文献类型：期刊文献

英文题名：Lattice Strain-Induced d-p Orbital Hybridization Stabilizes Frustrated Lewis Pairs for Ultra-Stable CO2 Hydrogenation to Methanol

作者：An, Xin[1];He, Chuyuan[1];Zou, Lian[1];Wang, Zhengcheng[1];Zhang, Shanshan[1];Wang, Xinlan[1];Zhang, Meng[1];Li, Jinhua[1];Zhou, Yanbo[1,2,3];Zhang, Yayun[1];Tian, Chengcheng[1,3]

机构：[1]East China Univ Sci & Technol, Integrated Res Platform Greener Hydrogen Prod & Ut, Shanghai 200237, Peoples R China;[2]Jinggangshan Univ, Sch Life Sci, Key Lab Jiangxi Prov Funct Biol & Pollut Control R, Jian 343009, Peoples R China;[3]Shanghai Inst Pollut Control & Ecol Secur, Shanghai 200092, Peoples R China

年份：2026

外文期刊名：ACS CATALYSIS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:001839407300001)】；

基金：This work was supported by the China Baowu Iron & Steel Group Co., Ltd. Low-carbon Metallurgy Innovation Fund Project (BWLCF202408), National Key Technology and Development Program (2025AA001), and the Innovation Program of Shanghai Municipal Education Commission (2023ZKZD41).

语种：英文

外文关键词：methanol; stable FLPs; d-p orbital hybridization; lattice strain engineering; CO(2)Hydrogenation

摘要：Frustrated Lewis pairs (FLPs) offer a powerful platform for CO2 activation, yet their practical implementation in heterogeneous catalysis is limited by poor thermal stability at high temperatures. Here, we propose a defect-mediated lattice strain strategy to stabilize surface FLPs that achieve efficient CO2 hydrogenation to methanol. Systematic theoretical screening of heteroatoms with ionic dimensions matching that of Ce4+ reveals that Zr-doping-induced lattice strain stabilizes surface hydroxyl via the precise manipulation of Ce 5d-O 2p orbital hybridization behaviors, which ultimately sustains abundant thermally persistent FLPs. Notably, the synthesized FLP-enriched CeO2 compounded with Cu exhibits a markedly enhanced methanol space-time yield of 361.5 g & centerdot;kg(cat)(-1)& centerdot;h(-1) for 150 h at 260 degrees C, more than doubling that of the unstrained analogue without Zr doping. Comprehensive mechanistic investigations further elucidate that the stable FLPs facilitate the charge-polarization-driven CO2 activation toward adsorbed CHO3* intermediates. Meanwhile, these FLP sites cooperate with tailored Cu species to construct a dual-active-site architecture capable of simultaneously activating CO2 and cleaving H-2, thereby efficiently driving methanol synthesis via the formate-mediated pathway. This work establishes lattice strain as a key physicochemical lever for controlling FLPs stability and functionality, unlocking promising avenues for high-temperature FLP-enabled catalysis.