文献类型：期刊文献

英文题名：Electronic-geometric synergy in sub-nanometer iridium clusters enables efficient m-dinitrobenzene hydrogenation

作者：Ma, Shang[1];Fei, Nina[1];Jing, Yundao[1];Chen, Minhao[1];Ge, Xiaohu[1];Cao, Yueqiang[1];Zhang, Jing[1];Qian, Gang[1];Zhou, Xinggui[1];Chen, De[1,2];Duan, Xuezhi[1]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Chem Engn & Low Carbon Technol, Shanghai, Peoples R China;[2]Norwegian Univ Sci & Technol, Dept Chem Engn, Trondheim, Norway

年份：2026

外文期刊名：AICHE JOURNAL

收录：;EI(收录号：20262320858708);WOS:【SCI-EXPANDED(收录号:WOS:001784784800001)】；

基金：This work was financially supported by the National Key R&D Program of China (2022YFA1503804), the Natural Science Foundation of China (22538004, 22332003, 22478106, and 22408097), the Chang Jiang Scholars Program of the Ministry of Education of China (T2022163), the Natural Science Foundation of Shanghai (24ZR1415300), Shanghai Rising-star Program (23QA1401900), and Fundamental and Interdisciplinary Disciplines Breakthrough Plan of the Ministry of Education of China (JYB2025XDXM404). We thank the SSRF at BL16U1 (https://cstr.cn/31124.02.SSRF.BL16U1) and BL11B (https://cstr.cn/31124.02.SSRF.BL11B) for the assistance on GIWAXS measurements.

语种：英文

外文关键词：adsorption behavior; H2 dissociation; m-dinitrobenzene hydrogenation; selectivity toward m-phenylenediamine; sub-nanometer metal clusters

摘要：Sub-nanometer metal clusters provide an effective platform to bridge the gap between isolated atoms and nanoparticles in heterogeneous catalysis. Herein, we report the rational construction of Ir-based catalysts with precisely controlled nuclearity on defect-rich nanodiamond@graphene (ND@G), including single atoms (Ir-1-ND@G), sub-nanoclusters (Ir-6-ND@G), and well-defined nanoparticles (Ir-N-ND@G), for the selective hydrogenation of m-dinitrobenzene. Advanced microscopy and spectroscopy confirm the precise structural evolution and electronic modulation of Ir species. Among them, Ir-6-ND@G exhibits good catalytic performance, achieving complete conversion with >98.5% selectivity toward m-phenylenediamine under mild reaction conditions and high stability. Combined experimental studies and DFT calculations reveal that sub-nanoclusters provide optimal ensemble sites for strong substrate adsorption, efficient H-2 activation, and facile product desorption while effectively suppressing undesired side reactions arising from partial hydrogenation and N-N coupling. This work demonstrates that sub-nanometer Ir clusters effectively overcome the intrinsic activity-selectivity trade-off and establishes a versatile strategy for designing high-performance heterogeneous hydrogenation catalysts.