Synthesis of methanol via CO2 hydrogenation catalyzed by La2O2CO3/Cu catalysts

Jun He; Chenglong Yu; Zhijuan Zhao; Bo Guan; Bin Zhang; Yanru Zhang; Longbo Zhang; Yanyan Wang; Ying Wang; Yahui Wu; Jia Guo; Yang Li; Tianbin Wu; Qingli Qian; Hongxing Wang; Buxing Han

doi:10.26599/NR.2025.94907130

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Research Article | Open Access

Synthesis of methanol via CO₂ hydrogenation catalyzed by La₂O₂CO₃/Cu catalysts

Jun He^{¹^,²}, Chenglong Yu^{¹^,³}, Zhijuan Zhao^⁴, Bo Guan^⁴, Bin Zhang^¹, Yanru Zhang^{¹^,³}, Longbo Zhang^{¹^,³}, Yanyan Wang^{¹^,³}, Ying Wang^¹, Yahui Wu^¹, Jia Guo^{¹^,³}, Yang Li^{¹^,³}, Tianbin Wu^¹, Qingli Qian^{¹^,³}(), Hongxing Wang^²(), Buxing Han^{¹^,³^,⁵}

()

1Beijing National Laboratory for Molecular Sciences, Key Laboratory of Colloid and Interface and Thermodynamics, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

2College of Chemical Engineering and Materials Science, Tianjin University of Science and Technology, Tianjin 300457, China

3School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049, China

4Center for Physicochemical Analysis Measurements, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

5Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular and Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China

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The poor and rich electrons of Cu surface could be derived from different Cu loading content in La₂O₂CO₃/Cu catalysts, which could remarkably affect the selectivity of CH₄ and CH₃OH in CO₂ hydrogenation.

Abstract

The development of efficient Cu-based heterogeneous catalysts for CO₂ hydrogenation to methanol has been an appealing subject. Inspired by the concept of inverse catalysts, a series of La₂O₂CO₃/Cu nanorod composites with varying Cu contents (denoted as LOC/Cu-x, where x stands for the mass ratio of La and Cu in the catalysts) were prepared by combining coprecipitation and calcination processes. Remarkable composition-dependence of catalytic activity and selectivity were observed when different LOC/Cu-x (x = 0.1, 0.2, 0.5, 1, 3 and 5) were used to catalyze the CO₂ hydrogenation. The predominant product shifted from methane to methanol with the increasing Cu content. The highest reaction rate (13.3 mmol·g_Cu⁻¹·h⁻¹) and methanol selectivity (85.5%) were achieved when LOC/Cu-1 was tested at 200 °C. The LOC was not active for the reaction, while the Cu itself displayed poor catalytic performance. The Cu–LOC interactions significantly affected the nature of the catalysts, including mutual electron transfer, crystal structure, morphology, porosity, surface Cu valence and capability of adsorbing the reactant gases, etc., which account for the outstanding behavior of the LOC/Cu-1 catalyst. This work provides a new strategy for the design and optimization of Cu-based catalysts.

Keywords

CO₂ hydrogenation methanol heterogeneous catalysts Cu–La₂O₂CO₃ (LOC) interaction

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References

[1]

He, M. Y.; Sun, Y. H.; Han, B. X. Green carbon science: Efficient carbon resource processing, utilization, and recycling towards carbon neutrality. Angew. Chem. 2022, 134, e202112835.

Entries	Solvent	T (°C)	Selectivity (C-mol.%)			Activity (mmol·g_Cu⁻¹·h⁻¹)
Entries	Solvent	T (°C)	MeOH	CO	CH₄	Activity (mmol·g_Cu⁻¹·h⁻¹)
^aReaction conditions: catalyst 20 mg, solvent 2 mL, initial pressure 8.0 MPa (H₂/CO₂ = 3:1), 200 °C, and 8 h.
Entry 1	None	200	—	—	—	—
Entry 2	Cyclohexane	200	2.1	83.4	14.5	0.11
Entry 3	n-Decane	200	18.7	72.2	9.1	0.58
Entry 4	H₂O	200	63.2	30	6.8	8.9
Entry 5	NMP	200	14.3	27.5	58.2	4.9
Entry 6	DMI	200	85.5	9.1	5.4	13.3