Site dependent reactivity of Pt single atoms on anatase TiO2(101) in an aqueous environment

doi:10.1039/C9CP05097C

Title: 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 (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 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 »« less

Authors:

^[1]; Yin, Wen-Jin ^[2];

^[3]; Liu, Li-Min ^[4]

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:: 2019-10-14

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 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.

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                    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.

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                    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.  https://www.osti.gov/servlets/purl/1594492.

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@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       = 19,

  volume       = 22,

  place        = {United States},

  year         = {2019},

  month        = {10}

}

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DOI: 10.1039/C9CP05097C

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Title: Site dependent reactivity of Pt single atoms on anatase TiO2(101) in an aqueous environment

Abstract

Citation Formats

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Ab Initio Simulation of the Effects of Hydrogen Concentration on Anatase TiO 2 journal, April 2016

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

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal, April 2010

Structure and Reactivity of Water Layers on Defect-Free and Defective Anatase TiO 2 (101) Surfaces journal, April 2004

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

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

Evidence for the Predominance of Subsurface Defects on Reduced Anatase TiO 2 ( 101 ) journal, March 2009

Small Au and Pt Clusters at the Anatase TiO 2 (101) Surface: Behavior at Terraces, Steps, and Surface Oxygen Vacancies journal, January 2008

Quantifying Support Interactions and Reactivity Trends of Single Metal Atom Catalysts over TiO 2 journal, October 2018

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

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

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

Separable dual-space Gaussian pseudopotentials journal, July 1996

The Mechanism of the Hydrogen Evolution Reaction on Platinum, Silver and Tungsten surfaces in Acid Solutions journal, July 1957

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

Deep versus Shallow Behavior of Intrinsic Defects in Rutile and Anatase TiO 2 Polymorphs journal, November 2010

Proton-Promoted Electron Transfer in Photocatalysis: Key Step for Photocatalytic Hydrogen Evolution on Metal/Titania Composites journal, March 2017

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

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

Inhomogeneous Electron Gas journal, March 1973

Title: Site dependent reactivity of Pt single atoms on anatase TiO₂(101) in an aqueous environment

Direct Imaging of Pt Single Atoms Adsorbed on TiO ₂ (110) Surfaces
journal, December 2013

Generalized Gradient Approximation Made Simple
journal, October 1996

Photocatalytic and Photovoltaic Properties of TiO 2 Nanoparticles Investigated by Ab Initio Simulations
journal, December 2014

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

Key Steps of the cis -Platin-DNA Interaction: Density Functional Theory-Based Molecular Dynamics Simulations
journal, February 2000

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

Synthesis-Dependent Oxidation State of Platinum on TiO ₂ and Their Influences on the Solar Simulated Photocatalytic Hydrogen Production from Water
journal, August 2013

Facet-dependent trapping and dynamics of excess electrons at anatase TiO2 surfaces and aqueous interfaces
journal, June 2016

Heterogeneous single-atom catalysis
journal, May 2018

Titania-water interactions: a review of theoretical studies
journal, January 2010

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

Role of Platinum Deposited on TiO 2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions
journal, January 2014

Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach
journal, April 2005

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

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

Theoretical Studies on Anatase and Less Common TiO ₂ Phases: Bulk, Surfaces, and Nanomaterials
journal, May 2014

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

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

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

Structure and Reactivity of Water Layers on Defect-Free and Defective Anatase TiO 2 (101) Surfaces
journal, April 2004

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

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

Evidence for the Predominance of Subsurface Defects on Reduced Anatase ${TiO}_{2} (101)$
journal, March 2009

Small Au and Pt Clusters at the Anatase TiO ₂ (101) Surface: Behavior at Terraces, Steps, and Surface Oxygen Vacancies
journal, January 2008

Quantifying Support Interactions and Reactivity Trends of Single Metal Atom Catalysts over TiO 2
journal, October 2018

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

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

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

Separable dual-space Gaussian pseudopotentials
journal, July 1996

The Mechanism of the Hydrogen Evolution Reaction on Platinum, Silver and Tungsten surfaces in Acid Solutions
journal, July 1957

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

Deep versus Shallow Behavior of Intrinsic Defects in Rutile and Anatase TiO ₂ Polymorphs
journal, November 2010

Proton-Promoted Electron Transfer in Photocatalysis: Key Step for Photocatalytic Hydrogen Evolution on Metal/Titania Composites
journal, March 2017

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

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

Inhomogeneous Electron Gas
journal, March 1973