Water-mediated interfacial modulation for enhanced selectivity in nitroarene hydrogenation over Pt/Fe2O3 catalysts
Anqi Li1,2, Lin Li1, Xiaoli Pan1
1State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences Dalian 116023 China yangxf2003@dicp.ac.cn aqwang@dicp.ac.cn taozhang@dicp.ac.cn.
None:
The selective hydrogenation of nitroarenes containing multiple reducible groups to aromatic amines is of considerable importance in fine chemical synthesis. Despite extensive efforts being devoted to catalyst design, the role of water, ubiquitous as a byproduct and a common solvent in these reactions, remains greatly underexplored. In this work, a well-defined PtNP/Fe2O3-sheet model catalyst, featuring uniformly dispersed Pt nanoparticles (NPs) on the (001) facet of Fe2O3 nanoplates, was synthesized to specifically elucidate the effect of water on nitroarene hydrogenation. The selectivity for 3-aminostyrene exhibits a marked enhancement in the presence of water, reaching over 98% at an optimal 10 vol% water content. Combined kinetic studies, in situ infrared spectroscopy, and density functional theory (DFT) calculations reveal that the competitive water dissociation at the Pt δ+ interfacial sites suppresses both -C[double bond, length as m-dash]C- adsorption and H2 dissociation. This interfacial blocking effect promotes preferential hydrogenation of the nitro-group over the low-valent Fe sites at the Pt-Fe2O3 interface. These findings provide atomic-level insights into the key role of water in modulating catalytic performance, offering a distinctive way of optimizing solvents by leveraging the interfacial blocking of water.
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