Activated Carbon , Carbon Nanofibers and Carbon-Covered Alumina as Support for W 2 C in Stearic Acid Hydrodeoxygenation

Carbon materials play a crucial role in sorbents and heterogeneous catalysis and are widely used as catalyst support for several reactions. This paper reports on an investigation of tungsten carbide (W2C) catalyst on three types of carbon support, namely activated carbon (AC), carbon nanofibers (CNF) and carbon-covered alumina (CCA). We evaluated their activity and selectivity in stearic acid hydrodeoxygenation at 350 ◦C and 30 bar H2. Although all three W2C catalysts displayed similar intrinsic catalytic activities, the support did influence product distribution. At low conversions (<5%), W2C/AC yielded the highest amount of oxygenates relative to W2C/CNF and W2C/CCA. This suggests that the conversion of oxygenates into hydrocarbons is more difficult over W2C/AC than over W2C/CNF and W2C/CCA, which we relate to the lower acidity and smaller pore size of W2C/AC. The support also had an influence on the C18-unsaturated/C18-saturated ratio. At conversions below 30%, W2C/CNF presented the highest C18-unsaturated/C18-saturated ratio in product distribution, which we attribute to the higher mesopore volume of CNF. However, at higher conversions (>50%), W2C/CCA presented the highest C18-unsaturated/C18-saturated ratio in product distribution, which appears to be linked to W2C/CCA having the highest ratio of acid/metallic sites.


Introduction
Carbon materials play a crucial role in sorbents and heterogeneous catalysis [1][2][3][4].A supported heterogeneous catalyst consists of a support on which an active phase has been dispersed and optionally some promoters have been added.The support can play a prime role in determining catalytic activity and selectivity.It can do so by influencing the electronic structure of the active phase by changing its density of states [5][6][7] or its dispersion [8].In addition, support acidity may affect the product distribution by affecting the orientation of molecule adsorption [9].Moreover the physical properties of the support (e.g., pore size) may influence the diffusion of reactant and product molecules to and from the active sites [10].
Activated carbon (AC) is the workhorse among the carbon based catalyst supports [11][12][13].Activated carbon supports contain layers of graphene with curved sections and pronounced cross-linking.These carbons have micropores and, depending on the precursor used to make it, may also have mesopores and macropores [14].Activated carbon presents several advantages as a support for catalysts, such as low synthesis cost, high specific surface area, resistance to acidic and alkaline environments, easy control of textural properties (pore volume and pore size distribution) and thermal stability.On the other hand, activated carbon has low mechanical strength and, because it is mostly microporous, may impose mass transfer limitations [15].Other carbon materials, such as carbon nanofibers, have larger pores than microporous activated carbon and consequently are less associated with mass transfer limitations.
Carbon nanofibers (CNF) supports contain organized graphene sheets in their structure and have the beneficial properties of both activated carbon and graphite.Carbon nanofibers have desirable characteristics for use as catalyst support, such as high specific surface area, purity, inertness and, are mesoporous thus allowing easy diffusion of reactant and product molecules [16].Carbon nanofibers have been used as catalyst support for different reactions, such as cinnamaldehyde hydrogenation [9,17] and deoxygenation of triglycerides [18][19][20].
Another promising carbon-based material for use as catalyst support is carbon-covered alumina (CCA).Alumina (aluminum oxide) already is a widely used material as catalyst support because of its mechanical and textural properties; however it has some drawbacks, mainly its strong interaction with metals which can result in a loss of the active (metal) phase.To overcome this drawback, alumina can be covered with a thin carbon layer to result in CCA.As a consequence CCA combines the mechanical and textural properties of alumina with the surface chemistry of carbon [21].The first time CCA was used as catalyst support it was synthesized via the pyrolysis of cyclohexane or ethene over the γ-Al 2 O 3 surface [15].This material was used as support for cobalt sulfide and tested in the thiophene hydrodesulfurization reaction [15].Although X-ray photoelectron spectroscopy results showed that alumina was not fully covered by carbon, the catalyst supported on CCA was three times more active than the catalyst supported on γ-Al 2 O 3 [15], demonstrating that CCA is a promising material in the catalysis field.
Although AC, CNF and CCA are effective supports for various catalysts and reactions, these three carbon-based materials have never been directly compared in the same reaction conditions and with the same active phase, as far as we know.In this paper, we report on an evaluation of the effects of these three different carbon-based supports (activated carbon, carbon nanofibers and carbon-covered alumina) on the structure and deoxygenation performance of tungsten carbide.Tungsten carbide is an active catalyst for reactions that involve the transfer of hydrogen [22,23], as is the case in fatty acid deoxygenation reactions, and it is considered a potential replacement for the scarce and expensive noble metal.Here, we characterized the catalysts by means of N 2 sorption, X-ray diffraction, CO chemisorption as well as temperature-programmed desorption of NH 3 , and we used the deoxygenation of stearic acid to evaluate catalyst performance.We analyzed the effect of the support on tungsten carbide activity and selectivity in stearic acid deoxygenation by correlating catalyst performance with structure.The stearic acid is a representative model molecule of triglycerides/vegetable oil present in biomass [24,25].

Synthesis of Supports
Carbon nanofibers (CNF) were synthesized using a reduced 5 wt % Ni/SiO 2 growth catalyst (5 g) and a mixture of hydrogen (102 mL•min −1 ), nitrogen (450 mL•min −1 ) and carbon monoxide (266 mL•min −1 ) at 550 • C and 3.8 bar for 24 h, as previously reported [26].After synthesis, the CNF were refluxed in 400 mL 1M KOH for 1 h to remove the SiO 2 , followed by decanting and washing of the residue with 200 mL 1M KOH.This treatment was repeated three times.After the final reflux, the material was washed with demi water.Subsequently, the solid was treated by refluxing it in 400 mL 65% HNO 3 for 1.5 h to remove exposed nickel and to add oxygen-containing groups on the surface of the CNF.Finally, the CNF were washed with demi water to a neutral pH of the washing water.
Carbon-covered alumina (CCA) was synthesized as follows.A sucrose solution was added to alumina (BASF) via incipient wetness impregnation (weight sucrose/alumina = 0.624).A calcination step was carried out under He flow at 700 • C for 2 h to form two (theoretical) monolayers of carbon covering the alumina.The procedure was repeated to add another (theoretical) carbon monolayer (weight sucrose/alumina = 0.380) over the previous two layers.

