Tracking Mechanistic Pathway of Photocatalytic CO2 Reaction at Ni Sites Using Operando, Time-Resolved Spectroscopy

被引:161
作者
Hu, Yangguang [1 ,2 ]
Zhan, Fei [4 ,6 ]
Wang, Qian [1 ,2 ]
Sun, Yujian [1 ,2 ]
Yu, Can [4 ,7 ]
Zhao, Xuan [3 ]
Wang, Hao [4 ,6 ]
Long, Ran [1 ,2 ]
Zhang, Guozhen [1 ,2 ]
Gao, Chao [1 ,2 ]
Zhang, Wenkai [3 ]
Jiang, Jun [1 ,2 ]
Tao, Ye [4 ]
Xiong, Yujie [1 ,2 ,5 ]
机构
[1] Univ Sci & Technol China, Sch Chem & Mat Sci, Hefei Natl Lab Phys Sci Microscale, iChEM, Hefei 230026, Anhui, Peoples R China
[2] Univ Sci & Technol China, Natl Synchrotron Radiat Lab, Hefei 230026, Anhui, Peoples R China
[3] Beijing Normal Univ, Dept Phys, Beijing 100875, Peoples R China
[4] Chinese Acad Sci, Inst High Energy Phys, Beijing Synchrotron Radiat Facil, Beijing 100049, Peoples R China
[5] Dalian Natl Lab Clean Energy, Dalian 116023, Liaoning, Peoples R China
[6] Chem & Chem Engn Guangdong Lab, Shantou 515031, Guangdong, Peoples R China
[7] Univ Chinese Acad Sci, Beijing 100049, Peoples R China
基金
北京市自然科学基金; 国家重点研发计划;
关键词
PROTON REDUCTION CATALYST; ABSORPTION-SPECTROSCOPY; METAL-COMPLEXES; WATER;
D O I
10.1021/jacs.9b12443
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Harvesting solar energy for catalytic conversion of CO2 into valuable chemical fuels/feedstocks is an attractive yet challenging strategy to realize a sustainable carbon-cycle utilization. Homogeneous catalysts typically exhibit higher activity and selectivity as compared with heterogeneous counterparts, benefiting from their atomically dispersed catalytic sites and versatile coordination structures. However, it is still a "black box" how the coordination and electronic structures of catalysts dynamically evolve during the reaction, forming the bottleneck for understanding their reaction pathways. Herein, we demonstrate to track the mechanistic pathway of photocatalytic CO2 reduction using a terpyridine nickel(II) complex as a catalyst model. Integrated with a typical homogeneous photosensitizer, the catalytic system offers a high selectivity of 99% for CO2-to-CO conversion with turnover number and turnover frequency as high as 2.36 x 10(7) and 385.6 s(-1), respectively. We employ operando and time-resolved X-ray absorption spectroscopy, in combination with other in situ spectroscopic techniques and theoretical computations, to track the intermediate species of Ni catalyst in the photocatalytic CO2 reduction reaction for the first time. Taken together with the charge dynamics resolved by optical transient absorption spectroscopy, the investigation elucidates the full mechanistic reaction pathway including some key factors that have been often overlooked. This work opens the "black box" for CO2 reduction in the system of homogeneous catalysts and provides key information for developing efficient catalysts toward artificial photosynthesis.
引用
收藏
页码:5618 / 5626
页数:9
相关论文
共 29 条
[11]   Coordination chemistry in the design of heterogeneous photocatalysts [J].
Gao, Chao ;
Wang, Jin ;
Xu, Hangxun ;
Xiong, Yujie .
CHEMICAL SOCIETY REVIEWS, 2017, 46 (10) :2799-2823
[12]   Selectivity control of CO versus HCOO- production in the visible-light-driven catalytic reduction of CO2 with two cooperative metal sites [J].
Guo, Zhenguo ;
Chen, Gui ;
Cometto, Claudio ;
Ma, Bing ;
Zhao, Hongyan ;
Groizard, Thomas ;
Chen, Lingjing ;
Fan, Hongbo ;
Man, Wai-Lun ;
Yiu, Shek-Man ;
Lau, Kai-Chung ;
Lau, Tai-Chu ;
Robert, Marc .
NATURE CATALYSIS, 2019, 2 (09) :801-808
[13]   New aspects of operando Raman spectroscopy applied to electrochemical CO2 reduction on Cu foams [J].
Jiang, Shan ;
Klingan, Katharina ;
Pasquini, Chiara ;
Dau, Holger .
JOURNAL OF CHEMICAL PHYSICS, 2019, 150 (04)
[14]   Selective Photocatalytic CO2 Reduction in Water through Anchoring of a Molecular Ni Catalyst on CdS Nanocrystals [J].
Kuehnel, Moritz F. ;
Orchard, Katherine L. ;
Dalle, Kristian E. ;
Reisner, Erwin .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (21) :7217-7223
[15]   Visible-Light-Driven CO2 Reduction with Carbon Nitride: Enhancing the Activity of Ruthenium Catalysts [J].
Kuriki, Ryo ;
Sekizawa, Keita ;
Ishitani, Osamu ;
Maeda, Kazuhiko .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (08) :2406-2409
[16]   Tracking Co(I) Intermediate in Operando in Photocatalytic Hydrogen Evolution by X-ray Transient Absorption Spectroscopy and DFT Calculation [J].
Li, Zhi-Jun ;
Zhan, Fei ;
Xiao, Hongyan ;
Zhang, Xiaoyi ;
Kong, Qing-Yu ;
Fan, Xiang-Bing ;
Liu, Wen-Qiang ;
Huang, Mao-Yong ;
Huang, Cheng ;
Gao, Yu-Ji ;
Li, Xu-Bing ;
Meng, Qing-Yuan ;
Feng, Ke ;
Chen, Bin ;
Tung, Chen-Ho ;
Zhao, Hai-Feng ;
Tao, Ye ;
Wu, Li-Zhu .
JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 2016, 7 (24) :5253-5258
[17]   Mechanistic Evaluation of a Nickel Proton Reduction Catalyst Using Time-Resolved X-ray Absorption Spectroscopy [J].
Moonshiram, Dooshaye ;
Guda, Alexander ;
Kohler, Lars ;
Picon, Antonio ;
Guda, Sergey ;
Lehmann, C. Stefan ;
Zhang, Xiaoyi ;
Southworth, Stephen H. ;
Mulfort, Karen L. .
JOURNAL OF PHYSICAL CHEMISTRY C, 2016, 120 (36) :20049-20057
[18]   Tracking the Structural and Electronic Configurations of a Cobalt Proton Reduction Catalyst in Water [J].
Moonshiram, Dooshaye ;
Gimbert-Surinach, Carolina ;
Guda, Alexander ;
Picon, Antonio ;
Lehrnann, C. Stefan ;
Zhang, Xiaoyi ;
Doumy, Gilles ;
March, Anne Marie ;
Benet-Buchholz, Jordi ;
Soldatov, Alexander ;
Llobet, Antoni ;
Southworth, Stephen H. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (33) :10586-10596
[19]   Eigen and Zundel forms of small protonated water clusters: Structures and infrared spectra [J].
Park, Mina ;
Shin, Ilgyou ;
Singh, N. Jiten ;
Kim, Kwang S. .
JOURNAL OF PHYSICAL CHEMISTRY A, 2007, 111 (42) :10692-10702
[20]   Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis [J].
Prier, Christopher K. ;
Rankic, Danica A. ;
MacMillan, David W. C. .
CHEMICAL REVIEWS, 2013, 113 (07) :5322-5363