文献类型：期刊文献

英文题名：Deciphering Metal-Ligand Hybridization for Directing Selective C-Cl Bond Activation in HCFC-244bb Dehydrohalogenation

作者：Zhu, Ningchao[1];Chen, Chunlan[2];Zhang, Zhongyao[1];Ge, Xiaohu[1];Cao, Yueqiang[1];Liao, Xiangzhou[2];Zhou, Xinggui[1];Chen, De[1,3];Yuan, Weikang[1];Duan, Xuezhi[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn & Low Carbon Technol, Shanghai 200237, Peoples R China;[2]Shanghai Res Inst Chem Ind Co Ltd, Shanghai 200062, Peoples R China;[3]Norwegian Univ Sci & Technol, Dept Chem Engn, N-7491 Trondheim, Norway

年份：2026

卷号：16

期号：11

起止页码：10679

外文期刊名：ACS CATALYSIS

收录：;EI(收录号：20262320859552);WOS:【SCI-EXPANDED(收录号:WOS:001776324400001)】；

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), and the Fundamental and Interdisciplinary Disciplines Breakthrough Plan of the Ministry of Education of China (JYB2025XDXM404). This work was also supported by Shanghai Synchrotron Radiation Facility of BL16U1 (https://cstr.cn/31124.02.SSRF.BL16U1) for assistance with XAS measurements.

语种：英文

外文关键词：HCFC-244bb dehydrohalogenation; HFO-1234yf selectivity; Lewis acidity; conduction band minimum; structure engineering

摘要：Selective dehydrochlorination of HCFC-244bb is a key step toward the synthesis of next-generation HFO-1234yf refrigerants, yet achieving high selectivity is hindered by competitive C-F bond activation. Herein, we report a series of Ni- and Cr-based catalysts with systematically tuned surface Lewis acidity. Mechanistically informed spectroscopic characterization and electronic structure analysis demonstrate that ligand electronegativity and metal oxidation state regulate the metal-ligand bonding continuum from predominantly covalent to increasingly ionic character. Catalytic testing reveals a pronounced trade-off between activity and selectivity, with NiO achieving an HFO-1234yf selectivity of 91.36%. Density functional theory calculations and frontier molecular orbital analyses identify the conduction band minimum (CBM) energy as a decisive electronic descriptor for selectivity. An S-shaped correlation between CBM energy and selectivity thereby emerges, providing a predictive framework for the rational design of high-performance dehydrohalogenation catalysts through band-structure engineering.