Water Splitting with a Single-Atom Cu/TiO 2 Photocatalyst: Atomistic Origin of High Efficiency and Proposed Enhancement by Spin Selection

Cheng, Cheng; Fang, Wei-Hai; Long, Run; Prezhdo, Oleg V.

doi:10.1021/jacsau.1c00004

Title: Water Splitting with a Single-Atom Cu/TiO ₂ Photocatalyst: Atomistic Origin of High Efficiency and Proposed Enhancement by Spin Selection

Journal Article · Mon Apr 26 00:00:00 EDT 2021 · JACS Au

DOI:https://doi.org/10.1021/jacsau.1c00004· OSTI ID:1780483

Cheng, Cheng ^[1];

^[1];

^[2]

College of Chemistry, Key Laboratory of Theoretical & Computational Photochemistry of Ministry of Education, Beijing Normal University, Beijing 100875, P.R. China
Department of Chemistry, University of Southern California, Los Angeles, California 90089, United States

Anatase TiO₂ is an intensely investigated photocatalytic material due to its abundance and chemical stability. However, it suffers from weak light harvesting and low photocatalytic efficiency. Experiments show that light absorption and photocatalytic properties can be enhanced simultaneously by TiO₂ doping with well-dispersed Cu atoms, forming a single-atom catalyst (Cu/TiO₂) that can be used for solar water splitting and other applications. By performing ab initio nonadiabatic molecular dynamics simulations, we demonstrate that Cu/TiO₂ is inactive before light irradiation due to rapid electron–hole recombination via both shallow and deep traps. Surprisingly, the shallow trap is more detrimental to the Cu/TiO₂ performance than the deep trap because it couples better to free carriers. After light irradiation, leading to electron transfer and Cu/TiO₂ protonation, the shallow trap is eliminated, and a local distortion around the Cu atom stabilizes the deep trap state on the Cu d-orbital, decoupling it from free charges and giving rise to high photocatalytic hydrogen generation activity. We further demonstrate that the photocatalytic performance of Cu/TiO₂ can be enhanced by spin selection, achievable experimentally via optical intersite spin transfer or chiral semiconductor coating. Both H adsorption and spin selection enhance charge carrier lifetimes by an order of magnitude. The spin selection mechanism does not require formation of the H species, which necessitates concurrent sources of electrons and protons and which is intrinsically unstable because water splitting involves frequent proton shuffling. Our results rationalize the experimental observations at the atomistic level, provide mechanistic insights into operation of single atom photocatalysis, and demonstrate that spin selection can be used to develop advanced and efficient systems for solar energy conversion.

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Research Organization:: Beijing Normal Univ. (China)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation of China

Grant/Contract Number:: SC0014429; 51861135101; 21973006; 21688102; 21590801

OSTI ID:: 1780483

Alternate ID(s):: OSTI ID: 1784858

Journal Information:: JACS Au, Journal Name: JACS Au Vol. 1 Journal Issue: 5; ISSN 2691-3704

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (60)