Catalyst Synthesis
W 2 C catalysts (15 wt %) were synthesized via incipient wetness impregnation of (NH 4 ) 6 H 2 W 12 O 40 •xH 2 O (Sigma-Aldrich) solution on the supports-AC (Activated charcoal Norit®, Sigma-Aldrich), CNF and CCA.After each impregnation (total of three), the materials were dried at 120 • C for 1 h in static air.When the whole solution was impregnated, the catalysts were activated under argon flow from 25 • C to 900 • C (β = 5 • C•min −1 ) for 6 h.To allow a direct comparison with earlier works we kept the synthesis conditions the same as in [19] even though these conditions can be improved with respect to holding times and gas use.

Catalyst Characterization
X-Ray diffraction (XRD) was used to explore the crystalline structures of the sample by using a Rigaku Miniflex instrument with copper radiation (CuK α ).The diffraction angle was varied from 10 • to 90 • , with steps of 1 degree•min −1 and counting at 2 s•step −1 .
Nitrogen physisorption was used to assess the textural properties of the catalysts.Nitrogen adsorption/desorption isotherms were recorded at liquid nitrogen temperature using a Micromeritics TriStar.Before the measurement, samples were pretreated under a vacuum at 200 • C for 20 h (Micromeritics VacPrep 061).
Chemisorbed CO was measured in situ to quantify potential active sites.After synthesis, we flushed the catalyst samples with 50 mL•min −1 helium at 30 • C for 30 min.CO-pulse chemisorption measurements were performed using a custom-made multipurpose machine by pulsing calibrated volumes of a 20% (v/v) CO/He gas mixture over the catalyst.Mass spectrometry (Pfeiffer Vacuum, model D-35614 Asslar) was used to assess the CO uptake.
Temperature-programmed desorption (TPD) of CO was performed after the CO chemisorption to explore the nature of the active sites.Samples were heated from 30 • C to 1000 • C under He flow (100 mL•min −1 and β = 15 • C•min −1 ) and the ion signal of m/z = 28 was followed in a mass spectrometer (Pfeiffer Vacuum, model D-35614 Asslar).
Transmission electron microscopy (TEM) was used to analyze particle size and particle size distribution.We mounted the samples on a 200 mesh copper grid covered with a pure carbon film, by dusting them onto the surface of the grid.TEM was performed in a JEOL JEM2100 transmission electron microscope operated at 200 kV, and images (4k × 4k) were taken with a Gatan US4000 camera.
Temperature-programmed desorption (TPD) of NH 3 was performed to explore the acidity of catalysts.The total acid sites of catalysts were quantified by adsorption of a 4% (v/v) NH 3 /He gas mixture at room temperature, performed in a custom-made machine, where the ion signals m/z = 17 was followed in a mass spectrometer (Pfeiffer Vacuum, model D-35614 Asslar).After purging the synthesized carbides with He (60 mL•min −1 ), 4% (v/v) NH 3 /He (60 mL•min −1 ) gas mixture was added to the system resulting in a negative peak (A1) in the ion signal m/z = 17, corresponding to chemisorbed NH 3 + physisorbed NH 3 + NH 3 in the system dead volume.After the ion signal m/z = 17 returned to the baseline, He was flushed into the system to remove the physisorbed NH 3 from the catalyst surface and the NH 3 present in the system dead volume.A 4% (v/v) NH 3 /He (60 mL•min −1 ) gas mixture was, flushed again into the system resulting in another negative peak (A2) in the ion signal m/z = 17, representing the physisorbed NH 3 and the NH 3 present in the system dead volume.Therefore, the amount of chemisorbed NH 3 on the catalysts was calculated via the subtraction of the areas A1-A2.
To explore the efficiency of the carbon cover in CCA, we carried out Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) in an infrared spectrometer (Nicolet NEXUS 470 FT-IR) equipped with diffuse reflectance accessories and heating chamber (MCT-A detector, cooled with liquid nitrogen and with ZnSe windows).Prior to analysis, samples were heated to 500 • C for 1 h under He flow and cooled to room temperature.Samples were then saturated with CO 2 , the chamber was cleaned with He to remove non-adsorbed CO 2 , and the spectrum was taken in the range of 4000 cm −1 to 500 cm −1 with a resolution of 4 cm −1 and 150 scans.
Gas chromatography (GC) was used to analyze the reaction mixture (Shimadzu 2014, equipped with CP-FFAP column and photoionization detector).We used the following column temperature program: 50 • C for 1 min, heating to 170 , dwell time 15 min.Prior to GC, we diluted the samples in CH 3 Cl:MeOH (2:1 v/v).Trimethylsulphonium hydroxide (Sigma-Aldrich, ~0.25 M in methanol, for GC derivatization) was added to methylate free acids.The injected volume was 1 µL for all analysis.

