Interface-engineered S-scheme 2D/1D heterojunction of Cs0.32WO3/WO3·2H2O for boosted CO2 photoreduction: Synergistic charge separation and activation

doi:10.1016/S1872-2067(25)64818-2

Abstract

Abstract:

Developing efficient photocatalysts for CO₂ conversion under full-spectrum irradiation remains a key challenge for solar-to-chemical energy conversion. In this study, a novel S-scheme heterojunction composed of reduction Cs_0.32WO₃ (CWO) nanosheets with hexagonal structure and oxidation WO₃·2H₂O (WO) nanorods with monoclinic structure photocatalyst was successfully constructed via an ultrasound strategy. Under full-spectrum irradiation for 4 h, the optimized 2D/1D of heterostructure CWO/WO-0.8 exhibited superior photocatalytic performance, achieving CO and CH₃OH yields of 29.74 and 63.71 μmol·g^-1, respectively. The enhanced activity is primarily ascribed to the formation of an S-scheme charge transfer pathway, which facilitates efficient separation and directional migration of photogenerated charge carriers through the internal electric field at the CWO/WO interface. This process facilitates the electron enrichment on the CWO surface and significantly enhances its CO₂ reduction ability. Besides, the results of various characterizations show that CWO/WO-0.8 possesses enhanced optical response capability. The results of density functional theory calculations and CO₂-temperature programmed desorption analysis confirmed that the CWO/WO heterojunction exhibits stronger CO₂ adsorption and activation abilities compared to the pristine CWO and WO. The reaction pathway for CH₃OH production was elucidated by in-situ diffused reflectance Fourier transformed infrared tests. This work provides new insights into the rational design of S-scheme photocatalysts for efficient and selective CO₂ conversion.

Key words: S-scheme heterojunction, Photocatalysts CO₂ reduction, Cs_0.32WO₃, WO₃·2H₂O, CH₃OH

Guangmei Gan, Lin Yin, Xiaotian Wang, Juyuan Xing, Yuan Li, Gaoke Zhang. Interface-engineered S-scheme 2D/1D heterojunction of Cs_0.32WO₃/WO₃·2H₂O for boosted CO₂ photoreduction: Synergistic charge separation and activation[J]. Chinese Journal of Catalysis, 2025, 79: 219-230.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64818-2

https://www.cjcatal.com/EN/Y2025/V79/I12/219

Figures/Tables 6

Fig. 1. XRD patterns (a), Raman spectra (b), full XPS survey spectra (c), TEM image (d) and EDX elemental mappings images (e-g), HRTEM images (h,i), corresponding crystal faces pacings and FFT images (j) of the CWO/WO-0.8 sample.

Fig. 2. Cs 3d (a),) W 4f (b), and O 1s (c) XPS spectra of CWO, WO and CWO/WO-0.8. Electrostatic potentials of WO (d) and CWO (e), corresponding planar averaged charge difference density along z axis (f).

Fig. 3. (a) AFM image of CWO/WO-0.8. Corresponding surface potential difference in dark (b) and under light irradiation (c). (d) Corresponding surface potential difference in dark and under light irradiation along the marked line. (e) The formation mechanism of the CWO/WO-0.8 p-n heterojunction.

Fig. 4. (a) CO and CH3OH yields of the prepared materials under the full-spectrum irradiation. (b) The reaction performance under different conditions. (c) Photocatalytic cycling tests. (d) XRD patterns of CWO/WO-0.8 before and after the reaction.

Fig. 5. DRS spectra (a) and corresponding Tauc plots (b) of the prepared materials. The pseudocolor plots and transient absorption spectra of CWO/WO-0.8 (c,e) and WO (d,f). Normalized transient absorption kinetics for CWO/WO-0.8 (g) and WO (h). PL spectra (i), transient photocurrent-time response curves (j), and electrochemical impedance plots (k) of the prepared samples. (l) Mechanism schematic of photocatalytic CO2 reduction on CWO/WO S-scheme heterojunction.

Fig. 6. DOS (a), d band values (b), and CO2 adsorption energies (c) of CWO, WO and CWO/WO-0.8. The charge density difference of CO2 adsorbed on CWO/WO-0.8 (d), CWO (e), and WO (f). (g) CO2-TPD curves of CWO, WO and CWO/WO-0.8. In-situ DRIFTS spectra of CWO/WO-0.8 at dark (h) and under full spectrum irradiation (i).

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Interface-engineered S-scheme 2D/1D heterojunction of Cs_0.32WO₃/WO₃·2H₂O for boosted CO₂ photoreduction: Synergistic charge separation and activation

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