Site dependent reactivity of Pt single atoms on anatase TiO2(101) in an aqueous environment
Abstract
The TiO2–Pt–water interface is of great relevance in photocatalysis where Pt is widely used as a co-catalyst for The TiO2–Pt–water interface is of great relevance in photocatalysis where Pt is widely used as a co-catalyst for enhancing hydrogen evolution in aqueous TiO2. Using ab initio molecular dynamics, we investigated this interface focusing on Pt single atoms supported on anatase TiO2(101) in a water environment. Based on recent experiments showing a broad distribution of Pt coordination sites in TiO2, we examined six distinct single-Pt supported species with different nominal Pt oxidation states, namely: Pt, PtOH, and PtO2 species adsorbed on the stoichiometric surface; Pt adsorbed at a surface oxygen vacancy (Ov); and Pt substituting a surface Ti cation (PtTi), both without and with an accompanying Ov (PtTi + Ov). As found for the pristine anatase surface, interfacial water remained intact in the presence of a nearly neutral Pt adatom within the time duration of our simulations (~15 ps). Similarly, no (or only temporary) water dissociation was observed at the PtTi + Ov and PtO2 interfaces, due to the formation of very stable planar Pt coordination structures that interact only weakly with water. In contrast, water dissociated with OH– (H+) on themore »
- Authors:
-
[1];
[3];
- Beijing Computational Science Research Center, Beijing (China); Princeton Univ., NJ (United States)
- Hunan Univ. of Science and Technology, Xiangtan (China)
- Princeton Univ., NJ (United States)
- Beihang Univ., Beijing (China)
- Publication Date:
- Research Org.:
- Princeton Univ., NJ (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Natural Science Foundation of China (NSFC); Tianhe-2JK
- OSTI Identifier:
- 1594492
- Grant/Contract Number:
- SC0007347; TZ20180; 51572016; U1930402; 11804090; 11847213; 51861130360; U1501501; NAFR1180242
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 22; Journal Issue: 19; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Wen, Bo, Yin, Wen-Jin, Selloni, Annabella, and Liu, Li-Min. Site dependent reactivity of Pt single atoms on anatase TiO2(101) in an aqueous environment. United States: N. p., 2019.
Web. doi:10.1039/C9CP05097C.
Wen, Bo, Yin, Wen-Jin, Selloni, Annabella, & Liu, Li-Min. Site dependent reactivity of Pt single atoms on anatase TiO2(101) in an aqueous environment. United States. https://doi.org/10.1039/C9CP05097C
Wen, Bo, Yin, Wen-Jin, Selloni, Annabella, and Liu, Li-Min. Mon .
"Site dependent reactivity of Pt single atoms on anatase TiO2(101) in an aqueous environment". United States. https://doi.org/10.1039/C9CP05097C. https://www.osti.gov/servlets/purl/1594492.
@article{osti_1594492,
title = {Site dependent reactivity of Pt single atoms on anatase TiO2(101) in an aqueous environment},
author = {Wen, Bo and Yin, Wen-Jin and Selloni, Annabella and Liu, Li-Min},
abstractNote = {The TiO2–Pt–water interface is of great relevance in photocatalysis where Pt is widely used as a co-catalyst for The TiO2–Pt–water interface is of great relevance in photocatalysis where Pt is widely used as a co-catalyst for enhancing hydrogen evolution in aqueous TiO2. Using ab initio molecular dynamics, we investigated this interface focusing on Pt single atoms supported on anatase TiO2(101) in a water environment. Based on recent experiments showing a broad distribution of Pt coordination sites in TiO2, we examined six distinct single-Pt supported species with different nominal Pt oxidation states, namely: Pt, PtOH, and PtO2 species adsorbed on the stoichiometric surface; Pt adsorbed at a surface oxygen vacancy (Ov); and Pt substituting a surface Ti cation (PtTi), both without and with an accompanying Ov (PtTi + Ov). As found for the pristine anatase surface, interfacial water remained intact in the presence of a nearly neutral Pt adatom within the time duration of our simulations (~15 ps). Similarly, no (or only temporary) water dissociation was observed at the PtTi + Ov and PtO2 interfaces, due to the formation of very stable planar Pt coordination structures that interact only weakly with water. In contrast, water dissociated with OH– (H+) on the Pt atom when this substituted a surface Ti (oxygen) ion as well as on PtOH. Lastly, the significant proton affinity of Pt atoms at surface oxygen vacancies suggests that negatively charged Pt species are particularly efficient at catalyzing hydrogen evolution in aqueous TiO2.hydrogen evolution in aqueous TiO2.},
doi = {10.1039/C9CP05097C},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 19,
volume = 22,
place = {United States},
year = {2019},
month = {10}
}
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Figure 1: Optimized structures of a Pt adatom (A-PtS), Pt substituting a surface Oxygen atom (A-PtO), Pt substituting a surface Ti atom (A-PtTi) and PtOH (A-PtOH) on the Anatase (101) surface. Blue, red, white and grey spheres represent Ti, O, H and Pt atoms, respectively.
