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Elucidating protonation pathways in CO2 photoreduction using the kinetic isotope effect

Author

Listed:
  • Shikang Yin

    (Jiangsu University)

  • Yiying Zhou

    (Jiangsu University)

  • Zhonghuan Liu

    (Jiangsu University)

  • Huijie Wang

    (Jiangsu University)

  • Xiaoxue Zhao

    (Jiangsu University)

  • Zhi Zhu

    (Jiangsu University)

  • Yan Yan

    (Jiangsu University)

  • Pengwei Huo

    (Jiangsu University)

Abstract

The surge in anthropogenic CO2 emissions from fossil fuel dependence demands innovative solutions, such as artificial photosynthesis, to convert CO2 into value-added products. Unraveling the CO2 photoreduction mechanism at the molecular level is vital for developing high-performance photocatalysts. Here we show kinetic isotope effect evidence for the contested protonation pathway for CO2 photoreduction on TiO2 nanoparticles, which challenges the long-held assumption of electron-initiated activation. Employing isotopically labeled H2O/D2O and in-situ diffuse reflectance infrared Fourier transform spectroscopy, we observe H+/D+-protonated intermediates on TiO2 nanoparticles and capture their inverse decay kinetic isotope effect. Our findings significantly broaden our understanding of the CO2 uptake mechanism in semiconductor photocatalysts.

Suggested Citation

  • Shikang Yin & Yiying Zhou & Zhonghuan Liu & Huijie Wang & Xiaoxue Zhao & Zhi Zhu & Yan Yan & Pengwei Huo, 2024. "Elucidating protonation pathways in CO2 photoreduction using the kinetic isotope effect," Nature Communications, Nature, vol. 15(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-44753-x
    DOI: 10.1038/s41467-024-44753-x
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    References listed on IDEAS

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    1. Xiaodong Li & Yongfu Sun & Jiaqi Xu & Yanjie Shao & Ju Wu & Xiaoliang Xu & Yang Pan & Huanxin Ju & Junfa Zhu & Yi Xie, 2019. "Selective visible-light-driven photocatalytic CO2 reduction to CH4 mediated by atomically thin CuIn5S8 layers," Nature Energy, Nature, vol. 4(8), pages 690-699, August.
    2. Shaolei Wang & Min Xu & Tianyou Peng & Chengxin Zhang & Tao Li & Irshad Hussain & Jingyu Wang & Bien Tan, 2019. "Porous hypercrosslinked polymer-TiO2-graphene composite photocatalysts for visible-light-driven CO2 conversion," Nature Communications, Nature, vol. 10(1), pages 1-10, December.
    3. Sandra Haschke & Michael Mader & Stefanie Schlicht & André M. Roberts & Alfredo M. Angeles-Boza & Johannes A. C. Barth & Julien Bachmann, 2018. "Direct oxygen isotope effect identifies the rate-determining step of electrocatalytic OER at an oxidic surface," Nature Communications, Nature, vol. 9(1), pages 1-8, December.
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