Structure engineering of CeO2 for boosting the Au/CeO2 nanocatalyst in the green and selective hydrogenation of nitrobenzene

Abstract

Exploring eco-friendly and cost-effective strategies for structure engineering at the nanoscale is important for boosting heterogeneous catalysis but still under a long-standing challenge. Herein, multifunctional polyphenol tannic acid, a low-cost natural biomass containing catechol and galloyl species, was employed as a green reducing agent, chelating agent, and stabilizer to prepare Au nanoparticles, which were dispersed on different-shaped CeO₂ supports (e.g., rod, flower, cube, and octahedral). Systematic characterizations revealed that Au/CeO₂-rod had the highest oxygen vacancy density and Ce(III) proportion, favoring the dispersion and stabilization of the metal active sites. Using isopropanol as a hydrogen-transfer reagent, deep insights into the structure–activity relationship of the Au/CeO₂ catalysts with various morphologies of CeO₂ in the catalytic nitrobenzene transfer hydrogenation reaction were gained. Notably, the catalytic performance followed the order: Au/CeO₂-rod (110), (100), (111) > Au/CeO₂-flower (100), (111) > Au/CeO₂-cube (100) > Au/CeO₂-octa (111). Au/CeO₂-rod displayed the highest conversion of 100% nitrobenzene and excellent stability under optimal conditions. Moreover, DFT calculations indicated that nitrobenzene molecules had a suitable adsorption energy and better isopropanol dehydrogenation capacity on the Au/CeO₂ (110) surface. A reaction pathway and the synergistic catalytic mechanism for catalytic nitrobenzene transfer hydrogenation are proposed based on the results. This work demonstrates that CeO₂ structure engineering is an efficient strategy for fabricating advanced and environmentally benign materials for nitrobenzene hydrogenation.