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Works referenced in this record:
Direct Imaging of Pt Single Atoms Adsorbed on TiO 2 (110) Surfaces
journal, December 2013
- Chang, Teng-Yuan; Tanaka, Yusuke; Ishikawa, Ryo
- Nano Letters, Vol. 14, Issue 1
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Photocatalytic and Photovoltaic Properties of TiO 2 Nanoparticles Investigated by Ab Initio Simulations
journal, December 2014
- Mattioli, Giuseppe; Amore Bonapasta, Aldo; Bovi, Daniele
- The Journal of Physical Chemistry C, Vol. 118, Issue 51
Surface Polarons Reducing Overpotentials in the Oxygen Evolution Reaction
journal, May 2018
- Gono, Patrick; Wiktor, Julia; Ambrosio, Francesco
- ACS Catalysis, Vol. 8, Issue 7
Interplay between Adsorbates and Polarons: CO on Rutile TiO 2 ( 110 )
journal, January 2019
- Reticcioli, Michele; Sokolović, Igor; Schmid, Michael
- Physical Review Letters, Vol. 122, Issue 1
Generalized Hartree-Fock theory and the Hubbard model
journal, July 1994
- Bach, Volker; Lieb, Elliott H.; Solovej, Jan Philip
- Journal of Statistical Physics, Vol. 76, Issue 1-2
Key Steps of the cis -Platin-DNA Interaction: Density Functional Theory-Based Molecular Dynamics Simulations
journal, February 2000
- Carloni, Paolo; Sprik, Michiel; Andreoni, Wanda
- The Journal of Physical Chemistry B, Vol. 104, Issue 4
Iced photochemical reduction to synthesize atomically dispersed metals by suppressing nanocrystal growth
journal, November 2017
- Wei, Hehe; Huang, Kai; Wang, Da
- Nature Communications, Vol. 8, Issue 1
Structure, Polarization, and Sum Frequency Generation Spectrum of Interfacial Water on Anatase TiO 2
journal, November 2018
- Calegari Andrade, Marcos F.; Ko, Hsin-Yu; Car, Roberto
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 23
Synthesis-Dependent Oxidation State of Platinum on TiO 2 and Their Influences on the Solar Simulated Photocatalytic Hydrogen Production from Water
journal, August 2013
- Parayil, Sreenivasan Koliyat; Kibombo, Harrison S.; Wu, Chia-Ming
- The Journal of Physical Chemistry C, Vol. 117, Issue 33
Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces and aqueous interfaces
journal, June 2016
- Selcuk, Sencer; Selloni, Annabella
- Nature Materials, Vol. 15, Issue 10
Heterogeneous single-atom catalysis
journal, May 2018
- Wang, Aiqin; Li, Jun; Zhang, Tao
- Nature Reviews Chemistry, Vol. 2, Issue 6
Titania-water interactions: a review of theoretical studies
journal, January 2010
- Sun, Chenghua; Liu, Li-Min; Selloni, Annabella
- Journal of Materials Chemistry, Vol. 20, Issue 46
The Role of Interstitial Sites in the Ti3d Defect State in the Band Gap of Titania
journal, June 2008
- Wendt, S.; Sprunger, P. T.; Lira, E.
