Metal-free photocatalytic reduction of CO2 on a covalent organic framework-based heterostructure

doi:10.1016/S1872-2067(24)60027-6

Abstract

Abstract:

Photocatalytic reduction of CO₂ with H₂O is thought as an environment friendly approach for sustainable development. It is highly desirable but remains challenging to develop photocatalyst with metal-free site for CO₂ reduction. Here, we fabricated a heterostructure by integrating azine-based COF with ZnIn₂S₄, where the azine unit in COF acts as metal-free sites for CO₂ adsorption and reduction. The as-formed interfused heterointerface in the heterostructure ensures the effective electron transfer from ZnIn₂S₄ across the interface to the COF, resulting in a spatial separation of redox sites for CO₂ reduction and water oxidation. The hybrid catalyst exhibits remarkably enhanced photocatalytic activity for CO₂ reduction to CO, which is 8 and 6 times than the COF and ZnIn₂S₄, respectively, and is even comparable with some metal-catalyzed CO₂ reduction systems. This study provides a new paradigm to mimic natural photosynthesis by using metal-free site for CO₂ reduction.

Key words: Covalent organic framework, Photocatalysis, CO₂ reduction, Heterostructure, Metal-free site

Haoming Huang, Qingqing Lin, Qing Niu, Jiangqi Ning, Liuyi Li, Jinhong Bi, Yan Yu. Metal-free photocatalytic reduction of CO₂ on a covalent organic framework-based heterostructure[J]. Chinese Journal of Catalysis, 2024, 60: 201-208.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60027-6

https://www.cjcatal.com/EN/Y2024/V60/I5/201

Figures/Tables 6

Fig. 1. Schematic illustration of COF-based heterostructure for photocatalytic CO2 reduction with H2O.

Fig. 2. (a) Schematic synthesis of ZnIn2S4@TAz-COF. SEM (b), TEM (c), HRTEM (d) and EDX mapping (e) images of ZnIn2S4@TAz-COF. (f) PXRD patterns of ZnIn2S4@TAz-COF, ZnIn2S4 and TAz-COF.

Fig. 3. (a) UV-vis DRS spectra. (b) Schematic diagram of the band structure alignment for ZnIn2S4 and TAz-COF. Photocurrent response (c), EIS (d), steady-state solid PL (e), and time-resolved PL (f) spectra for TAz-COF, ZnIn2S4, and ZnIn2S4@TAz-COF.

Fig. 4. (a) XPS spectra for N 1s in TAz-COF and ZnIn2S4@TAz-COF under darkness and in light. (b) XPS spectra for Zn 2p in ZnIn2S4 and the ZnIn2S4@TAz-COF under darkness and in light. (c) EPR of TAz-COF, ZnIn2S4, and ZnIn2S4@TAz-COF under light irradiation. (d) Top and side views of the averaged charge density difference for ZnIn2S4@TAz-COF. Red and green regions represent electron accumulation and depletion, respectively. C (dark gray), N (blue), H (light gray), Zn (pink), In (violet) and S (yellow).

Fig. 5. (a) Photocatalytic CO2 conversion rates of TAz-COF, ZnIn2S4 and ZnIn2S4@TAz-COF with different mass ratios (x = 5, 10, 15, 20, 30). (b) Evolution rates of CO, CH4 and O2 over ZnIn2S4@TAz-COF. (c) GC-MS spectra of 13CO and 18O2 by using ZnIn2S4@TAz-COF as photocatalyst with 13CO2 and H218O. (d) Stability test of ZnIn2S4@TAz-COF in four repeats with each run lasting 4 h.

Fig. 6. (a) In-situ FTIR experiment over ZnIn2S4@TAz-COF under light irradiation. (b) CO2 binding energy on triazine and azine units. (c) Gibbs free energy diagrams of photocatalytic reduction of CO2 on azine units of TAz-COF and ZnIn2S4@TAz-COF. Where the asterisk (*) indicated the adsorption state on the photocatalyst surface. (d) Proposed mechanism of photocatalytic reduction of CO2 by ZnIn2S4@TAz-COF.

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Metal-free photocatalytic reduction of CO₂ on a covalent organic framework-based heterostructure

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