Construction and Photocatalytic Activity of Monoclinic Tungsten Oxide/Red Phosphorus Step-scheme Heterojunction

doi:10.15541/jim20220478

Abstract

Abstract:

S-scheme heterojunction has been extensively investigated for hydrogen evolution and environmental pollution issues. In this study, a monoclinic WO₃/hydrothermally treated red phosphorus (HRP) S-scheme composite was prepared by hydrothermal method. XPS and EPR characterization confirmed that the monoclinic WO₃/HRP composite formed S-scheme heterojunction. 5%WO₃/HRP composite displayed the optimal photocatalytic activity under visible light irradiation, and its degradation rate of Rhodamine B (RhB) reached 97.6% after 4 min of visible light irradiation, while its hydrogen evolution rate reached 870.69 μmol·h^-1·g^-1 which was 3.62 times of that of pure HRP. This could be ascribed to the tight interfacial bonding between WO₃ and HRP, and the formation of S-scheme heterostructure, enabling rapid separation of photogenerated carriers and therefore improving the strong redox capacity. This study provided a promising RP-based photocatalyst to meet the demand for clean energy and drinking water.

Key words: WO₃, red phosphorus, photocatalytic hydrogen evolution, S-scheme heterojunction

CLC Number:

O643

TUERHONG Munire, ZHAO Honggang, MA Yuhua, QI Xianhui, LI Yuchen, YAN Chenxiang, LI Jiawen, CHEN Ping. Construction and Photocatalytic Activity of Monoclinic Tungsten Oxide/Red Phosphorus Step-scheme Heterojunction[J]. Journal of Inorganic Materials, 2023, 38(6): 701-707.

Figures/Tables 11

Fig. 1 XRD patterns of HRP, WO3 and 5%WO3/HRP composite

Fig. 2 TEM images of (a, b) HRP, (c, d) WO3 and (e, f) 5%WO3/HRP composite

Fig. 3 (a) P2p and (b) W4f XPS spectra of samples

Fig. 4 (a) Photodegradation curves, (b) rate curves, and (c) hydrogen production rates of HRP, WO3, 3%WO3/HRP, 5%WO3/HRP, and 7%WO3/HRP composites

Fig. 5 (a) UV-Vis DRS spectra of HRP, WO3 and 5%WO3/HRP composite, (b) Tauc plots of HRP and WO3, and (c) I-t curves of HRP, WO3 and 5%WO3/HRP composite

Fig. 6 (a) EIS spectra of HRP, WO3 and 5%WO3/HRP composite, (b) Mott-Schottky curves of HRP and WO3, and (c) EPR spectra of HRP, WO3 and 5%WO3/HRP composite

Fig. 7 Photocatalytic mechanism of the WO3/HRP composite (a) Before contact; (b) After contact in darkness; (c) S-scheme transfer process of photogenerated carriers under visible light irradiation

Fig. S1 FT-IR spectra of HRP, WO3 and 5%WO3/HRP composite

Fig. S2 SEM images of (a, d) HRP, (b, e) WO3, (c, f) 5%WO3/HRP composite, and (g) corresponding elemental mapping of P, O and W, and (h) EDS spectra of 5%WO3/HRP composite

Fig. S3 (a) XPS survey spectra of HRP, WO3, 5%WO3/HRP composite, (b) cycling performance of RhB photodegradation by 5%WO3/HRP composite and (c) PL spectra of HRP, WO3, 5%WO3/HRP composite

