Conjugated Crosslinking Modification of Graphitic Carbon Nitrides and Its Effect on Visible Light-Driven Photocatalytic Hydrogen Production

doi:10.6023/A22040183

Abstract

Owing to their features of easy preparation, low cost and good stability, graphitic carbon nitrides (GCNs) have attracted increasing attention in the field of photocatalytic water-splitting hydrogen production for green and renewable energy as an alternative to fossil. However, their narrow light absorption spectra and low efficiencies in photogenerated charge separation and transfer processes restrict their photocatalytic performance. In this work, 4,4'-(benzo[c][1,2,5]thiadiazole- 4,7-diyl)dibenzaldehyde (BTD) was used to conjugated crosslink and surface modify GCN via acid-catalyzed Shiff-base condensation reaction at 260 ℃, affording four BTD-modified graphitic carbon nitride materials denoted as GCN-BTD_x (x represents the amount of BTD in mg used in the reaction with 100 mg GCN and equals to 20, 40, 80, and 160). Elemental analysis, Fourier transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, UV-vis diffuse reflectance spectroscopy, Mott-Schottky analysis, electrochemical impedance spectroscopy and photocurrent responsive measurements were used to characterize and investigate the synthesized materials. Using these materials as photocatalysts, triethanolamine as electron sacrificial agent, Pt nanoparticle as cocatalyst, visible light-driven photocatalytic hydrogen production from water have been studied. It was found the BTD modification can extend light absorption spectrum, tune energy band structure, and reduce interfacial charge transfer resistance, and thus finally improve the material photocatalytic hydrogen production performance. Among the family, GCN-BTD₁₆₀ behaved the best with the highest hydrogen evolution rate (863 μmol•g^–1•h^–1) and excellent stability and recyclability. Its hydrogen evolution rate is more than 2 folds as that of unmodified GCN. Moreover, GCN-BTD₁₆₀ exhibited good visible light responsibility, with apparent quantum yields of 2.4% at 420 nm, 1.8% at 450 nm, and 1.6% at 500 nm. Therefore, this work paves a new method in graphitic carbon nitride modification for photocatalytic performance improvement.

Key words: graphitic carbon nitrides, photocatalysis, water splitting hydrogen production, visible light, conjugated modification, benzothiadiazole

Cite this article

Zhongshu Xie, Zhongxin Xue, Ziwen Xu, Qian Li, Hongyu Wang, Wei-Shi Li. Conjugated Crosslinking Modification of Graphitic Carbon Nitrides and Its Effect on Visible Light-Driven Photocatalytic Hydrogen Production[J]. Acta Chimica Sinica, 2022, 80(9): 1231-1237.

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Fig. & Tab. 7

Scheme 1. Synthesis of GCN-BTDx

样品	C (%)	N (%)	H (%)	S (%)
GCN	37.0	59.0	2.0	0
GCN-BTD₂₀	39.1	52.7	2.2	1.2
GCN-BTD₄₀	45.3	46.8	2.4	2.3
GCN-BTD₈₀	47.4	43.2	2.5	2.9
GCN-BTD₁₆₀	53.0	34.0	2.7	4.7
GCN-BTD₅₀₀	54.7	32.9	2.8	5.0

Table 1. Elemental analysis of GCN-BTDx

Figure 1. (a) FT-IR and (b) powder XRD of GCN, BTD and GCN- BTDx. SEM images of (c) GCN, (d) GCN-BTD40, (e) GCN-BTD80 and (f) GCN-BTD160

Figure 2. (a) Survey scanning, and high resolution (b) C 1s, (c) N 1s, and (d) S 2p XPS spectra of GCN and GCN-BTDx

Figure 3. (a) UV-vis diffuse reflectance spectra, (b) Tauc plots, (c) Mott-Schottky curves and (d) energy band structures of GCN and GCN-BTDx

Figure 4. (a, b) The time course and (c) hydrogen evolution rate of visible light photocatalytic hydrogen production from water with GCN and GCN-BTDx as photocatalysts (a) in the absence of cocatalyst and (b) in the presence of w=3% Pt cocatalyst. (d) Repetitive use and (e) apparent quantum yield of GCN-BTD160 in photocatalysis. Other conditions: 15 mg tested catalyst, 15 mL H2O, 1.5 mL TEOA, irradiated with a 300 W Xe lamp equipped with a UV cut filter (λ>420 nm), or λ=420, 450, or 500 nm monochromatic band-pass filters

Figure 5. (a) Steady-state photoluminescence spectra, (b) EIS profiles and (c) photocurrent responsive curves of GCN and GCN-BTDx

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