Home Nano Research Article
Article Link
Cite
EndNote(RIS) BibTeX
Collect
Submit Manuscript
Show Outline
Outline
Graphical Abstract
Abstract
Keywords
Electronic Supplementary Material
References
Show full outline
Hide outline
Research Article

Electrostatic self-assembly of 2D/2D CoWO4/g-C3N4 p–n heterojunction for improved photocatalytic hydrogen evolution: Built-in electric field modulated charge separation and mechanism unveiling

Haiyang Wang1,§, Ranran Niu1,§, Jianhui Liu1, Sheng Guo2(), Yongpeng Yang1, Zhongyi Liu1, Jun Li1()
Henan Institute of Advanced Technology, College of Chemistry, Zhengzhou University, Zhengzhou 450052, China
School of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Wuhan 430205, China

§ Haiyang Wang and Ranran Niu contributed equally to this work.

Show Author Information

Graphical Abstract

View original image Download original image
An 2D/2D p–n heterojunction was successfully synthesized by self-assembled strategy for efficient photocatalytic H2 generation. This work demonstrates a high-efficient p–n heterojunction photocatalyst with II-scheme charge migration pathway and paves the way to design highly active p–n junction photocatalysts for H2 generation.

Abstract

Two-dimensional (2D) semiconductor heterojunctions are considered as an effective strategy to achieve fast separation of photoinduced carriers. Herein, a novel CoWO4/g-C3N4 (CWO/CN) p–n junction was synthesized using an electrostatic self-assembly method. The constructed 2D/2D p–n heterostructure had a rich hetero-interface, increased charge density, and fast separation efficiency of photoinduced carriers. The in-situ Kelvin probe force microscopy confirmed that the separation pathway of photoinduced carriers through the interface obeyed an II-scheme charge transfer mechanism. Experimental results and density functional theory calculations indicated the differences of work function between CWO and CN induced the generation of built-in electric field, ensuring an efficient separation and transfer process of photoinduced carriers. Under the optimized conditions, the CWO/CN heterojunction displayed enhanced photocatalytic H2 generation activity under full spectrum and visible lights irradiation, respectively. Our study provides a novel approach to design 2D/2D hetero-structured photocatalysts based on p–n type semiconductor for photocatalytic H2 generation.

Keywords

p–n junctioninterfacial charge transfertwo-dimensional/two-dimensionalphotocatalytic H2 generation CoWO4/g-C3N4 heterojunction

Electronic Supplementary Material

Download File(s)
12274_2022_4329_MOESM1_ESM.pdf (1 MB)

References

1

Cai, H. R.; Wang, B.; Xiong, L, F.; Bi, J. L.; Hao, H. J.; Yu, X. J.; Li, C.; Liu, J. M.; Yang, S. C. Boosting photocatalytic hydrogen evolution of g-C3N4 catalyst via lowering the Fermi level of co-catalyst. Nano Res. 2022, 15, 1128–1134.

Crossref Google Scholar
2

Zhu, Z. Z.; Li, X. X.; Qu, Y. T.; Zhou, F. Y.; Wang, Z. Y.; Wang, W. Y.; Zhao, C. M.; Wang, H. J.; Li, L. Q.; Yao, Y. G. et al. A hierarchical heterostructure of CdS QDs confined on 3D ZnIn2S4 with boosted charge transfer for photocatalytic CO2 reduction. Nano Res. 2021, 14, 81–90.

Crossref Google Scholar
3

Wang, L. X.; Zhang, J. J.; Zhang, Y.; Yu, H. G.; Qu, Y. H.; Yu, J. G. Inorganic metal-oxide photocatalyst for H2O2 production. Small 2021, 18, 2104561.

Google Scholar
4

Jian, S. J.; Tian, Z. W.; Hu, J. P.; Zhang, K. Y.; Zhang, L.; Duan, G. G.; Yang, W. S.; Jiang. S. H. Enhanced visible light photocatalytic efficiency of La-doped ZnO nanofibers via electrospinning-calcination technology. Adv. Powder Mater. 2022, 1, 100004.

