镓离子掺杂和硫空位调控的In_(2)S_(3)增强可见光下光催化生成过氧化氢  

Boosting the hydrogen peroxide production over In_(2)S_(3) crystals under visible light illumination by gallium ions doping and sulfur vacancies modulation

作　　者：李锋 唐小龙 胡卓锋 黎相明 李方 谢宇[5] 江燕斌 余长林[1] Feng Li;Xiaolong Tang;Zhuofeng Hu;Xiangming Li;Fang Li;Yu Xie;Yanbin Jiang;Changlin Yu(School of Chemical Engineering,Guangdong University of Petrochemical Technology,Maoming 525000,Guangdong,China;School of Chemistry and Chemical Engineering,South China University of Technology,Guangzhou 510000,Guangdong,China;School of Environmental Science and Engineering,Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology,Sun Yat-sen University,Guangzhou 510006,Guangdong,China;School of Materials Sciences and Technology,Guangdong University of Petrochemical Technology,Maoming 525000,Guangdong,China;College of Environment and Chemical Engineering,Nanchang Hangkong University,Nanchang 330063,Jiangxi,China)

机构地区：[1]广东石油化工学院化学工程学院,广东茂名525000 [2]华南理工大学化学与化工学院,广东广州510000 [3]中山大学环境科学与工程学院,广东省环境污染控制与修复技术重点实验室,广东广州510006 [4]广东石油化工学院材料科学与工程学院,广东茂名525000 [5]南昌航空大学环境与化学工程学院,江西南昌330063

出　　处：《Chinese Journal of Catalysis》2023年第12期253-264,共12页催化学报（英文）

基　　金：国家自然科学基金(22272034,22102034);广东省基础与应用基础研究基金(202201011695,2022A1515011900,2023A1515012948);广东省高校珠江学者资助计划(2019);广东省高校环境与能源绿色催化创新团队(2022KCXTD019);江西省双千人才计划;茂名市绿色化工研究院扬帆应用创新项目(MMGCIRI-2022YFJH-Y-002);茂名市科技项目(2020KJZX035).

摘　　要：过氧化氢(H_(2)O_(2))是一种绿色氧化剂,广泛用于日常生活和工业中.传统的蒽醌法制备H_(2)O_(2)的工艺流程繁琐,并且大量使用有机溶剂,对环境很不友好;小规模H_(2)O_(2)生产一般采用H2和O2直接合成,但是也存在高温、高压下使用氢气的安全隐患.人工光催化合成H_(2)O_(2)原料(水和氧气)易得且太阳能清洁可再生,是一个非常有前景的策略.然而,在光催化过程中,电子-空穴对(e^(-)-h^(+))的高复合率大大抑制了氧还原反应(ORR)生成H_(2)O_(2)的效率.本文提出了在合成In_(2)S_(3)的金属有机框架(MOF)前驱体中加入Ga^(3+)离子(IGS5),并将IGS5在管式炉中在Ar保护下焙烧,调控S空位,制得具有高活性的Ga^(3+)离子掺杂和S空位调控的In_(2)S_(3)光催化剂.通过X射线粉末衍射和X射线光电子能谱证明了成功掺杂Ga^(3+)离子.扫描电镜、透射电镜和氮气等温吸附脱附曲线结果表明,Sv-IGS-90 (焙烧90 min)为介孔材料.紫外-可见漫反射光谱结果表明,所有催化剂均可吸收部分可见光,结合莫特肖特基曲线结果,说明催化剂的导带、价带位置均满足光催化生成H_(2)O_(2)的最低要求.采用光致发光光谱、时间分辨光致发光光谱、光电流强度曲线和电化学阻抗曲线研究了催化剂的载流子分离和重组行为.电子顺磁共振谱结果表明,Sv-IGS-90中存在S空位,结合O2程序升温解吸结果,可以推断S空位可以促进O2的吸附.计算了ORR每一步所需的热力学自由能,结果表明,Ga^(3+)离子和S空位协同作用可以提高2eORR的选择性并促进O_(2)的吸附与活化.制备的Sv-IGS5-90在异丙醇:水为1:9体系中(10vol%)连续照射(λ≥420 nm)1 h后,H_(2)O_(2)浓度达到352.58μmol L-1,是纯In_(2)S_(3)的7.5倍,450 nm处的表观量子产率为4.64%.对Sv-IGS5-90光催化产H_(2)O_(2)的机理进行了深入研究,DMPO·O_(2)^(-),DMPO·OH和TEMP ~1O_(2)信号峰表明,·O_(2)^(-),·OH,~1O_(2),e^(-)和h^(+)均参与到整个反应,�Hydrogen peroxide(H_(2)O_(2)) is a green oxidant that is widely used in daily life and industry.Artificial photocatalytic synthesis of H_(2)O_(2) is a green and sustainable scheme,but the high complexation rate of electron-hole pairs during photocatalysis and the low activation capacity of the catalyst for O_(2) greatly inhibit the oxygen reduction reaction.Herein,the first synergistic modification of In_(2)S_(3) using ion doping and vacancy modulation is used in this paper.An In_(2)S_(3)-based photocatalyst containing S vacancies and Ga^(3+) ions is designed and synthesized.After continuous irradiation under visible light(λ ≥ 420 nm) for 1 h,the H_(2)O_(2) concentration of the system reaches 352.58 μmol L^(–1),which is 7.5 times than that of pure In_2S_3,and the apparent quantum yield at 450 nm is 4.64%.Appropriate concentrations of S vacancies promoted O_(2) adsorption,and theoretical calculations demonstrates that Ga^(3+) ions and S vacancies synergistically promote O_(2) activation and more favorable for 2 e–oxygen reduction reaction.All these phenomena facilitate H_(2)O_(2) generation.Furthermore,ESR analysis and radical trapping experiments show that the interaction between superoxide anion radicals(·O_(2)^(–)),singlet oxygen(^(1)O_(2)),h^(+),and proton donor(isopropanol) in the solution phase plays a key role in the photocatalytic synthesis of H_(2)O_(2),which has been largely neglected in previous studies.We suggest that the S vacancy-regulated Ga^(3+) ion-doped In_(2)S_(3) catalyst could provide a reference for the design of high-performance materials for the photocatalytic production of hydrogen peroxide.

关 键 词：光催化 硫化铟 过氧化氢 硫空位 镓离子 

分 类 号：O64[理学—物理化学]