title: Integration of Quantum Confinement and Alloy Effect to Modulate Electronic Properties of RhW Nanocrystals for Improved Catalytic Performance toward CO2Hydrogenation.
abstract: The d-band center and surface negative charge density generally determine the adsorption and activation of CO2, thus serving as important descriptors of the catalytic activity toward CO2hydrogenation. Herein, we engineered the d-band center and negative charge density of Rh-based catalysts by tuning their dimensions and introducing non-noble metals to form an alloy. During the hydrogenation of CO2into methanol, the catalytic activity of Rh75W25nanosheets was 5.9, 4.0, and 1.7 times as high as that of Rh nanoparticles, Rh nanosheets, and Rh73W27nanoparticles, respectively. Mechanistic studies reveal that the remarkable activity of Rh75W25nanosheets is owing to the integration of quantum confinement and alloy effect. Specifically, the quantum confinement in one dimension shifts up the d-band center of Rh75W25nanosheets, strengthening the adsorption of CO2. Moreover, the alloy effect not only promotes the activation of CO2to form CO2δ-but also enhances the adsorption of intermediates to facilitate further hydrogenation of the intermediates into methanol.
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, Anhui 230026, P. R. 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, Anhui 230026, P. R. 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, Anhui 230026, P. R. China.
authors.forename: Haoyu
authors.initials: H
authors.lastname: Liu
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, Anhui 230026, P. R. China.
authors.forename: Yiping
authors.initials: Y
authors.lastname: Hao
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, Anhui 230026, P. R. 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, Anhui 230026, P. R. China.
authors.forename: Munir Ullah
authors.initials: MU
authors.lastname: Khan
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, Anhui 230026, P. R. China.
authors.forename: Jie
authors.identifier: 0000-0002-8812-0298
authors.initials: J
authors.lastname: Zeng
mesh_terms: D000327:Adsorption; D000497:Alloys / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D004581:Electronics; D006859:Hydrogen / Q000737:chemistry; D006865:Hydrogenation; D000432:Methanol / Q000737:chemistry; D008962:Models, Theoretical; D053758:Nanoparticles / Q000737:chemistry*; D010316:Particle Size; D012238:Rhodium / Q000737:chemistry*; D013499:Surface Properties; D014414:Tungsten / Q000737:chemistry*
chemical_list: D000497:Alloys; D002245:Carbon Dioxide; D006859:Hydrogen; D012238:Rhodium; D014414:Tungsten; D000432:Methanol
keywords: Carbon dioxide; charge transfer; d-band center; rhodium; tungsten