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Molecular tuning of CO2-to-ethylene conversion

Author

Listed:
  • Fengwang Li

    (University of Toronto)

  • Arnaud Thevenon

    (California Institute of Technology)

  • Alonso Rosas-Hernández

    (California Institute of Technology)

  • Ziyun Wang

    (University of Toronto)

  • Yilin Li

    (University of Toronto)

  • Christine M. Gabardo

    (University of Toronto)

  • Adnan Ozden

    (University of Toronto)

  • Cao Thang Dinh

    (University of Toronto)

  • Jun Li

    (University of Toronto
    University of Toronto)

  • Yuhang Wang

    (University of Toronto)

  • Jonathan P. Edwards

    (University of Toronto)

  • Yi Xu

    (University of Toronto)

  • Christopher McCallum

    (University of Toronto)

  • Lizhi Tao

    (University of California)

  • Zhi-Qin Liang

    (University of Toronto)

  • Mingchuan Luo

    (University of Toronto)

  • Xue Wang

    (University of Toronto)

  • Huihui Li

    (University of Toronto)

  • Colin P. O’Brien

    (University of Toronto)

  • Chih-Shan Tan

    (University of Toronto)

  • Dae-Hyun Nam

    (University of Toronto)

  • Rafael Quintero-Bermudez

    (University of Toronto)

  • Tao-Tao Zhuang

    (University of Toronto)

  • Yuguang C. Li

    (University of Toronto)

  • Zhiji Han

    (California Institute of Technology)

  • R. David Britt

    (University of California)

  • David Sinton

    (University of Toronto)

  • Theodor Agapie

    (California Institute of Technology)

  • Jonas C. Peters

    (California Institute of Technology)

  • Edward H. Sargent

    (University of Toronto)

Abstract

The electrocatalytic reduction of carbon dioxide, powered by renewable electricity, to produce valuable fuels and feedstocks provides a sustainable and carbon-neutral approach to the storage of energy produced by intermittent renewable sources1. However, the highly selective generation of economically desirable products such as ethylene from the carbon dioxide reduction reaction (CO2RR) remains a challenge2. Tuning the stabilities of intermediates to favour a desired reaction pathway can improve selectivity3–5, and this has recently been explored for the reaction on copper by controlling morphology6, grain boundaries7, facets8, oxidation state9 and dopants10. Unfortunately, the Faradaic efficiency for ethylene is still low in neutral media (60 per cent at a partial current density of 7 milliamperes per square centimetre in the best catalyst reported so far9), resulting in a low energy efficiency. Here we present a molecular tuning strategy—the functionalization of the surface of electrocatalysts with organic molecules—that stabilizes intermediates for more selective CO2RR to ethylene. Using electrochemical, operando/in situ spectroscopic and computational studies, we investigate the influence of a library of molecules, derived by electro-dimerization of arylpyridiniums11, adsorbed on copper. We find that the adhered molecules improve the stabilization of an ‘atop-bound’ CO intermediate (that is, an intermediate bound to a single copper atom), thereby favouring further reduction to ethylene. As a result of this strategy, we report the CO2RR to ethylene with a Faradaic efficiency of 72 per cent at a partial current density of 230 milliamperes per square centimetre in a liquid-electrolyte flow cell in a neutral medium. We report stable ethylene electrosynthesis for 190 hours in a system based on a membrane-electrode assembly that provides a full-cell energy efficiency of 20 per cent. We anticipate that this may be generalized to enable molecular strategies to complement heterogeneous catalysts by stabilizing intermediates through local molecular tuning.

