硫取代氮增强g-C3N4光催化产氢性能

doi:10.3866/PKU.WHXB202305047

Abstract

Abstract:

The use of solar energy as an inexhaustible resource to conduct photocatalytic water splitting in hydrogen (H₂) production can alleviate the worldwide energy crisis and achieve carbon neutrality. However, research in photocatalytic H₂ evolution reaction (HER) is extremely challenging in terms of exploring the current development of an active and durable graphitic carbon nitride (g-C₃N₄)-based photocatalyst. Several parameters of pristine g-C₃N₄ require structural, physical, and chemical improvements, such as optimization of the surface area, electron transfer, and photo-generated carrier recombination, to render the g-C₃N₄ suitable for photocatalysis. In this study, the development of an efficient and robust S-doped g-C₃N₄ (S-g-CN) catalyst was pursued that involves doping nitrogen (N) active sites of g-C₃N₄ with sulfur (S) dopants via one-step calcination of the sulphate and melamine precursors. A combination of structural and spectroscopic fingerprints was established to distinctly determine the realization of S-doping onto the g-C₃N₄ structure. We obtained the optimum Gibbs free energy of adsorbed hydrogen (ΔG_H*) for S-g-CN at the S active sites, which is nearly zero (~0.26 eV), suggesting that the filled S dopants play an essential role in optimizing the adsorption and desorption processes of H-active intermediates. The results of atomic force and transmission electron microscopies (AFM and TEM) demonstrated that the produced S-g-CN catalyst has an ultrathin nanosheet structure with a lamellar thickness of approximately 2.5 nm. A subsequent N₂ sorption isotherms test revealed a substantial increase in the specific surface area after the integration of S dopants into the g-C₃N₄ nanoskeleton. Moreover, the incorporation of S atoms into the g-C₃N₄ significantly increased the carrier concentrations, improving the transfer, separation, as well as the oxidation and reduction abilities of the photo-generated electron-hole pairs. Leveraging the favorable material characteristics of the S-doped two-dimensional nanostructures, the resulting S-g-CN achieved a high H₂ evolution rate of 4923 μmol·g⁻¹·h⁻¹, which is 28 times higher than that of the pristine g-C₃N₄. Additionally, the developed S-g-CN possessed a high apparent quantum efficiency (3.64%) at visible-light irradiation. When compared to the recently reported S-doped g-C₃N₄-based photocatalysts, our optimal S-g-CN catalyst (S-CN_1.0) showed one of the best HER catalytic activities. Our rational design is based on an effective strategy that not only explored a promising HER photocatalyst but also aimed to pave the way for the development of other high-performance g-C₃N₄ based catalysts.

Key words: Theoretical prediction, S-doping, g-C₃N₄, Hydrogen evolution, Photocatalysis

Haitao Wang, Lianglang Yu, Jizhou Jiang, Arramel, Jing Zou. S-Doping of the N-Sites of g-C₃N₄ to Enhance Photocatalytic H₂ Evolution Activity[J]. Acta Phys. -Chim. Sin. 2024, 40(5), 2305047. doi: 10.3866/PKU.WHXB202305047

Figures/Tables 7

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References 61

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Photocatalyst	Loading (mg)	Co-catalyst	H₂ evolution rate (μmol∙g⁻¹∙h⁻¹)	Reference
S-g-CN_1.0	50	1 wt% Pt	4923	this work
PCNS	15	2 wt% Pt	880.2	44
SPCN_0.1	50	3 wt% Pt	4200.3	45
SCN1.0	50	3 wt% Pt	141.9	46
SCND-3	50	3 wt% Pt	1404	47
MA-Fe-S-CN	50	–	2965.5	48
g-CN-TM1	10	0.5 wt% Pt	4430	49
Co-S-CN	20	1 wt% Pt	910.6	50
0.3S-CN	10	1 wt% Pt	952	51
S@g-C₃N₄	5	1 wt% Pt	736.8	52
PSCN	20	3 wt% Pt	1969	53
SS-CN	50	1 wt% Pt	982.3	54

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S-Doping of the N-Sites of g-C₃N₄ to Enhance Photocatalytic H₂ Evolution Activity

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