Published November 20, 2023 | Version v1
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Dual activation and C-C coupling on single atom catalyst for CO₂ photoreduction

  • 1. H-PSI Computational Chemistry Lab, Institute of Industrial Catalysis, State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, P.R. China.
  • 2. Surface Lab 10, Institute of Physics, Chinese Academy of Sciences, P.R. China.

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Description

An excellent single-atomic photocatalyst, Ti@C₄N₃, is theoretically found to effectively convert CO₂ to C₂H₆ by density functional theory (DFT) calculations and non-adiabatic molecular dynamics (NAMD) simulations. The Ti@C₄N₃ photocatalyst has remarkable stability both thermally, chemically, and mechanically. Electronically, it has strong absorption properties, suitable band positions, and a long photogenerated electron lifetime, allowing photogenerated electrons to migrate to the surface. Notably, the high-valence active site effectively activates two CO₂ through dual activation: Under light irradiation, the weakly adsorbed CO₂ undergoes photo-induced activation by the photoelectron of conduction band minimum (CBM); without light, the high Lewis acidity of the Ti site induces CO₂ activation through back-donating π-bond. Contrast simulation results uncovered that dual activation of CO₂ is attributed to the thermal and photonic synergy. Furthermore, two activated CO₂ species under light easily couple to form oxalate with the barrier of 0.19 eV, and further reduced to C₂H₆ with a low activation energy of 1.09 eV.

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References

Journal reference
F. Sun, C. Lin, W. Zhang, Q. Chen, W. Chen, X. Li, G. Zhuang, To be submitted, 2023