Crossref Google Scholar
5

Tong, X. J.; Cao, X.; Han, T.; Cheong, W. C.; Lin, R.; Chen, Z.; Wang, D. S.; Chen, C.; Peng, Q.; Li, Y. D. Convenient fabrication of BiOBr ultrathin nanosheets with rich oxygen vacancies for photocatalytic selective oxidation of secondary amines. Nano Res. 2019, 12, 1625–1630.

Crossref Google Scholar
6

Zulfiqar, S.; Liu, S.; Rahman, N.; Tang, H.; Shah, S.; Yu, X. H.; Liu, Q. Q. Construction of S-scheme MnO2@CdS heterojunction with core-shell structure as H2-production photocatalyst. Rare Met. 2021, 40, 2381–2391.

Crossref Google Scholar
7

Liu, Y. J.; Zhu, Q. H.; Tayyab, M.; Zhou, L.; Lei, J. Y.; Zhang, J. L. Single-atom Pt loaded Zinc vacancies ZnO-ZnS induced type-V electron transport for efficiency photocatalytic H2 evolution. Solar RRL 2021, 5, 2100536.

Crossref Google Scholar
8

Gong, Y. N.; Shao, B. Z.; Mei, J. H.; Yang, W.; Zhong, D. C.; Lu, T. B. Facile synthesis of C3N4-supported metal catalysts for efficient CO2 photoreduction. Nano Res. 2022, 15, 551–556.

Crossref Google Scholar
9

Aggarwal, M.; Basu, S.; Shetti, N. P.; Nadagouda, M. N.; Kwon, E. E.; Park, Y. K.; Aminabhavi, T. M. Photocatalytic carbon dioxide reduction: Exploring the role of ultrathin 2D graphitic carbon nitride (g-C3N4). Chem. Eng. J. 2021, 425, 131402.

Crossref Google Scholar
10

Shen, J. X.; Li, Y. Z.; Zhao, H. Y.; Pan, K.; Li, X.; Qu, Y.; Wang, G. F.; Wang, D. S. Modulating the photoelectrons of g-C3N4 via coupling MgTi2O5 as appropriate platform for visible-light-driven photocatalytic solar energy conversion. Nano Res. 2019, 12, 1931–1936.

Crossref Google Scholar
11

Xing, M. Y.; Xu, W. J.; Dong, C. C.; Bai, Y. C.; Zeng, J. B.; Zhou, Y.; Zhang, J. L.; Yin, Y. D. Metal sulfides as excellent co-catalysts for H2O2 decomposition in advanced oxidation processes. Chem 2018, 4, 1359–1372.

Crossref Google Scholar
12

Liu, J.; Guo, S.; Wu, H. Z.; Zhang, X. L.; Li, J.; Zhou, K. Synergetic effects of Bi5+ and oxygen vacancies in Bismuth(V)-rich Bi4O7 nanosheets for enhanced near-infrared light driven photocatalysis. J. Mater. Sci. Technol. 2021, 85, 1–10.

Crossref Google Scholar
13

Wang, H.; Jiang, S. L.; Shao, W.; Zhang, X. D.; Chen, S. C.; Sun, X. S.; Zhang, Q.; Luo, Y.; Xie, Y. Optically switchable photocatalysis in ultrathin black phosphorus nanosheets. J. Am. Chem. Soc. 2018, 140, 3474–3480.

Crossref Google Scholar
14

Xiao, X. D.; Lin, S. Y.; Zhang, L. P.; Meng, H. Y.; Zhou, J.; Li, Q.; Liu, J. N.; Qiao, P. Z.; Jiang, B. J. Constructing Pd−N interactions in Pd/g-C3N4 to improve the charge dynamics for efficient photocatalytic hydrogen evolution. Nano Res. 2022, 15, 2928–2934.

Crossref Google Scholar
15
Xiao, M.; Jiao, Y. L.; Luo, B.; Wang, S. C.; Chen, P.; Lyu, M. Q.; Du, A. J.; Wang, L. Z. Understanding the roles of carbon in carbon/g-C3N4 based photocatalysts for H2 evolution. Nano Res., in press, DOI: 10.1007/s12274-021-3897-7.
16

Wang, K.; Jiang, L. S.; Wu, X. Y.; Zhang, G. K. Vacancy mediated Z-scheme charge transfer in a 2D/2D La2Ti2O7/g-C3N4 nanojunction as a bifunctional photocatalyst for solar-to-energy conversion. J. Mater. Chem. A 2020, 8, 13241–13247.

