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Title: Site dependent reactivity of Pt single atoms on anatase TiO 2(101) in an aqueous environment

Abstract

The TiO 2–Pt–water interface is of great relevance in photocatalysis where Pt is widely used as a co-catalyst for The TiO 2–Pt–water interface is of great relevance in photocatalysis where Pt is widely used as a co-catalyst for enhancing hydrogen evolution in aqueous TiO 2. Using ab initio molecular dynamics, we investigated this interface focusing on Pt single atoms supported on anatase TiO 2(101) in a water environment. Based on recent experiments showing a broad distribution of Pt coordination sites in TiO 2, we examined six distinct single-Pt supported species with different nominal Pt oxidation states, namely: Pt, PtOH, and PtO 2 species adsorbed on the stoichiometric surface; Pt adsorbed at a surface oxygen vacancy (O v); and Pt substituting a surface Ti cation (PtTi), both without and with an accompanying O v (Pt Ti + O v). 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 Pt Ti + O v and PtO 2 interfaces, due to the formation of very stable planar Pt coordination structures that interactmore » 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 TiO 2.hydrogen evolution in aqueous TiO 2.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [4]
  1. Beijing Computational Science Research Center, Beijing (China); Princeton Univ., NJ (United States)
  2. Hunan Univ. of Science and Technology, Xiangtan (China)
  3. Princeton Univ., NJ (United States)
  4. Beihang Univ., Beijing (China)
Publication Date:
Research Org.:
Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Natural Science Foundation of China (NNSFC); 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 (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); 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. doi: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. doi:10.1039/C9CP05097C.
@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 (Print)},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {10}
}

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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
  • DOI: 10.1021/nl403520c

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
  • DOI: 10.1103/PhysRevLett.77.3865

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
  • DOI: 10.1021/jp509830w

Surface Polarons Reducing Overpotentials in the Oxygen Evolution Reaction
journal, May 2018


Interplay between Adsorbates and Polarons: CO on Rutile TiO 2 ( 110 )
journal, January 2019


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
  • DOI: 10.1007/BF02188656

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
  • DOI: 10.1021/jp992590x

Iced photochemical reduction to synthesize atomically dispersed metals by suppressing nanocrystal growth
journal, November 2017


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
  • DOI: 10.1021/acs.jpclett.8b03103

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
  • DOI: 10.1021/jp405727k

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
  • DOI: 10.1038/nmat4672

Heterogeneous single-atom catalysis
journal, May 2018


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
  • DOI: 10.1039/c0jm01491e

The Role of Interstitial Sites in the Ti3d Defect State in the Band Gap of Titania
journal, June 2008


Reversible and cooperative photoactivation of single-atom Cu/TiO2 photocatalysts
journal, April 2019


Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
journal, August 1995


Highly efficient Pt/TiO2Pt/TiO2 photocatalyst for hydrogen generation prepared by a cold plasma method
journal, August 2007


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
  • DOI: 10.1021/ar300361m

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
  • DOI: 10.1155/2014/503516

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
  • DOI: 10.1016/j.cpc.2004.12.014

Nature of stable single atom Pt catalysts dispersed on anatase TiO2
journal, November 2018


Single-atom catalysis of CO oxidation using Pt1/FeOx
journal, July 2011

  • Qiao, Botao; Wang, Aiqin; Yang, Xiaofeng
  • Nature Chemistry, Vol. 3, Issue 8
  • DOI: 10.1038/nchem.1095

Interplay between Water and TiO 2 Anatase (101) Surface with Subsurface Oxygen Vacancy
journal, May 2014


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
  • DOI: 10.1038/ncomms13638

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
  • DOI: 10.1021/cr500055q

Reaction of O2 with Subsurface Oxygen Vacancies on TiO2 Anatase (101)
journal, August 2013


Coverage Dependence of Methanol Dissociation on TiO 2 (110)
journal, July 2015


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
  • DOI: 10.1021/acs.jpcc.6b00019

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
  • DOI: 10.1063/1.4982933

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
  • DOI: 10.1063/1.3382344

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
  • DOI: 10.1021/jp037685k

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


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
  • DOI: 10.1021/ja0773148

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
  • DOI: 10.1021/acs.jpcc.8b05611

A molecular dynamics method for simulations in the canonical ensemble
journal, June 1984


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
  • DOI: 10.1021/jp302273m

Structure and dynamics of liquid water on rutile TiO 2 ( 110 )
journal, October 2010


Pt···H Nonclassical Interaction in Water-Dissolved Pt(II) Complexes: Coaction of Electronic Effects with Solvent-Assisted Stabilization
journal, March 2016


Enhancing Hydrogen Evolution Activity in Water Splitting by Tailoring Li+-Ni(OH)2-Pt Interfaces
journal, December 2011


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
  • DOI: 10.1039/C6CP08789B

Theoretical analysis of small Pt particles on rutile TiO 2 ( 110 ) surfaces
journal, November 2010


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
  • DOI: 10.1038/srep26670

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
  • DOI: 10.1021/j150553a008

Role of Polarons in Water Splitting: The Case of BiVO 4
journal, June 2018


Inhomogeneous Electron Gas
journal, November 1964


Surface reconstructions: Polaron bricklayers at work
journal, October 2017


Adsorption and diffusion of Pt and Au on the stoichiometric and reduced Ti O 2 rutile (110) surfaces
journal, August 2005


Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985


Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts
journal, August 2003


Structural evolution of atomically dispersed Pt catalysts dictates reactivity
journal, April 2019


Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles
journal, April 2018


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
  • DOI: 10.1021/acs.jpclett.8b02286

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
  • DOI: 10.1021/jp1041316

Electronic Structure of Defect States in Hydroxylated and Reduced Rutile TiO 2 ( 110 ) Surfaces
journal, October 2006

  • Di Valentin, Cristiana; Pacchioni, Gianfranco; Selloni, Annabella
  • Physical Review Letters, Vol. 97, Issue 16
  • DOI: 10.1103/PhysRevLett.97.166803

Electronic correlation effects in reduced rutile TiO 2 within the LDA + U method
journal, September 2010


Surface and subsurface oxygen vacancies in anatase TiO 2 and differences with rutile
journal, March 2009


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
  • DOI: 10.1021/ic2013107