- Science, Vol. 320, Issue 5884
Reversible and cooperative photoactivation of single-atom Cu/TiO2 photocatalysts
journal, April 2019
- Lee, Byoung-Hoon; Park, Sunghak; Kim, Minho
- Nature Materials, Vol. 18, Issue 6
Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
journal, August 1995
- Liechtenstein, A. I.; Anisimov, V. I.; Zaanen, J.
- Physical Review B, Vol. 52, Issue 8
Highly efficient Pt/TiO2Pt/TiO2 photocatalyst for hydrogen generation prepared by a cold plasma method
journal, August 2007
- Zou, Ji-Jun; He, Hei; Cui, Lan
- International Journal of Hydrogen Energy, Vol. 32, Issue 12
Single-Atom Catalysts: A New Frontier in Heterogeneous Catalysis
journal, April 2013
- Yang, Xiao-Feng; Wang, Aiqin; Qiao, Botao
- Accounts of Chemical Research, Vol. 46, Issue 8
Role of Platinum Deposited on TiO 2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions
journal, January 2014
- Ahmed, Luma M.; Ivanova, Irina; Hussein, Falah H.
- International Journal of Photoenergy, Vol. 2014
Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
journal, April 2005
- VandeVondele, Joost; Krack, Matthias; Mohamed, Fawzi
- Computer Physics Communications, Vol. 167, Issue 2
Nature of stable single atom Pt catalysts dispersed on anatase TiO2
journal, November 2018
- Thang, Ho Viet; Pacchioni, Gianfranco; DeRita, Leo
- Journal of Catalysis, Vol. 367
Single-atom catalysis of CO oxidation using Pt1/FeOx
journal, July 2011
- Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng
- Nature Chemistry, Vol. 3, Issue 8
Interplay between Water and Anatase (101) Surface with Subsurface Oxygen Vacancy
journal, May 2014
- Li, Yadong; Gao, Yi
- Physical Review Letters, Vol. 112, Issue 20
Platinum single-atom and cluster catalysis of the hydrogen evolution reaction
journal, November 2016
- Cheng, Niancai; Stambula, Samantha; Wang, Da
- Nature Communications, Vol. 7, Issue 1
Theoretical Studies on Anatase and Less Common TiO 2 Phases: Bulk, Surfaces, and Nanomaterials
journal, May 2014
- De Angelis, Filippo; Di Valentin, Cristiana; Fantacci, Simona
- Chemical Reviews, Vol. 114, Issue 19
Reaction of O2 with Subsurface Oxygen Vacancies on TiO2 Anatase (101)
journal, August 2013
- Setvin, M.; Aschauer, U.; Scheiber, P.
- Science, Vol. 341, Issue 6149
Coverage Dependence of Methanol Dissociation on TiO 2 (110)
journal, July 2015
- Liu, Shuo; Liu, An-an; Wen, Bo
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 16
Ab Initio Simulation of the Effects of Hydrogen Concentration on Anatase TiO 2
journal, April 2016
- Ataei, S. Samaneh; Mohammadizadeh, M. Reza; Seriani, Nicola
- The Journal of Physical Chemistry C, Vol. 120, Issue 16
Effect of reducible oxide–metal cluster charge transfer on the structure and reactivity of adsorbed Au and Pt atoms and clusters on anatase TiO 2
journal, May 2017
- Wang, Honghong; An, Taicheng; Selloni, Annabella
- The Journal of Chemical Physics, Vol. 146, Issue 18
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
Structure and Reactivity of Water Layers on Defect-Free and Defective Anatase TiO 2 (101) Surfaces
journal, April 2004
- Tilocca, Antonio; Selloni, Annabella
- The Journal of Physical Chemistry B, Vol. 108, Issue 15
Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO 2
journal, September 2017
- DeRita, Leo; Dai, Sheng; Lopez-Zepeda, Kimberly
- Journal of the American Chemical Society, Vol. 139, Issue 40
Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965
- Kohn, W.; Sham, L. J.
