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Domino electroreduction of CO2 to methanol on a molecular catalyst

Author

Listed:
  • Yueshen Wu

    (Yale University
    Yale University)

  • Zhan Jiang

    (Southern University of Science and Technology)

  • Xu Lu

    (Yale University
    Yale University)

  • Yongye Liang

    (Southern University of Science and Technology)

  • Hailiang Wang

    (Yale University
    Yale University)

Abstract

Electrochemical carbon dioxide (CO2) reduction can in principle convert carbon emissions to fuels and value-added chemicals, such as hydrocarbons and alcohols, using renewable energy, but the efficiency of the process is limited by its sluggish kinetics1,2. Molecular catalysts have well defined active sites and accurately tailorable structures that allow mechanism-based performance optimization, and transition-metal complexes have been extensively explored in this regard. However, these catalysts generally lack the ability to promote CO2 reduction beyond the two-electron process to generate more valuable products1,3. Here we show that when immobilized on carbon nanotubes, cobalt phthalocyanine—used previously to reduce CO2 to primarily CO—catalyses the six-electron reduction of CO2 to methanol with appreciable activity and selectivity. We find that the conversion, which proceeds via a distinct domino process with CO as an intermediate, generates methanol with a Faradaic efficiency higher than 40 per cent and a partial current density greater than 10 milliamperes per square centimetre at −0.94 volts with respect to the reversible hydrogen electrode in a near-neutral electrolyte. The catalytic activity decreases over time owing to the detrimental reduction of the phthalocyanine ligand, which can be suppressed by appending electron-donating amino substituents to the phthalocyanine ring. The improved molecule-based electrocatalyst converts CO2 to methanol with considerable activity and selectivity and with stable performance over at least 12 hours.

Suggested Citation

  • Yueshen Wu & Zhan Jiang & Xu Lu & Yongye Liang & Hailiang Wang, 2019. "Domino electroreduction of CO2 to methanol on a molecular catalyst," Nature, Nature, vol. 575(7784), pages 639-642, November.
  • Handle: RePEc:nat:nature:v:575:y:2019:i:7784:d:10.1038_s41586-019-1760-8
    DOI: 10.1038/s41586-019-1760-8
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    1. Kumar, Vikas & Nabaterega, Resty & Khoei, Shiva & Eskicioglu, Cigdem, 2021. "Insight into interactions between syntrophic bacteria and archaea in anaerobic digestion amended with conductive materials," Renewable and Sustainable Energy Reviews, Elsevier, vol. 144(C).
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    3. Wenjun Fan & Zhiyao Duan & Wei Liu & Rashid Mehmood & Jiating Qu & Yucheng Cao & Xiangyang Guo & Jun Zhong & Fuxiang Zhang, 2023. "Rational design of heterogenized molecular phthalocyanine hybrid single-atom electrocatalyst towards two-electron oxygen reduction," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
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    6. Haozhou Yang & Na Guo & Shibo Xi & Yao Wu & Bingqing Yao & Qian He & Chun Zhang & Lei Wang, 2024. "Potential-driven structural distortion in cobalt phthalocyanine for electrocatalytic CO2/CO reduction towards methanol," Nature Communications, Nature, vol. 15(1), pages 1-14, December.
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    10. Jia-Wei Wang & Fengyi Zhao & Lucia Velasco & Maxime Sauvan & Dooshaye Moonshiram & Martina Salati & Zhi-Mei Luo & Sheng He & Tao Jin & Yan-Fei Mu & Mehmed Z. Ertem & Tianquan Lian & Antoni Llobet, 2024. "Molecular catalyst coordinatively bonded to organic semiconductors for selective light-driven CO2 reduction in water," Nature Communications, Nature, vol. 15(1), pages 1-14, December.
    11. Shoujie Li & Wei Chen & Xiao Dong & Chang Zhu & Aohui Chen & Yanfang Song & Guihua Li & Wei Wei & Yuhan Sun, 2022. "Hierarchical micro/nanostructured silver hollow fiber boosts electroreduction of carbon dioxide," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    12. Philipp Keller & Michael A. Reiter & Patrick Kiefer & Thomas Gassler & Lucas Hemmerle & Philipp Christen & Elad Noor & Julia A. Vorholt, 2022. "Generation of an Escherichia coli strain growing on methanol via the ribulose monophosphate cycle," Nature Communications, Nature, vol. 13(1), pages 1-13, December.
    13. Baiyu Yang & Ling Chen & Songlin Xue & Hao Sun & Kun Feng & Yufeng Chen & Xiang Zhang & Long Xiao & Yongze Qin & Jun Zhong & Zhao Deng & Yan Jiao & Yang Peng, 2022. "Electrocatalytic CO2 reduction to alcohols by modulating the molecular geometry and Cu coordination in bicentric copper complexes," Nature Communications, Nature, vol. 13(1), pages 1-13, December.
    14. Yizhou Dai & Huan Li & Chuanhao Wang & Weiqing Xue & Menglu Zhang & Donghao Zhao & Jing Xue & Jiawei Li & Laihao Luo & Chunxiao Liu & Xu Li & Peixin Cui & Qiu Jiang & Tingting Zheng & Songqi Gu & Yao , 2023. "Manipulating local coordination of copper single atom catalyst enables efficient CO2-to-CH4 conversion," Nature Communications, Nature, vol. 14(1), pages 1-12, December.
    15. Yirong Tang & Zhan Jiang & Yubo Yuan & Li Xu & Chuyao Jin & Bulin Chen & Zhichao Lin & Jie Zao & Jianwei Du & Xiao Zhang & Xiang Gao & Yongye Liang, 2024. "Selective electrosynthesis of hydroxylamine from aqueous nitrate/nitrite by suppressing further reduction," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    16. Ji Wei Sun & Xuefeng Wu & Peng Fei Liu & Jiacheng Chen & Yuanwei Liu & Zhen Xin Lou & Jia Yue Zhao & Hai Yang Yuan & Aiping Chen & Xue Lu Wang & Minghui Zhu & Sheng Dai & Hua Gui Yang, 2023. "Scalable synthesis of coordinatively unsaturated metal-nitrogen sites for large-scale CO2 electrolysis," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
    17. Jiahui Bi & Pengsong Li & Jiyuan Liu & Shuaiqiang Jia & Yong Wang & Qinggong Zhu & Zhimin Liu & Buxing Han, 2023. "Construction of 3D copper-chitosan-gas diffusion layer electrode for highly efficient CO2 electrolysis to C2+ alcohols," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    18. Han Li & Leitao Xu & Shuowen Bo & Yujie Wang & Han Xu & Chen Chen & Ruping Miao & Dawei Chen & Kefan Zhang & Qinghua Liu & Jingjun Shen & Huaiyu Shao & Jianfeng Jia & Shuangyin Wang, 2024. "Ligand engineering towards electrocatalytic urea synthesis on a molecular catalyst," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    19. Jun Bu & Siyu Chang & Jinjin Li & Sanyin Yang & Wenxiu Ma & Zhenpeng Liu & Siying An & Yanan Wang & Zhen Li & Jian Zhang, 2023. "Highly selective electrocatalytic alkynol semi-hydrogenation for continuous production of alkenols," Nature Communications, Nature, vol. 14(1), pages 1-9, December.

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