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Gallia- Versus Alumina-Supported Cu : Dynamics of Ga in Catalysts for Green Methanol Production

Baumgarten, Lorena ; Hauberg, Patrik ; Mangelsen, Sebastian ; Coppex, Claude ; Jelic, Jelena ; Schulte, Mariam Lena ; Wolf, Anna ; Taetz, Bjarne ; Reller, Hinrich Klamor and Saedimarghmaleki, Morteza , et al. (2026) In ChemCatChem 18(2).
Abstract

The transformation of CO2 and green hydrogen into methanol presents a sustainable route for chemical and fuel production. Conventional methanol synthesis catalysts, such as Cu/ZnO/Al2O3, employ Al2O3 as a structural promoter, while Ga2O3 has recently emerged as a promising alternative. This study compares Cu-based catalysts supported on Al2O3 (CA) and Ga2O3 (CG), prepared via coprecipitation of layered double hydroxide precursors with identical molar Cu:M (M = Al or Ga) ratio of 70:30. Using in situ and operando X-ray absorption spectroscopy and X-ray powder diffraction, we investigate the structural and redox... (More)

The transformation of CO2 and green hydrogen into methanol presents a sustainable route for chemical and fuel production. Conventional methanol synthesis catalysts, such as Cu/ZnO/Al2O3, employ Al2O3 as a structural promoter, while Ga2O3 has recently emerged as a promising alternative. This study compares Cu-based catalysts supported on Al2O3 (CA) and Ga2O3 (CG), prepared via coprecipitation of layered double hydroxide precursors with identical molar Cu:M (M = Al or Ga) ratio of 70:30. Using in situ and operando X-ray absorption spectroscopy and X-ray powder diffraction, we investigate the structural and redox dynamics of Ga during activation and CO2 hydrogenation. Gallium from its precursor state undergoes several phase transitions. At elevated temperatures, Ga exhibits redox activity, transitioning from Ga3+ to metallic Ga0 and forming CuxGay alloys at 480 °C, followed by de-alloying and re-oxidation at even higher temperatures. Our results suggest that the beneficial role of Ga reported in literature arises from metal-oxide interfacial effects rather than bulk alloying. Excess Ga2O3 leads to low conversion levels and pronounced deactivation compared to the Al2O3-supported Cu catalyst and thus should be prevented. These findings highlight the importance of controlling promoter loading and dynamic behavior in catalyst design to optimize activity, stability, and selectivity for CO2-to-methanol conversion.

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organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
CO-hydrogenation, Cu/AlO, Cu/GaO, operando XAS, operando XRPD
in
ChemCatChem
volume
18
issue
2
article number
e01338
publisher
Wiley-VCH Verlag
external identifiers
  • scopus:105028087495
ISSN
1867-3880
DOI
10.1002/cctc.202501338
language
English
LU publication?
yes
id
abdc3a61-0330-47cf-b2b8-e82d9c9a21c6
date added to LUP
2026-02-19 13:44:48
date last changed
2026-02-19 13:45:46
@article{abdc3a61-0330-47cf-b2b8-e82d9c9a21c6,
  abstract     = {{<p>The transformation of CO<sub>2</sub> and green hydrogen into methanol presents a sustainable route for chemical and fuel production. Conventional methanol synthesis catalysts, such as Cu/ZnO/Al<sub>2</sub>O<sub>3</sub>, employ Al<sub>2</sub>O<sub>3</sub> as a structural promoter, while Ga<sub>2</sub>O<sub>3</sub> has recently emerged as a promising alternative. This study compares Cu-based catalysts supported on Al<sub>2</sub>O<sub>3</sub> (CA) and Ga<sub>2</sub>O<sub>3</sub> (CG), prepared via coprecipitation of layered double hydroxide precursors with identical molar Cu:M (M = Al or Ga) ratio of 70:30. Using in situ and operando X-ray absorption spectroscopy and X-ray powder diffraction, we investigate the structural and redox dynamics of Ga during activation and CO<sub>2</sub> hydrogenation. Gallium from its precursor state undergoes several phase transitions. At elevated temperatures, Ga exhibits redox activity, transitioning from Ga<sup>3+</sup> to metallic Ga<sup>0</sup> and forming Cu<sub>x</sub>Ga<sub>y</sub> alloys at 480 °C, followed by de-alloying and re-oxidation at even higher temperatures. Our results suggest that the beneficial role of Ga reported in literature arises from metal-oxide interfacial effects rather than bulk alloying. Excess Ga<sub>2</sub>O<sub>3</sub> leads to low conversion levels and pronounced deactivation compared to the Al<sub>2</sub>O<sub>3</sub>-supported Cu catalyst and thus should be prevented. These findings highlight the importance of controlling promoter loading and dynamic behavior in catalyst design to optimize activity, stability, and selectivity for CO<sub>2</sub>-to-methanol conversion.</p>}},
  author       = {{Baumgarten, Lorena and Hauberg, Patrik and Mangelsen, Sebastian and Coppex, Claude and Jelic, Jelena and Schulte, Mariam Lena and Wolf, Anna and Taetz, Bjarne and Reller, Hinrich Klamor and Saedimarghmaleki, Morteza and Studt, Felix and Saraçi, Erisa and Just, Justus and Behrens, Malte and Grunwaldt, Jan Dierk}},
  issn         = {{1867-3880}},
  keywords     = {{CO-hydrogenation; Cu/AlO; Cu/GaO; operando XAS; operando XRPD}},
  language     = {{eng}},
  number       = {{2}},
  publisher    = {{Wiley-VCH Verlag}},
  series       = {{ChemCatChem}},
  title        = {{Gallia- Versus Alumina-Supported Cu : Dynamics of Ga in Catalysts for Green Methanol Production}},
  url          = {{http://dx.doi.org/10.1002/cctc.202501338}},
  doi          = {{10.1002/cctc.202501338}},
  volume       = {{18}},
  year         = {{2026}},
}