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).
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)
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)。
作者简介
Haibing Liu received his Bachelor’s degree from Nanchang Hangkong University in 2020 and his Master’s degree from Fuzhou University in 2023.His research interest is the synthesis of advanced catalysts using MOF precursors for CO_(2) photoreduction,contributed equally;Yanbin Qiu received his Bachelor’s degree from Fujian Normal University in 2021.Currently,he is a graduate student at Fuzhou University.His research focuses on building structure–performance relationships based on DFT calculations,contributed equally;Corresponding author:Feifei Chen received his Bachelor’s degree from Xiamen University in 2014,and Doctor’s degree from Shanghai Institute of Ceramics,Chinese Academy of Sciences in 2019.Currently,he is an associate professor at Fuzhou University.His research interest is the development of ecological materials for water and air purification,email:ffchen@fzu.edu.cn;Corresponding author:Chengkai Yang received his Bachelor’s degree from Tianjin University,and Doctor’s degree from Peking University in 2019.Currently,he is an associate professor at Fuzhou University.His research interests include energy materials,the electrochemistry of zinc-ion/lithium-ion/lithium–sulfur batteries,and material calculations,email:chengkai_yang@fzu.edu.cn;Corresponding author:Yan Yu received her Bachelor’s,Master’s,and Doctor’s degrees from Fuzhou University.She was a postdoctoral fellow at Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,in 2010–2013.Currently,she is a professor at Fuzhou University.Her research interests include water purification,utilization of solid waste,ecological materials,and photocatalytic CO_(2) reduction and H_(2) production.email:yuyan@fzu.edu.cn。
