title: Atomic-level insights in optimizing reaction paths for hydroformylation reaction over Rh/CoO single-atom catalyst.
abstract: Rh-based heterogeneous catalysts generally have limited selectivity relative to their homogeneous counterparts in hydroformylation reactions despite of the convenience of catalyst separation in heterogeneous catalysis. Here, we develop CoO-supported Rh single-atom catalysts (Rh/CoO) with remarkable activity and selectivity towards propene hydroformylation. By increasing Rh mass loading, isolated Rh atoms switch to aggregated clusters of different atomicity. During the hydroformylation, Rh/CoO achieves the optimal selectivity of 94.4% for butyraldehyde and the highest turnover frequency number of 2,065 h-1among the obtained atomic-scale Rh-based catalysts. Mechanistic studies reveal that a structural reconstruction of Rh single atoms in Rh/CoO occurs during the catalytic process, facilitating the adsorption and activation of reactants. In kinetic view, linear products are determined as the dominating products by analysing reaction paths deriving from the two most stable co-adsorbed configurations. As a bridge of homogeneous and heterogeneous catalysis, single-atom catalysts can be potentially applied in other industrial reactions.
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Hefei Science Center &National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Liangbing
authors.initials: L
authors.lastname: Wang
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Hefei Science Center &National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Wenbo
authors.initials: W
authors.lastname: Zhang
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Hefei Science Center &National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Shenpeng
authors.initials: S
authors.lastname: Wang
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Hefei Science Center &National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Zehua
authors.initials: Z
authors.lastname: Gao
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Hefei Science Center &National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Zhiheng
authors.initials: Z
authors.lastname: Luo
authors.affiliation: Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China.
authors.forename: Xu
authors.initials: X
authors.lastname: Wang
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Hefei Science Center &National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Rui
authors.initials: R
authors.lastname: Zeng
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Hefei Science Center &National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Aowen
authors.initials: A
authors.lastname: Li
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Hefei Science Center &National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Hongliang
authors.initials: H
authors.lastname: Li
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Hefei Science Center &National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Menglin
authors.initials: M
authors.lastname: Wang
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Hefei Science Center &National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Xusheng
authors.initials: X
authors.lastname: Zheng
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Hefei Science Center &National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Junfa
authors.identifier: 0000-0003-0888-4261
authors.initials: J
authors.lastname: Zhu
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Hefei Science Center &National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Wenhua
authors.initials: W
authors.lastname: Zhang
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Hefei Science Center &National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Chao
authors.initials: C
authors.lastname: Ma
authors.affiliation: Shanghai Synchrotron Radiation Facility, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201204, China.
authors.forename: Rui
authors.initials: R
authors.lastname: Si
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, Key Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of Sciences, Hefei Science Center &National Synchrotron Radiation Laboratory, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China.
authors.forename: Jie
authors.initials: J
authors.lastname: Zeng