ilano Bay in southern Mindanao; the Balanini, from the Balanguingui isles of the Sulu archipelago. They plundered the shores of the Philippines and adjacent seas in various fleets. The latter, however, were a recent mixture of former slaves captured in various islands of the Philippines, and who, after one generation, were becoming predators of other people, and hence were an "emerging society" in the nineteenth century of slave raiders within a wider maritime economy of the Sulu sultanate.

The growth of Jolo market at the end of the eighteenth century was reflected in the enormous increase in war stores in Jolo market of lead, iron, gunpowder and cannon. The control over the exchange and distribution of these goods, together with slaves, enabled the expansion of the Sultanate and domination of the regional trade network. (Warren 1985, 255) The Ilanun and Balanini were famous for their fearless aggression, their numbers, the swiftness and agility of their prahus-the lanong and more particularly the garay, a beautiful boat made of wood, bamboo, rattan, and nipa palm. Yet their powerwhich was a recent one-would be broken by the ironclad steamships of another emerging power-which dominated the seas after 1860.

In the last quarter of the nineteenth century, James Brooke and the British Navy conducted a number of naval battles to stop piracy by the Iban Dayaks in the estuaries, and the Teanun in the South China Sea on the western coasts of Borneo. Meanwhile, the Spanish naval campaigns had already destroyed the Balangingi in the Jolo enclave between 1846 and 1852.

However, as late as 1995, there were still "reports of similar raids but with different objectivesnamely, money instead of slaves-very swift attacks, a multitude of raiders with modern boats and weapons" (see Bernad 1995, 7).

Territorial Conflict

As said earlier, among Palawan neighboring groups, there was also internal warfare waged in order to snatch the harvested paddy or to steal a spouse (agäw). These are still major cases under today's customary law.

Conflict and warfare could likewise arise when one group sought to move to a place within another group's territory. Territorial space was specific to each group of about twenty to thirty households under the responsibility of one pänglimaq. If this headman opposed the move, he and his men attacked the group that wanted to settle nearby. Such action was based on the jural notion of päsläd rurungan ("each one in his hamlet") and the territorial limits were rivers, mountains, springs, and the sea, the partition following the valleys and the major spatial axes daya/napan/dipag, upstream/downstream/across. Such is linked to a custom of endogamy in the region and of course to slash-and-burn agriculture-the necessary space to rotate in order to let the fields lie fallow up to twelve years so as not to exhaust the soil. Visits were allowed, but settlement was a casus belli preceded by ngasa (threatening omens), such as rastun (poison), theft, a bird entering the house and dying, blood spilling from the roof of a temporary shelter, tandaq (evidence) of rejection, and eventually of conflict and bunug (war).

Barter Trade and Valued Objects

The seashore was an ambivalent place-where Jama Mapun had settled several centuries ago, raising känyugan (coconut groves), and making copra-exposed to raids by seafaring merchants, yet a place for barter trade as well. The Palawan were careful in avoiding contact, in keeping a distance to protect their family and household from the alien merchants. Hence "silent trade," bartering without direct contact and without discussion or dispute, was the way they conducted trade till World War II.

On the one hand, sea merchants brought over Chinese earthenware and ceramics (celadons, jars, bowls, and plates); barung knives, swords (bälansyung), gongs, and other brassware: sälapaq, a box for keeping the array needed to make a quid of betel leaves, lime, and areca nut; trays and various containers; together with pieces of cotton cloth for women and loincloth for men.

On the other hand, the Palawan laid out a big quantity of rice and forest products-almaciga resin to make lacquers, wax, rattan, as well as wild honey and sparrows' nests. For centuries, these were the terms of the silent barter trade, or sambiq.

Mämiminbin sings about the hero's pets, the green imperial pigeons, Balud, referred to also as Putyän Nutmeg Pigeons, who work wonders by creating all the objects that are usually acquired by trade with seafaring people, such as betel boxes. Golden gongs were considered the most beautiful metalware, ideal for the pusakaq, the heirloom of a kindred.

And as for the Nutmeg Pigeons, as soon as they perch on the tree, they begin to coo and they imitate so many bird songs that you confuse them all.

And when they spit out the seeds of the bäribidan fruit, these all turn into betel boxes of pure gold.

And when their feathers fall, they turn into objects that land on the level where Labit is sitting.

And they are of pure gold, with no alloys. And when the down quill falls, the same thing happens again . . . You don't know what to choose. Everything is turned into white pounded rice, sacks and sacks of rice.

And they have not been there long. They have been there for seven days, the story says, and the only empty place is where Labit is sitting. Everywhere it is full of objects, the rice is ready, the two small rimmed gongs of gold, the large golden agong, everything has been gathered together. And what happens? When Labit looks at his house, it is as if it were lit by a torch. "What splendor!" he says. "Little Sister, come out, I beg you, my dear. Our friend's pet birds seem to work wonders! As for me, I am very moved!" Objects glow like the moon shining over the sea. . . . As for him, he is silent. He doesn't even take time to eat. He gazes at the Nutmeg Pigeons. What do you think happens? All the feathers and all the down quills keep falling into objects and fill even the space under the house. It is as if his house were ablaze with unalloyed gold.

