Highly Dispersed ZnO Sites in a ZnO/ZrO2 Catalyst Promote Carbon Dioxide-to-Methanol Conversion

Xibo Zhang, Xiang Yu, Rafael G Mendes, Peter Matvija, Angela E M Melcherts, Chunning Sun, Xinwei Ye, Bert M Weckhuysen, Matteo Monai*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

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 languageEnglish
Article numbere202416899
Number of pages11
JournalAngewandte Chemie-International Edition
Early online date8 Oct 2024
DOIs
Publication statusPublished - 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.

FundersFunder number
Advanced Research Center Chemical Building Blocks Consortium
China Scholarship Council
Australian Research Council184.034.014
Australian Research Council
Nederlandse Organisatie voor Wetenschappelijk Onderzoek20227190
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
Ministerstvo Školství, Mládeže a TělovýchovyLM2023072
Ministerstvo Školství, Mládeže a Tělovýchovy
SURFEINF‐6932

    Keywords

    • CO hydrogenation
    • Methanol
    • Support effects
    • Zinc oxide
    • Zirconia

    Fingerprint

    Dive into the research topics of 'Highly Dispersed ZnO Sites in a ZnO/ZrO2 Catalyst Promote Carbon Dioxide-to-Methanol Conversion'. Together they form a unique fingerprint.

    Cite this