Site requirements of supported W2C nanocatalysts for efficient hydrodeoxygenation of m-cresol to aromatics

doi:10.1016/S1872-2067(24)60138-5

Abstract

Abstract:

Selective hydrodeoxygenation of lignin derivatives into aromatic compounds is a promising route for the upgrading of lignin feedstocks. Metal carbide catalysts have exhibited excellent selectivity in hydrodeoxygenation reactions, while their structure-activity relationship is still in ambiguity. Herein, a liquid-phase atomic layer deposition method was employed to synthesize W₂C/SiO₂ catalysts with uniform and size-controllable W₂C nanoparticles. For gas-phase hydrodeoxygenation of lignin-derived m-cresol at 350 °C, these W₂C/SiO₂ catalysts showed superior toluene selectivities (>95%) regardless of the W₂C particle size. An optimal W₂C particle size of ~7 nm was obtained for achieving the highest W₂C-based hydrodeoxygenation rate. In contrast, the turnover rate per surface W site increased almost monotonously as the W₂C particle size increased within 0.7‒15 nm, attributable to high-index planes appeared on the larger W₂C nanoparticles. Kinetic effects of m-cresol and H₂, taken together with temperature-programmed desorption of probe molecules and theoretical treatments, further indicate that the W₂C surface is nearly saturated by adsorbed m-cresol or its derivates under the reaction condition and the H-addition of the C₇H₇* intermediate to form toluene, instead of the initial C-O cleavage in m-cresol, acts as the rate-determining step. A side-by-side comparison between W₂C(102) and W₂C(001) catalyst surfaces in theoretical simulations of m-cresol hydrodeoxygenation verifies that high-index planes can stabilize kinetically-relevant transition states more effectively than the low-index ones, as a result of more available less-coordinated active sites on the former. The above findings bring new mechanistic insights into the site requirements of supported W₂C nanocatalysts, distinct from those metal-catalyzed hydrodeoxygenation of oxygenates.

Key words: Lignin derivative, Hydrodeoxygenation, Tungsten carbide, Heterogeneous catalysis, Structure-activity relationship, Size effect, Kinetics, Density functional theory calculation

Yanling Yang, Peijie Han, Yuanbao Zhang, Jingdong Lin, Shaolong Wan, Yong Wang, Haichao Liu, Shuai Wang. Site requirements of supported W₂C nanocatalysts for efficient hydrodeoxygenation of m-cresol to aromatics[J]. Chinese Journal of Catalysis, 2024, 67: 91-101.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60138-5

https://www.cjcatal.com/EN/Y2024/V67/I12/91

Figures/Tables 8

Fig. 1. Structural characterization of WO3/SiO2 precursors with bulk WO3 as reference. (a) Illustration of the synthesis strategy of high-loading WO3/SiO2 samples via the liquid-phase atomic layer deposition method. XRD patterns (b), UV-vis-determined edge energy values (c), and surface area and averaged WO3 size values (d) for the xWO3/SiO2 and bulk WO3 samples. Representative TEM images and corresponding statistical results of WO3 particle size for 1.0WO3/SiO2 (e) and 15WO3/SiO2 (f).

Fig. 2. Characterization of WO3/SiO2 precursors in the carburization process. (a) Mass singles of CH4, H2O and H2 during the temperature-programmed carbonization process of 15WO3/SiO2 in flowing 20% CH4/H2. (b) XRD patterns of 15WO3/SiO2 after the carbonization at 650 °C for 3 and 6 h with the standard diffraction peak positions of metallic W labeled. (c) Schematics of the stepwise conversion of WO3/SiO2 in the carburization process.

Fig. 3. Structural characterization of W2C/SiO2 and bulk W2C catalysts. XRD patterns (a) and TEM-determined average W2C particle sizes (b) for the W2C/SiO2 and bulk W2C catalysts. (c-h) (HR)TEM images of W2C/SiO2-3.0 nm and W2C-14.9 nm catalysts with corresponding fast Fourier transformed (FFT) patterns. (i) Schematics of exposed planes of W2C on the SiO2 support varied with the W2C loading.

Fig. 4. Evaluation of W2C/SiO2 catalysts in hydrodeoxygenation of m-cresol. (a) Schematics of m-cresol hydrodeoxygenation to toluene on W2C. (b) Effects of W2C particle size on hydrodeoxygenation rates and toluene selectivity. (c) Turnover rate of m-cresol hydrodeoxygenation as a function of W2C particle size. Effects of m-cresol (d) and H2 (e) partial pressures on the hydrodeoxygenation rate of m-cresol. Reaction conditions: 350 °C, 0.5 kPa m-cresol, 40 kPa H2, ca. 20% m-cresol conversion obtained by varying catalyst amount, balanced by N2, if not stated otherwise. The partial pressure of H2 was kept at 40 kPa in (d), and the corresponding value of m-cresol was kept at 0.15 kPa in (e).

Table 1 Proposed elementary steps of m-cresol hydrodeoxygenation on W2C surface a.

Fig. 5. Structure-activity relationship of W2C-based catalysts in m-cresol hydrodeoxygenation. (a) Parity plot for all measured m-cresol hydrodeoxygenation rates vs. those predicted using Eq. (3) (measured data adopted from Fig. 4). (b) Regression-fitted kinetic parameters of Eq. (3) for the m-cresol hydrodeoxygenation rates shown in (a). (c) Desorption temperature of m-cresol on W2C/SiO2 or bulk W2C determined by TGA. (d) CO-TPD profiles for W2C/SiO2 and W2C bulk catalysts.

Fig. 6. Comparison of m-cresol adsorption on W2C(001) and W2C(102) surfaces. (a) DFT-optimized structures for adsorbed m-cresol. (b) Corresponding adsorption energies in terms of electronic energy, enthalpy, and Gibbs free energy (300 °C and 100 kPa). Charge density difference analysis for adsorbed m-cresol on W2C(001) (c) and W2C(102) (d) surfaces. Cyan and yellow stand for positive and negative charge regions, respectively.

Fig. 7. Reaction pathway and activity of m-cresol hydrodeoxygenation on W2C surfaces. (a) DFT-derived Gibbs free energy diagram of m-cresol hydrodeoxygenation on W2C(001) (red) and W2C(102) (black) surfaces at 300 °C and 100 kPa. (b) DFT-optimized structures for the transition states involved in (a). The balls refer to the atoms of W (blue), C (grey), O (red), and H (white), respectively.

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Site requirements of supported W₂C nanocatalysts for efficient hydrodeoxygenation of m-cresol to aromatics

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