Results and Discussion
Table 1 displays textural properties of the pure supports (activated carbon-AC, carbon-covered alumina-CCA and carbon nanofibers-CNF) and of the three supported W 2 C catalysts as inferred from nitrogen physisorption.Figure A1 in Appendix A shows nitrogen adsorption/desorption isotherms for the pure supports and the supported W 2 C catalysts.AC presented a higher specific surface area (823 m 2 •g −1 ) compared with CCA (193 m 2 •g −1 ) and CNF (171 m 2 •g −1 ).AC also showed a higher micropore area and volume (394 m 2 •g −1 and 200 × 10 −9 m 3 •g −1 ) than the other supports CCA (44 m 2 •g −1 and 20 × 10 −9 m 3 •g −1 ) and CNF (20 m 2 •g −1 and 9 × 10 −9 m 3 •g −1 ).On the other hand, CNF had a larger pore size than AC and CCA (CNF: 15.1 nm, AC: 8.7 nm and CCA: 9.3 nm).These results indicate that the supports had significant differences in textural properties, especially regarding surface area and pore size.
The specific Brunauer-Emmett-Teller (BET) surface area of W 2 C/AC and W 2 C/CCA was around 15% lower than for the pure supports.Since these catalysts were synthesized with a 15 wt % loading, a decrease of up to 15% of the surface area can be attributed to the carbide addition to the support.Thus, W 2 C/AC and W 2 C/CCA presented similar textural surface areas as the respective pure supports.
On the other hand, the specific surface area, micropore area and micropore volume values of W 2 C/CNF (124 m 2 •g −1 , 7 m 2 •g −1 and 3 × 10 −9 m 3 •g −1 ) are smaller than for pure CNF (171 m 2 •g −1 , 20 m 2 •g −1 and 9 × 10 −9 m 3 •g −1 ), even when considering that 15% of active phase had been added to the support.These results suggest that some micropores of the CNF were blocked during W 2 C/CNF synthesis.However, since total pore volume and pore average size of W 2 C/CNF (370 × 10 −9 m 3 •g −1 and 15.1 nm) were similar to those of the pure CNF (450 × 10 −9 m 3 •g −1 and 15.1 nm), taking a margin of 15% into account, we conclude that although micropores might be blocked during W 2 C/CNF synthesis, larger pores in the support were still present in the catalyst structure.
To investigate the crystalline structure of the catalysts, we used X-ray diffraction (XRD).Figure 1A-C) presents the diffractograms of W 2 C supported on AC, CCA and CNF, with the respective precursors and pure supports.were similar to those of the pure CNF (450 × 10 −9 m 3 •g −1 and 15.1 nm), taking a margin of 15% into account, we conclude that although micropores might be blocked during W2C/CNF synthesis, larger pores in the support were still present in the catalyst structure.
To investigate the crystalline structure of the catalysts, we used X-ray diffraction (XRD).Figure 1A-C) presents the diffractograms of W2C supported on AC, CCA and CNF, with the respective precursors and pure supports.The diffractograms of W2C supported on AC, CNF and CCA show peaks at 2θ values of 36.8° and 42.7°, which correspond to the oxy-carbide W2(C,O) phase (PDF#22-0959), indicated by the green triangles, as well as peaks at a 2θ of 39.6°, 61.7° and 72.7°, which correspond to the W2C phase (PDF#20-1315), indicated by the red squares.Since the catalysts were passivated with 0.5% (v/v) O2/N2 (50 mL•min −1 ) at 25 °C for 24 h before XRD analysis to avoid their complete oxidation when exposed to air, we attribute the presence of the oxy-carbide phase to partial oxidation of catalyst during the passivation treatment.
The diffractograms of W2C/AC and its precursor present a small peak at 2θ value of 26°, which is unexplained.It could be a contamination (SiO2) or a recrystallization of carbon species, though that is unlikely at these temperatures.
To analyze the particle size of the carbide, high-resolution transmission electron microscopy (HR-TEM) was performed.The diffractograms of W 2 C/AC and its precursor present a small peak at 2θ value of 26 • , which is unexplained.It could be a contamination (SiO 2 ) or a recrystallization of carbon species, though that is unlikely at these temperatures.
To analyze the particle size of the carbide, high-resolution transmission electron microscopy (HR-TEM) was performed.Figure 2 displays representative HR-TEM images of tungsten carbide supported on AC, CCA and CNF.Black spots represent the active phase carbide (indicated with the red arrows) and the dark grey area is the support.
ChemEngineering 2019, 3, x FOR PEER REVIEW 5 of 15 were similar to those of the pure CNF (450 × 10 −9 m 3 •g −1 and 15.1 nm), taking a margin of 15% into account, we conclude that although micropores might be blocked during W2C/CNF synthesis, larger pores in the support were still present in the catalyst structure.
To investigate the crystalline structure of the catalysts, we used X-ray diffraction (XRD).Figure 1A-C) presents the diffractograms of W2C supported on AC, CCA and CNF, with the respective precursors and pure supports.The diffractograms of W2C supported on AC, CNF and CCA show peaks at 2θ values of 36.8° and 42.7°, which correspond to the oxy-carbide W2(C,O) phase (PDF#22-0959), indicated by the green triangles, as well as peaks at a 2θ of 39.6°, 61.7° and 72.7°, which correspond to the W2C phase (PDF#20-1315), indicated by the red squares.Since the catalysts were passivated with 0.5% (v/v) O2/N2 (50 mL•min −1 ) at 25 °C for 24 h before XRD analysis to avoid their complete oxidation when exposed to air, we attribute the presence of the oxy-carbide phase to partial oxidation of catalyst during the passivation treatment.
The diffractograms of W2C/AC and its precursor present a small peak at 2θ value of 26°, which is unexplained.It could be a contamination (SiO2) or a recrystallization of carbon species, though that is unlikely at these temperatures.
To analyze the particle size of the carbide, high-resolution transmission electron microscopy (HR-TEM) was performed.Figure 2 displays representative HR-TEM images of tungsten carbide supported on AC, CCA and CNF.Black spots represent the active phase carbide (indicated with the red arrows) and the dark grey area is the support.We estimated the average particle size based on 250 to 400 particles for each catalyst.Table 2 shows the average particle sizes and Figure 3 displays the particle size distributions.We estimated the average particle size based on 250 to 400 particles for each catalyst.Table 2 shows the average particle sizes and Figure 3 displays the particle size distributions.The average particle size of W2C/AC, W2C/CCA and W2C/CNF was 6, 2 and 3 nm, respectively.Although the W2C/AC catalyst presented a higher particle size average than W2C/CCA and W2C/CNF, Figure 3 shows that the largest particles of W2C/CCA and W2C/CNF catalysts have a diameter of 10 nm, while the diameter of the largest particles of W2C/AC is 20 nm.The presence of a few larger particles (>10 nm) in the W2C/AC catalyst accounts for its higher average particle size.Since large particles present a high volume-to-surface ratio, those particles likely did not make a significant contribution to the overall weight-based activity.Furthermore, most particles of the three catalysts had an average diameter of less than 6 nm.We therefore concluded that differences in average particle size of the catalysts were not a significant factor.
To enable a fair comparison between the catalytic performance of W2C/AC, W2C/CNF and W2C/CCA, we used CO chemisorption to quantify potential active sites.Table 3 displays the CO chemisorption results for the three catalysts.CO uptake for tungsten carbide catalysts follows the order W2C/CCA (80 µmol•g −1 ) > W2C/AC (60 µmol•g −1 ) > W2C/CNF (34 µmol•g −1 ).The CO uptake value is related to the number of accessible sites that can interact with CO molecules, which means that the catalyst that presents the highest CO uptake value may have more accessible sites available for reaction according to Lee et al. [27].
CO uptake for the AC, CCA and CNF supports was 0, 0 and 1 µmol•g −1 , respectively.This result indicates that the CO uptake values of supported catalysts are exclusively related to the active phase.Although CO chemisorption provides information about the density of potential active sites, it does not inform about the nature of these sites.We therefore performed CO TPD analysis, which enabled us to compare the nature of the active sites through the CO-binding strength.Active sites of a different nature bind CO with a different strength, which is indicated by the temperature of the peaks in the CO TPD profile.Stronger bonds result in higher temperatures of CO desorption.Figure 4 displays the CO TPD results of the supported tungsten carbide catalysts, each showing three peaks at 90, 150 and 200 °C, indicated by the red squares in the figure.These results suggest that although The average particle size of W 2 C/AC, W 2 C/CCA and W 2 C/CNF was 6, 2 and 3 nm, respectively.Although the W 2 C/AC catalyst presented a higher particle size average than W 2 C/CCA and W 2 C/CNF, Figure 3 shows that the largest particles of W 2 C/CCA and W 2 C/CNF catalysts have a diameter of 10 nm, while the diameter of the largest particles of W 2 C/AC is 20 nm.The presence of a few larger particles (>10 nm) in the W 2 C/AC catalyst accounts for its higher average particle size.Since large particles present a high volume-to-surface ratio, those particles likely did not make a significant contribution to the overall weight-based activity.Furthermore, most particles of the three catalysts had an average diameter of less than 6 nm.We therefore concluded that differences in average particle size of the catalysts were not a significant factor.
