Ion Irradiation-Induced Coordinatively Unsaturated Zn Sites for Enhanced CO Hydrogenation
Defect engineering critically influences metal oxide catalysis, yet controlling coordinatively unsaturated metal sites remains challenging due to their inherent instability under reaction conditions. Here, we demonstrate that high-flux argon ion (Ar<sup>+</sup>) irradiation above recrystallization temperatures generated well-defined coordinatively unsaturated Zn (CUZ) sites on ZnO(101̅0) surfaces that exhibited enhanced stability and activity for CO hydrogenation. Combining low-temperature scanning probe microscopy, ambient pressure X-ray photoelectron spectroscopy, and surface-ligand infrared spectroscopy with density functional theory calculations, we identified <12̅10> step edges exposing CUZ sites as the dominant active sites. These sites facilitate hydrogen-assisted CO dissociation through a mechanism distinct from formate-mediated pathways on stoichiometric ZnO. The ion-irradiation approach effectively addressed instability of Zn species, a major problem in ZnO catalysis, enabling stable performance in syngas conversion when combined with zeolites. Our atomic scale investigation provided spectroscopic fingerprints for active sites on the ZnO catalyst and insights into the structure-activity relationships of ZnO for CO hydrogenation. Our approach for engineering thermally stable defect sites in oxide catalysts provided opportunities for rational catalyst design beyond traditional preparation methods.
Authors
- P. Hu (ORCID: https://orcid.org/0000-0002-6318-1051)
- Yunjun Cao (ORCID: https://orcid.org/0000-0001-8446-2242)
- Huiqi Chen (ORCID: https://orcid.org/0000-0002-4608-4495)
- Qiang Fu (ORCID: https://orcid.org/0000-0001-5316-6758)
- Wei-Peng Shao (ORCID: https://orcid.org/0000-0003-4126-1568)
- Yifeng Zhu (ORCID: https://orcid.org/0000-0001-8965-5051)
- Jie Luo (ORCID: https://orcid.org/0000-0002-0932-8331)
- Xinhe Bao (ORCID: https://orcid.org/0000-0001-9404-6429)
- Yuemin Wang (ORCID: https://orcid.org/0000-0002-9963-5473)
- Wei‐Xue Li (ORCID: https://orcid.org/0000-0002-5043-3088)
- Bowen Zhu (ORCID: https://orcid.org/0009-0004-1791-1107)
- Christof Wöll (ORCID: https://orcid.org/0000-0003-1078-3304)
- Xin Ou (ORCID: https://orcid.org/0000-0002-0316-9958)
- Feng Jiao (ORCID: https://orcid.org/0000-0001-9376-7208)
- Hongru Peng
- Xiulian Pan (ORCID: https://orcid.org/0000-0002-5906-6675)
- Jiayu Lv (ORCID: https://orcid.org/0000-0002-5396-9478)
- Yun Liu (ORCID: https://orcid.org/0000-0001-9630-7610)
- Yuxiang Chen (ORCID: https://orcid.org/0000-0003-4733-123X)
- Na Li (ORCID: https://orcid.org/0000-0002-1267-6185)
- Zhi Liu (ORCID: https://orcid.org/0000-0002-8973-6561)
- Fan Yang (ORCID: https://orcid.org/0000-0002-1406-9717)
- Jun Cai (ORCID: https://orcid.org/0000-0002-3806-7230)
- Yunjian Ling
- Yihua Ran
Institutions
- Karlsruhe Institute of Technology (DE)
- University of Science and Technology of China (CN)
- Dalian Institute of Chemical Physics (CN)
- Chinese Academy of Sciences (CN)
- Fudan University (CN)
- ShanghaiTech University (CN)
- Institute of Catalysis and Petrochemistry (RU)
- Hefei National Center for Physical Sciences at Nanoscale (CN)
- Institute of Urban Environment (CN)
- CAS Key Laboratory of Urban Pollutant Conversion (CN)
- Microscale (United States) (US)
- Shanghai Institute of Microsystem and Information Technology (CN)
- State Key Laboratory of Catalysis
- Ruhr University Bochum (DE)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-02-04
- DOI
- https://doi.org/10.1021/jacs.4c13234
- Citations
- 7
- Primary Topic
- Catalytic Processes in Materials Science
- Type
- article
- Field-Weighted Citation Impact
- 3.62
Funders
- National Natural Science Foundation of China
- China Postdoctoral Science Foundation
- ShanghaiTech University
- National Key Research and Development Program of China