文献类型：期刊文献

英文题名：Integrating first-principles calculations and diffusion-based generative models to unveil optimal metal-doped oxides for syngas conversion

作者：Chen, Ye[1,2];Yang, Changxi[1,2];Han, Yulan[4];Liu, Huihui[1,2];Xie, Wenbo[3];Hu, P.[1,2,3,4]

机构：[1]East China Univ Sci & Technol, Ctr Computat Chem, State Key Lab Green Chem Engn & Ind Catalysis, Key Lab Adv Mat, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Res Inst Ind Catalysis, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]ShanghaiTech Univ, Sch Phys Sci & Technol, 393 Middle Huaxia Rd, Shanghai 201210, Peoples R China;[4]Queens Univ Belfast, Sch Chem & Chem Engn, Belfast BT9 5AG, North Ireland

年份：2025

卷号：15

期号：24

起止页码：7404

外文期刊名：CATALYSIS SCIENCE & TECHNOLOGY

收录：;EI(收录号：20255019706088);WOS:【SCI-EXPANDED(收录号:WOS:001610355800001)】；

基金：We are grateful to the National Natural Science Foundation of China (22433004, 92045303) and the National Key R&D Program of China (2021YFA1500700).

语种：英文

外文关键词：Aluminum compounds - Catalyst activity - Chemical activation - Design for testability - Diffusion barriers - Indium compounds - Oxygen vacancies - Semiconductor doping - Synthesis gas - Zinc chloride - Zinc oxide

摘要：Oxide-zeolite bifunctional catalysts (OX-ZEO) represent a promising strategy for the direct conversion of syngas into light olefins (C2-C4), yet the configurational space of the oxide remains vast for experiments, especially for metal-doping. Here, we coupled systematic DFT investigation with a diffusion-based generative model to discover highly active, metal-doped oxides for CO activation, the rate-limiting step. A DFT database of more than 100 surface models was calculated based on a range of host oxides (In2O3, ZnO, t-ZrO2, ZnCr2O4, ZnAl2O4 and ZnGa2O4) doped with diverse metal cations. Taking oxygen vacancies (OVs) into account, we show that the Al dopant can most effectively lower the CO activation barrier and Al-doped ZnCr2O4 being the most active surface in the presence of sufficient OVs. Trained on these data, the diffusion model iteratively generated and screened a cluster of low-barrier candidates. The Al-doped ZnCr2O4 remains the most active surface; notably, a slight modification in the lattice constant significantly enhances its intrinsic catalytic activity. Across all systems, the barrier correlates linearly with the summed C and O adsorption energies, yielding separate BEP relations for simple and complex oxides. This combined DFT and generative model workflow offers valuable guidance for the rational design of efficient catalysts for syngas conversion.