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

被引：0

作者：

Yang, Yanling ^{[1
,2
,3
]}

Han, Peijie ^{[1
]}

Zhang, Yuanbao ^{[1
]}

Lin, Jingdong ^{[1
]}

Wan, Shaolong ^{[1
]}

Wang, Yong ^{[4
]}

Liu, Haichao ^{[5
]}

Wang, Shuai ^{[1
]}

机构：

[1] State Key Laboratory for Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, College of Chemistry and Chemical Engineering, Xiamen University, Fujian, Xiamen

[2] College of Marine Engineering, Jimei University, Fujian, Xiamen

[3] Key Laboratory for Marine Corrosion and Intelligent Protection Materials of Xiamen, Jimei University, Fujian, Xiamen

[4] Voiland School of Chemical Engineering and Bioengineering, Washington State University, Pullman, 99164, WA

[5] Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing

来源：

Chinese Journal of Catalysis | 2024年 / 67卷

基金：

中国国家自然科学基金;

关键词：

Density functional theory calculation; Heterogeneous catalysis; Hydrodeoxygenation; Kinetics; Lignin derivative; Size effect; Structure-activity relationship; Tungsten carbide;

D O I：

10.1016/S1872-2067(24)60138-5

中图分类号：

学科分类号：

摘要：

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. © 2024 Dalian Institute of Chemical Physics, the Chinese Academy of Sciences

引用

页码：91 / 101

页数：10

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