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Effect of F Doping on CO2 Electrocatalytic Performance of Zinc-Based Rare Earth Layered Double Hydroxides

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Abstract

As one of the major greenhouse gases, CO2 is significantly influencing global climate change. Efficient utilization of CO2 is considered an important approach to address the current environmental and energy challenges. In particular, using CO2 as a raw material for the production of hydrocarbons is an attractive strategy for reducing carbon emissions while ensuring a stable energy supply. In this study, fluorine (F) doped ZnLa layered double hydroxide (F-ZL-LDH) and F-doped ZnCe layered double hydroxide (F-ZC-LDH) were prepared using a hydrothermal synthesis method. The materials’ structural composition and morphology were analyzed using X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The research results demonstrate that both catalysts exhibit abundant active sites, high selectivity, and excellent electrocatalytic performance for CO2RR to generate CO, with Faradaic efficiencies reaching 89.29% and 89.87% for F-ZL-LDH and F-ZC-LDH, respectively. The doping of fluorine results in the presence of numerous defects and pore structures on the surfaces of F-ZC-LDH and F-ZL-LDH, increasing the surface active area and enhancing charge transfer rates. Meanwhile, F doping facilitates CO2 adsorption and mass transfer on the electrode surface. Moreover, F doping in the catalysts also restricts the adsorption and desorption of *H during the competing hydrogen evolution reaction (HER) process.

Graphical Abstract

The effective management and rapid conversion of CO2 to various organic compounds and chemical fuels to facilitate carbon cycle and reduce atmospheric CO2 concentration have become a hot topic in current technological advances worldwide. Among the various electrocatalytic CO2 reduction reaction (CO2RR) products, carbon monoxide (CO) is the product with the highest kinetic accessibility. In this paper, F-ZL-LDH and F-ZC-LDH composite materials were prepared using a hydrothermal synthesis method. Based on preliminary studies, a molar ratio of M2+:M3+ of 3:1 was determined to provide better catalytic performance,and ammonium fluoride content of 30% of the cation molar ratio of M2+ + M3+. The introduction of fluorine (F) improves the catalytic performance of both materials, with a greater enhancement observed for ZL-LDH. At − 1.3V vs. RHE potential, The research results demonstrate that both catalysts exhibit abundant active sites, high selectivity, and excellent electrocatalytic performance for CO2RR to generate CO, with Faradaic efficiencies reaching 89.29% and 89.87% for F-ZL-LDH and F-ZC-LDH, respectively. the fluorination treatment of ZC-LDH and ZL-LDH catalysts significantly enhances their electrocatalytic activity for the CO2 reduction reaction, particularly for the production of CO. These findings contribute to the development of efficient catalysts for CO2 electrochemical reduction and hold promise for advancing the field of CO2 utilization and renewable energy conversion.

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Acknowledgements

This work was financially supported by the Chinese National Natural Science Foundation (U20A20125), the Foreign experts project of Ningxia Hui Autonomous Region, the Innovation team of clean energy and green chemical Engineering, State Ethnic Affairs Commission, and the Ningxia low-grade resource high-value utilization and environmental chemical integration technology innovation team project, North Minzu University.

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, North Minzu University, Yinchuan, 750021, People’s Republic of China

    Jinyu Wang, Tianxia Liu & Rongsheng Xu

  2. Key Laboratory for Chemical Engineering and Technology, State Ethnic Affairs Commission, North Minzu University, Yinchuan, 750021, People’s Republic of China

    Tianxia Liu

  3. School of Materials Science and Chemistry, Southwest University of Science and Technology, Mianyang, 621010, People’s Republic of China

    Yaping Zhang

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  1. Jinyu Wang
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  2. Tianxia Liu
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  3. Rongsheng Xu
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Contributions

JW and TL: conceived and designed the experiments; JW: performed the experiments; TL: supplied the condition of experiments; RX and YZ: helped some results analysis and discussion; JW and TL: cooperated to complete the paper.

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Correspondence to Tianxia Liu.

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Wang, J., Liu, T., Xu, R. et al. Effect of F Doping on CO2 Electrocatalytic Performance of Zinc-Based Rare Earth Layered Double Hydroxides. Catal Lett (2024). https://doi.org/10.1007/s10562-023-04526-5

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