摘要
利用溶剂热法,将Cu(Ⅱ)和光敏性9,10-二(4-羧基苯基)蒽(H2ADBA)通过配位自组装制备了具有光致配体到金属的电子转移(LMCT)行为的二维蒽基铜金属有机框架(MOF)(Cu-ADBA)。通过单晶X射线衍射和粉末X射线衍射表征了晶体结构。采用SEM、TEM、AFM对Cu-ADBA进行了表征,评价了其催化性能。通过UV-Vis吸收光谱、荧光光谱、Raman光谱、XPS和EPR推测了其机理。结果表明,Cu-ADBA在无水乙醇中可以发生剥离,形成约4 nm厚的薄片,有利于暴露出更多的催化活性位点。在365 nm LED光照下,以葡萄糖为电子牺牲剂,Cu-ADBA可高效地催化苄基叠氮和炔烃的环加成Click反应,产率为46%~92%。以苯乙炔和苄基叠氮为底物,催化剂重复使用3次后,产率从85%降为80%,没有明显下降。配体H_(2)ADBA在350~410 nm处具有良好的吸收,激发态还原电位为–1.56 V(vs.Ag/AgCl),足以还原Cu-ADBA金属节点的Cu(Ⅱ)。Cu-ADBA的荧光强度远小于配体。光照下MOF中的配体受到激发,会将金属节点中的Cu(Ⅱ)还原为Cu(Ⅰ)。
A new 2D metal organic framework(MOF)(Cu-ADBA)with photoinduced ligand-to-metal charge transfer(LMCT)behavior was constructed from self-assembly between Cu(Ⅱ)and photoredox 9,10-di(p-carboxyphenyl)anthracene(H2ADBA)via solvothermal method,with the crystal structure characterized by single-crystal X-ray diffraction and powder X-ray diffraction.The Cu-ADBA obtained was characterized by SEM,TEM and AFM,and evaluated for its catalytic performance,with the catalytic mechanism analyzed by UV-Vis absorption spectroscopy,fluorescence spectroscopy,Raman spectroscopy,XPS and EPR.The results indicated that Cu-ADBA in ethanol absolute could be exfoliated and form nanosheets with about 4 nm thickness,favorable for more exposure of catalytic sites.Under 365 nm LED light,the cycloaddition Click reaction of alkynes and benzyl azides was efficiently catalyzed by Cu-ADBA using glucose as electron-sacrificing agent,with a product yield of 46%~92%.The catalysts could be recycled for three times without obvious deactivation with the yield merely decreased from 85%to 80%using phenylacetylene and(azidomethyl)benzene as substrates.The ligand H2ADBA had a wide absorption band at 350~410 nm,the excited state reduction potential of H_(2)ADBA was–1.56 V(vs.Ag/AgCl),which could reduce Cu(Ⅱ)in the metal node of Cu-ADBA.The fluorescence intensity of Cu-ADBA was much smaller than that of the ligand,and the ligand in MOF was excited under the illumination,which reduced the Cu(Ⅱ)in the metal node to Cu(Ⅰ).
作者
安洋
Muhammad Saqaf JAGIRANI
史雨生
段春迎
张铁欣
AN Yang;Muhammad Saqaf JAGIRANI;SHI Yusheng;DUAN Chunying;ZHANG Tiexin(State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024,Liaoning,China;State Key Laboratory of Structural Chemistry,Fujian Institute of Research on Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,Fujian,China;State Key Laboratory of Coordination Chemistry,Nanjing University,Nanjing 210023,Jiangsu,China)
出处
《精细化工》
北大核心
2026年第2期397-406,共10页
Fine Chemicals
基金
国家自然科学基金项目(22472020、22301028)
国家外国专家项目(QN2023127001L)
辽宁省科技计划联合计划项目(2023JH2/101700297)
中央高校基本科研业务费项目(DUT24YG123)。
关键词
金属有机框架
二维材料
铜
蒽
配体到金属的电子转移
光催化
催化技术
metal organic frameworks
2D materials
copper
anthracene
ligand-to-metal charge transfer
photocatalysis
catalysis technology
