Asymmetric nickel single-atom and nitrogen vacancy dual sites on g-C3N4 for efficient CO2 photoreduction to CO

doi:10.1016/S1872-2067(26)65255-2

Abstract

Abstract:

Photocatalytic CO₂ reduction using pure water offers a sustainable route for solar‐to‐fuel conversion, yet its efficiency is limited by sluggish charge separation and the insufficient activation of CO₂ and H₂O. Here, we construct asymmetric dual sites on graphitic carbon nitride by coupling nickel single atoms with nitrogen vacancies (Ni₁-N_V/CN). The optimized catalyst achieves an outstanding CO production rate of 55.32 μmol g^-1 h^-1 without sacrificial agents, representing an 8.3-fold enhancement over the nitrogen-deficient graphitic carbon nitride (N_V/CN) with excellent CO selectivity. Mechanistic investigations reveal a clear functional asymmetry: Ni single atoms serve as high-affinity centers for CO₂ adsorption and activation, whereas nitrogen vacancies promote H₂O adsorption and proton generation. This spatial cooperation accelerates proton-coupled electron-transfer steps, enhances charge separation, and substantially lowers the free-energy barrier for *COOH formation. This work establishes asymmetric dual-site engineering as an effective strategy for activating multi-molecule substrates in photocatalytic CO₂ conversion and offers mechanistic insights for designing advanced metal-defect architectures.

Key words: Asymmetric dual sites, CO2 photoreduction, g-C3N4, Ni single atoms, Nitrogen vacancy

Lijun Wu, Yu Xia, Chaogang Ban, Yang Wang, Xiaoxing Wang, Lujie Ruan, Zilong Zhang, Yaohan Du, Jiangping Ma, Li Hu, Haodi Ran, Ao Zhang, Xiaoping Tao, Liyong Gan, Xiaoyuan Zhou. Asymmetric nickel single-atom and nitrogen vacancy dual sites on g-C₃N₄ for efficient CO₂ photoreduction to CO[J]. Chinese Journal of Catalysis, 2027, 92: 206-218.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65255-2

https://www.cjcatal.com/EN/Y2027/V92/I1/206

Figures/Tables 6

Fig. 1. XRD patterns (a) and FTIR spectra (b) of NV/CN and Ni1-NV/CN. (c) TEM image of Ni1-NV/CN. AC HAADF-STEM (d) and elemental mapping (e) images of Ni1-NV/CN.

Fig. 2. (a) EPR spectra of CN, NV/CN and Ni1-NV/CN. C 1s (b) and N 1s (c) XPS spectra of NV/CN and Ni1-NV/CN. Ni K-edge XANES (d) and FT-EXAFS R space (e) spectra for Ni1-NV/CN, Ni foil and NiPc. (f) FT-EXAFS R space fitting curves for Ni1-NV/CN. Wavelet transform plots for Ni foil (g), NiPc (h), and Ni1-NV/CN (i).

Fig. 3. (a) Time-dependent CO production over different photocatalysts. (b) Performance of photocatalytic CO2 reduction on Ni1-NV/CN as a function of Ni loading mass. (c) Product selectivity of CH4 and CO on CN, NV/CN and Ni1-NV/CN, respectively. (d) Cycling stability test of the Ni1-NV/CN.

Fig. 4. (a) UV-vis DRS and the corresponding Tauc plots (inset) of NV/CN and Ni1-NV/CN. Mott-Schottky plots of NV/CN (b) and Ni1-NV/CN (c). (d) Schematic diagram of the energy band structure. Carrier concentration (e), PL (f), TRPL (g), photocurrent response (h), and EIS plots (i) of NV/CN and Ni1-NV/CN.

Fig. 5. (a, b) In-situ DRIFTS of CO2 photoreduction over NV/CN and Ni1-NV/CN. (c) Density of states of CN, NV/CN and Ni1-NV/CN. (d) Differential charge density of Ni1-NV/CN. (e, f) Adsorption configurations of CO2 on the Ni site and H2O on the NV site in Ni1-NV/CN, respectively. (g) Adsorption energies of CO2 and H2O at the Ni single atom site and NV site on Ni1-NV/CN, respectively. (h) Gibbs free energy diagrams of CO2 photoreduction to CO for CN, NV/CN, and Ni1-NV/CN.

Fig. 6. The reaction mechanism for photocatalytic CO2 reduction on Ni1-NV/CN.

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Asymmetric nickel single-atom and nitrogen vacancy dual sites on g-C₃N₄ for efficient CO₂ photoreduction to CO

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