Suggested Citation

  • Fengwang Li & Arnaud Thevenon & Alonso Rosas-Hernández & Ziyun Wang & Yilin Li & Christine M. Gabardo & Adnan Ozden & Cao Thang Dinh & Jun Li & Yuhang Wang & Jonathan P. Edwards & Yi Xu & Christopher , 2020. "Molecular tuning of CO2-to-ethylene conversion," Nature, Nature, vol. 577(7791), pages 509-513, January.
  • Handle: RePEc:nat:nature:v:577:y:2020:i:7791:d:10.1038_s41586-019-1782-2
    DOI: 10.1038/s41586-019-1782-2
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    Citations

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    Cited by:

    1. Ke Xie & Adnan Ozden & Rui Kai Miao & Yuhang Li & David Sinton & Edward H. Sargent, 2022. "Eliminating the need for anodic gas separation in CO2 electroreduction systems via liquid-to-liquid anodic upgrading," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    2. Xinyi Ren & Jian Zhao & Xuning Li & Junming Shao & Binbin Pan & Aude Salamé & Etienne Boutin & Thomas Groizard & Shifu Wang & Jie Ding & Xiong Zhang & Wen-Yang Huang & Wen-Jing Zeng & Chengyu Liu & Ya, 2023. "In-situ spectroscopic probe of the intrinsic structure feature of single-atom center in electrochemical CO/CO2 reduction to methanol," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    3. Yufei Cao & Zhu Chen & Peihao Li & Adnan Ozden & Pengfei Ou & Weiyan Ni & Jehad Abed & Erfan Shirzadi & Jinqiang Zhang & David Sinton & Jun Ge & Edward H. Sargent, 2023. "Surface hydroxide promotes CO2 electrolysis to ethylene in acidic conditions," Nature Communications, Nature, vol. 14(1), pages 1-8, December.
    4. Jongyoun Kim & Taemin Lee & Hyun Dong Jung & Minkyoung Kim & Jungsu Eo & Byeongjae Kang & Hyeonwoo Jung & Jaehyoung Park & Daewon Bae & Yujin Lee & Sojung Park & Wooyul Kim & Seoin Back & Youngu Lee &, 2024. "Vitamin C-induced CO2 capture enables high-rate ethylene production in CO2 electroreduction," Nature Communications, Nature, vol. 15(1), pages 1-13, December.
    5. Meng Wang & Bingqing Wang & Jiguang Zhang & Shibo Xi & Ning Ling & Ziyu Mi & Qin Yang & Mingsheng Zhang & Wan Ru Leow & Jia Zhang & Yanwei Lum, 2024. "Acidic media enables oxygen-tolerant electrosynthesis of multicarbon products from simulated flue gas," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    6. Siqi Zhao & Oliver Christensen & Zhaozong Sun & Hongqing Liang & Alexander Bagger & Kristian Torbensen & Pegah Nazari & Jeppe Vang Lauritsen & Steen Uttrup Pedersen & Jan Rossmeisl & Kim Daasbjerg, 2023. "Steering carbon dioxide reduction toward C–C coupling using copper electrodes modified with porous molecular films," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    7. Sung-Fu Hung & Aoni Xu & Xue Wang & Fengwang Li & Shao-Hui Hsu & Yuhang Li & Joshua Wicks & Eduardo González Cervantes & Armin Sedighian Rasouli & Yuguang C. Li & Mingchuan Luo & Dae-Hyun Nam & Ning W, 2022. "A metal-supported single-atom catalytic site enables carbon dioxide hydrogenation," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    8. Xiaoxia Chang & Sudarshan Vijay & Yaran Zhao & Nicholas J. Oliveira & Karen Chan & Bingjun Xu, 2022. "Understanding the complementarities of surface-enhanced infrared and Raman spectroscopies in CO adsorption and electrochemical reduction," Nature Communications, Nature, vol. 13(1), pages 1-12, December.
    9. Jie Ding & Zhiming Wei & Fuhua Li & Jincheng Zhang & Qiao Zhang & Jing Zhou & Weijue Wang & Yuhang Liu & Zhen Zhang & Xiaozhi Su & Runze Yang & Wei Liu & Chenliang Su & Hong Bin Yang & Yanqiang Huang , 2023. "Atomic high-spin cobalt(II) center for highly selective electrochemical CO reduction to CH3OH," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    10. Ke Xie & Rui Kai Miao & Adnan Ozden & Shijie Liu & Zhu Chen & Cao-Thang Dinh & Jianan Erick Huang & Qiucheng Xu & Christine M. Gabardo & Geonhui Lee & Jonathan P. Edwards & Colin P. O’Brien & Shannon , 2022. "Bipolar membrane electrolyzers enable high single-pass CO2 electroreduction to multicarbon products," Nature Communications, Nature, vol. 13(1), pages 1-12, December.