Recent progress on single atom/sub-nano electrocatalysts for energy applications Tran, Duy Thanh; Nguyen, Dinh Chuong; Le, Huu Tuan Progress in Materials Science, Vol. 115 https://doi.org/10.1016/j.pmatsci.2020.100711	journal	January 2021
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Electrochemical Photolysis of Water at a Semiconductor Electrode Fujishima, Akira; Honda, Kenichi Nature, Vol. 238, Issue 5358, p. 37-38 https://doi.org/10.1038/238037a0	journal	July 1972
Molten‐Salt‐Mediated Synthesis of an Atomic Nickel Co‐catalyst on TiO ₂ for Improved Photocatalytic H ₂ Evolution Xiao, Mu; Zhang, Lei; Luo, Bin Angewandte Chemie International Edition, Vol. 59, Issue 18 https://doi.org/10.1002/anie.202001148	journal	March 2020
Near-Complete Suppression of Oxygen Evolution for Photoelectrochemical H ₂ O Oxidative H ₂ O ₂ Synthesis Zhang, Kan; Liu, Jiali; Wang, Luyang Journal of the American Chemical Society, Vol. 142, Issue 19 https://doi.org/10.1021/jacs.9b13410	journal	March 2020
A Stable, Narrow-Gap Oxyfluoride Photocatalyst for Visible-Light Hydrogen Evolution and Carbon Dioxide Reduction Kuriki, Ryo; Ichibha, Tom; Hongo, Kenta Journal of the American Chemical Society, Vol. 140, Issue 21 https://doi.org/10.1021/jacs.8b02822	journal	May 2018
The PYXAID Program for Non-Adiabatic Molecular Dynamics in Condensed Matter Systems Akimov, Alexey V.; Prezhdo, Oleg V. Journal of Chemical Theory and Computation, Vol. 9, Issue 11 https://doi.org/10.1021/ct400641n	journal	October 2013
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Structural and thermal parameters for rutile and anatase Howard, C. J.; Sabine, T. M.; Dickson, F. Acta Crystallographica Section B Structural Science, Vol. 47, Issue 4 https://doi.org/10.1107/S010876819100335X	journal	August 1991
Perspectives on the Development of Oxide-Based Photocathodes for Solar Fuel Production Lumley, Margaret A.; Radmilovic, Andjela; Jang, Youn Jeong Journal of the American Chemical Society, Vol. 141, Issue 46 https://doi.org/10.1021/jacs.9b07976	journal	October 2019
A DFT+U description of oxygen vacancies at the TiO2 rutile (110) surface Morgan, Benjamin J.; Watson, Graeme W. Surface Science, Vol. 601, Issue 21 https://doi.org/10.1016/j.susc.2007.08.025	journal	November 2007
Formation of Hierarchical Co ₉ S ₈ @ZnIn ₂ S ₄ Heterostructured Cages as an Efficient Photocatalyst for Hydrogen Evolution Wang, Sibo; Guan, Bu Yuan; Wang, Xiao Journal of the American Chemical Society, Vol. 140, Issue 45 https://doi.org/10.1021/jacs.8b07721	journal	October 2018
Trajectory Surface Hopping in the Time-Dependent Kohn-Sham Approach for Electron-Nuclear Dynamics Craig, Colleen F.; Duncan, Walter R.; Prezhdo, Oleg V. Physical Review Letters, Vol. 95, Issue 16 https://doi.org/10.1103/PhysRevLett.95.163001	journal	October 2005
Control of Electrons’ Spin Eliminates Hydrogen Peroxide Formation During Water Splitting Mtangi, Wilbert; Tassinari, Francesco; Vankayala, Kiran Journal of the American Chemical Society, Vol. 139, Issue 7 https://doi.org/10.1021/jacs.6b12971	journal	February 2017
Persistent Electronic Coherence Despite Rapid Loss of Electron–Nuclear Correlation Akimov, Alexey V.; Prezhdo, Oleg V. The Journal of Physical Chemistry Letters, Vol. 4, Issue 22 https://doi.org/10.1021/jz402035z	journal	November 2013
Donor–Acceptor Interaction Determines the Mechanism of Photoinduced Electron Injection from Graphene Quantum Dots into TiO ₂ : π-Stacking Supersedes Covalent Bonding Long, Run; Casanova, David; Fang, Wei-Hai Journal of the American Chemical Society, Vol. 139, Issue 7 https://doi.org/10.1021/jacs.6b09598	journal	February 2017
