Nature of Zirconia on a Copper Inverse Catalyst Under CO2 Hydrogenation Conditions

Kumari, Simran; Alexandrova, Anastassia N.; Sautet, Philippe

doi:10.1021/jacs.3c09947

Title: Nature of Zirconia on a Copper Inverse Catalyst Under CO₂ Hydrogenation Conditions

Journal Article · 16 November 2023 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.3c09947 · OSTI ID:2337932

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Univ. of California, Los Angeles, CA (United States); UCLA
Univ. of California, Los Angeles, CA (United States)
Univ. of California, Los Angeles, CA (United States); California NanoSystems Institute, Los Angeles, CA (United States)

The growing concern over the escalating levels of anthropogenic CO₂ emissions necessitates effective strategies for its conversion to valuable chemicals and fuels. In this research, we embark on a comprehensive investigation of the nature of zirconia on a copper inverse catalyst under the conditions of CO₂ hydrogenation to methanol. We employ density functional theory calculations in combination with the Grand Canonical Basin Hopping method, enabling an exploration of the free energy surface including a variable amount of adsorbates within the relevant reaction conditions. Our focus centers on a model three-atom Zr cluster on a Cu(111) surface decorated with various OH, O, and formate ligands, noted Zr₃O_x (OH)_y (HCOO)_z/Cu(111), revealing major changes in the active site induced by various reaction parameters such as the gas pressure, temperature, conversion levels, and CO₂/H₂ feed ratios. Further, through our analysis, we have unveiled insights into the dynamic behavior of the catalyst. Specifically, under reaction conditions, we observe a large number of composition and structures with similar free energy for the catalyst, with respect to changing the type, number, and binding sites of adsorbates, suggesting that the active site should be regarded as a statistical ensemble of diverse structures that interconvert.

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Research Organization:: Univ. of California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019152; AC02-06CH11357; AC02-05CH11231

OSTI ID:: 2337932

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 48 Vol. 145; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
adsorption
catalysts
chemical structure
cluster chemistry
hydroxyls

Title: Nature of Zirconia on a Copper Inverse Catalyst Under CO2 Hydrogenation Conditions

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Title: Nature of Zirconia on a Copper Inverse Catalyst Under CO₂ Hydrogenation Conditions