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Stable CO2 Hydrogenation to Methanol by Cu Interacting with Isolated Zn Cations in Zincosilicate CIT-6

Gao, Yu ; Fan, Yonghui ; Zhang, Hao ; Pornsetmetakul, Peerapol ; Mezari, Brahim ; Wagemakers, Jorden ; Ramakrishnan, Mahesh LU ; Klementiev, Konstantin LU ; Kosinov, Nikolay and Hensen, Emiel J.M. (2025) In ACS Catalysis 15(3). p.1807-1818
Abstract

The catalytic conversion of carbon dioxide (CO2) to methanol over Cu/ZnO catalysts is expected to become valuable for recycling CO2. The nature of the Cu-Zn interplay remains a subject of intense debate due to many different Zn species encountered in Cu/ZnO catalysts. In this study, we designed a Cu-Zn catalyst by ion-exchanging Cu into CIT-6, a crystalline microporous zincosilicate with the BEA* topology. The catalyst exhibited high and stable CO2 hydrogenation rate to methanol. In contrast, its aluminosilicate counterparts Cu-Beta and CuZn-Beta mainly converted CO2 to CO. Operando X-ray absorption spectroscopy combined with X-ray diffraction confirmed the stability of Zn cations in the... (More)

The catalytic conversion of carbon dioxide (CO2) to methanol over Cu/ZnO catalysts is expected to become valuable for recycling CO2. The nature of the Cu-Zn interplay remains a subject of intense debate due to many different Zn species encountered in Cu/ZnO catalysts. In this study, we designed a Cu-Zn catalyst by ion-exchanging Cu into CIT-6, a crystalline microporous zincosilicate with the BEA* topology. The catalyst exhibited high and stable CO2 hydrogenation rate to methanol. In contrast, its aluminosilicate counterparts Cu-Beta and CuZn-Beta mainly converted CO2 to CO. Operando X-ray absorption spectroscopy combined with X-ray diffraction confirmed the stability of Zn cations in the zincosilicate framework during reduction in H2 and reaction in CO2/H2. The active phase consisted of highly dispersed Cu particles. These particles located near isolated Zn2+ species represent a different type of active site for methanol synthesis than the active phases proposed for Cu-Zn catalysts, such as Cu-Zn alloy particles and Cu particles decorated with ZnOx. In situ IR spectroscopy showed the formation of Zn-formate species during CO2 hydrogenation, indicating that Zn2+ ions stabilize formate as a reaction intermediate in the hydrogenation of CO2 to methanol.

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author
; ; ; ; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
CIT-6, CO hydrogenation, Cu-Zn, methanol, zincosilicate
in
ACS Catalysis
volume
15
issue
3
pages
12 pages
publisher
The American Chemical Society (ACS)
external identifiers
  • scopus:85215602132
ISSN
2155-5435
DOI
10.1021/acscatal.4c07496
language
English
LU publication?
yes
id
fe8ebb55-0fdd-42a2-9bad-a2e47590770c
date added to LUP
2025-04-02 14:31:15
date last changed
2025-04-04 15:02:42
@article{fe8ebb55-0fdd-42a2-9bad-a2e47590770c,
  abstract     = {{<p>The catalytic conversion of carbon dioxide (CO<sub>2</sub>) to methanol over Cu/ZnO catalysts is expected to become valuable for recycling CO<sub>2</sub>. The nature of the Cu-Zn interplay remains a subject of intense debate due to many different Zn species encountered in Cu/ZnO catalysts. In this study, we designed a Cu-Zn catalyst by ion-exchanging Cu into CIT-6, a crystalline microporous zincosilicate with the BEA* topology. The catalyst exhibited high and stable CO<sub>2</sub> hydrogenation rate to methanol. In contrast, its aluminosilicate counterparts Cu-Beta and CuZn-Beta mainly converted CO<sub>2</sub> to CO. Operando X-ray absorption spectroscopy combined with X-ray diffraction confirmed the stability of Zn cations in the zincosilicate framework during reduction in H<sub>2</sub> and reaction in CO<sub>2</sub>/H<sub>2</sub>. The active phase consisted of highly dispersed Cu particles. These particles located near isolated Zn<sup>2+</sup> species represent a different type of active site for methanol synthesis than the active phases proposed for Cu-Zn catalysts, such as Cu-Zn alloy particles and Cu particles decorated with ZnO<sub>x</sub>. In situ IR spectroscopy showed the formation of Zn-formate species during CO<sub>2</sub> hydrogenation, indicating that Zn<sup>2+</sup> ions stabilize formate as a reaction intermediate in the hydrogenation of CO<sub>2</sub> to methanol.</p>}},
  author       = {{Gao, Yu and Fan, Yonghui and Zhang, Hao and Pornsetmetakul, Peerapol and Mezari, Brahim and Wagemakers, Jorden and Ramakrishnan, Mahesh and Klementiev, Konstantin and Kosinov, Nikolay and Hensen, Emiel J.M.}},
  issn         = {{2155-5435}},
  keywords     = {{CIT-6; CO hydrogenation; Cu-Zn; methanol; zincosilicate}},
  language     = {{eng}},
  number       = {{3}},
  pages        = {{1807--1818}},
  publisher    = {{The American Chemical Society (ACS)}},
  series       = {{ACS Catalysis}},
  title        = {{Stable CO<sub>2</sub> Hydrogenation to Methanol by Cu Interacting with Isolated Zn Cations in Zincosilicate CIT-6}},
  url          = {{http://dx.doi.org/10.1021/acscatal.4c07496}},
  doi          = {{10.1021/acscatal.4c07496}},
  volume       = {{15}},
  year         = {{2025}},
}