Crossref Google Scholar
17

Ren, Y. Y.; Li, Y.; Wu, X. Y.; Wang, J. L.; Zhang, G. K. S-scheme Sb2WO6/g-C3N4 photocatalysts with enhanced visible-light-induced photocatalytic NO oxidation performance. Chin. J. Catal. 2021, 42, 69–77.

Crossref Google Scholar
18

Guo, S. Q.; Zhang, H. J.; Hu, Z. Z.; Zhen, M. M.; Yang, B.; Shen, B. X.; Dong, F. Composition-dependent micro-structure and photocatalytic performance of g-C3N4 quantum dots@SnS2 heterojunction. Nano Res. 2021, 14, 4188–4196.

Crossref Google Scholar
19

Che, H. N.; Liu, C. B.; Che, G. B.; Liao, G. F.; Dong, H. J.; Li, C. X.; Song, N.; Li, C. M. Facile construction of porous intramolecular g-C3N4-based donor-acceptor conjugated copolymers as highly efficient photocatalysts for superior H2 evolution. Nano Energy 2020, 67, 104273.

Crossref Google Scholar
20

Chai, B.; Yan, J. T.; Fan, G. Z.; Song, G. S.; Wang. C. L. In situ fabrication of CdMoO4/g-C3N4 composites with improved charge separation and photocatalytic activity under visible light irradiation. Chin. J. Catal. 2020, 41, 170–179.

Crossref Google Scholar
21

Wu, X. Y.; Li, Y.; Zhang, G. K.; Chen, H.; Li, J.; Wang, K.; Pan, Y.; Zhao, Y.; Sun, Y. F.; Xie, Y. Photocatalytic CO2 conversion of M0.33WO3 directly from the air with high selectivity: Insight into full spectrum-induced reaction Mechanism. J. Am. Chem. Soc. 2019, 141, 5267–5274.

Crossref Google Scholar
22

Zeng, Y.; Luo, X.; Li, F.; Huang, A. H.; Wu, H. M.; Xu, G. Q.; Wang, S. L. Noble metal-free FeOOH/Li0.1WO3 core-shell nanorods for selective oxidation of methane to methanol with visible-NIR light. Environ. Sci. Technol. 2021, 55, 7711–7720.

Crossref Google Scholar
23

Jin, Z. L.; Yan, X.; Hao, X. Q. Rational design of a novel p-n heterojunction based on 3D layered nanoflower MoSx supported CoWO4 nanoparticles for superior photocatalytic hydrogen generation. J. Colloid Interface Sci. 2020, 569, 34–49.

Crossref Google Scholar
24

Zhang, H. Y.; Tian, W. J.; Li, Y. G.; Sun, H. Q.; Tadé, M. O.; Wang, S. B. Heterostructured WO3@CoWO4 bilayer nanosheets for enhanced visible-light photo, electro and photoelectro-chemical oxidation of water. J. Mater. Chem. A 2018, 6, 6265–6272.

Crossref Google Scholar
25

Cui, H. J.; Li, B. B.; Zhang, Y. Z.; Zheng, X. D.; Li, X. Z.; Li, Z. Y.; Xu, S. Constructing Z-scheme based CoWO4/CdS photocatalysts with enhanced dye degradation and H2 generation performance. Int. J. Hydrogen Energy 2018, 43, 18242–18252.

Crossref Google Scholar
26

Kresse, G. Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15–50.

Crossref Google Scholar
27

Bryk, P.; Patrykiejew, A.; Pizio, O.; Sokolowski, S. The chemical potential of Lennard-Jones associating fluids from osmotic monte Carlo simulations. Mol. Phys. 1997, 92, 949–956.