To enable a fair comparison between the catalytic performance of W 2 C/AC, W 2 C/CNF and W 2 C/CCA, we used CO chemisorption to quantify potential active sites.Table 3 displays the CO chemisorption results for the three catalysts.CO uptake for tungsten carbide catalysts follows the order W 2 C/CCA (80 µmol•g −1 ) > W 2 C/AC (60 µmol•g −1 ) > W 2 C/CNF (34 µmol•g −1 ).The CO uptake value is related to the number of accessible sites that can interact with CO molecules, which means that the catalyst that presents the highest CO uptake value may have more accessible sites available for reaction according to Lee et al. [27].CO uptake for the AC, CCA and CNF supports was 0, 0 and 1 µmol•g −1 , respectively.This result indicates that the CO uptake values of supported catalysts are exclusively related to the active phase.
Although CO chemisorption provides information about the density of potential active sites, it does not inform about the nature of these sites.We therefore performed CO TPD analysis, which enabled us to compare the nature of the active sites through the CO-binding strength.Active sites of a different nature bind CO with a different strength, which is indicated by the temperature of the peaks in the CO TPD profile.Stronger bonds result in higher temperatures of CO desorption.CO TPD analysis was also performed on the pure supports from 25 to 1000 °C (not shown).We observed a significant increase on the amount of desorbed CO at temperatures higher than 500 °C, indicating that the surface groups are released from the support at this temperature.Thus, we expect that no surfaces groups remain attached to the support after it is exposed to 900 °C for 6 h (during catalyst synthesis).
NH3 TPD was performed to analyze the acidity of the catalysts.Table 4 displays the density of the catalysts' acidic sites.W2C/CCA had the highest density of acidic sites (217 µmol•g −1 ) compared with W2C/AC and W2C/CNF (44 and 46 µmol•g −1 , respectively).The higher acidity of tungsten carbide supported on carbon-covered alumina may be attributed to the acidity of alumina.Although the alumina was completely covered by carbon, as shown by CO2 Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) analysis (Figure A2), the higher amount of desorbed NH3 (Table 4) suggests that the porosity of carbon enables the alumina to be available for interaction with external molecules, such as ammonia during NH3 TPD.
Stearic acid hydrodeoxygenation was performed over supported tungsten carbide catalysts at 350 °C and 30 bar H2. Figure 5 displays the stearic acid conversion over time.CO TPD analysis was also performed on the pure supports from 25 to 1000 • C (not shown).We observed a significant increase on the amount of desorbed CO at temperatures higher than 500 • C, indicating that the surface groups are released from the support at this temperature.Thus, we expect that no surfaces groups remain attached to the support after it is exposed to 900 • C for 6 h (during catalyst synthesis).
NH 3 TPD was performed to analyze the acidity of the catalysts.Table 4 displays the density of the catalysts' acidic sites.W 2 C/CCA had the highest density of acidic sites (217 µmol•g −1 ) compared with W 2 C/AC and W 2 C/CNF (44 and 46 µmol•g −1 , respectively).The higher acidity of tungsten carbide supported on carbon-covered alumina may be attributed to the acidity of alumina.Although the alumina was completely covered by carbon, as shown by CO 2 Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) analysis (Figure A2), the higher amount of desorbed NH 3 (Table 4) suggests that the porosity of carbon enables the alumina to be available for interaction with external molecules, such as ammonia during NH 3 TPD.
Stearic acid hydrodeoxygenation was performed over supported tungsten carbide catalysts at 350 • C and 30 bar H 2 .Figure 5 displays the stearic acid conversion over time.W2C supported on CCA presented the lowest stearic acid conversion relative to W2C supported on AC and CNF (although W2C/CCA showed the highest CO uptake value).We propose that this result can be explained by the textural properties.The combination of a lower surface area (161 m 2 •g −1 ) with a smaller pore size (9.4 nm) of the CCA-supported catalyst limits the access of stearic acid to active sites, resulting in a lower stearic acid conversion.
The conversion over the W2C/AC and W2C/CNF catalysts was similar and reached the maximum value of 85% at 360 min.W2C/AC presented a higher CO uptake value (61 µmol•g −1 ), higher specific surface area (696 m 2 •g −1 ) and smaller pore size (8.3 nm) than W2C/CNF (34 µmol•g −1 , 124 m 2 •g −1 and 15.1 nm, respectively).While the higher specific surface area favors the interaction of stearic acid molecules with the catalyst surface, the smaller pore size may limit it.Thus, a balance between pore size and surface area may explain that the stearic acid conversion over the W2C/AC and W2C/CNF catalysts was similar.Note that the reaction is not limited by mass transfer limitations (see Figure A3).
To investigate the intrinsic activity of the catalysts, the turnover frequency (TOF) was calculated based on initial reaction rate (see equation in supplementary information).Table 5 lists the results.The TOF of the described carbides was 1-3 s −1 .Therefore, all three catalysts presented a similar TOF for stearic acid HDO (hydrodeoxygenation) reaction at 350 °C and 30 bar H2, which indicates that the catalysts have the same intrinsic activity.This result is in accordance with the CO TPD profiles (Figure 5), which shows that the nature of the active sites on the three catalysts was the same.The TOF of noble metals and sulfides are up to one order of magnitude lower than that of the carbides [28,29].Thus, the intrinsic activity of tungsten carbides studied in this work is similar or even higher compared to others catalysts previously reported in the literature.[18,23], as summarized in Figure 6.In the DCO (decarbonylation/decarboxylation) pathway, oxygen is removed as CO2 (decarboxylation) or as CO and H2O (decarbonylation) followed by hydrogenation resulting in heptadecane as final product.In the HDO pathway, oxygen is removed as H2O producing aldehyde as the first intermediate.The aldehyde is further dehydrated and hydrogenated resulting in octadecane as final product [30].A third reaction pathway, called HDCO (hydrogenation followed W 2 C supported on CCA presented the lowest stearic acid conversion relative to W 2 C supported on AC and CNF (although W 2 C/CCA showed the highest CO uptake value).We propose that this result can be explained by the textural properties.The combination of a lower surface area (161 m 2 •g −1 ) with a smaller pore size (9.4 nm) of the CCA-supported catalyst limits the access of stearic acid to active sites, resulting in a lower stearic acid conversion.
The conversion over the W 2 C/AC and W 2 C/CNF catalysts was similar and reached the maximum value of 85% at 360 min.W 2 C/AC presented a higher CO uptake value (61 µmol•g −1 ), higher specific surface area (696 m 2 •g −1 ) and smaller pore size (8.3 nm) than W 2 C/CNF (34 µmol•g −1 , 124 m 2 •g −1 and 15.1 nm, respectively).While the higher specific surface area favors the interaction of stearic acid molecules with the catalyst surface, the smaller pore size may limit it.Thus, a balance between pore size and surface area may explain that the stearic acid conversion over the W 2 C/AC and W 2 C/CNF catalysts was similar.Note that the reaction is not limited by mass transfer limitations (see Figure A3).
To investigate the intrinsic activity of the catalysts, the turnover frequency (TOF) was calculated based on initial reaction rate (see equation in Appendix A).Table 5 lists the results.The TOF of the described carbides was 1-3 s −1 .Therefore, all three catalysts presented a similar TOF for stearic acid HDO (hydrodeoxygenation) reaction at 350 • C and 30 bar H 2 , which indicates that the catalysts have the same intrinsic activity.This result is in accordance with the CO TPD profiles (Figure 5), which shows that the nature of the active sites on the three catalysts was the same.The TOF of noble metals and sulfides are up to one order of magnitude lower than that of the carbides [28,29].Thus, the intrinsic activity of tungsten carbides studied in this work is similar or even higher compared to others catalysts previously reported in the literature.

