title: Isolation of Cu Atoms in Pd Lattice: Forming Highly Selective Sites for Photocatalytic Conversion of CO2to CH4.
abstract: Photocatalytic conversion of CO2to CH4, a carbon-neutral fuel, represents an appealing approach to remedy the current energy and environmental crisis; however, it suffers from the large production of CO and H2by side reactions. The design of catalytic sites for CO2adsorption and activation holds the key to address this grand challenge. In this Article, we develop highly selective sites for photocatalytic conversion of CO2to CH4by isolating Cu atoms in Pd lattice. According to our synchrotron-radiation characterizations and theoretical simulations, the isolation of Cu atoms in Pd lattice can play dual roles in the enhancement of CO2-to-CH4conversion: (1) providing the paired Cu-Pd sites for the enhanced CO2adsorption and the suppressed H2evolution; and (2) elevating the d-band center of Cu sites for the improved CO2activation. As a result, the Pd7Cu1-TiO2photocatalyst achieves the high selectivity of 96% for CH4production with a rate of 19.6 μmol gcat-1h-1. This work provides fresh insights into the catalytic site design for selective photocatalytic CO2conversion, and highlights the importance of catalyst lattice engineering at atomic precision to catalytic performance.
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Ran
authors.initials: R
authors.lastname: Long
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Yu
authors.initials: Y
authors.lastname: Li
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Yan
authors.initials: Y
authors.lastname: Liu
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Shuangming
authors.initials: S
authors.lastname: Chen
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Xusheng
authors.initials: X
authors.lastname: Zheng
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Chao
authors.initials: C
authors.lastname: Gao
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Chaohua
authors.initials: C
authors.lastname: He
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Nanshan
authors.initials: N
authors.lastname: Chen
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Zeming
authors.initials: Z
authors.lastname: Qi
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Li
authors.identifier: 0000-0003-0585-8519
authors.initials: L
authors.lastname: Song
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Jun
authors.initials: J
authors.lastname: Jiang
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Junfa
authors.initials: J
authors.lastname: Zhu
authors.affiliation: Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), School of Chemistry and Materials Science, Hefei Science Center (CAS), and National Synchrotron Radiation Laboratory, University of Science and Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Yujie
authors.identifier: 0000-0002-1995-8257
authors.initials: Y
authors.lastname: Xiong