Crossref Google Scholar
28

VandeVondele, J.; Krack, M.; Mohamed, F.; Parrinello, M.; Chassaing, T.; Hutter, J. QUICKSTEP: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach. Comput. Phys. Commun. 2005, 167, 103–128.

Crossref Google Scholar
29

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953–17979.

Crossref Google Scholar
30

Kohn, W.; Sham, L. J. Self-consistent equations including exchange and correlation effects. Phys. Rev. 1965, 140, A1133–A1138.

Crossref Google Scholar
31

Li, J.; Huang, B. J.; Guo, Q.; Guo, S.; Peng, Z. K.; Liu, J.; Tian, Q. Y.; Yang, Y. P.; Xu, Q.; Liu, Z. Y. et al. Van der Waals heterojunction for selective visible-light-driven photocatalytic CO2 reduction. Appl. Catal. B:Environ. 2021, 284, 119733.

Crossref Google Scholar
32

Zhang, L. L.; Meng, G.; Fan, G. F.; Chen, K. L.; Wu, Y. L.; Liu, J. High flux photocatalytic self-cleaning nanosheet C3N4 membrane supported by cellulose nanofibers for dye wastewater purification. Nano Res. 2021, 14, 2568–2573.

Crossref Google Scholar
33

Xia, D. H.; Wang, W. J.; Yin, R.; Jiang, Z. F.; An, T. C.; Li, G. Y.; Zhao, H. J.; Wong, P. K. Enhanced photocatalytic inactivation of Escherichia coli by a novel Z-scheme g-C3N4/m-Bi2O4 hybrid photocatalyst under visible light: The role of reactive oxygen species. Appl. Catal. B:Environ. 2017, 214, 23–33.

Crossref Google Scholar
34

Deng, Y. C.; Liu, J.; Huang, Y. B.; Ma, M. M.; Liu, K.; Dou, X. M.; Wang, Z. J.; Qu, S. C.; Wang, Z. G. Engineering the photocatalytic behaviors of g/C3N4-based metal-free materials for degradation of a representative antibiotic. Adv. Funct. Mater. 2020, 30, 2002353.

Crossref Google Scholar
35

Zhao, X.; Fan, Y. Y.; Zhang, W. S.; Zhang, X. J.; Han, D. X.; Niu, L.; Ivaska, A. Nanoengineering construction of Cu2O nanowire arrays encapsulated with g-C3N4 as 3D spatial reticulation all-solid-state direct Z-scheme photocatalysts for photocatalytic reduction of carbon dioxide. ACS Catal. 2020, 10, 6367–6376.

Crossref Google Scholar
36

Liu, D. N.; Chen, D. Y.; Li, N. J.; Xu, Q. F.; Li, H.; He, J. H.; Lu, J. M. Surface engineering of g-C3N4 by stacked BiOBr sheets rich in oxygen vacancies for boosting photocatalytic performance. Angew. Chem. , Int. Ed. 2020, 59, 4519–4524.

Crossref Google Scholar
37

Feng, C. Y.; Tang, L.; Deng, Y. C.; Wang, J. J.; Luo, J.; Liu, Y. N.; Ouyang, X. L.; Yang, H. R.; Yu, J. F.; Wang, J. J. Synthesis of leaf-vein-like g-C3N4 with tunable band structures and charge transfer properties for selective photocatalytic H2O2 evolution. Adv. Funct. Mater. 2020, 30, 2001922.

Crossref Google Scholar
38

Zou, Y. D.; Yang, B. B.; Liu, Y.; Ren, Y.; Ma, J. H.; Zhou, X. R.; Cheng, X. W.; Deng, Y. H. Controllable interface-induced Co-assembly toward highly ordered mesoporous Pt@TiO2/g-C3N4 heterojunctions with enhanced photocatalytic performance. Adv. Funct. Mater. 2018, 28, 1806214.

Crossref Google Scholar
39

Kong, L. Q.; Ji, Y. J.; Dang, Z. Z.; Yan, J. Q.; Li, P.; Li, Y. Y.; Liu, S. Z. g-C3N4 loading black phosphorus quantum dot for efficient and stable photocatalytic H2 generation under visible light. Adv. Funct. Mater. 2018, 28, 1800668.

