title: Highly Efficient and Exceptionally Durable CO2Photoreduction to Methanol over Freestanding Defective Single-Unit-Cell Bismuth Vanadate Layers.
abstract: Unearthing an ideal model for disclosing the role of defect sites in solar CO2reduction remains a great challenge. Here, freestanding gram-scale single-unit-cell o-BiVO4layers are successfully synthesized for the first time. Positron annihilation spectrometry and X-ray fluorescence unveil their distinct vanadium vacancy concentrations. Density functional calculations reveal that the introduction of vanadium vacancies brings a new defect level and higher hole concentration near Fermi level, resulting in increased photoabsorption and superior electronic conductivity. The higher surface photovoltage intensity of single-unit-cell o-BiVO4layers with rich vanadium vacancies ensures their higher carriers separation efficiency, further confirmed by the increased carriers lifetime from 74.5 to 143.6 ns revealed by time-resolved fluorescence emission decay spectra. As a result, single-unit-cell o-BiVO4layers with rich vanadium vacancies exhibit a high methanol formation rate up to 398.3 μmol g-1h-1and an apparent quantum efficiency of 5.96% at 350 nm, much larger than that of single-unit-cell o-BiVO4layers with poor vanadium vacancies, and also the former's catalytic activity proceeds without deactivation even after 96 h. This highly efficient and spectrally stable CO2photoconversion performances hold great promise for practical implementation of solar fuel production.
authors.affiliation: Hefei National Laboratory for Physical Sciences at Microscale, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Chemistry for Energy Materials, International Center for Quantum Design of Functional Materials, Department of Physics, Synergetic Innovation Center of Quantum Information and Quantum Physics, Key Laboratory of Strongly-Coupled Quantum Matter Physics, University of Science & Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Shan
authors.initials: S
authors.lastname: Gao
authors.affiliation: Hefei National Laboratory for Physical Sciences at Microscale, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Chemistry for Energy Materials, International Center for Quantum Design of Functional Materials, Department of Physics, Synergetic Innovation Center of Quantum Information and Quantum Physics, Key Laboratory of Strongly-Coupled Quantum Matter Physics, University of Science & Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Bingchuan
authors.initials: B
authors.lastname: Gu
authors.affiliation: Hefei National Laboratory for Physical Sciences at Microscale, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Chemistry for Energy Materials, International Center for Quantum Design of Functional Materials, Department of Physics, Synergetic Innovation Center of Quantum Information and Quantum Physics, Key Laboratory of Strongly-Coupled Quantum Matter Physics, University of Science & Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Xingchen
authors.initials: X
authors.lastname: Jiao
authors.affiliation: Hefei National Laboratory for Physical Sciences at Microscale, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Chemistry for Energy Materials, International Center for Quantum Design of Functional Materials, Department of Physics, Synergetic Innovation Center of Quantum Information and Quantum Physics, Key Laboratory of Strongly-Coupled Quantum Matter Physics, University of Science & Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Yongfu
authors.identifier: 0000-0002-4420-5708
authors.initials: Y
authors.lastname: Sun
authors.affiliation: Hefei National Laboratory for Physical Sciences at Microscale, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Chemistry for Energy Materials, International Center for Quantum Design of Functional Materials, Department of Physics, Synergetic Innovation Center of Quantum Information and Quantum Physics, Key Laboratory of Strongly-Coupled Quantum Matter Physics, University of Science & Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Xiaolong
authors.initials: X
authors.lastname: Zu
authors.affiliation: Hefei National Laboratory for Physical Sciences at Microscale, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Chemistry for Energy Materials, International Center for Quantum Design of Functional Materials, Department of Physics, Synergetic Innovation Center of Quantum Information and Quantum Physics, Key Laboratory of Strongly-Coupled Quantum Matter Physics, University of Science & Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Fan
authors.initials: F
authors.lastname: Yang
authors.affiliation: Hefei National Laboratory for Physical Sciences at Microscale, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Chemistry for Energy Materials, International Center for Quantum Design of Functional Materials, Department of Physics, Synergetic Innovation Center of Quantum Information and Quantum Physics, Key Laboratory of Strongly-Coupled Quantum Matter Physics, University of Science & Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Wenguang
authors.initials: W
authors.lastname: Zhu
authors.affiliation: Hefei National Laboratory for Physical Sciences at Microscale, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Chemistry for Energy Materials, International Center for Quantum Design of Functional Materials, Department of Physics, Synergetic Innovation Center of Quantum Information and Quantum Physics, Key Laboratory of Strongly-Coupled Quantum Matter Physics, University of Science & Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Chengming
authors.initials: C
authors.lastname: Wang
authors.affiliation: Hefei National Laboratory for Physical Sciences at Microscale, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Chemistry for Energy Materials, International Center for Quantum Design of Functional Materials, Department of Physics, Synergetic Innovation Center of Quantum Information and Quantum Physics, Key Laboratory of Strongly-Coupled Quantum Matter Physics, University of Science & Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Zimou
authors.initials: Z
authors.lastname: Feng
authors.affiliation: Hefei National Laboratory for Physical Sciences at Microscale, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Chemistry for Energy Materials, International Center for Quantum Design of Functional Materials, Department of Physics, Synergetic Innovation Center of Quantum Information and Quantum Physics, Key Laboratory of Strongly-Coupled Quantum Matter Physics, University of Science & Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Bangjiao
authors.initials: B
authors.lastname: Ye
authors.affiliation: Hefei National Laboratory for Physical Sciences at Microscale, CAS Center for Excellence in Nanoscience, Collaborative Innovation Center of Chemistry for Energy Materials, International Center for Quantum Design of Functional Materials, Department of Physics, Synergetic Innovation Center of Quantum Information and Quantum Physics, Key Laboratory of Strongly-Coupled Quantum Matter Physics, University of Science & Technology of China , Hefei, Anhui 230026, P. R. China.
authors.forename: Yi
authors.identifier: 0000-0002-1416-5557
authors.initials: Y
authors.lastname: Xie