Atomically dispersed Fe sites on TiO2 for boosting photocatalytic CO2 reduction: Enhanced catalytic activity, DFT calculations and mechanistic insight

doi:10.1016/S1872-2067(23)64484-5

Abstract

Abstract:

The design of photocatalysts for the stable and efficient photocatalytic reduction of CO₂ without sacrificial agents remains challenging. In this study, Fe atoms were anchored on the surface of TiO₂ with atomic-level dispersion using a novel negative-pressure encapsulation and pyrolysis strategy. The photoelectrochemical test results confirmed that the introduction of single Fe atoms accelerated the separation of photogenerated carriers and enhanced the TiO₂utilization rate of visible light. The optimal catalyst with atomically dispersed Fe showed excellent photocatalytic conversion of CO₂ to CO (48.2 μmol·g^-1·h^-1) and CH₄ (113.4 μmol·g^-1·h^-1), whereas the TiO₂ system produced only trace amounts of CO (2.7 μmol·g^-1·h^-1). The increased CO₂ adsorption energy and movement of the d-band center toward the Fermi level confirmed that single Fe sites were more favorable for the adsorption of CO₂. The differential charge density distribution of CO₂ adsorbed on the catalyst surface confirmed the rapid transfer of electrons along the Ti-O-Fe-C path, and the Gibbs free energy calculation further confirmed that the Fe sites were conducive to reducing the energy barrier required for the reaction. In addition, the key intermediate (*COOH) of CO₂ conversion to CH₄ was detected by in situ diffuse reflectance infrared Fourier transform spectroscopy, and a possible reaction pathway was proposed. This work provides an effective strategy for designing single-atom catalysts that can efficiently reduce CO₂ to high-value-added products.

Key words: Photocatalytic reduction of CO₂, Negative-pressure encapsulation, Fe SA/TiO₂, Single atom catalyst, d-Band center

Jiaming Li, Yuan Li, Xiaotian Wang, Zhixiong Yang, Gaoke Zhang. Atomically dispersed Fe sites on TiO₂ for boosting photocatalytic CO₂ reduction: Enhanced catalytic activity, DFT calculations and mechanistic insight[J]. Chinese Journal of Catalysis, 2023, 51: 145-156.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64484-5

https://www.cjcatal.com/EN/Y2023/V51/I8/145

Figures/Tables 6

Fig. 1. XRD patterns (a), Raman spectra (b), and FTIR spectra (c) of TiO2 and Fe SA/TiO2 catalysts. High resolution TEM images (d), HAADF-STEM images (e,f), and corresponding elemental mapping images (g?j) of 10Fe SA/TiO2.

Fig. 2. (a) Normalized XANES spectra at the Fe K-edge of 10Fe SA/TiO2 in comparison with FeO, Cu foil, and Fe2O3 references. (b) Comparison of the Fourier-transformed magnitudes of the experimental Fe K-edge. XPS survey spectra (c) and high-resolution Ti 2p (d), O 1s (e), and Fe 2p (f) XPS spectra of Fe SA/TiO2.

Fig. 3. UV-visible DRS (a), Tauc plot(b), XPS valence band spectrum (c), band structure (d), time-resolved PL spectra (e), and electrochemical impedance spectroscopy (f) of TiO2 and Fe SA/TiO2.

Fig. 4. Production rates of CH4 (a) and CO2 (b) from the photocatalytic reduction of CO2 under full spectrum irradiation within 4 h. Comparison of the photocatalytic property under full spectrum (Insert selective calculation results) (c) and visible light irradiation (d) of TiO2 and Fe SA/TiO2. Conditional control experiment (e) and 13C isotope labeling experiment (f). (g) Cycling performance test of 10Fe SA/TiO2. (h) XRD patterns of fresh and used 10Fe SA/TiO2 catalysts. (i) Comparison of CO2 performance for the photocatalytic reduction of different systems.

Fig. 5. (a) Calculated DOS of TiO2 and Fe SA/TiO2 catalysts with different crystal phases. (b-g) Differential charge density distribution of CO2 adsorbed on TiO2 and Fe SA/TiO2 catalysts.

Fig. 6. (a) CO2 adsorption and temperature-programmed isotherms of TiO2 and Fe SA/TiO2. (b) In situ DRIFTS spectra of 10Fe SAs/TiO2. (c) Schematic diagram of the CO2 reaction path for the surface photocatalytic reduction of 10Fe SAs/TiO2. (d) Gibbs free energy (ΔG) diagrams of CO2 photoreduction to CO and CH4 through different paths over TiO2 and Fe SA/TiO2.

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Atomically dispersed Fe sites on TiO₂ for boosting photocatalytic CO₂ reduction: Enhanced catalytic activity, DFT calculations and mechanistic insight

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