LSPR-enhanced carbon-coated In2O3/W18O49 S-scheme heterojunction for efficient CO2 photoreduction

doi:10.1016/S1872-2067(23)64420-1

Abstract

Abstract:

The special defect structure and localized surface plasmon resonance (LSPR) effect offer W₁₈O₄₉ extraordinary potential and research value in photocatalysis. The LSPR effect optimizes the design of W₁₈O₄₉-sensitized photocatalytic composites and broadens the light-response range of W₁₈O₄₉. However, the high-energy “hot electrons” generated by W₁₈O₄₉ under the LSPR effect exhibit an extremely short lifetime and cannot be fully utilized. Therefore, the high electron conductivity of carbon can be used to increase the rate of hot-electron transfer, thereby extending the lifetime of hot electrons. In this study, a heterojunction photocatalyst was formed by growing a high-absorbance one-dimensional nanowire W₁₈O₄₉ on the surface of carbon-coated porous In₂O₃ nanorods (C-In₂O₃) derived from In-MOF. The C-In₂O₃/W₁₈O₄₉ composites exhibited optical responses in both the visible and near-infrared regions. The carbon coatings acted as transport channels to accelerate the transfer of carriers and hot electrons, and the activity of photocatalytic CO₂ reduction (PCR) was significantly enhanced. The 40%C-In₂O₃/W₁₈O₄₉ composites had the highest CO yield in the photocatalytic reactions, which was 2.99 and 2.84 times greater than that of pure C-In₂O₃ and W₁₈O₄₉, respectively. The internal electronic transfer in the S-scheme heterojunction and LSPR-induced hot electrons injected into C-In₂O₃ achieved dual-path electron transfer for PCR.

Key words: Photocatalytic CO₂ reduction, S-scheme heterojunction, Localized surface plasmon resonance, Carbon-coated In₂O₃, W₁₈O₄₉

Houwei He, Zhongliao Wang, Kai Dai, Suwen Li, Jinfeng Zhang. LSPR-enhanced carbon-coated In₂O₃/W₁₈O₄₉ S-scheme heterojunction for efficient CO₂ photoreduction[J]. Chinese Journal of Catalysis, 2023, 48: 267-278.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64420-1

https://www.cjcatal.com/EN/Y2023/V48/I5/267

Figures/Tables 10

Fig. 1. Schematic diagram of the synthetic route of C-In2O3/W18O49 composites.

Fig. 2. SEM images of C-In2O3 (a), W18O49 (b), and 40%C-In2O3/W18O49 (c). (d) TEM image of C-In2O3. (e) HRTEM image of 40%C-In2O3/W18O49. (f-i) Element mapping images of C-In2O3/W18O49.

Fig. 3. (a) XRD patterns of In2O3, X%C-In2O3/W18O49, and W18O49. Full spectrum (b), C 1s (c), W 4f (d), In 3d (e), and O 1s (f) XPS spectra of samples.

Fig. 4. (a) UV-Vis diffuse reflectance spectra of different photocatalysts. (b) Plots of (αhν)2 versus energy (hν) for W18O49 and C-In2O3. (c,d) Mott-Schottky curve of W18O49 and C-In2O3. (e) Transient photocurrent response patterns of the photocatalysts. (f) EIS curves for C-In2O3, 40%C-In2O3/W18O49, and W18O49.

Fig. 5. (a) PL spectra of the prepared samples. (b) Time-resolved PL spectra.

Table 1 Dynamics analysis of the emission decay for different samples.

Sample	A₁ (%)	τ₁ (ns)	A₂ (%)	τ₂ (ns)	A₃ (%)	τ₃ (ns)	τ_A (ns)
W₁₈O₄₉	48.40	0.4861	34.87	2.4622	16.73	10.8105	2.9025
C-In₂O₃	59.21	0.5868	25.58	2.6342	15.21	11.9292	2.8358
C-In₂O₃/W₁₈O₄₉	49.56	0.8126	34.41	3.5399	19.02	13.4359	4.0707

Fig. 6. (a) Nitrogen adsorption/desorption isotherms. (b) BET specific surface area.

Fig. 7. (a) CO evolution rate of all the samples. (b) Performance cycle experiments. (c) Performance comparison of the catalysts with and without carbon coating. (d) CO evolution rate of the catalysts under different experimental conditions. (e,f) The mass spectroscopy analysis result of CO stemmed from the 13CO2 isotope experiment of 40%C-In2O3/W18O49 and in situ DRIFTS spectra.

Fig. 8. (a) Optimized structural models of W18O49 (100) and (b) In2O3 (100). (c,d) Calculated Fermi levels and work functions for W18O49 (100) and In2O3 (111).

Fig. 9. Photocatalytic mechanism of the C-In2O3/W18O49 composite under simulated sunlight illumination.

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LSPR-enhanced carbon-coated In₂O₃/W₁₈O₄₉ S-scheme heterojunction for efficient CO₂ photoreduction

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