Bimetallic oxide catalysts for CO2 hydrogenation to methanol: Recent advances and challenges

doi:10.1016/S1872-2067(25)64689-4

Chinese Journal of Catalysis ›› 2025, Vol. 73: 62-78.DOI: 10.1016/S1872-2067(25)64689-4

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Bimetallic oxide catalysts for CO₂ hydrogenation to methanol: Recent advances and challenges

Jian-Feng Wu^a^,^b^,¹(), Li-Ye Liang^a^,^b^,¹, Zheng Che^b^,¹, Yu-Ting Miao^b, Lingjun Chou^a()

^aState Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China
^bState Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metals Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, Gansu, China

Received:2024-12-28 Accepted:2025-03-07 Online:2025-06-18 Published:2025-06-12
Contact: *E-mail: wjf@licp.cas.cn (J.-F. Wu),ljchou@licp.cas.cn (L. Chou).
About author:Jian-Feng Wu, PhD, is an Associate Research Fellow at the State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences. He obtained his B.A. degree in 2008 and Ph.D. degree in 2014 from Lanzhou University, China. Following this, he conducted postdoctoral research at the Center for Environmentally Beneficial Catalysis at the University of Kansas, USA, from 2014 to 2017. Wu has held positions at the School of Chemistry and Chemical Engineering, Lanzhou University (2017-2023), and currently at the State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences (since 2023). He was recognized as a beneficiary of the key talent program in Gansu Province in 2024 and the talent introduction program of the Chinese Academy of Sciences in 2025. His research primarily focuses on low carbon catalysis, encompassing CO₂ hydrogenation to methanol and methane conversion to CH₃OH, CH₃COOH, and HCOOH.
Lingjun Chou, PhD, Professor in the State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences. Research major field is on catalytic material and catalytic processes related to energy conversion.
¹ Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22472181);Key Talent Project of Gansu Province;Natural Science Foundation of Gansu Province(24JRRA050);enterprise project of China Northern Rare Earth (Group) High-Tech Co., Ltd(BFXT-2023-D-0048);Hui-Chun Chin and Tsung-Dao Lee Chinese Undergraduate Research Endowment(LZU-JZH2534)

Abstract

Abstract:

Against the backdrop of global energy and environmental crises, the technology of CO₂ hydrogenation to produce methanol is garnering widespread attention as an innovative carbon capture and utilization solution. Bimetallic oxide catalysts have emerged as the most promising research subject in the field due to their exceptional catalytic performance and stability. The performance of bimetallic oxide catalysts is influenced by multiple factors, including the selection of carrier materials, the addition of promoters, and the synthesis process. Different types of bimetallic oxide catalysts exhibit significant differences in microstructure, surface active sites, and electronic structure, which directly determine the yield and selectivity of methanol. Although bimetallic oxide catalysts offer significant advantages over traditional copper-based catalysts, they still encounter challenges related to activity and cost. In order to enhance catalyst performance, future investigations must delve into microstructure control, surface modification, and reaction kinetics.

Key words: CO₂ hydrogenation, Methanol, Bimetallic oxide catalyst, Catalytic performance, Reaction mechanism

Jian-Feng Wu, Li-Ye Liang, Zheng Che, Yu-Ting Miao, Lingjun Chou. Bimetallic oxide catalysts for CO₂ hydrogenation to methanol: Recent advances and challenges[J]. Chinese Journal of Catalysis, 2025, 73: 62-78.

