MOF衍生Co_(3)O_(4)/ZrO_(2)介孔八面体:优化电荷转移和中间体转化用于高效CO_(2)光还原  

MOF-derived Co_(3)O_(4)/ZrO_(2) mesoporous octahedrons with optimized charge transfer and intermediate conversion for efficient CO_(2) photoreduction

作　　者：刘海兵 邱衍滨 甘文秀 庄国鑫 陈飞飞 杨程凯 于岩 Haibing Liu;Yanbin Qiu;Wenxiu Gan;Guoxin Zhuang;Feifei Chen;Chengkai Yang;Yan Yu(Key Laboratory of Advanced Materials Technologies,International(HongKong Macao and Taiwan)Joint Laboratory on Advanced Materials Technologies,College of Materials Science and Engineering,Fuzhou University,Fuzhou 350108,China;Scientific Research and Experiment Center,Fujian Police College,Fuzhou 350007,China)

机构地区：[1]Key Laboratory of Advanced Materials Technologies,International(HongKong Macao and Taiwan)Joint Laboratory on Advanced Materials Technologies,College of Materials Science and Engineering,Fuzhou University,Fuzhou 350108,China [2]Scientific Research and Experiment Center,Fujian Police College,Fuzhou 350007,China

出　　处：《Science China Materials》2024年第2期588-597,共10页中国科学（材料科学）（英文版）

基　　金：supported by the National Key Research and Development Program of China(2020YFA0710303);the National Natural Science Foundation of China(52002072,U1905215,52072076);the Natural Science Foundation of Fujian Province(2021J01589,2023J05082)。

摘　　要：调控电荷转移和反应路径是促进光催化CO_(2)还原的两种有效策略.本研究通过热解UIO-66@ZIF-67核壳八面体,合成了Co_(3)O_(4)/ZrO_(2)介孔八面体.该介孔八面体由高度分散的小尺寸纳米颗粒组装而成,平均颗粒尺寸为13 nm,平均孔径为5.8 nm,比表面积为43.11 m^(2)g^(-1).受益于活性位点设计,电荷转移动力学和CO_(2)吸附得以增强.此外,密度泛函理论计算结果显示,ZrO_(2)能够有效调控CO_(2)还原的反应路径,包括促进CO_(2)活化为*CO_(2)、中间体(*COOH和*CO)的形成、以及减小限速步(*CO→CO)的能垒.因此,Co_(3)O_(4)/ZrO_(2)介孔八面体的周转率高达28.82,是纯Co_(3)O_(4)的16.95倍.Regulating charge transfer and reaction pathways are effective strategies for boosting photocatalytic CO_(2) reduction.Herein,Co_(3)O_(4)/ZrO_(2) mesoporous octahedrons are synthesized through facile pyrolysis of UIO-66@ZIF-67 core/shell octahedrons.The as-obtained Co_(3)O_(4)/ZrO_(2) mesoporous octahedrons are assembled by highly dispersive and smallsized nanoparticles,with 13 nm average particle size and 5.8 nm pore width,leading to a high specific surface area of 43.11 m^(2) g^(−1).Benefiting from active-site engineering,the charge-transfer kinetics and CO_(2) adsorption are successfully enhanced.In addition,density functional theory calculations reveal that ZrO_(2) tailors the reaction pathway of CO_(2) reduction by promoting CO_(2) activation to*CO_(2) and intermediate formation(*COOH and*CO),as well as decreasing the energy barrier of the rate-limiting step(*CO→CO).Thus,the Co_(3)O_(4)/ZrO_(2) mesoporous octahedrons afford a turnover frequency of 28.82 h−1,16.95-fold larger than pure Co_(3)O_(4).

关 键 词：metal-organic frameworks MESOPOROUS OXIDES photocatalysis CO_(2)reduction 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学]