- Physical Review, Vol. 140, Issue 4A, p. A1133-A1138
Evidence for the Predominance of Subsurface Defects on Reduced Anatase
journal, March 2009
- He, Yunbin; Dulub, Olga; Cheng, Hongzhi
- Physical Review Letters, Vol. 102, Issue 10
Small Au and Pt Clusters at the Anatase TiO 2 (101) Surface: Behavior at Terraces, Steps, and Surface Oxygen Vacancies
journal, January 2008
- Gong, Xue-Qing; Selloni, Annabella; Dulub, Olga
- Journal of the American Chemical Society, Vol. 130, Issue 1
Quantifying Support Interactions and Reactivity Trends of Single Metal Atom Catalysts over TiO 2
journal, October 2018
- Iyemperumal, Satish Kumar; Pham, Thang Duc; Bauer, Jack
- The Journal of Physical Chemistry C, Vol. 122, Issue 44
A molecular dynamics method for simulations in the canonical ensemble
journal, June 1984
- Nosé, Shūichi
- Molecular Physics, Vol. 52, Issue 2
Growth of Pt Particles on the Anatase TiO 2 (101) Surface
journal, May 2012
- Zhou, Yun; Muhich, Christopher L.; Neltner, Brian T.
- The Journal of Physical Chemistry C, Vol. 116, Issue 22
Structure and dynamics of liquid water on rutile
journal, October 2010
- Liu, Li-Min; Zhang, Changjun; Thornton, Geoff
- Physical Review B, Vol. 82, Issue 16
Pt···H Nonclassical Interaction in Water-Dissolved Pt(II) Complexes: Coaction of Electronic Effects with Solvent-Assisted Stabilization
journal, March 2016
- Kroutil, Ondřej; Předota, Milan; Chval, Zdeněk
- Inorganic Chemistry, Vol. 55, Issue 7
Enhancing Hydrogen Evolution Activity in Water Splitting by Tailoring Li+-Ni(OH)2-Pt Interfaces
journal, December 2011
- Subbaraman, R.; Tripkovic, D.; Strmcnik, D.
- Science, Vol. 334, Issue 6060
Adatom surface diffusion of catalytic metals on the anatase TiO 2 (101) surface
journal, January 2017
- Alghannam, Afnan; Muhich, Christopher L.; Musgrave, Charles B.
- Physical Chemistry Chemical Physics, Vol. 19, Issue 6
Theoretical analysis of small Pt particles on rutile TiO 2 ( 110 ) surfaces
journal, November 2010
- Çelik, Veysel; Ünal, Hatice; Mete, Ersen
- Physical Review B, Vol. 82, Issue 20
Surface Plasmon Enhanced Photocatalysis of Au/Pt-decorated TiO2 Nanopillar Arrays
journal, May 2016
- Shuang, Shuang; Lv, Ruitao; Xie, Zheng
- Scientific Reports, Vol. 6, Issue 1
Separable dual-space Gaussian pseudopotentials
journal, July 1996
- Goedecker, S.; Teter, M.; Hutter, J.
- Physical Review B, Vol. 54, Issue 3
The Mechanism of the Hydrogen Evolution Reaction on Platinum, Silver and Tungsten surfaces in Acid Solutions
journal, July 1957
- Bockris, J. O. M.; Ammar, I. A.; Huq, A. K. M. S.
- The Journal of Physical Chemistry, Vol. 61, Issue 7
Role of Polarons in Water Splitting: The Case of BiVO 4
journal, June 2018
- Wiktor, Julia; Ambrosio, Francesco; Pasquarello, Alfredo
- ACS Energy Letters, Vol. 3, Issue 7
Inhomogeneous Electron Gas
journal, November 1964
- Hohenberg, P.; Kohn, W.
- Physical Review, Vol. 136, Issue 3B, p. B864-B871
Surface reconstructions: Polaron bricklayers at work
journal, October 2017
- Pacchioni, Giulia
- Nature Reviews Materials, Vol. 2, Issue 11
Adsorption and diffusion of Pt and Au on the stoichiometric and reduced Ti O 2 rutile (110) surfaces
journal, August 2005
- Iddir, Hakim; Öğüt, Serdar; Browning, Nigel D.