Fig. S4 EIS Bode plots of (a) HRP and (b) 5%WO3/HRP composite

References 32

[1]	TAO J, ZHANG M, GAO X, et al. Photocatalyst Co₃O₄/red phosphorus for efficient degradation of malachite green under visible light irradiation. Materials Chemistry and Physics, 2020, 240: 122185. DOI URL
[2]	LIU E, QI L, CHEN J, et al. In situ fabrication of a 2D Ni₂P/red phosphorus heterojunction for efficient photocatalytic H₂ evolution. Materials Research Bulletin, 2019, 115: 27. DOI URL
[3]	LIANG Z, DONG X, HAN Y, et al. In-situ growth of 0D/2D Ni2P quantum dots/red phosphorus nanosheets with p-n heterojunction for efficient photocatalytic H₂ evolution under visible light. Applied Surface Science, 2019, 484: 293. DOI URL
[4]	WU C, JING L, DENG J, et al. Elemental red phosphorus-based photocatalysts for environmental remediation: a review. Chemosphere, 2021, 274: 129793. DOI URL
[5]	WANG Z, BAI Y, LI Y, et al. Bi₂O₂CO₃/red phosphorus S-scheme heterojunction for H₂ evolution and Cr(VI) reduction. Journal of Colloid and Interface Science, 2022, 609: 320. DOI URL
[6]	ZHU Y, LI J, DONG C, et al. Red phosphorus decorated and doped TiO₂ nanofibers for efficient photocatalytic hydrogen evolution from pure water. Applied Catalysis B: Environmental, 2019, 255: 117764. DOI URL
[7]	AIHEMAITI X, WANG X, LI Y, et al. Enhanced photocatalytic and antibacterial activities of S-scheme SnO₂/Red phosphorus photocatalyst under visible light. Chemosphere, 2022, 296: 134013. DOI URL
[8]	ZHU E, MA Y, DU H, et al. Three-dimensional bismuth oxide/red phosphorus heterojunction composite with enhanced photoreduction activity. Applied Surface Science, 2020, 528: 146932. DOI URL
[9]	WANG Z, BAI Y, LI Y, et al. Bi₂O₂CO₃/red phosphorus S-scheme heterojunction for H₂ evolution and Cr(VI) reduction. Journal of Colloid and Interface Science, 2022, 609: 320. DOI URL
[10]	WANG W, LI G, AN T, et al. Photocatalytic hydrogen evolution and bacterial inactivation utilizing sonochemical-synthesized g-C₃N₄/red phosphorus hybrid nanosheets as a wide-spectral- responsive photocatalyst: the role of type I band alignment. Applied Catalysis B: Environmental, 2018, 238: 126. DOI URL
[11]	ZHU E, ZHAO S, DU H, et al. Construction of Bi₂Fe₄O₉/red phosphorus heterojunction for rapid and efficient photo-reduction of Cr(VI). Journal of the American Ceramic Society, 2021, 104: 5411. DOI URL
[12]	ZHOU L, LI Y, YANG S, et al. Preparation of novel 0D/2D Ag₂WO₄/WO₃step-scheme heterojunction with effective interfacial charges transfer for photocatalytic contaminants degradation and mechanism insight. Chemical Engineering Journal, 2021, 420: 130361. DOI URL
[13]	ZHANG J, LIU Z, LIU Z. Novel WO₃/Sb₂S₃ heterojunction photocatalyst based on WO₃ of different morphologies for enhanced efficiency in photoelectrochemical water splitting. ACS Applied Materials & Interfaces, 2016, 8(15):9684.
[14]	LING Y, DAI Y. Direct Z-scheme hierarchical WO₃/BiOBr with enhanced photocatalytic degradation performance under visible light. Applied Surface Science, 2020, 509: 145201. DOI URL
[15]	SONG C, WANG X, ZHANG J, et al. Enhanced performance of direct Z-scheme CuS-WO₃ system towards photocatalytic decomposition of organic pollutants under visible light. Applied Surface Science, 2017, 425: 788. DOI URL
[16]	JIANG S, CAO J, GUO M, et al. Novel S-scheme WO₃/RP composite with outstanding overall water splitting activity for H₂ and O₂ evolution under visible light. Applied Surface Science, 2021, 558: 149882. DOI URL
