LSPR-assisted W18O49/ZnO S-scheme heterojunction for efficient photocatalytic CO2 N-formylation of aniline

doi:10.1016/S1872-2067(24)60149-X

Abstract

Abstract:

Designing highly efficient photocatalyst for the valorization of CO₂ is an ideal strategy to reduce greenhouse gas emissions and utilize solar energy. In this study, a S-scheme heterojunction photocatalyst is fabricated by solvothermal impregnation of ZnO on W₁₈O₄₉ for photocatalytic CO₂ N-formylation of aniline. The localized surface plasmon resonance effect of W₁₈O₄₉ improves the absorption capacity for long-wave light significantly, and the hot electrons generated in W₁₈O₄₉ with a high energy can migrate to the conduction band of ZnO and thus enhance the photocatalytic reduction ability. Meanwhile, the S-scheme heterojunction facilitates the separation of photoinduced charge carriers and preserves the redox ability of W₁₈O₄₉/ZnO composite photocatalyst. The conversion of aniline reaches 99.1% after 5 h reaction under visible light irradiation at room temperature with an N-formylaniline selectivity of 100%. A possible photocatalytic reaction mechanism is proposed. This study paves a promising way for the design of highly efficient photocatalyst and the sustainable utilization of CO₂.

Key words: Photocatalysis, CO₂ valorization, N-formylation, Step-scheme heterojunction, Tungsten oxide, ZnO

Jiafa Chen, Peng Bai, Shibo Yuan, Yi He, Zifan Niu, Yicheng Zhao, Yongdan Li. LSPR-assisted W₁₈O₄₉/ZnO S-scheme heterojunction for efficient photocatalytic CO₂ N-formylation of aniline[J]. Chinese Journal of Catalysis, 2024, 67: 124-134.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60149-X

https://www.cjcatal.com/EN/Y2024/V67/I12/124

Figures/Tables 9

Fig. 1. XRD patterns of the photocatalysts.

Fig. 2. SEM images of ZnO (a), W18O49 (b) and 30WZ composite (c). HRTEM image (d), SAED pattern (e) and STEM image and EDX elemental mappings (f) of 30WZ composite.

Fig. 3. (a) Aniline conversion and FA selectivity over different samples after 1 h reaction. (b) Mass spectra of the products with 12CO2 and 13CO2 as the feedstocks over 30WZ composite. (c) Aniline conversion and FA selectivity over 30WZ composite as a function of reaction time. (d) Stability of 30WZ composite during five 5-h reaction cycles.

Table 1 Photocatalytic N-formylation of various amines with CO2 over 30WZ.

Entry	Conversion (%)	Selectivity (%)
1	99.1	100
2	94.5	98.3
3	86.8	93.9
4	99.1	97.3
5	100	99.4
6	63.1	97.6
7	76.9	96.6
8	95.1	100
9	100	97.0
10	100	100
11	100	93.6
12	99.5	100

Fig. 4. UV-vis diffuse reflectance spectra (a), Tauc plots (b), Mott-Schottky plots (500 Hz) (c) and PL spectra (d) of the samples.

Fig. 5. Calculated Fermi levels and work functions for ZnO (101) face (a) and W18O49 (010) face (b). High-resolution XPS spectra of Zn 2p (c) and W 4f (d) of the samples.

Fig. 6. Mechanism of charge-transfer processes in S-scheme W18O49/ZnO heterojunction.

Fig. 7. (a) Aniline conversion and FA selectivity over 30WZ composite after 1 h reaction under various conditions. (b) In situ FTIR spectra during the reaction over 30WZ composite. (c) In situ EPR spectra after 10 min reaction over 30WZ composite in the dark and under light irradiation.

Fig. 8. Possible mechanism of photocatalytic N-formylation of aniline with CO2 over W18O49/ZnO composite.

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LSPR-assisted W₁₈O₄₉/ZnO S-scheme heterojunction for efficient photocatalytic CO₂ N-formylation of aniline

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