Thin film photoelectrodes for solar water splitting He, Yumin; Hamann, Thomas; Wang, Dunwei Chemical Society Reviews, Vol. 48, Issue 7 https://doi.org/10.1039/C8CS00868J	journal	January 2019
Heterogeneous single-atom catalysis Wang, Aiqin; Li, Jun; Zhang, Tao Nature Reviews Chemistry, Vol. 2, Issue 6 https://doi.org/10.1038/s41570-018-0010-1	journal	May 2018
Decoherence-induced surface hopping Jaeger, Heather M.; Fischer, Sean; Prezhdo, Oleg V. The Journal of Chemical Physics, Vol. 137, Issue 22 https://doi.org/10.1063/1.4757100	journal	December 2012
Reversible and cooperative photoactivation of single-atom Cu/TiO2 photocatalysts Lee, Byoung-Hoon; Park, Sunghak; Kim, Minho Nature Materials, Vol. 18, Issue 6 https://doi.org/10.1038/s41563-019-0344-1	journal	April 2019
Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators Liechtenstein, A. I.; Anisimov, V. I.; Zaanen, J. Physical Review B, Vol. 52, Issue 8 https://doi.org/10.1103/PhysRevB.52.R5467	journal	August 1995
A fast and robust algorithm for Bader decomposition of charge density Henkelman, Graeme; Arnaldsson, Andri; Jónsson, Hannes Computational Materials Science, Vol. 36, Issue 3 https://doi.org/10.1016/j.commatsci.2005.04.010	journal	June 2006
Superoxide/Peroxide Chemistry Extends Charge Carriers’ Lifetime but Undermines Chemical Stability of CH ₃ NH ₃ PbI ₃ Exposed to Oxygen: Time-Domain ab Initio Analysis He, Jinlu; Fang, Wei-Hai; Long, Run Journal of the American Chemical Society, Vol. 141, Issue 14 https://doi.org/10.1021/jacs.8b13392	journal	March 2019
Nanoporous BiVO₄ Photoanodes with Dual-Layer Oxygen Evolution Catalysts for Solar Water Splitting Kim, Tae Woo; Choi, Kyoung-Shin Science, Vol. 343, Issue 6174, p. 990-994 https://doi.org/10.1126/science.1246913	journal	February 2014
Successive redox-mediated visible-light ferrophotovoltaics Noguchi, Yuji; Taniguchi, Yuki; Inoue, Ryotaro Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-14763-6	journal	February 2020
Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao Accounts of Chemical Research, Vol. 46, Issue 8 https://doi.org/10.1021/ar300361m	journal	April 2013
Modeling the polaronic nature of p-type defects in Cu2O: The failure of GGA and GGA+U Scanlon, David O.; Morgan, Benjamin J.; Watson, Graeme W. The Journal of Chemical Physics, Vol. 131, Issue 12 https://doi.org/10.1063/1.3231869	journal	September 2009
Artificial photosynthesis for solar water-splitting Tachibana, Yasuhiro; Vayssieres, Lionel; Durrant, James R. Nature Photonics, Vol. 6, Issue 8 https://doi.org/10.1038/nphoton.2012.175	journal	July 2012
Control of Charge Carriers Trapping and Relaxation in Hematite by Oxygen Vacancy Charge: Ab Initio Non-adiabatic Molecular Dynamics Zhou, Zhaohui; Liu, Jin; Long, Run Journal of the American Chemical Society, Vol. 139, Issue 19 https://doi.org/10.1021/jacs.7b02121	journal	May 2017
Insight on Shallow Trap States-Introduced Photocathodic Performance in n-Type Polymer Photocatalysts Ruan, Qiushi; Miao, Tina; Wang, Hui Journal of the American Chemical Society, Vol. 142, Issue 6 https://doi.org/10.1021/jacs.9b10476	journal	January 2020
Covalent Linking Greatly Enhances Photoinduced Electron Transfer in Fullerene-Quantum Dot Nanocomposites: Time-Domain Ab Initio Study Chaban, Vitaly V.; Prezhdo, Victor V.; Prezhdo, Oleg V. The Journal of Physical Chemistry Letters, Vol. 4, Issue 1 https://doi.org/10.1021/jz301878y	journal	December 2012
Trends in the Exchange Current for Hydrogen Evolution Nørskov, J. K.; Bligaard, T.; Logadottir, A. Journal of The Electrochemical Society, Vol. 152, Issue 3 https://doi.org/10.1149/1.1856988	journal	January 2005