Catalyst
TOF (s −1 ) Stearic acid deoxygenation can occur via different pathways [18,23], as summarized in Figure 6.In the DCO (decarbonylation/decarboxylation) pathway, oxygen is removed as CO 2 (decarboxylation) or as CO and H 2 O (decarbonylation) followed by hydrogenation resulting in heptadecane as final product.In the HDO pathway, oxygen is removed as H 2 O producing aldehyde as the first intermediate.The aldehyde is further dehydrated and hydrogenated resulting in octadecane as final product [30].A third reaction pathway, called HDCO (hydrogenation followed by decarbonylation), can be considered when the aldehyde (formed via hydrogenation of stearic acid) is decarbonylated, resulting in heptadecane as final product.
ChemEngineering 2019, 3, x FOR PEER REVIEW 9 of 15 by decarbonylation), can be considered when the aldehyde (formed via hydrogenation of stearic acid) is decarbonylated, resulting in heptadecane as final product.To explore the influence of the supports' pore size and acidity on the product distribution in stearic acid HDO, the product distribution is plotted as function of conversion (Figure 7). Figure 7 shows a number of differences between the performance of the catalysts, such as the following, which we will discuss subsequently: • The selectivity towards oxygenates was higher over W2C/AC compared with W2C/CNF and W2C/CCA at low conversion rates (<5%).• The ratio of octadecene (C18-unsat) to octadecane (C18-sat) was higher over W2C/CCA than over W2C/CNF and W2C/AC.Only for W2C/CNF at lower conversion rates (<30%), the selectivity towards octadecene surpassed that of octadecane.

