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Modulating the mechanism of electrocatalytic CO2 reduction by cobalt phthalocyanine through polymer coordination and encapsulation

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  • Yingshuo Liu

    (University of Michigan)

  • Charles C. L. McCrory

    (University of Michigan)

Abstract

The selective and efficient electrochemical reduction of CO2 to single products is crucial for solar fuels development. Encapsulating molecular catalysts such as cobalt phthalocyanine within coordination polymers such as poly-4-vinylpyridine leads to dramatically increased activity and selectivity for CO2 reduction. In this study, we use a combination of kinetic isotope effect and proton inventory studies to explain the observed increase in activity and selectivity upon polymer encapsulation. We provide evidence that axial-coordination from the pyridyl moieties in poly-4-vinylpyridine to the cobalt phthalocyanine complex changes the rate-determining step in the CO2 reduction mechanism accounting for the increased activity in the catalyst-polymer composite. Moreover, we show that proton delivery to cobalt centers within the polymer is controlled by a proton relay mechanism that inhibits competitive hydrogen evolution. These mechanistic findings provide design strategies for selective CO2 reduction electrocatalysts and serve as a model for understanding the catalytic mechanism of related heterogeneous systems.

Suggested Citation

  • Yingshuo Liu & Charles C. L. McCrory, 2019. "Modulating the mechanism of electrocatalytic CO2 reduction by cobalt phthalocyanine through polymer coordination and encapsulation," Nature Communications, Nature, vol. 10(1), pages 1-10, December.
  • Handle: RePEc:nat:natcom:v:10:y:2019:i:1:d:10.1038_s41467-019-09626-8
    DOI: 10.1038/s41467-019-09626-8
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    Cited by:

    1. 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.

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