Photocatalytic reduction of CO2 over porous ultrathin NiO nanosheets with oxygen vacancies

doi:10.1016/S1872-2067(25)64687-0

Abstract

Abstract:

In recent years, photocatalytic CO₂ reduction reaction has been recognized as a crucial approach to solve the greenhouse effect. However, the low concentration of CO₂ in the atmosphere necessitates a catalyst with excellent CO₂ enrichment capability. Herein, we designed and synthesized a series of NiO nanosheets featuring oxygen vacancies. Under the condition of pure CO₂ and photosensitizer [Ru(bpy)₃]Cl₂, the yield of CO reaches 16.8 μmol/h with a selectivity of 96%. Through characterization and theoretical calculations, we demonstrate that the presence of oxygen vacancies not only enhances the adsorption capacity of catalysts but also induces lattice distortion in NiO, leading to an increased dipole moment and formation of an internal electric field that facilitates photogenerated carrier separation. Furthermore, we conducted CO₂ reduction reactions under atmospheric condition and surprisingly observed a changing of selectivity from CO to CO and CH₄. A series of control experiments showed that [Ru(bpy)₃]Cl₂ acts as a reduction reaction site due to the presence of O₂ in the atmosphere. Simultaneously, oxygen promotes water splitting, which results in abundant proton generation and subsequent changes in carbon products.

Key words: Photocatalytic CO₂ reduction, [Ru(bpy)₃]Cl₂, NiO, Oxygen vacancy, Low concentration CO₂

Rui Li, Pengfei Feng, Bonan Li, Jiayu Zhu, Yali Zhang, Ze Zhang, Jiangwei Zhang, Yong Ding. Photocatalytic reduction of CO₂ over porous ultrathin NiO nanosheets with oxygen vacancies[J]. Chinese Journal of Catalysis, 2025, 73: 242-251.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64687-0

https://www.cjcatal.com/EN/Y2025/V73/I6/242

Figures/Tables 9

Fig. 1. The synthesis method of NiO nanosheets.

Fig. 2. SEM images of different NiO samples.

Fig. 3. (a,b) AFM images and thickness of NiO-1. (c) TEM image of NiO-1. (d) HRTEM image of NiO-1.

Fig. 4. (a) XRD patterns of as-prepared samples. Ni 2p (b) and O 1s (c) XPS spectra of NiO-1 and NiO-9. Ni K-edge XANES spectra (d), FT k3-weighted EXAFS curves (e) and structural representations (f) of NiO-1 and NiO-9.

Fig. 5. (a) Photocatalytic CO2 reduction activities of NiO-1 to NiO-9. (b) Photocatalytic CO2 reduction activities of different masses NiO-1. (c)Kinetic curves for gas evolution amount of NiO-1. (d) Single variable control experiments for photocatalytic CO2 reduction over NiO-1. (e) Isotopic 13CO2 experiment of NiO-1. (f) Recycling experiments for photocatalytic CO2 reduction over NiO-1.

Fig. 6. (a) Photocatalytic CO2 reduction activities of NiO-1 in atmosphere. (b,c) Kinetic curves for gas evolution amount of NiO-1 with Ar and O2. (d) Controlled experiment with or without catalyst under atmospheric condition. (e) In situ FT-IR spectra for the photocatalytic CO2 reduction in atmosphere.

Fig. 7. Steady state PL spectra (a) and time-resolved PL spectra (b) of NiO-1, NiO-9 and [Ru(bpy)3]Cl2. Transient photocurrent curves (c) and EIS (d) for NiO-1 and NiO-9. (e) BET curves of NiO-1 and NiO-9. (f) CO2 adsorption curves of NiO-1 and NiO-9.

Fig. 8. (a) Theoretical dipole moments for NiO-1 and NiO-9. (b) The surface electrostatic potential distribution of NiO-1. (c-f) Side view the charge density difference of NiO-1 and NiO-9 adsorbed with CO2 with an isosurface of 1.5 × 10-3 e/?3.

Fig. 9. (a) In situ FTIR spectra for the photocatalytic CO2 reduction on NiO-1. (b) Transformation diagram for CO2 photoreduction over NiO-1. (c) Free energy diagrams for the adsorption and activation on NiO-1 and NiO-9.

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Photocatalytic reduction of CO₂ over porous ultrathin NiO nanosheets with oxygen vacancies

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