The selectivity towards oxygenates was higher over W2C/AC than over W2C/CNF and W2C/CCA at low conversion (<5%).
Oxygenates (octadecanal and octadecanol) were the primary products over all three catalysts, which matches observations by other researchers [31].However, at conversion below 5%, To explore the influence of the supports' pore size and acidity on the product distribution in stearic acid HDO, the product distribution is plotted as function of conversion (Figure 7).To explore the influence of the supports' pore size and acidity on the product distribution in stearic acid HDO, the product distribution is plotted as function of conversion (Figure 7). Figure 7 shows a number of differences between the performance of the catalysts, such as the following, which we will discuss subsequently: • The selectivity towards oxygenates was higher over W2C/AC compared with W2C/CNF and W2C/CCA at low conversion rates (<5%).• The ratio of octadecene (C18-unsat) to octadecane (C18-sat) was higher over W2C/CCA than over W2C/CNF and W2C/AC.Only for W2C/CNF at lower conversion rates (<30%), the selectivity towards octadecene surpassed that of octadecane.

The selectivity towards oxygenates was higher over W2C/AC than over W2C/CNF and W2C/CCA at low conversion (<5%).
Oxygenates (octadecanal and octadecanol) were the primary products over all three catalysts, which matches observations by other researchers [31].However, at conversion below 5%, Figure 7 shows a number of differences between the performance of the catalysts, such as the following, which we will discuss subsequently:

•
The selectivity towards oxygenates was higher over W 2 C/AC compared with W 2 C/CNF and W 2 C/CCA at low conversion rates (<5%).

•
The ratio of octadecene (C18-unsat) to octadecane (C18-sat) was higher over W 2 C/CCA than over W 2 C/CNF and W 2 C/AC.Only for W 2 C/CNF at lower conversion rates (<30%), the selectivity towards octadecene surpassed that of octadecane.
The selectivity towards oxygenates was higher over W 2 C/AC than over W 2 C/CNF and W 2 C/CCA at low conversion (<5%).
Oxygenates (octadecanal and octadecanol) were the primary products over all three catalysts, which matches observations by other researchers [31].However, at conversion below 5%, oxygenates represented 70% (mol) of all products over the W 2 C/AC catalyst while they represented only 40% (mol) over the W 2 C/CNF and W 2 C/CCA catalysts.
According to Kim et al.
[32], a carbon-based support with a large pore size facilitates the transport of reactants during hydrodeoxygenation.In addition, Schaidle et al.
[31] concluded via experimental and theoretical calculations that acid catalysts favor dehydration of oxygenates in the hydrodeoxygenation reaction.Figure 8 summarizes the effect of pore size (A) and acidity (B) on the oxygenates selectivity at 3% conversion of stearic acid HDO.Clearly, neither the pore size nor the acidity related directly to the selectivity.Therefore, we believe that the combination of acidity and porosity determined the performance of the catalysts.However, the exact contribution of each parameter currently remains an enigma.
At conversions below 30%, W2C/CNF produced compounds resulting in a C18-unsat:C18-sat ratio greater than 1 while W2C/AC and W2C/CCA produced compounds resulting in a C18-unsat:C18-sat ratio of less than 1.Higher amounts of the unsaturated octadecene were initially formed over the support with the greatest mesopore volume (CNF), which were subsequently hydrogenated to octadecane.This suggests that the conversion of octadecene into octadecane was slower over the catalyst supported on CNF than over the catalysts supported on AC and CCA.
Figure 9 summarizes the influence of pore size on the C18-unsat:C18-sat selectivity for 25% conversion.At higher conversions, i.e. above 50%, the C18-unsat:C18-sat ratio over the W2C/CCA catalyst was higher than over the W2C/AC and W2C/CNF catalysts.According to Schaidle et al. [31], the relative extents of hydrogenation and dehydration of oxygenates (aldehyde and alcohol) is related to Clearly, neither the pore size nor the acidity related directly to the selectivity.Therefore, we believe that the combination of acidity and porosity determined the performance of the catalysts.However, the exact contribution of each parameter currently remains an enigma.
The ratio C18-unsat: C18-sat was higher over W 2 C/CCA than over W 2 C/CNF and W 2 C/AC.Only for W 2 C/CNF at lower conversion rates (<30%), the selectivity towards C18-unsat surpassed that of C18-sat.
At conversions below 30%, W 2 C/CNF produced compounds resulting in a C18-unsat:C18-sat ratio greater than 1 while W 2 C/AC and W 2 C/CCA produced compounds resulting in a C18-unsat:C18-sat ratio of less than 1.Higher amounts of the unsaturated octadecene were initially formed over the support with the greatest mesopore volume (CNF), which were subsequently hydrogenated to octadecane.This suggests that the conversion of octadecene into octadecane was slower over the catalyst supported on CNF than over the catalysts supported on AC and CCA.
Figure 9 summarizes the influence of pore size on the C18-unsat:C18-sat selectivity for 25% conversion.Clearly, neither the pore size nor the acidity related directly to the selectivity.Therefore, we believe that the combination of acidity and porosity determined the performance of the catalysts.However, the exact contribution of each parameter currently remains an enigma.
At conversions below 30%, W2C/CNF produced compounds resulting in a C18-unsat:C18-sat ratio greater than 1 while W2C/AC and W2C/CCA produced compounds resulting in a C18-unsat:C18-sat ratio of less than 1.Higher amounts of the unsaturated octadecene were initially formed over the support with the greatest mesopore volume (CNF), which were subsequently hydrogenated to octadecane.This suggests that the conversion of octadecene into octadecane was slower over the catalyst supported on CNF than over the catalysts supported on AC and CCA.
Figure 9 summarizes the influence of pore size on the C18-unsat:C18-sat selectivity for 25% conversion.At higher conversions, i.e. above 50%, the C18-unsat:C18-sat ratio over the W2C/CCA catalyst was higher than over the W2C/AC and W2C/CNF catalysts.According to Schaidle et al. [31], the relative extents of hydrogenation and dehydration of oxygenates (aldehyde and alcohol) is related to At higher conversions, i.e. above 50%, the C18-unsat:C18-sat ratio over the W 2 C/CCA catalyst was higher than over the W 2 C/AC and W 2 C/CNF catalysts.According to Schaidle et al. [31], the relative extents of hydrogenation and dehydration of oxygenates (aldehyde and alcohol) is related to the ratio between metallic and acidic sites on the carbide surface.Since C18-unsat is produced via dehydration of oxygenates and C18-sat is produced via hydrogenation of C18-unsat, it is expected that catalysts with a higher ratio of acid to metallic sites favor C18-unsat production and catalysts with a lower acid:metallic site ratio favor C18-sat production.
The combination of CO chemisorption (metallic sites) and NH 3 TPD (acid sites) analysis indicates that the W 2 C/CCA catalyst had a higher ratio of acid:metallic sites (2.7) than the W 2 C/AC (0.7) and W 2 C/CNF (1.3) catalysts.This explains why the W 2 C/CCA catalyst had the highest C18-unsat:C18-sat ratio (0.87) relative to W 2 C/AC (0.3) and W 2 C/CNF (0.4) for conversions above 50%.
Figure 10 summarizes the effect of acidity on the C18-unsat:C18-sat rate at 60% conversion of stearic acid HDO.
ChemEngineering 2019, 3, x FOR PEER REVIEW 11 of 15 the ratio between metallic and acidic sites on the carbide surface.Since C18-unsat is produced via dehydration of oxygenates and C18-sat is produced via hydrogenation of C18-unsat, it is expected that catalysts with a higher ratio of acid to metallic sites favor C18-unsat production and catalysts with a lower acid:metallic site ratio favor C18-sat production.The combination of CO chemisorption (metallic sites) and NH3 TPD (acid sites) analysis indicates that the W2C/CCA catalyst had a higher ratio of acid:metallic sites (2.7) than the W2C/AC (0.7) and W2C/CNF (1.3) catalysts.This explains why the W2C/CCA catalyst had the highest C18-unsat:C18-sat ratio (0.87) relative to W2C/AC (0.3) and W2C/CNF (0.4) for conversions above 50%.
Figure 10 summarizes the effect of acidity on the C18-unsat:C18-sat rate at 60% conversion of stearic acid HDO.In addition to the pore size and acidity, the particle size could also be pointed to as responsible for differences in the selectivity.However, previous studies [19] have shown that W2C/CNF with bigger particles produced more C17 compounds (heptadecane/heptadecene) than W2C/CNF with smaller particles.In this paper, W2C/AC was the catalyst with the biggest average particle size (although the difference was not significant), but Figure 7A did not show a higher production of C17 over this catalyst.Therefore, we confirm that W2C particle size distribution did not affect the performance of catalysts.

