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Room-temperature photosynthesis of propane from CO2 with Cu single atoms on vacancy-rich TiO2

Author

Listed:
  • Yan Shen

    (Nanjing University
    Nanjing University)

  • Chunjin Ren

    (Southeast University)

  • Lirong Zheng

    (Chinese Academy of Sciences)

  • Xiaoyong Xu

    (Yangzhou University)

  • Ran Long

    (University of Science and Technology of China)

  • Wenqing Zhang

    (University of Science and Technology of China)

  • Yong Yang

    (Nanjing University of Science and Technology)

  • Yongcai Zhang

    (Yangzhou University)

  • Yingfang Yao

    (Nanjing University
    Nanjing University
    the Chinese University of Hong Kong (Shenzhen))

  • Haoqiang Chi

    (Nanjing University)

  • Jinlan Wang

    (Southeast University)

  • Qing Shen

    (Graduate School of Informatics and Engineering)

  • Yujie Xiong

    (University of Science and Technology of China)

  • Zhigang Zou

    (Nanjing University
    Nanjing University
    the Chinese University of Hong Kong (Shenzhen))

  • Yong Zhou

    (Nanjing University
    the Chinese University of Hong Kong (Shenzhen)
    Anhui Polytechnic University)

Abstract

Photochemical conversion of CO2 into high-value C2+ products is difficult to achieve due to the energetic and mechanistic challenges in forming multiple C-C bonds. Herein, an efficient photocatalyst for the conversion of CO2 into C3H8 is prepared by implanting Cu single atoms on Ti0.91O2 atomically-thin single layers. Cu single atoms promote the formation of neighbouring oxygen vacancies (VOs) in Ti0.91O2 matrix. These oxygen vacancies modulate the electronic coupling interaction between Cu atoms and adjacent Ti atoms to form a unique Cu-Ti-VO unit in Ti0.91O2 matrix. A high electron-based selectivity of 64.8% for C3H8 (product-based selectivity of 32.4%), and 86.2% for total C2+ hydrocarbons (product-based selectivity of 50.2%) are achieved. Theoretical calculations suggest that Cu-Ti-VO unit may stabilize the key *CHOCO and *CH2OCOCO intermediates and reduce their energy levels, tuning both C1-C1 and C1-C2 couplings into thermodynamically-favourable exothermal processes. Tandem catalysis mechanism and potential reaction pathway are tentatively proposed for C3H8 formation, involving an overall (20e− – 20H+) reduction and coupling of three CO2 molecules at room temperature.

Suggested Citation

  • Yan Shen & Chunjin Ren & Lirong Zheng & Xiaoyong Xu & Ran Long & Wenqing Zhang & Yong Yang & Yongcai Zhang & Yingfang Yao & Haoqiang Chi & Jinlan Wang & Qing Shen & Yujie Xiong & Zhigang Zou & Yong Zh, 2023. "Room-temperature photosynthesis of propane from CO2 with Cu single atoms on vacancy-rich TiO2," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
  • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-36778-5
    DOI: 10.1038/s41467-023-36778-5
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    1. Yao Chai & Yuehua Kong & Min Lin & Wei Lin & Jinni Shen & Jinlin Long & Rusheng Yuan & Wenxin Dai & Xuxu Wang & Zizhong Zhang, 2023. "Metal to non-metal sites of metallic sulfides switching products from CO to CH4 for photocatalytic CO2 reduction," Nature Communications, Nature, vol. 14(1), pages 1-11, December.

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