物理化学学报2024，Vol.40Issue(5)：38-41,4.DOI:10.3866/PKU.WHXB202305047
硫取代氮增强g-C3N4光催化产氢性能
S-Doping of the N-Sites of g-C3N4 to Enhance Photocatalytic H2 Evolution Activity
摘要
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(ΔGH*)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-CN1.0)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.关键词
理论预测/硫掺杂/g-C3N4/产氢/光催化Key words
Theoretical prediction/S-doping/g-C3N4/Hydrogen evolution/Photocatalysis分类
化学化工引用本文复制引用
王海涛,余良浪,江吉周,Arramel,邹菁..硫取代氮增强g-C3N4光催化产氢性能[J].物理化学学报,2024,40(5):38-41,4.基金项目
This work is supported by the National Natural Science Foundation of China(62004143),the Key R&D Program of Hubei Province,China(2022BAA084),the Natural Science Foundation of Hubei Province,China(2021CFB133),the National Key R&D Program of China(2022YFC3902703),the Innovation Project of Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education,China(LCX2021003)and the Open Research Fund of Key Laboratory of Material Chemistry for Energy Conversion and Storage(HUST),Ministry of Education,China(2021JYBKF05). 国家自然科学基金(62004143),湖北省重点研发计划(2022BAA084),湖北省自然科学基金(2021CFB133),国家重点研发计划(2022YFC3902703),磷资源开发利用教育部工程研究中心创新项目(LCX2021003),能量转换与存储材料化学教育部重点实验室开放基金(2021JYBKF05)资助 （62004143）
