Cation rearrangement at tetrahedral sites in the Cu/ZnAl2O4 spinel enhancing CO2 hydrogenation to methanol

被引：0

作者：

Song, Lixin ^{[1
]}

Liu, Guobin ^{[1
]}

Qu, Zhenping ^{[1
]}

机构：

[1] Dalian Univ Technol, Sch Environm Sci & Technol, Key Lab Ind Ecol & Environm Engn, Minist Educ, Linggong Rd 2, Dalian 116024, Peoples R China

来源：

APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY | 2025年 / 362卷

基金：

中国国家自然科学基金;

关键词：

CO2; hydrogenation; ZnAl2O4; spinel; Cation arrangement; Formate intermediates; MSI; SURFACE-STRUCTURE; CATALYSTS; SPECTROSCOPY; MECHANISM; CU/CEO2;

D O I：

10.1016/j.apcatb.2024.124742

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Cu/ZnAl2O4 spinel is a promising catalyst for CO2-to-methanol due to its dual-site H-2 activation. However, controlling surface properties and metal-support interactions (MSI) through the coordination environment of spinel cations remains underexplored. Herein, the occupancy of Zn2+ and Al3+ cations in Cu/ZnAl2O4 spinel is fine-tuned by manipulating the calcination atmosphere. More disordered structures (AlO4 and ZnO6) observed on the CZA-Ar catalyst benefit the creation of oxygen vacancies and surface hydroxyl groups, which facilitate the formation of highly dispersed small-sized Cu species. This enhances MSI and hydrogen spillover effects, thereby boosting CO2 conversion and the space-time yield (STY) of methanol. High-pressure in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results reveal that the crucial formate intermediates form at tetrahedral sites in ZnAl2O4 spinel, with more Al-HCOO- species observed on the CZA-Ar catalyst due to the formation of AlO4. This work advances the understanding of spinel catalysts in CO2 hydrogenation to methanol.

引用

页数：11