Boosting hydrogen peroxide photosynthesis via a 1D/2D S-scheme heterojunction constructed by a covalent triazine framework with dual O_(2) reduction centers  

基于双氧还原中心的共价三嗪框架构建的1D/2DS型异质结促进过氧化氢光合作用

作　　者：Bingquan Xia Gaoxiong Liu Kun Fan Rundong Chen Xin Liu Laiquan Li 夏兵全;刘高雄;樊坤;陈润东;刘欣;李来全(武汉工程大学化学与环境工程学院,湖北武汉430074;上海理工大学能源材料科学研究院,上海200093;哈尔滨理工大学电子与电气工程学院,黑龙江哈尔滨150080)

机构地区：[1]Key Laboratory of Green Chemical Engineering Process of Ministry of Education,School of Chemistry and Environmental Engineering,Wuhan Institute of Technology,Wuhan 430074,Hubei,China [2]Institute of Energy Materials Science,University of Shanghai for Science and Technology,Shanghai 200093,China [3]Key Laboratory of Engineering Dielectric and Applications(Ministry of Education),School of Electrical and Electronic Engineering,Harbin University of Science and Technology,Harbin 150080,Heilongjiang,China

出　　处：《Chinese Journal of Catalysis》2025年第2期315-326,共12页催化学报(英文)

基　　金：国家自然科学基金(22409151,22405173);湖北省自然科学基金(2023AFB181);武汉工程大学科学研究基金(23QD02)。

摘　　要：Emerging as lamellar materials,covalent triazine frameworks(CTFs)exhibited great potential for photocatalysis,but their photocatalytic performance is always hindered by the prone recombination of photogenerated carriers.To overcome this obstacle,a 1D/2D step-scheme(S-scheme)heterojunction is constructed for photocatalytic synthesis of H_(2)O_(2).The S-scheme heterojunction fabricated with CTF and ZnO effectively enhances light absorption,redox capabilities,and charge carrier separation and transfer.In particular,the CTF is decorated with benzothiadiazole and triazine groups as dual O2 reduction active centers,boosting photocatalytic H_(2)O_(2) production.The optimal ZC-10 hybrid delivers a maximum H2O2 generation rate of 12000μmol g^(–1) h^(–1),10.3 and 164 times higher than those of zinc oxide nanorods and CTFs,respectively.Moreover,the charge transfer mechanism in the S-scheme heterojunction is well investigated with in situ spectroscopic measurements and theoretical calculations.过氧化氢(H_(2)O_(2))作为环保型氧化剂,其国内年需求量约10万吨.目前主要的生产方法葱醌法要用昂贵的钯催化剂,同时会产生有毒的副产品,因此利用太阳能开发一种可持续的H_(2)O_(2)生产方法迫在眉睫.具有芳香族三嗪结构的共价三嗪框架(CTFs)具有高电子亲和性和杂原子效应,有着丰富的活性位点.然而共价三嗪框架内部载流子快速重组和固有光捕获能力的不足,使得其光催化性能受到阻碍。目前常用策略是在结构中引入电子供体,使其在分子水平上形成供体-受体结构,通过强大的推拉式分子内电荷转移将载流子和空穴集中在相应的基团附近,从而改善电荷分离和传输受此启发,本文采用将无供体CTFs与ZnO结合的策略,以ZnO作为电子供体构筑S型异质结,利用异质结修饰策略来增加电子供体,充分发挥CTFs中的活性位点进行O_(2)还原的整体光合H_(2)O_(2)生产.通过构建S型异质结,解决了分离电荷容易重组的问题,并改变了电荷转移机制,提高了光催化效率,最终促进H_(2)O_(2)的生成.通过物理自组装方法将一维(1D)ZnO纳米棒和二维(2D)CTF组合构筑成了ZnO/CTFS型异质结构的光催化剂,研究了其对生成H_(2)O_(2)的光催化性能.在模拟可见光照射下,ZC-10的H_(2)O_(2)生成速率为12000μmolg^(-1)h^(-1),分别是ZnO纳米棒和CTF的10.3倍和164倍。原位X-射线光电子能谱(XPS)结果表明,在黑暗条件下ZC-10存在内置静电场,在光照条件下,ZC-10中ZnO失去电子,而CTF得到电子,这与S型异质结的电荷转移机理一致.原位开尔文探针力显微镜进一步证实了ZC-10在黑暗条件下内置静电场存在,同时光照之后电荷转移与原位XPS测试结果一致,再次证明了S型异质结形成.电子顺磁共振和自由基淬灭实验表明,超氧自由基是光催化合成过氧化氢的主要活性物种,同时ZC-10的超氧自由基和羟基自由基的光催化产率明显超过ZnO和CTF,表明�

关 键 词：Covalent triazine frameworks Photocatalytic H_(2)O_(2)production S-scheme heterojunction Dual O_(2)reduction centers 

分 类 号：O643.36[理学—物理化学]