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

• Published in: Nature communications Vol. 14; no. 1; p. 1117
• Main Authors: Shen, Yan, Ren, Chunjin, Zheng, Lirong, Xu, Xiaoyong, Long, Ran, Zhang, Wenqing, Yang, Yong, Zhang, Yongcai, Yao, Yingfang, Chi, Haoqiang, Wang, Jinlan, Shen, Qing, Xiong, Yujie, Zou, Zhigang, Zhou, Yong
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 27.02.2023; Nature Publishing Group; Nature Portfolio
• Subjects: 639/301/299; 639/4077/909; 639/638/439/890; 639/638/77/887; Acoustics; Carbon dioxide; Catalysis; Catalysts; Chemistry; Collaboration; Conversion; Coupling (molecular); Couplings; Energy; Energy levels; Engineering; Humanities and Social Sciences; Hydrocarbons; Intermediates; Laboratories; multidisciplinary; Oxygen; Photocatalysts; Photochemicals; Photosynthesis; Physics; Reaction intermediates; Room temperature; Science; Science (multidisciplinary); Selectivity; Thin films; Titanium dioxide; Transmission electron microscopy
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-023-36778-5

Photochemical conversion of CO 2 into high-value C 2+ 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 CO 2 into C 3 H 8 is prepared by implanting Cu single atoms on Ti 0.91 O 2 atomically-thin single layers. Cu single atoms promote the formation of neighbouring oxygen vacancies (V O s) in Ti 0.91 O 2 matrix. These oxygen vacancies modulate the electronic coupling interaction between Cu atoms and adjacent Ti atoms to form a unique Cu-Ti-V O unit in Ti 0.91 O 2 matrix. A high electron-based selectivity of 64.8% for C 3 H 8 (product-based selectivity of 32.4%), and 86.2% for total C 2+ hydrocarbons (product-based selectivity of 50.2%) are achieved. Theoretical calculations suggest that Cu-Ti-V O unit may stabilize the key *CHOCO and *CH 2 OCOCO intermediates and reduce their energy levels, tuning both C 1 -C 1 and C 1 -C 2 couplings into thermodynamically-favourable exothermal processes. Tandem catalysis mechanism and potential reaction pathway are tentatively proposed for C 3 H 8 formation, involving an overall ( 20 e − – 20 H + ) reduction and coupling of three CO 2 molecules at room temperature. A photocatalyst for CO2 reduction to C3H8 is prepared by implanting Cu single atoms on vacancy rich TiO2 single layers. Key reaction intermediates, *CHOCO and *CH2OCOCO, are stabilized on the catalyst which promotes C-C bond formation.