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Electroreduction of CO2 to methane with triazole molecular catalysts

Nature Energy volume 9, pages 1397–1406 (2024)Cite this article

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Abstract

The electrochemical CO2 reduction reaction towards value-added fuel and feedstocks often relies on metal-based catalysts. Organic molecular catalysts, which are more acutely tunable than metal catalysts, are still unable to catalyse CO2 to hydrocarbons under industrially relevant current densities for long-term operation, and the catalytic mechanism is still elusive. Here we report 3,5-diamino-1,2,4-triazole-based membrane electrode assemblies for CO2-to-CH4 conversion with Faradaic efficiency of (52 ± 4)% and turnover frequency of 23,060 h−1 at 250 mA cm−2. Our mechanistic studies suggest that the CO2 reduction at the 3,5-diamino-1,2,4-triazole electrode proceeds through the intermediary *CO2–*COOH–*C(OH)2–*COH to produce CH4 due to the spatially distributed active sites and the suitable energy level of the molecular orbitals. A pilot system operated under a total current of 10 A (current density = 123 mA cm−2) for 10 h is able to produce CH4 at a rate of 23.0 mmol h−1.

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Fig. 1: Catalyst screening for CO2RR.
Fig. 2: CO2RR performance on molecular catalysts.
Fig. 3: Mechanistic insights into the CO2 to CH4 on DAT.
Fig. 4: Scaled-up molecular electrode for power to fuel.

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The authors declare that all data supporting the findings of this study are available within the paper, Supplementary Information and Source Data files. Source data are provided with this paper.

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Acknowledgements

Y.W., Z.X., W.W. and Q.L. acknowledge the financial support from the Excellent Young Scientist Fund (Hong Kong and Macau) from the National Natural Science Foundation of China (project number 22222208) and the Research Grants Council of the Hong Kong Special Administrative Region (project number 14307322). The computational study is supported by the Marsden Fund Council from Government funding (21-UOA-237) and Catalyst: Seeding General Grant (22-UOA-031-CGS), managed by Royal Society Te Apārangi. Z.W. and R.L. wish to acknowledge the use of New Zealand eScience Infrastructure (NeSI) high-performance computing facilities, consulting support and/or training services as part of this research. S.-F.H., Z.-Y.L. and H.-J.T. gratefully acknowledge the support from the National Science and Technology Council, Taiwan (contract number NSTC 112-2628-M-A49-001) and the support from the Yushan Young Scholar Program and the Center for Emergent Functional Matter Science of National Yang Ming Chiao Tung University, Ministry of Education, Taiwan.

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  1. These authors contributed equally: Zhanyou Xu, Ruihu Lu, Zih-Yi Lin.

Authors and Affiliations

  1. Department of Chemistry, The Chinese University of Hong Kong, Hong Kong S. A. R., Hong Kong, China

    Zhanyou Xu, Weixing Wu, Qian Lu, Chunshan Song, Jimmy C. Yu & Ying Wang

  2. School of Chemical Sciences, University of Auckland, Auckland, New Zealand

    Ruihu Lu & Ziyun Wang

  3. Department of Applied Chemistry and Center for Emergent Functional Matter Science, National Yang Ming Chiao Tung University, Hsinchu, Taiwan

    Zih-Yi Lin, Hsin-Jung Tsai & Sung-Fu Hung

  4. Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, NY, USA

    Yuguang C. Li

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Contributions

Y.W., Z.W. and S.-F.H. designed and supervised the project. Z.X. carried out the electrochemical measurements, NMR, Fourier transform infrared, X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICP-MS), X-ray fluorescence (XRF) and scanning electron microscopy (SEM) measurements and analysed the data. R.L. carried out DFT calculations and analysed the data. Z.-Y.L. and H.-J.T. performed in situ Raman analysis. Z.X., R.L., W.W., Q.L., Y.C.L., C.S., J.C.Y., S.-F.H., Z.W. and Y.W. co-wrote the paper. All authors discussed the results and contributed to the preparation of the paper.

Corresponding authors

Correspondence to Sung-Fu Hung, Ziyun Wang or Ying Wang.

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Competing interests

Y.W. and Z.X. declare that a US provisional patent titled ‘Small Molecules Based Electrode for Green Methane and Town Gas Production from Carbon Dioxide at High Rates’ has been granted (application number 63/587,837), and a Patent Cooperation Treaty (PCT) application is filed (application number PCT/CN2024/103140). The other authors declare no competing interests.

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Nature Energy thanks Mei Wang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Methods 1 and 2, Notes 1–4, Figs. 1–35 and Tables 1–12.

Supplementary Data 1

Source data for supplementary figures.

Supplementary Data 2

The atomic coordinates of the optimized models.

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Source Data Fig. 2

Statistical source data.

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Xu, Z., Lu, R., Lin, ZY. et al. Electroreduction of CO2 to methane with triazole molecular catalysts. Nat Energy 9, 1397–1406 (2024). https://doi.org/10.1038/s41560-024-01645-0

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