Conclusions
In our study, activated carbon, carbon nanofiber and carbon-covered alumina supports did not appear to influence the nature of the active sites of tungsten carbide catalysts.As a consequence, W2C/AC, W2C/CCA and W2C/CNF presented the same intrinsic activity (TOF) for stearic acid HDO.However, differences in support acidity and pore size did appear to influence stearic acid product distribution.While the larger pore size of W2C/CNF favored the conversion of oxygenates into hydrocarbons and the production of C18-unsat at low conversions (<30%), the higher acidity of W2C/CCA favored the conversion of oxygenates at low conversions (<30%) and the higher production of C18-unsat at high conversions (>50%).For a complete understanding of catalyst pore size and acidity effects on the product distribution of stearic acid HDO, further studies might be performed using catalysts with similar acidity but different pore size, and catalysts with similar pore size but different acidity.In addition to the pore size and acidity, the particle size could also be pointed to as responsible for differences in the selectivity.However, previous studies [19] have shown that W 2 C/CNF with bigger particles produced more C17 compounds (heptadecane/heptadecene) than W 2 C/CNF with smaller particles.In this paper, W 2 C/AC was the catalyst with the biggest average particle size (although the difference was not significant), but Figure 7A did not show a higher production of C17 over this catalyst.Therefore, we confirm that W 2 C particle size distribution did not affect the performance of catalysts.

Conclusions
In our study, activated carbon, carbon nanofiber and carbon-covered alumina supports did not appear to influence the nature of the active sites of tungsten carbide catalysts.As a consequence, W 2 C/AC, W 2 C/CCA and W 2 C/CNF presented the same intrinsic activity (TOF) for stearic acid HDO.However, differences in support acidity and pore size did appear to influence stearic acid product distribution.While the larger pore size of W 2 C/CNF favored the conversion of oxygenates into hydrocarbons and the production of C18-unsat at low conversions (<30%), the higher acidity of W 2 C/CCA favored the conversion of oxygenates at low conversions (<30%) and the higher production of C18-unsat at high conversions (>50%).For a complete understanding of catalyst pore size and acidity effects on the product distribution of stearic acid HDO, further studies might be performed using catalysts with similar acidity but different pore size, and catalysts with similar pore size but different acidity.To confirm that alumina was completely covered by carbon monolayers (CCA support), we performed CO 2 DRIFTS analysis.Figure A2 shows the results.The spectrum for alumina shows infrared bands at 1665, 1440 and 1225 cm −1 .These bands are related to symmetric and asymmetric stretching of OCO bonds and to the deformation modes of COH from adsorbed bicarbonates species.Bicarbonates species are formed by interaction between CO2 and alumina's nucleophilic centers.Since there are no bands that refer to bicarbonates on CCA profile, we conclude that alumina is fully covered by carbon over the support.The spectrum for alumina shows infrared bands at 1665, 1440 and 1225 cm −1 .These bands are related to symmetric and asymmetric stretching of OCO bonds and to the deformation modes of COH from adsorbed bicarbonates species.Bicarbonates species are formed by interaction between CO 2 and alumina's nucleophilic centers.Since there are no bands that refer to bicarbonates on CCA profile, we conclude that alumina is fully covered by carbon over the support.
Figure 2 displays representative HR-TEM images of tungsten carbide supported on AC, CCA and CNF.Black spots represent the active phase carbide (indicated with the red arrows) and the dark grey area is the support.

