Biodiesel production generates abundant low-value glycerol, and its green conversion to high-value dihydroxyacetone (DHA) is critical for sustainable biomass utilization. Traditional photoelectrocatalytic systems struggle with severe carrier recombination and poor selectivity, largely due to lattice mismatch at heterojunction interfaces that weakens charge transfer efficiency, limiting their practical application.
A research team led by Prof. Yiming Liu (Taiyuan University of Science and Technology & Taiyuan University of Technology, Shanxi Key Laboratory of Catalysis and Energy Coupling) developed a lattice-matching engineering strategy to address this core challenge, with findings published in Chinese Journal of Catalysis. By precisely controlling annealing temperatures (300 °C for hexagonal and 500 °C for monoclinic phases), the team constructed two WO₃/TiO₂ composite photoanodes: hexagonal (h-WT) and monoclinic (m-WT). The key breakthrough lies in the h-WT's atomic-level coherent interface, achieved via near-epitaxial growth of hexagonal WO₃ on TiO₂ nanorods, resulting in an ultra-low lattice mismatch of 0.027%.
This atomic-scale lattice matching induces a robust 3.71 eV built-in electric field and optimizes S-scheme charge transfer. It also strengthens the adsorption affinity of glycerol's secondary hydroxyl group (adsorption energy of -1.854 eV), steering the reaction toward DHA. The h-WT photoanode achieves 35% DHA selectivity—1.9 times that of m-WT—along with a 40% higher glycerol conversion rate (788.6 mmol m⁻² h⁻¹) and over 90% total C₃-product selectivity. Notably, it maintains exceptional stability for 40 consecutive hours without structural damage, demonstrating strong potential for industrial application.
Mechanistic studies, combining advanced characterization techniques (XPS, KPFM, EQCM) and density functional theory calculations, confirm that surface-adsorbed •OH radicals dominate the selective cleavage of glycerol's C–H bonds. The secondary hydroxyl oxidation pathway to DHA also holds clear thermodynamic advantages, explaining the high selectivity. Prof. Liu's team emphasizes that this work uncovers the critical role of atomic-scale lattice matching in synchronizing heterojunction charge dynamics and surface reactions, providing a novel strategy for designing high-efficiency, high-selectivity catalysts. The team plans to expand this lattice-matching strategy to more catalytic systems, aiming to drive breakthroughs in sustainable energy and biomass valorization applications. The results were published in Chinese Journal of Catalysis (DOI: 10.1016/S1872-2067(26)64955-8 )
About the Journal
Chinese Journal of Catalysis is co-sponsored by Dalian Institute of Chemical Physics, Chinese Academy of Sciences and Chinese Chemical Society, and it is currently published by Elsevier group. This monthly journal publishes in English timely contributions of original and rigorously reviewed manuscripts covering all areas of catalysis. The journal publishes Reviews, Accounts, Communications, Articles, Highlights, Perspectives, and Viewpoints of highly scientific values that help understanding and defining of new concepts in both fundamental issues and practical applications of catalysis. Chinese Journal of Catalysis ranks among the top one journals in Applied Chemistry with a current SCI impact factor of 17.7. The Editors-in-Chief are Profs. Can Li and Tao Zhang.
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