Advanced Capabilities of the PYXAID Program: Integration Schemes, Decoherence Effects, Multiexcitonic States, and Field-Matter Interaction Akimov, Alexey V.; Prezhdo, Oleg V. Journal of Chemical Theory and Computation, Vol. 10, Issue 2 https://doi.org/10.1021/ct400934c	journal	January 2014
Reduced and n-Type Doped TiO ₂ : Nature of Ti ³⁺ Species Di Valentin, Cristiana; Pacchioni, Gianfranco; Selloni, Annabella The Journal of Physical Chemistry C, Vol. 113, Issue 48 https://doi.org/10.1021/jp9061797	journal	September 2009
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Raman spectrum of anatase, TiO2 Ohsaka, Toshiaki; Izumi, Fujio; Fujiki, Yoshinori Journal of Raman Spectroscopy, Vol. 7, Issue 6 https://doi.org/10.1002/jrs.1250070606	journal	December 1978
Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
Increasing Solar Absorption for Photocatalysis with Black Hydrogenated Titanium Dioxide Nanocrystals Chen, X.; Liu, L.; Yu, P. Y. Science, Vol. 331, Issue 6018 https://doi.org/10.1126/science.1200448	journal	January 2011
Optical inter-site spin transfer probed by energy and spin-resolved transient absorption spectroscopy Willems, Felix; von Korff Schmising, Clemens; Strüber, Christian Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-14691-5	journal	February 2020
Thermally Assisted Sub-10 fs Electron Transfer in Dye-Sensitized Nanocrystalline TiO2 Solar Cells Stier, W.; Duncan, W. R.; Prezhdo, O. V. Advanced Materials, Vol. 16, Issue 3 https://doi.org/10.1002/adma.200306027	journal	February 2004
Persistent Quantum Coherence and Strong Coupling Enable Fast Electron Transfer across the CdS/TiO ₂ Interface: A Time-Domain ab Initio Simulation Mehdipour, Hamid; Akimov, Alexey V.; Jankowska, Joanna The Journal of Physical Chemistry C, Vol. 122, Issue 44 https://doi.org/10.1021/acs.jpcc.8b06425	journal	October 2018
Enhanced Photocatalytic and Antibacterial Ability of Cu-Doped Anatase TiO ₂ Thin Films: Theory and Experiment Alotaibi, Abdullah M.; Williamson, Benjamin A. D.; Sathasivam, Sanjayan ACS Applied Materials & Interfaces, Vol. 12, Issue 13 https://doi.org/10.1021/acsami.9b22056	journal	February 2020
Extending Carrier Lifetimes in Lead Halide Perovskites with Alkali Metals by Passivating and Eliminating Halide Interstitial Defects Qiao, Lu; Fang, Wei‐Hai; Long, Run Angewandte Chemie International Edition, Vol. 59, Issue 12 https://doi.org/10.1002/anie.201911615	journal	February 2020
Charge Separation and Recombination in Two-Dimensional MoS ₂ /WS ₂ : Time-Domain ab Initio Modeling Li, Linqiu; Long, Run; Prezhdo, Oleg V. Chemistry of Materials, Vol. 29, Issue 6 https://doi.org/10.1021/acs.chemmater.6b03727	journal	November 2016
Strong Interaction at the Perovskite/TiO ₂ Interface Facilitates Ultrafast Photoinduced Charge Separation: A Nonadiabatic Molecular Dynamics Study Long, Run; Fang, Wei-Hai; Prezhdo, Oleg V. The Journal of Physical Chemistry C, Vol. 121, Issue 7 https://doi.org/10.1021/acs.jpcc.6b12921	journal	February 2017
Photo/Electrochemical Applications of Metal Sulfide/TiO ₂ Heterostructures Zheng, Lingxia; Teng, Feng; Ye, Xiaoying Advanced Energy Materials, Vol. 10, Issue 1 https://doi.org/10.1002/aenm.201902355	journal	November 2019
Function-switchable metal/semiconductor junction enables efficient photocatalytic overall water splitting with selective water oxidation products Wei, Daixing; Tan, Yubo; Wang, Yiqing Science Bulletin, Vol. 65, Issue 16 https://doi.org/10.1016/j.scib.2020.04.042	journal	August 2020
