Component-Specific Functions of Cu, Zn, and Zr in Inverse ZnZrOx/Cu Catalysts for CO2Hydrogenation to Methanol
(2026) In Journal of the American Chemical Society 148(7). p.7378-7387- Abstract
Cu-based ternary catalysts often outperform their binary counterparts in the hydrogenation of CO2 to methanol. Unraveling the underlying synergistic effects among multiple components remains challenging and requires comprehensive operando characterization. In this study, we present a detailed investigation into the synergistic Cu−Zn−Zr interactions in inverse ZnZrOx/Cu catalysts, which show strong promise for enhancing the synthesis of methanol from CO2. In situ X-ray diffraction revealed that ZrO2 clusters effectively stabilize Cu nanoparticles against sintering during the H2 reduction. Operando X-ray absorption spectroscopy at the Cu, Zn, and Zr K-edges demonstrated that the... (More)
Cu-based ternary catalysts often outperform their binary counterparts in the hydrogenation of CO2 to methanol. Unraveling the underlying synergistic effects among multiple components remains challenging and requires comprehensive operando characterization. In this study, we present a detailed investigation into the synergistic Cu−Zn−Zr interactions in inverse ZnZrOx/Cu catalysts, which show strong promise for enhancing the synthesis of methanol from CO2. In situ X-ray diffraction revealed that ZrO2 clusters effectively stabilize Cu nanoparticles against sintering during the H2 reduction. Operando X-ray absorption spectroscopy at the Cu, Zn, and Zr K-edges demonstrated that the enhanced reducibility of Zn and Zr species arises from synergistic Cu–Zn–Zr interactions. Upon H2 reduction, partially reduced ZrO2 facilitated CO2 adsorption and activation. Initially dispersed Zn2+ species were partially transformed into the CuZn alloy, which remained stable under reaction conditions. Notably, the CuZn alloy significantly enhanced the hydrogenation of key formate reaction intermediates to methanol. Moreover, Zn incorporation in Cu inhibited methanol decomposition to CO. The combined effects of efficient H2 activation on highly dispersed metallic Cu, enhanced CO2 activation by reduced ZrO2 clusters, and rapid formate hydrogenation facilitated by the CuZn alloy rendered inverse ZnZrOx/Cu catalysts superior in methanol formation rates as compared to inverse ZnOx/Cu, ZrOx/Cu catalysts, a commercial CuZnAl catalyst, and previously reported CuZnZr catalysts.
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- author
- Gao, Yu ; Shahroudi, Erfan ; Bouts, Stefan ; Fan, Yonghui ; Li, Yin ; Chaipornchalerm, Peeranat ; Wang, Junbu ; Klementiev, Konstantin LU ; Kosinov, Nikolay and Hensen, Emiel J.M.
- organization
- publishing date
- 2026-02-25
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of the American Chemical Society
- volume
- 148
- issue
- 7
- pages
- 10 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- scopus:105030932846
- pmid:41662465
- ISSN
- 0002-7863
- DOI
- 10.1021/jacs.5c19915
- language
- English
- LU publication?
- yes
- additional info
- Publisher Copyright: © 2026 The Authors. Published by American Chemical Society. This article is licensed under CC-BY 4.0. https://creativecommons.org/licenses/by/4.0/
- id
- b9347812-a34f-44bd-9265-f6d4c2dd50da
- date added to LUP
- 2026-04-09 14:55:38
- date last changed
- 2026-05-22 20:10:57
@article{b9347812-a34f-44bd-9265-f6d4c2dd50da,
abstract = {{<p>Cu-based ternary catalysts often outperform their binary counterparts in the hydrogenation of CO<sub>2</sub> to methanol. Unraveling the underlying synergistic effects among multiple components remains challenging and requires comprehensive operando characterization. In this study, we present a detailed investigation into the synergistic Cu−Zn−Zr interactions in inverse ZnZrO<sub>x</sub>/Cu catalysts, which show strong promise for enhancing the synthesis of methanol from CO<sub>2</sub>. In situ X-ray diffraction revealed that ZrO<sub>2</sub> clusters effectively stabilize Cu nanoparticles against sintering during the H<sub>2</sub> reduction. Operando X-ray absorption spectroscopy at the Cu, Zn, and Zr K-edges demonstrated that the enhanced reducibility of Zn and Zr species arises from synergistic Cu–Zn–Zr interactions. Upon H<sub>2</sub> reduction, partially reduced ZrO<sub>2</sub> facilitated CO<sub>2</sub> adsorption and activation. Initially dispersed Zn<sup>2+</sup> species were partially transformed into the CuZn alloy, which remained stable under reaction conditions. Notably, the CuZn alloy significantly enhanced the hydrogenation of key formate reaction intermediates to methanol. Moreover, Zn incorporation in Cu inhibited methanol decomposition to CO. The combined effects of efficient H<sub>2</sub> activation on highly dispersed metallic Cu, enhanced CO<sub>2</sub> activation by reduced ZrO<sub>2</sub> clusters, and rapid formate hydrogenation facilitated by the CuZn alloy rendered inverse ZnZrO<sub>x</sub>/Cu catalysts superior in methanol formation rates as compared to inverse ZnO<sub>x</sub>/Cu, ZrO<sub>x</sub>/Cu catalysts, a commercial CuZnAl catalyst, and previously reported CuZnZr catalysts.</p>}},
author = {{Gao, Yu and Shahroudi, Erfan and Bouts, Stefan and Fan, Yonghui and Li, Yin and Chaipornchalerm, Peeranat and Wang, Junbu and Klementiev, Konstantin and Kosinov, Nikolay and Hensen, Emiel J.M.}},
issn = {{0002-7863}},
language = {{eng}},
month = {{02}},
number = {{7}},
pages = {{7378--7387}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Journal of the American Chemical Society}},
title = {{Component-Specific Functions of Cu, Zn, and Zr in Inverse ZnZrO<sub>x</sub>/Cu Catalysts for CO<sub>2</sub>Hydrogenation to Methanol}},
url = {{http://dx.doi.org/10.1021/jacs.5c19915}},
doi = {{10.1021/jacs.5c19915}},
volume = {{148}},
year = {{2026}},
}