Precise Fabrication of Tetrametallic Metal-Organic Frameworks and Multivariate Hybrids for Enhanced Photothermal Tandem Catalysis  

作　　者：FAN Yiwen WANG Yang WANG Huijuan CHEN Yuzhen LI Zhibo 

机构地区：[1]Department of Chemistry,College of Chemistry and Chemical Engineering,Qingdao University of Science and Technology,Qingdao 266071,P.R.China [2]Experimental Center of Engineering and Material Science,University of Science and Technology of China,Hefei 230026,P.R.China

出　　处：《Chemical Research in Chinese Universities》2024年第6期1141-1150,共10页高等学校化学研究（英文版）

基　　金：supported by the Excellent Youth Foundation of Natural Science Foundation of Shandong Province,China(No.ZR2020YQ08);the National Natural Science Foundation of China(No.22275108).

摘　　要：Multiple metal sites doped in metal-organic frameworks (MOFs) are essential for their promising application in cascade reactions.However,precision synthesis of tetrametallic MOFs with total coordination and regular shapes is challenging due to the different coordination abilities of four metal ions.Herein,a series of tetrametallic MOFs (t-MOFs) with four regular morphologies is successfully constructed by regulating the metal ratio,amount of morphologic modulating reagent or growth time.The t-MOFs can be flexibly oxidized to afford porous metal oxides (MxCo_(3)O_(4),M=CuZnNi) under air or reduced to carbon-encapsulated CuCoNi under H_(2)/Ar for different reactions to maximize the value-in-use of MOFs.In particular,the t-MOF@MxCo_(3)O_(4) obtained upon the surface oxidation of t-MOF well integrates the Lewis-base sites from MOF core with photothermal oxidation activity from MxCo_(3)O_(4) shell.The hybrid effectively catalyzes the cascade reaction of styrene oxidation coupling Knoevenagel condensation under visible light.Thus,the by-product,benzaldehyde,is successfully converted to easily separated benzylidene malononitrile to finally obtain pure styrene epoxide (SO).In MxCo_(3)O_(4),Ni species afford good photothermal effect,Cu and Co species provide catalytic activity,and Zn species increase SO selectivity.The host-object coordination and the synergy among objects may greatly boost more complex reactions in the future.

关 键 词：Metal-organic framework Multimetallic site Photothermal catalysis Cascade reaction Host-object coordination 

分 类 号：O62[理学—有机化学]