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Density functional theory studies on the structural and physical properties of Cu-doped anatase TiO 2 (101) surface Zhang, Wei; Yin, Jiu-Ren; Tang, Xian-Qiong Physica E: Low-dimensional Systems and Nanostructures, Vol. 85 https://doi.org/10.1016/j.physe.2016.09.008	journal	January 2017
Density-Functional Theory for Time-Dependent Systems Runge, Erich; Gross, E. K. U. Physical Review Letters, Vol. 52, Issue 12 https://doi.org/10.1103/PhysRevLett.52.997	journal	March 1984
TiO2 photocatalysis and related surface phenomena Fujishima, A.; Zhang, X.; Tryk, D. Surface Science Reports, Vol. 63, Issue 12 https://doi.org/10.1016/j.surfrep.2008.10.001	journal	December 2008
Plasmon-Mediated Electron Injection from Au Nanorods into MoS2: Traditional versus Photoexcitation Mechanism Zhang, Zhaosheng; Liu, Lihong; Fang, Wei-Hai Chem, Vol. 4, Issue 5 https://doi.org/10.1016/j.chempr.2018.02.025	journal	May 2018
Special Points in the Brillouin Zone Chadi, D. J.; Cohen, Marvin L. Physical Review B, Vol. 8, Issue 12 https://doi.org/10.1103/PhysRevB.8.5747	journal	December 1973
Cu-doped TiO2 systems with improved photocatalytic activity Colón, G.; Maicu, M.; Hidalgo, M. C. Applied Catalysis B: Environmental, Vol. 67, Issue 1-2 https://doi.org/10.1016/j.apcatb.2006.03.019	journal	September 2006
Grain Boundary Facilitates Photocatalytic Reaction in Rutile TiO ₂ Despite Fast Charge Recombination: A Time-Domain ab Initio Analysis Wei, Yaqing; Zhou, Zhaohui; Fang, Wei-Hai The Journal of Physical Chemistry Letters, Vol. 9, Issue 19 https://doi.org/10.1021/acs.jpclett.8b02761	journal	September 2018
Experimental and theoretical study of the electronic properties of Cu-doped anatase TiO2 Navas, Javier; Sánchez-Coronilla, Antonio; Aguilar, Teresa Physical Chemistry Chemical Physics, Vol. 16, Issue 8 https://doi.org/10.1039/c3cp54273d	journal	January 2014
Anharmonicity Extends Carrier Lifetimes in Lead Halide Perovskites at Elevated Temperatures Li, Wei; Vasenko, Andrey S.; Tang, Jianfeng The Journal of Physical Chemistry Letters, Vol. 10, Issue 20 https://doi.org/10.1021/acs.jpclett.9b02553	journal	September 2019
Minimizing Electron–Hole Recombination on TiO ₂ Sensitized with PbSe Quantum Dots: Time-Domain Ab Initio Analysis Long, Run; English, Niall J.; Prezhdo, Oleg V. The Journal of Physical Chemistry Letters, Vol. 5, Issue 17 https://doi.org/10.1021/jz5013627	journal	August 2014
Time-Dependent Density Functional Theory Marques, M. A. L.; Gross, E. K. U. Annual Review of Physical Chemistry, Vol. 55, Issue 1 https://doi.org/10.1146/annurev.physchem.55.091602.094449	journal	June 2004
Finite-size and pressure effects on the Raman spectrum of nanocrystalline anatase $Ti O_{2}$ Swamy, Varghese; Kuznetsov, Alexei; Dubrovinsky, Leonid S. Physical Review B, Vol. 71, Issue 18 https://doi.org/10.1103/PhysRevB.71.184302	journal	May 2005

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
TiO2 photocatalysis
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single-atom catalysts
spin-selective dynamics
dopant and passivation
nonadiabatic molecular dynamics
time-dependent density functional theory
carrier dynamics
oxides
energy
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Title: Water Splitting with a Single-Atom Cu/TiO 2 Photocatalyst: Atomistic Origin of High Efficiency and Proposed Enhancement by Spin Selection

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Title: Water Splitting with a Single-Atom Cu/TiO ₂ Photocatalyst: Atomistic Origin of High Efficiency and Proposed Enhancement by Spin Selection