2D/2D S-scheme heterojunction with a covalent organic framework and g-C3N4 nanosheets for highly efficient photocatalytic H2 evolution

doi:10.1016/S1872-2067(22)64094-4

Chinese Journal of Catalysis ›› 2022, Vol. 43 ›› Issue (10): 2592-2605.DOI: 10.1016/S1872-2067(22)64094-4

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2D/2D S-scheme heterojunction with a covalent organic framework and g-C₃N₄ nanosheets for highly efficient photocatalytic H₂ evolution

Pengyu Dong^a^,^†, Aicaijun Zhang^b^,^†, Ting Cheng^c, Jinkang Pan^b, Jun Song^a, Lei Zhang^a, Rongfeng Guan^a, Xinguo Xi^c^,^*(), Jinlong Zhang^d^,^#()

^aKey Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province, Yancheng Institute of Technology, Yancheng 224051, Jiangsu, China
^bSchool of Chemistry and Chemical Engineering, Yancheng Institute of Technology, Yancheng 224051, Jiangsu, China
^cKey Laboratory for Ecological-Environment Materials of Jiangsu Province, School of Materials Science and Engineering, Yancheng Institute of Technology, Yancheng 224051, Jiangsu, China
^dKey Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, Shanghai Engineering Research Center for Multi-media Environmental Catalysis and Resource Utilization, East China University of Science and Technology, Shanghai 200237, China

Received:2022-01-17 Accepted:2022-03-08 Online:2022-10-18 Published:2022-09-30
Contact: Xinguo Xi, Jinlong Zhang
About author:^†Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(51772258);National Natural Science Foundation of China(21403184);National Natural Science Foundation of China(21972040);National Natural Science Foundation of China(21878257);Qinglan Project of Jiangsu Province;Scientific Research and Practical Innovation Project for Graduate Students in Jiangsu Province(KYCX21_3147);Innovation Program of Shanghai Municipal Education Commission(2021-01-07-00-02-E00106);Outstanding Scientific and Technological Innovation Team of Universities of Jiangsu Province;Natural Science Foundation of Jiangsu Province(BK20191024);Science and Technology Commission of Shanghai Municipality(20DZ2250400)

Abstract

Abstract:

The fabrication of S-scheme heterojunctions with fast charge transfer and good interface contacts, such as intermolecular π-π interactions, is a promising approach to improve photocatalytic performance. A unique two-dimensional/two-dimensional (2D/2D) S-scheme heterojunction containing TpPa-1-COF/g-C₃N₄ nanosheets (denoted as TPCNNS) was developed. The established maximum interfacial interaction between TpPa-1-COF NS and g-C₃N₄ NS may result in a π-π conjugated heterointerface. Furthermore, the difference in the work functions of TpPa-1-COF and g-C₃N₄ results in a large Fermi level gap, leading to upward/downward band edge bending. The spontaneous interfacial charge transfer from g-C₃N₄ to TpPa-1-COF at the π-π conjugated interface area results in the presence of a built-in electric field, according to the charge density difference analysis based on density functional theory calculations. Such an enhanced built-in electric field can efficiently drive directional charge migration via the S-scheme mechanism, which enhances charge separation and utilization. Thus, an approximately 2.8 and 5.6 times increase in the photocatalytic hydrogen evolution rate was recorded in TPCNNS-2 (1153 μmol g^-1 h^-1) compared to pristine TpPa-1-COF and g-C₃N₄ NS, respectively, under visible light irradiation. Overall, this work opens new avenues in the fabrication of 2D/2D π-π conjugated S-scheme heterojunction photocatalysts with highly efficient hydrogen evolution performance.

Key words: Covalent organic framework, g-C₃N₄, π-π, Conjugated, 2D/2D material, S-Scheme heterojunction, Photocatalytic hydrogen evolution

Pengyu Dong, Aicaijun Zhang, Ting Cheng, Jinkang Pan, Jun Song, Lei Zhang, Rongfeng Guan, Xinguo Xi, Jinlong Zhang. 2D/2D S-scheme heterojunction with a covalent organic framework and g-C₃N₄ nanosheets for highly efficient photocatalytic H₂ evolution[J]. Chinese Journal of Catalysis, 2022, 43(10): 2592-2605.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64094-4

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Figures/Tables 9

Scheme 1. Preparation of TpPa-1-COF/g-C3N4 NS (TPCNNS) hybrid heterojunction.

Fig. 1. (a) PXRD patterns; (b) FT-IR spectra. (c) Raman spectra (excited at 532 nm). (d) N2 adsorption isotherms tested at 77 K (inset: pore size distributions). C 1s (e) and N 1s (f) high-resolution XPS spectra.

Fig. 2. SEM images of g-C3N4 NS (a), TpPa-1-COF NS (b), and TPCNNS-2 (c). TEM images of g-C3N4 NS (d), TpPa-1-COF NS (e), and TPCNNS-2 (f). (g?j) TEM-EDS mapping images (scale bar: 500 nm) of TPCNNS-2.

Fig. 3. AFM image (a) and corresponding height profiles (b) of TPCNNS-2.

Fig. 4. (a) Photocatalytic H2 evolution of as-prepared samples deposited with Pt co-catalyst (3 wt%) under visible light irradiation in 8 h. (b) Comparison of photocatalytic H2 evolution rate bar chart of all samples with error bar. (c) Cycle tests of photocatalytic H2 evolution over TPCNNS-2 and TpPa-1-COF NS. (d) AQE values at various wavelengths and the corresponding diffuse reflectance absorption spectrum of TPCNNS-2. XRD patterns (e) and FTIR spectra (f) of TPCNNS-2, before and after photocatalysis.

Fig. 5. (a) Steady-state PL spectra (excited at 280 nm). (b) Transient PL decay profiles of the light emission at 430 nm (excitation wavelength: 280 nm). (c) Photocurrent responses (I-t). (d) EIS Nyquist plots of various samples (inset shows the equivalent circuit model and the fitted results).

Fig. 6. (a) UV-vis diffuse reflectance absorption spectra; (b) Corresponding Tauc plots; (c) UPS spectra; (d) Schematic energy levels diagram of TpPa-1-COF NS and g-C3N4 NS.

Fig. 7. Electrostatic potential of TpPa-1-COF (001) surface (a) and g-C3N4 (001) surface (b) along the Z-axis direction (the insets show the corresponding optimized slab structures). The construction for simulating the interfaces of TpPa-1-COF (001)/g-C3N4 (001) heterojunction before geometry optimization (c,d) and after geometry optimization (e,f) from the top side and cross views with brown, grey, red, and light-pink representing N, C, O, and H, respectively. The calculated charge density differences in the TpPa-1-COF (001)/g-C3N4 (001) heterojunction from the top (g) and side views (h). The cyan region represents charge depletion, and the yellow region denotes charge accumulation. The isosurface value is 0.025 e Å-3 (i) Planar-averaged electron density difference of the TpPa-1-COF (001)/g-C3N4 (001) heterostructure.

Fig. 8. (a) DMPO spin-trapping EPR spectra of TpPa-1-COF NS, g-C3N4 NS, and TPCNNS. (b) Schematic illustration of two potential mechanisms (i.e., the systems of type II and S-scheme heterojunction) for charge-transfer of TPCNNS. (c) Schematic explanation of the charge migration mechanism in S-scheme TPCNNS heterostructure before contact, after contact in darkness, and irradiated with visible light.

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2D/2D S-scheme heterojunction with a covalent organic framework and g-C₃N₄ nanosheets for highly efficient photocatalytic H₂ evolution

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