- Physical Review B, Vol. 72, Issue 8
Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985
- Hoover, William G.
- Physical Review A, Vol. 31, Issue 3
Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts
journal, August 2003
- Fu, Q.
- Science, Vol. 301, Issue 5635
Structural evolution of atomically dispersed Pt catalysts dictates reactivity
journal, April 2019
- DeRita, Leo; Resasco, Joaquin; Dai, Sheng
- Nature Materials, Vol. 18, Issue 7
Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles
journal, April 2018
- Liu, Lichen; Corma, Avelino
- Chemical Reviews, Vol. 118, Issue 10
Defects, Adsorbates, and Photoactivity of Rutile TiO 2 (110): Insight by First-Principles Calculations
journal, August 2018
- Wen, Bo; Yin, Wen-Jin; Selloni, Annabella
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 18
Deep versus Shallow Behavior of Intrinsic Defects in Rutile and Anatase TiO 2 Polymorphs
journal, November 2010
- Mattioli, Giuseppe; Alippi, Paola; Filippone, Francesco
- The Journal of Physical Chemistry C, Vol. 114, Issue 49
Proton-Promoted Electron Transfer in Photocatalysis: Key Step for Photocatalytic Hydrogen Evolution on Metal/Titania Composites
journal, March 2017
- Wang, Dong; Liu, Zhi-Pan; Yang, Wei-Min
- ACS Catalysis, Vol. 7, Issue 4
Electronic Structure of Defect States in Hydroxylated and Reduced Rutile Surfaces
journal, October 2006
- Di Valentin, Cristiana; Pacchioni, Gianfranco; Selloni, Annabella
- Physical Review Letters, Vol. 97, Issue 16
Electronic correlation effects in reduced rutile within the method
journal, September 2010
- Park, Seong-Geon; Magyari-Köpe, Blanka; Nishi, Yoshio
- Physical Review B, Vol. 82, Issue 11
Surface and subsurface oxygen vacancies in anatase and differences with rutile
journal, March 2009
- Cheng, Hongzhi; Selloni, Annabella
- Physical Review B, Vol. 79, Issue 9
Simple, Unambiguous Theoretical Approach to Oxidation State Determination via First-Principles Calculations
journal, October 2011
- Sit, Patrick H. -L.; Car, Roberto; Cohen, Morrel H.
- Inorganic Chemistry, Vol. 50, Issue 20
Inhomogeneous Electron Gas
journal, March 1973
- Rajagopal, A. K.; Callaway, J.
- Physical Review B, Vol. 7, Issue 5
Ab initio phase diagram and nucleation of gallium
journal, May 2020
- Niu, Haiyang; Bonati, Luigi; Piaggi, Pablo M.
- Nature Communications, Vol. 11, Issue 1
Reaction of O₂ with Subsurface Oxygen Vacancies on TiO₂ Anatase (101)
text, January 2013
- Hou, W.; Setvin, M.; Schmid, M.
- American Association for the Advancement of Science
A molecular dynamics method for simulations in the canonical ensemble
journal, January 2002
- NosÉ, SH[Ubar]ICHI
- Molecular Physics, Vol. 100, Issue 1
Role of Platinum Deposited on TiO2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions
other, January 2014
- Ahmed, Luma M.; Ivanova, Irina; Hussein, Falah H.
- New York : Hindawi Publishing Corporation
QUICKSTEP: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
text, January 2005
- VandeVondele, J.; Krack, M.; Mohamed, F.
- Elsevier
Reaction of O2 with Subsurface Oxygen Vacancies on TiO2 Anatase (101)
text, January 2018
- Setvin, Martin; Aschauer, Ulrich; Scheiber, Philipp
- arXiv
Generalized Hartree-Fock Theory and the Hubbard Model
text, January 1993
- Bach, Volker; Lieb, Elliott H.; Solovej, Jan philip
- arXiv
Separable Dual Space Gaussian Pseudo-potentials
text, January 1995
- Goedecker, S.; Teter, M.; Hutter, J.
- arXiv
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