Crossref Google Scholar
40

Wang, D.; Qiao, S. S.; Guo, J.; Guo, Y.; Xu, Q.; Akram, N.; Wang, J. D. Efficient Co@Co3O4 core-shell catalysts for photocatalytic water oxidation and its behaviors in two different photocatalytic systems. J. Energy Chem. 2021, 57, 83–91.

Crossref Google Scholar
41
Li, X. J. ; Zhang, P. P. ; Zhang, H. Y. ; Tian, W. J. ; Yang, Y. Y. ; Hu, K. S. ; Chen, D. C. ; Li, Q. ; Duan, X. G. ; Sun, H. Q. et al. Van der Waals type II carbon nitride homojunctions for visible light photocatalytic hydrogen evolution. Nano Res., in press,DOI: 10.1007/s12274-021-3744-x.
42
He, Q. ; Viengkeo, B. ; Zhao, X. ; Qin, Z. Y. ; Zhang, J. ; Yu, X. H. ; Hu, Y. P. ; Huang, W. ; Li. Y. G. Multiscale structural engineering of carbon nitride for enhanced photocatalytic H2O2 production. Nano Res., in press,DOI: 10.1007/s12274-021-3882-1.
43

Manickathai, K.; Viswanathan, S. K.; Alagar, M. Synthesis and characterization of CdO and CdS nanoparticles. Indian J. Pure Appl. Phys. 2008, 46, 561–564.

Google Scholar
44

Matte, H. S. S. R.; Subrahmanyam, M. K. S.; Rao, K. V.; George, S. J.; Rao, C. N. R. Quenching of fluorescence of aromatic molecules by graphene due to electron transfer. Chem. Phys. Lett. 2011, 506, 260–264.

Crossref Google Scholar
45

Li, J.; Wu, X. Y.; Pan, W. F.; Zhang, G. K.; Chen, H. Vacancy-rich monolayer BiO2-x as a highly efficient UV, visible, and near-infrared responsive photocatalyst. Angew. Chem. , Int. Ed. 2018, 57, 491–495.

Crossref Google Scholar
46

Li, J.; Pan, W. F.; Liu, Q. Y.; Chen, Z. Q.; Chen, Z. J.; Feng, X. Z.; Chen, H. Interfacial engineering of Bi19Br3S27 nanowires promotes metallic photocatalytic CO2 reduction activity under near-infrared light irradiation. J. Am. Chem. Soc. 2021, 143, 6551–6559.

Crossref Google Scholar
47

Gaudreau, L.; Tielrooij, K. J.; Prawiroatmodjo, G. E. D. K.; Osmond, J.; De Abajo, F. J. G.; Koppens, F. H. L. Universal distance-scaling of nonradiative energy transfer to graphene. Nano Lett. 2013, 13, 2030–2035.

Crossref Google Scholar
48

Bandiello, E.; Rodríguez-Hernández, P.; Muñoz, A.; Buenestado, M. B.; Popescu, C.; Errandonea, D. Electronic properties and high-pressure behavior of wolframite-type CoWO4. Mater. Adv. 2021, 2, 5955–5966.

Crossref Google Scholar
49

Li, J.; Zhao, W. H.; Wang, J.; Song, S. X.; Wu, X. Y.; Zhang, G. K. Noble metal-free modified ultrathin carbon nitride with promoted molecular oxygen activation for photocatalytic formaldehyde oxidization and DFT study. Appl. Surf. Sci. 2018, 458, 59–69.

Crossref Google Scholar
Nano Research
Volume 15 Issue 8,
August 2022
Pages 6987-6998
DOI: 10.1007/s12274-022-4329-z
Cite this article:
Wang H, Niu R, Liu J, et al. Electrostatic self-assembly of 2D/2D CoWO4/g-C3N4 p–n heterojunction for improved photocatalytic hydrogen evolution: Built-in electric field modulated charge separation and mechanism unveiling. Nano Research, 2022, 15(8): 6987-6998. https://doi.org/10.1007/s12274-022-4329-z
Topics:
Photocatalysts
Metrics & Citations  
Article History
Copyright
Return