The values of traded objects as remembered today by a judge (ukum), in the jural law are as follows:

• One andug of wax is equivalent to one barung knife. An andug is a square container, a paniga for rice, with a depth equal to its length; • One banäy of honey has the value of one sulindang cloth, a batik with flower motifs. A banäy fills one length of an internode of bamboo, bungbung, and approximates one gallon; • One sukat of paddy, which is a twenty-five-kilogram basket, gives the counterpart of one tadyung cloth, a piece of cloth with square motifs; • Ten banäy of honey can be exchanged for one sanang, a small rimmed gong.

Often the settlement of the trade was not fair to the Palawan, who have a term for cheating, rugi; and their long sung narratives depict this relationship with the most sophisticated sense of humor.

In the first half of the twentieth century, a contingent of the Philippine Constabulary was stationed at Brooke's Point to fire at boats approaching the shore at nighttime. On the beach the seafaring groups would come and take the paddy (paräy) and the wax (taru), instead of following the terms of the barter agreement. They would come in large numbers and would take away the products of the Palawan. To prevent them from proceeding into the hinterland, the Palawan would set up traps of long rattan filled with thorns to stop the marauders.

Since World War II, there had been no barter trade, but money entered the economy of the Palawan people and later, small and then bigger markets developed. Somehow this transformed the relationship of the merchants with the Palawan; however, a hegemonic attitude remains.

The Palawan Epics as Oral Heritage

In sung narratives, like tultul, we find treasures of ancient memory, an intangible heritage endangered in all areas of the world by any or all of the following factors: the impact of modern technological and economic development, changes in social structure, wars and political or religious intolerance, vanishing traditions, and the advanced age of its last performers.

In Palawan, an epic is sung as a return gift: to honor a visitor; to entertain kin on the eve of a marriage discussion and particularly to instruct the couple about marriage; and to thank Si Läli, the "Master of Preys," for a lucky hunt in the forest. Singing an epic, then, acts as a return gift: it is gifted with a symbolic efficacy for it restores a disrupted balance in the biotope.

Here we find no theatricalization but rather a singer of tales, perhaps lying supine the entire night, singing the deeds and ordeals of a hero and his quest for a wife. The hero is no less than a model, or has to become one, committed to the rights and duties that rule the life among siblings and affines in this society. He projects an exemplary profile in relation to a specific family and social organization.

A sung narrative epic gives rise to an auditory pleasure and a multitude of emotions, not only in the bard who is inspired and captures an audience by his narrative, his voice, and his music, but also in those listening, who are equally active in reception. They perceive, understand, feel, marvel, and remember. The voice is a physical, physiological, and psychic power. During these lovely nights of singing and listening, an intense and comforting experience takes place; a special moment of social communication offers itself. Listening to an epic is an enjoyable, sometimes even jubilant, pastime: an epic opens minds and hearts in favor of fusion, a communal sharing in its exaltation. Moreover, the doxa is governed by the marvelous rather than the reasonable, belief rather than doubt.

The epic is given and received as the teaching of a set of values, and the ebb and flow of its melodies must capture the psychological, ethical, and metaphysical dimensions that poetry glorifies. In fact, there is a perfect correspondence between the hero's acts and the requirements for accomplishment, for fulfillment, and for wisdom, that is, for the values of the people listening. Thanks to the marvelous, they live adventurous and heroic deeds, existence and essence, being and destiny without dissociation. There is no difference between the self and the world. Through the epic, people of a given society experience an absolute, an apex, an ideal human condition.

In this give-and-take relationship, by means of a work of art, the human being communicates with the self. By an oral-musical code-poetic imagery, melodic lines, rhythmic formulas, prosody-manifest in the voice, and in various cultures also in gestures, through all these actions originating in our sensory-motor system, each culture expresses the world views to which it attaches values of cultural identity and a particular sense of belonging.

The meeting place of an ideological content and a poetic form in a given cultural context, an epic is the repository of an archetypal power. It is at one and the same time entertainment, teaching, the ideal, and the expression of an ethnic or a national sentiment.

Through the epic, a human society transmits the memory of the ancestors, a total and independent world and its very presence in the world.

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Notes

I presented part of this paper during the Fifteenth National Conference on Local and National History, held in Puerto Princesa, Palawan, 19-21 October 1994. I wish to thank the organizers, Dr. Leslie Bauzon and Dr. Bernardita Churchill, who allowed me to expand it and orient it toward some of the main interests of Dr. William Henry Scott.

1. The Palawan language consists of four vowels-a, ä (or back a), i, u-and sixteen consonants-p, b, t, d, k, g, h, q (or glottal stop), m, n, ng, s, l, r, w, and y. Stress is not relevant (Revel-Macdonald 1979, 46-60).

2. The musical units of the text are based on "breathing groups of words." This is a sequence of words or sentences variable in length, that begins with an opening syllable [hin…], and ends with a final syllable […in].

These particles have no connection to usage or syntax, but gain value when seen in the context of prosody. According to the singers of tales, the [. . . in] may be interchanged with [. . . bä], as in the epics known by Mäsinu and Kundipal. This particle serves as an aural punctuation.

3. The complexity of the social stratification and economic dependency mostly of the oripun strata-with eleven different words to identify the type of "slavery" in the Visayas-is elucidated in several publications by W. H. Scott (1982[START_REF] Scott | Oripun and alipin in the sixteenth-century Philippines[END_REF]Scott ( , 1988Scott ( , and 1991)).