MOF衍生Co3O4/ZrO2介孔八面体:优化电荷转移和中间体转化用于高效CO2光还原
MOF-derived Co3O4/ZrO2 mesoporous octahedrons with optimized charge transfer and intermediate conversion for efficient CO2 photoreduction
刘海兵 1邱衍滨 1甘文秀 1庄国鑫 2陈飞飞 1杨程凯 1于岩1
作者信息
- 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
- 折叠
摘要
调控电荷转移和反应路径是促进光催化CO2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Co3O4/ZrO2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 m2g-1.受益于活性位点设计,电荷转移动力学和CO2吸附得以增强.此外,密度泛函理论计算结果显示,ZrO2能够有效调控CO2还原的反应路径,包括促进CO2活化为*CO2、中间体(*COOH和*CO)的形成、以及减小限速步(*CO→CO)的能垒.因此,Co3O4/ZrO2介孔八面体的周转率高达28.82,是纯Co3O4的16.95倍.
Abstract
Regulating charge transfer and reaction path-ways are effective strategies for boosting photocatalytic CO2 reduction.Herein,Co3O4/ZrO2 mesoporous octahedrons are synthesized through facile pyrolysis of UIO-66@ZIF-67 core/shell octahedrons.The as-obtained Co3O4/ZrO2 mesoporous octahedrons are assembled by highly dispersive and small-sized nanoparticles,with 13 nm average particle size and 5.8 nm pore width,leading to a high specific surface area of 43.11 m2g-1.Benefiting from active-site engineering,the charge-transfer kinetics and CO2 adsorption are successfully enhanced.In addition,density functional theory calculations reveal that ZrO2 tailors the reaction pathway of CO2 reduction by promoting CO2 activation to*CO2 and intermediate for-mation(*COOH and*CO),as well as decreasing the energy barrier of the rate-limiting step(*CO→CO).Thus,the Co3O4/ZrO2 mesoporous octahedrons afford a turnover frequency of 28.82 h-1,16.95-fold larger than pure Co3O4.
关键词
metal-organic frameworks/mesoporous/oxides/photocatalysis/CO2 reductionKey words
metal-organic frameworks/mesoporous/oxides/photocatalysis/CO2 reduction引用本文复制引用
基金项目
National Key Research and Development Program of China(2020YFA0710303)
National Natural Science Foundation of China(52002072)
National Natural Science Foundation of China(U1905215)
National Natural Science Foundation of China(52072076)
Natural Science Foundation of Fujian Province(2021J01589)
Natural Science Foundation of Fujian Province(2023J05082)
出版年
2024
NETL
NSTL
万方数据