[17]	TUERHONG M, CHEN P, MA Y, et al. Bi₂MoO₆/red phosphorus heterojunction for reducing Cr(VI) and mitigating Escherichia coli infection. Journal of Solid State Chemistry, 2022, 315: 123468. DOI URL
[18]	PAN T, CHEN D, XU W, et al. Anionic polyacrylamide-assisted construction of thin 2D-2D WO₃/g-C₃N₄ step-scheme heterojunction for enhanced tetracycline degradation under visible light irradiation. Journal of Hazardous Materials, 2020, 393: 122366. DOI URL
[19]	ZHANG N, LI X, YE H, et al. Oxide defect engineering enables to couple solar energy into oxygen activation. Journal of the American Chemical Society, 2016, 138(28):8928. DOI PMID
[20]	XIAO T, TANG Z, YANG Y, et al. In situ construction of hierarchical WO₃/g-C₃N₄ composite hollow microspheres as a Z-scheme photocatalyst for the degradation of antibiotics. Applied Catalysis B: Environmental, 2018, 220: 417. DOI URL
[21]	GUO C, DU H, MA Y, et al. Visible-light photocatalytic activity enhancement of red phosphorus dispersed on the exfoliated kaolin for pollutant degradation and hydrogen evolution. Journal of Colloid and Interface Science, 2020, 585: 167. DOI URL
[22]	ZHOU J, AN X, TANG Q, et al. Dual channel construction of WO₃photocatalysts by solution plasma for the persulfate-enhanced photodegradation of bisphenol A. Applied Catalysis B: Environmental, 2020, 277: 119221. DOI URL
[23]	FENG C, TANG L, DENG Y, et al. Synthesis of branched WO₃@W₁₈O₄₉ homojunction with enhanced interfacial charge separation and full-spectrum photocatalytic performance. Chemical Engineering Journal, 2020, 389: 124474. DOI URL
[24]	ZHANG K, JIN B, PARK C, et al. Black phosphorene as a hole extraction layer boosting solar water splitting of oxygen evolution catalysts. Nature Communications, 2019, 10(1): 2001. DOI PMID
[25]	ZOU X, DONG Y, KE J, et al. Cobalt monoxide/tungsten trioxide p-n heterojunction boosting charge separation for efficient visible- light-driven gaseous toluene degradation. Chemical Engineering Journal, 2020, 400: 125919. DOI URL
[26]	YUE X, YI S, WANG R, et al. Well-controlled SrTiO₃@Mo₂C core-shell nanofiber photocatalyst: boosted photo-generated charge carriers transportation and enhanced catalytic performance for water reduction. Nano Energy, 2018, 47: 463. DOI URL
[27]	AIHEMAITI X, WANG X, WANG Z, et al. Effective prevention of charge trapping in red phosphorus with nanosized CdS modification for superior photocatalysis. Journal of Environmental Chemical Engineering, 2021, 9(6):106479. DOI URL
[28]	DONG C, YANG Y, HU X, et al. Self-cycled photo-Fenton-like system based on an artificial leaf with a solar-to-H₂O₂ conversion efficiency of 1.46%. Nature Communications, 2022, 13(1):4982. DOI
[29]	GE H, XU F, CHENG B, et al. S-scheme heterojunction TiO₂/CdS nanocomposite nanofiber as H₂-production photocatalyst. ChemCatChem, 2019, 11(24):6301. DOI URL
[30]	LIU Y, PAN D, XIONG M, et al. In-situ fabrication SnO₂/SnS₂heterostructure for boosting the photocatalytic degradation of pollutants. Chinese Journal of Catalysis, 2020, 41(10):1554. DOI URL
[31]	JIA Y, WANG Z, QIAO X, et al. A synergistic effect between S-scheme heterojunction and Noble-metal free cocatalyst to promote the hydrogen evolution of ZnO/CdS/MoS₂photocatalyst. Chemical Engineering Journal, 2021, 424: 130368. DOI URL
[32]	FU J, XU Q, LOW J, et al. Ultrathin 2D/2D WO₃/g-C₃N₄ step-scheme H₂-production photocatalyst. Applied Catalysis B: Environmental, 2019, 243: 556. DOI URL