Abstract
ZnO/ZrO2 catalysts have shown better activity in the CO2 hydrogenation to methanol compared with single component counterparts, but the interaction between ZnO and ZrO2 is still poorly understood. In particular, the effect of the ZrO2 support phase (tetragonal vs. monoclinic) was not systematically explored. Here, we have synthesized ZnO/ZrO2 catalysts supported on tetragonal ZrO2 (ZnO/ZrO2-t) and monoclinic ZrO2 (ZnO/ZrO2-m), which resulted in the formation of different ZnOx species, consisting of sub-nanometer ZnO moieties and large-sized ZnO particles, respectively. ZnO/ZrO2-t exhibited a higher methanol selectivity (81 vs. 39%) and methanol yield (1.25 vs. 0.67 mmol g-1 h-1) compared with ZnO/ZrO2-m. The difference in performance was attributed to the redox state and degree of dispersion of Zn, based on spectroscopy and microscopy results. ZnO/ZrO2-t had a high density of ZnOx-ZrOy sites, which favored the formation of active HCOO* species and enhanced the yield and selectivity of methanol along the formate pathway. Such ZnO clusters were further dispersed on ZrO2-t during catalysis, while larger ZnO particles on ZnO/ZrO2-m remained stable throughout the reaction. This study shows that the phase of ZrO2 supports can be used to control the dispersion of ZnO and the catalyst surface chemistry, and lead to enhanced catalytic performance.
Original language | English |
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Article number | e202416899 |
Number of pages | 11 |
Journal | Angewandte Chemie-International Edition |
Early online date | 8 Oct 2024 |
DOIs | |
Publication status | Published - 13 Nov 2024 |
Bibliographical note
Publisher Copyright:© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
Funding
M. Monai and B.M. Weckhuysen acknowledge the Advanced Research Center Chemical Building Blocks Consortium (ARC CBBC) for funding. For access to the electron microscopy methods, we acknowledge the Electron Microscopy Centre of Utrecht University, part of the National Roadmap Infrastructure NEMI, financed under project number 184.034.014 by the Dutch Research Council (NWO). The authors acknowledge the CERIC\u2010ERIC consortium for access to experimental facilities and financial support (proposal number 20227190). P. Matvija is grateful for financial support provided by the Czech Ministry of Education, Youth and Sports (project LM2023072). X. Zhang acknowledge the China Scholarship Council (CSC) for financial support. This work also made use of the Dutch National e\u2010Infrastructure with the support of the SURF Cooperative using grant no. EINF\u20106932.
Funders | Funder number |
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Advanced Research Center Chemical Building Blocks Consortium | |
China Scholarship Council | |
Australian Research Council | 184.034.014 |
Australian Research Council | |
Nederlandse Organisatie voor Wetenschappelijk Onderzoek | 20227190 |
Nederlandse Organisatie voor Wetenschappelijk Onderzoek | |
Ministerstvo Školství, Mládeže a Tělovýchovy | LM2023072 |
Ministerstvo Školství, Mládeže a Tělovýchovy | |
SURF | EINF‐6932 |
Keywords
- CO hydrogenation
- Methanol
- Support effects
- Zinc oxide
- Zirconia