    11. Xinyue Wang & Yuanjun Chen & Feng Li & Rui Kai Miao & Jianan Erick Huang & Zilin Zhao & Xiao-Yan Li & Roham Dorakhan & Senlin Chu & Jinhong Wu & Sixing Zheng & Weiyan Ni & Dongha Kim & Sungjin Park & , 2024. "Site-selective protonation enables efficient carbon monoxide electroreduction to acetate," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    12. Qinglu Liu & Tang Tang & Ziyu Tian & Shiwen Ding & Linqin Wang & Dexin Chen & Zhiwei Wang & Wentao Zheng & Husileng Lee & Xingyu Lu & Xiaohe Miao & Lin Liu & Licheng Sun, 2024. "A high-performance watermelon skin ion-solvating membrane for electrochemical CO2 reduction," Nature Communications, Nature, vol. 15(1), pages 1-13, December.
    13. Gong Zhang & Tuo Wang & Mengmeng Zhang & Lulu Li & Dongfang Cheng & Shiyu Zhen & Yongtao Wang & Jian Qin & Zhi-Jian Zhao & Jinlong Gong, 2022. "Selective CO2 electroreduction to methanol via enhanced oxygen bonding," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    14. Jie Ding & Fuhua Li & Xinyi Ren & Yuhang Liu & Yifan Li & Zheng Shen & Tian Wang & Weijue Wang & Yang-Gang Wang & Yi Cui & Hongbin Yang & Tianyu Zhang & Bin Liu, 2024. "Molecular tuning boosts asymmetric C-C coupling for CO conversion to acetate," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    15. 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.
    16. 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.
    17. Yan Lin & Tuo Wang & Lili Zhang & Gong Zhang & Lulu Li & Qingfeng Chang & Zifan Pang & Hui Gao & Kai Huang & Peng Zhang & Zhi-Jian Zhao & Chunlei Pei & Jinlong Gong, 2023. "Tunable CO2 electroreduction to ethanol and ethylene with controllable interfacial wettability," Nature Communications, Nature, vol. 14(1), pages 1-12, December.
    18. Wenpeng Ni & Houjun Chen & Naizhuo Tang & Ting Hu & Wei Zhang & Yan Zhang & Shiguo Zhang, 2024. "High-purity ethylene production via indirect carbon dioxide electrochemical reduction," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
    19. Ruiz-López, Estela & Gandara-Loe, Jesús & Baena-Moreno, Francisco & Reina, Tomas Ramirez & Odriozola, José Antonio, 2022. "Electrocatalytic CO2 conversion to C2 products: Catalysts design, market perspectives and techno-economic aspects," Renewable and Sustainable Energy Reviews, Elsevier, vol. 161(C).
    20. Zhenyu Jin & Yingqing Guo & Chaozhi Qiu, 2022. "Electro-Conversion of Carbon Dioxide to Valuable Chemicals in a Membrane Electrode Assembly," Sustainability, MDPI, vol. 14(9), pages 1-24, May.
    21. Huali Wu & Ji Li & Kun Qi & Yang Zhang & Eddy Petit & Wensen Wang & Valérie Flaud & Nicolas Onofrio & Bertrand Rebiere & Lingqi Huang & Chrystelle Salameh & Luc Lajaunie & Philippe Miele & Damien Voir, 2021. "Improved electrochemical conversion of CO2 to multicarbon products by using molecular doping," Nature Communications, Nature, vol. 12(1), pages 1-11, December.
    22. Ahmed M. Abdellah & Fatma Ismail & Oliver W. Siig & Jie Yang & Carmen M. Andrei & Liza-Anastasia DiCecco & Amirhossein Rakhsha & Kholoud E. Salem & Kathryn Grandfield & Nabil Bassim & Robert Black & G, 2024. "Impact of palladium/palladium hydride conversion on electrochemical CO2 reduction via in-situ transmission electron microscopy and diffraction," Nature Communications, Nature, vol. 15(1), pages 1-15, December.

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