1D S-scheme heterojunction of urchin-like SiC-W18O49 for enhancing photocatalytic CO2 reduction

doi:10.1016/S1872-2067(23)64477-8

Abstract

Abstract:

Constructing heterojunction is an important method to improve the performance of photocatalyst for CO₂ reduction. In this work, W₁₈O₄₉ nanosheets (NSs) were grown on the surface of SiC nanocages (NCs) to form the sea urchin ball morphology by solvothermal method. The SiC-W₁₈O₄₉ composite photocatalyst processes 1D S-scheme heterojunction electron transport pathway. The special urchin morphology provides a large surface area for the contact between photocatalyst and CO₂ reactants. Meantime, the S-scheme internal electric field at the heterogeneous interface of SiC-W₁₈O₄₉ composite photocatalyst can effectively promote the separation and migration of photogenerated carrier pairs owing to 1D heterojunction structure. The photocatalytic CO₂ reduction products (CO + CH₄ + CH₃OH) can be produced up to 21.87 μmol g^-1 h^-1 by SiC-W₁₈O₄₉ composite photocatalyst, which was 3.38 and 3.71 times of the total reduction activity of the parent SiC and W₁₈O₄₉, respectively. This work will provide a new idea for the design of heterojunction morphology and structure for boosting photocatalytic CO₂ reduction.

Key words: 1D heterojunction, S-scheme, Sea-urchin-structure, CO₂ reduction, SiC-W₁₈O₄₉

Min Lin, Meilan Luo, Yongzhi Liu, Jinni Shen, Jinlin Long, Zizhong Zhang. 1D S-scheme heterojunction of urchin-like SiC-W₁₈O₄₉ for enhancing photocatalytic CO₂ reduction[J]. Chinese Journal of Catalysis, 2023, 50: 239-248.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64477-8

https://www.cjcatal.com/EN/Y2023/V50/I7/239

Figures/Tables 11

Fig. 1. XRD patterns of W18O49, SiC and SiC-W18O49 composite samples.

Fig. 2. SEM and TEM images of SiC NCs (a,c) and SW-2 (b,d) samples. (e) HRTEM image of the SiC-W18O49 heterojunction.

Fig. 3. Nitrogen adsorption and desorption isotherms (a) and CO2 adsorption isotherms (b) of SiC NCs, SiC-W18O49 composites, and W18O49 NSs.

Fig. 4. (a) The photocatalytic product generation rate of SiC, W18O49, SiC-W18O49 composites. (b) Photocatalytic stability of the SiC-W18O49. (c) The formation rates of CO, CH4, and CH3OH in SW-2 samples under different reaction conditions. (d) Isotope labeling experiment (C13 isotope) test experiment.

Table 1 The results compared with other systems.

Photocatalyst	Major products (μmol g^‒1 h^‒1)	Ref.
SiC-W₁₈O₄₉ (SW-2)	(CO=11.96, CH₄=6.62, CH₃OH=3.29)	this work
SiC-W₁₈O₄₉ (SW-5)	(CO=3.53, CH₄=9.08, CH₃OH=3.21)	this work
SiC nanosheets	CO=6.29	[41]
NH₂-UiO-66/SiC	CO=7.30	[42]
VG@SiC/C	CO=25.48	[43]
α-Fe₂O₃/g-C₃N₄	CH₃OH= 5.63	[44]
BiVO₄/Bi₄Ti₃O₁₂	CH₃OH=16.6, CO=13.29	[45]
W₁₈O₄₉/Cu₂O	CH₄=17.20	[46]
g-C₃N₄/ZnO	CH₃OH=0.6	[47]
Bi₂MoO₆	CH₄=1.50	[48]
Ni₂O₃/SrTiO₃	CO=3.86, CH₄=0.50	[49]
SrTiO₃@NiFe LDH	CO= 7.9	[50]
ZnGa₂O₄ nanocubes	CH₄=1.28	[51]

Fig. 5. UV-vis DRS spectra (a) and Mott Schottky curve (b) of SiC. UV-vis DRS spectra (c) and Mott Schottky curve (d) of W18O49.

Fig. 6. W 4f (a) and Si 2p (b) XPS spectra of W18O49, SiC and SiC-W18O49 photocatalysts.

Fig. 7. (a) The measured CPD of W18O49 and SiC. (b) The band structure arrangement of SiC and W18O49. EPR signals of DMPO-O2?- of SiC, SW-2 (c) and DMPO-?OH of W18O49, SW-2 (d), under illumination for 5 min. (e) S-scheme charge transfer mechanism in SiC-W18O49 composite under visible light.

Fig. 8. Transient photocurrent response (a) and electrochemical impedance (b) of the SiC and SiC-W18O49. Steady-state PL spectra (c) and TRPL decay spectra (d) of the SiC, W18O49 and W18O49-SiC.

Fig. 9. In situ FTIR spectra of CO2 reduction with H2O vapor over SiC (a) and SiC-W18O49 (b) under the dark condition and light irradiation.

Fig. 10. Mechanism diagram of CO2 reduction by SiC-W18O49.

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1D S-scheme heterojunction of urchin-like SiC-W₁₈O₄₉ for enhancing photocatalytic CO₂ reduction

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