Figure 1 .
Figure 1.X-Ray diffraction (XRD) diffractograms of pure support, supported tungsten oxide precursor and tungsten carbide supported by (A) AC, (B) CCA and (C) CNF; • C W 2 (C,O) W 2 C. The diffractograms of W 2 C supported on AC, CNF and CCA show peaks at 2θ values of 36.8 • and 42.7 • , which correspond to the oxy-carbide W 2 (C,O) phase (PDF#22-0959), indicated by the green triangles, as well as peaks at a 2θ of 39.6 • , 61.7 • and 72.7 • , which correspond to the W 2 C phase (PDF#20-1315), indicated by the red squares.Since the catalysts were passivated with 0.5% (v/v) O 2 /N 2 (50 mL•min −1 ) at 25 • C for 24 h before XRD analysis to avoid their complete oxidation when exposed to air, we attribute the presence of the oxy-carbide phase to partial oxidation of catalyst during the passivation treatment.The diffractograms of W 2 C/AC and its precursor present a small peak at 2θ value of 26 • , which is unexplained.It could be a contamination (SiO 2 ) or a recrystallization of carbon species, though that is unlikely at these temperatures.To analyze the particle size of the carbide, high-resolution transmission electron microscopy (HR-TEM) was performed.Figure2displays representative HR-TEM images of tungsten carbide supported on AC, CCA and CNF.Black spots represent the active phase carbide (indicated with the red arrows) and the dark grey area is the support.

Figure 3 .
Figure 3. Particle size distribution for tungsten carbide supported on (A) AC, (B) CCA and (C) CNF.

Figure 3 .
Figure 3. Particle size distribution for tungsten carbide supported on (A) AC, (B) CCA and (C) CNF.
Figure 4 displays the CO TPD results of the supported tungsten carbide catalysts, each showing three peaks at 90, 150 and 200 • C, indicated by the red squares in the figure.These results suggest that although the catalysts are supported by different materials (AC, CCA and CNF), the nature of their active sites is the same.ChemEngineering 2019, 3, x FOR PEER REVIEW 7 of 15the catalysts are supported by different materials (AC, CCA and CNF), the nature of their active sites is the same.

Figure 4 .
Figure 4. Temperature-programmed desorption of CO from tungsten carbide supported on AC, CCA and CNF.

Figure 4 .
Figure 4. Temperature-programmed desorption of CO from tungsten carbide supported on AC, CCA and CNF.

ChemEngineering 2019, 3 ,
x FOR PEER REVIEW 9 of 15 by decarbonylation), can be considered when the aldehyde (formed via hydrogenation of stearic acid) is decarbonylated, resulting in heptadecane as final product.

ChemEngineering 2019, 3 ,
x FOR PEER REVIEW 10 of 15 oxygenates represented 70% (mol) of all products over the W2C/AC catalyst while they represented only 40% (mol) over the W2C/CNF and W2C/CCA catalysts.According to Kim et al.[32], a carbon-based support with a large pore size facilitates the transport of reactants during hydrodeoxygenation.In addition, Schaidle et al.[31] concluded via experimental and theoretical calculations that acid catalysts favor dehydration of oxygenates in the hydrodeoxygenation reaction.Figure8summarizes the effect of pore size (A) and acidity (B) on the oxygenates selectivity at 3% conversion of stearic acid HDO.

ChemEngineering 2019, 3 ,
x FOR PEER REVIEW 10 of 15 oxygenates represented 70% (mol) of all products over the W2C/AC catalyst while they represented only 40% (mol) over the W2C/CNF and W2C/CCA catalysts.According to Kim et al. [32], a carbon-based support with a large pore size facilitates the transport of reactants during hydrodeoxygenation.In addition, Schaidle et al. [31] concluded via experimental and theoretical calculations that acid catalysts favor dehydration of oxygenates in the hydrodeoxygenation reaction.
Figure 8  summarizes the effect of pore size (A) and acidity (B) on the oxygenates selectivity at 3% conversion of stearic acid HDO.
= reaction rate (mmol•g −1 •h −1 ), as follows: of stearic acid  = mass of catalyst (g)  = time (h) Internal and external mass transfer limitation analysis We carried out two groups of experiments to analyze the presence of internal and external mass transfer limitations during reaction.

Figure A3 .
Figure A3.Evaluation of (A) internal mass transfer limitations and (B) external mass transfer
Calculation of Turnover Frequency (TOF) TOF = −r A Active sites −r A = reaction rate (mmol•g −1 •h −1 ), as follows: − r A = N A0 × dx A dt W N A0 = moles of stearic acid W = mass of catalyst (g) t = time (h) Internal and External Mass Transfer Limitation Analysis We carried out two groups of experiments to analyze the presence of internal and external mass transfer limitations during reaction. = moles of stearic acid  = mass of catalyst (g)  = time (h) Internal and external mass transfer limitation analysis We carried out two groups of experiments to analyze the presence of internal and external mass transfer limitations during reaction.

Figure
Figure A3A depicts the performance of W 2 C/CNF catalysts with different granulometries, defined by siefting, evaluated to analyze internal mass transfer limitations (250 mg catalyst, 2 g stearic acid, 50 mL solvent, 30 bar H 2 , 350 • C).As Figure A3A makes clear, W 2 C/CNF with different granulometries (<90 µm, 90 to 212 µm, 212 to 425 µm) obtained the same conversion over time.This confirms that the reaction was not limited by internal mass transfer.Figure A3B displays the performance of W 2 C/AC at different mixing intensities (600, 800 and 1000 rpm), evaluated to analyze external mass transfer limitations (250 mg catalyst, 2 g stearic acid, 50 mL solvent, 30 bar H 2 , 350 • C).W 2 C/AC achieved the same conversion over time for different mixing intensities (600, 800 and 1000 rpm).This result confirms that the reaction was not limited by external mass transfer.

Table 2 .
Average particle size of supported W 2 C catalysts.

Table 2 .
Average particle size of supported W2C catalysts.

Table 3 .
CO uptake for AC, CCA, CNF supports and for supported tungsten carbides.

Table 3 .
CO uptake for AC, CCA, CNF supports and for supported tungsten carbides.

Table 4 .
Acidity of the catalyst as measured via NH3 temperature-programmed desorption.

Table 4 .
Acidity of the catalyst as measured via NH 3 temperature-programmed desorption.

Table 5 .
Turnover frequency (TOF) of W2C supported on AC, CNF and CCA.

Table 5 .
Turnover frequency (TOF) of W 2 C supported on AC, CNF and CCA.