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Catalyst	Preparation method	n_H2/n_CO2	T (K)	P (MPa)	GHSV ^a mL g_cat^‒1 h^‒1	CO₂ Conv. (%)	Methanol Sel. (%)	STY ^b g_MeOH kg_cat^‒1 h^‒1	Ref.
ZnO-ZrO₂	co-precipitation	3/1	593	5	24000	10	86	737	[36]
ZnO-ZrO₂	co-precipitation	3/1	573	2	24000	3.4	87	250	[36]
ZnO-ZrO₂	EISA^c	3/1	593	2	24000	6.4	78.5	413	[37]
ZnO/t-ZrO₂	microreaction	3/1	593	3	12000	9.2	93.1	350	[38]
ZnO_x/ZrO₂-600	impregnation	3/1	573	2	9000	5.5	75.1	106	[39]
ZnZrO_x	flame spray pyrolysis	4/1	593	5	24000	8.7	78.3	460	[40]
ZnZrO_x	reflux ammonia	6/1	563	5	24000	8.4	95.6	377	[41]
Pd/CNT+ZnZrO_x	mechanical mixed	4/1	593	5	24000	18.1	66.3	900	[42]
CdZrO_x	co-precipitation	3/1	573	2	24000^d	5.5	80	—	[43]
GaZrO_x	co-precipitation	3/1	573	2	24000^d	2.4	75	—	[43]
GaZrO_x	EISA^c	3/1	603	4	24000	10.8	72.9^e	760^f	[44]
ZnO-ZrO₂ (UiO-66)	thermal pyrolysis	3/1	593	3	18000	5.7	70	—	[45]
ZnO-ZrO₂ (MOF-808)	postsynthetic treatment	3/1	523	4	9000^d	2.1	>99	30.4	[46]
h-In₂O₃(104)	hydrothermal	6/1	573	5	9000	17.6	92.4	288	[47]
In₂O₃/ZrO₂	impregnation	4/1	573	5	16000^d	5.2	99.8	295	[48]
In₂O₃/ZrO₂	hydrothermal	3/1	573	3	12000^d	8.83	77.3	269	[49]
20MnO_x-Co₃O₄	sol-gel	3/1	523	1	88800^d	—	30	—	[50]
Ga-ZnZrO_x	co-precipitation	3/1	593	5	24000	8.8	87.5	630	[51]

Catalyst	Preparation method	n_H2/n_CO2	T (K)	P (MPa)	GHSV ^a mL g_cat^‒1 h^‒1	CO₂ Conv. (%)	Methanol Sel. (%)	STY ^b g_MeOH kg_cat^‒1 h^‒1	Ref.
ZnO-ZrO₂	co-precipitation	3/1	593	5	24000	10	86	737	[36]
ZnO-ZrO₂	co-precipitation	3/1	573	2	24000	3.4	87	250	[36]
ZnO-ZrO₂	EISA^c	3/1	593	2	24000	6.4	78.5	413	[37]
ZnO/t-ZrO₂	microreaction	3/1	593	3	12000	9.2	93.1	350	[38]
ZnO_x/ZrO₂-600	impregnation	3/1	573	2	9000	5.5	75.1	106	[39]
ZnZrO_x	flame spray pyrolysis	4/1	593	5	24000	8.7	78.3	460	[40]
ZnZrO_x	reflux ammonia	6/1	563	5	24000	8.4	95.6	377	[41]
Pd/CNT+ZnZrO_x	mechanical mixed	4/1	593	5	24000	18.1	66.3	900	[42]
CdZrO_x	co-precipitation	3/1	573	2	24000^d	5.5	80	—	[43]
GaZrO_x	co-precipitation	3/1	573	2	24000^d	2.4	75	—	[43]
GaZrO_x	EISA^c	3/1	603	4	24000	10.8	72.9^e	760^f	[44]
ZnO-ZrO₂ (UiO-66)	thermal pyrolysis	3/1	593	3	18000	5.7	70	—	[45]
ZnO-ZrO₂ (MOF-808)	postsynthetic treatment	3/1	523	4	9000^d	2.1	>99	30.4	[46]
h-In₂O₃(104)	hydrothermal	6/1	573	5	9000	17.6	92.4	288	[47]
In₂O₃/ZrO₂	impregnation	4/1	573	5	16000^d	5.2	99.8	295	[48]
In₂O₃/ZrO₂	hydrothermal	3/1	573	3	12000^d	8.83	77.3	269	[49]
20MnO_x-Co₃O₄	sol-gel	3/1	523	1	88800^d	—	30	—	[50]
Ga-ZnZrO_x	co-precipitation	3/1	593	5	24000	8.8	87.5	630	[51]

Catalyst type	Price range ($ kg⁻¹)
Cu/ZnO/Al₂O₃	~80 to ~200
ZnO-ZrO₂	~130 to ~275
GaZrO_x	~230 to ~400
In₂O₃/ZrO₂	~300 to ~600

Catalyst type	Price range ($ kg⁻¹)
Cu/ZnO/Al₂O₃	~80 to ~200
ZnO-ZrO₂	~130 to ~275
GaZrO_x	~230 to ~400
In₂O₃/ZrO₂	~300 to ~600

Bimetallic oxide catalysts for CO₂ hydrogenation to methanol: Recent advances and challenges

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