Conversion of Formic Acid on Single- and Nano-Crystalline Anatase TiO2(101)

Petrik, Nikolay G.; Wang, Yang; Wen, Bo; Wu, Yiqing; Ma, Runze; Dahal, Arjun P.; Gao, Feng; Rousseau, Roger J.; Wang, Yong; Kimmel, Gregory A.; Selloni, Annabella; Dohnálek, Zdenek

doi:10.1021/acs.jpcc.1c00571

Title: Conversion of Formic Acid on Single- and Nano-Crystalline Anatase TiO₂(101)

Abstract

Understanding thermochemical transformations of formic acid (FA) on metal oxide surfaces is important for many catalytical reactions. Here we study thermally induced reactions of FA on a single-crystalline and nanocrystalline anatase TiO₂(101). We employ a combination of scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), infrared reflection absorption spectroscopy (IRAS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and density functional theory (DFT) to follow the FA surface intermediates and reaction products above room temperature. We find that the primary reaction products desorbing at about 300, 480, and 515 K are molecular water, carbon monoxide, and formaldehyde, respectively. Bidentate (BD) formate and bridging hydroxyl (HO_b) are identified as central intermediates in the FA transformations. Bridging oxygen vacancies (V_O) are also likely participants despite their low stability at the surface. In conclusion, the parallel studies on single crystals and faceted TiO₂(101) nanoparticles reveal the spectroscopic commonalities of surface species and of the thermal conversion of molecular and deprotonated forms of FA.

Authors:

^[1]; Wang, Yang ^[1]; Wen, Bo ^[2]; Wu, Yiqing ^[1]; Ma, Runze ^[1];

^[3];

^[1];

^[4];

^[3]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Princeton Univ., NJ (United States); Washington State Univ., Pullman, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. of South Alabama, Mobile, AL (United States)
Princeton Univ., NJ (United States)

Publication Date:: Mon Apr 05 00:00:00 EDT 2021

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL); Princeton Univ., NJ (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)

OSTI Identifier:: 1787859

Alternate Identifier(s):: OSTI ID: 1774046

Report Number(s):: PNNL-SA-159116
Journal ID: ISSN 1932-7447

Grant/Contract Number:: AC05-76RL01830; SC0007347

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 125; Journal Issue: 14; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Desorption; Oxides; Minerals; Annealing (metallurgy); Scanning tunneling microscopy

Citation Formats


                    Petrik, Nikolay G., Wang, Yang, Wen, Bo, Wu, Yiqing, Ma, Runze, Dahal, Arjun P., Gao, Feng, Rousseau, Roger J., Wang, Yong, Kimmel, Gregory A., Selloni, Annabella, and Dohnálek, Zdenek. Conversion of Formic Acid on Single- and Nano-Crystalline Anatase TiO2(101).  United States: N. p., 2021. 
Web.  doi:10.1021/acs.jpcc.1c00571.

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                    Petrik, Nikolay G., Wang, Yang, Wen, Bo, Wu, Yiqing, Ma, Runze, Dahal, Arjun P., Gao, Feng, Rousseau, Roger J., Wang, Yong, Kimmel, Gregory A., Selloni, Annabella, & Dohnálek, Zdenek. Conversion of Formic Acid on Single- and Nano-Crystalline Anatase TiO2(101).  United States.  https://doi.org/10.1021/acs.jpcc.1c00571

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                    Petrik, Nikolay G., Wang, Yang, Wen, Bo, Wu, Yiqing, Ma, Runze, Dahal, Arjun P., Gao, Feng, Rousseau, Roger J., Wang, Yong, Kimmel, Gregory A., Selloni, Annabella, and Dohnálek, Zdenek. Mon .  
"Conversion of Formic Acid on Single- and Nano-Crystalline Anatase TiO2(101)".  United States.  https://doi.org/10.1021/acs.jpcc.1c00571.  https://www.osti.gov/servlets/purl/1787859.

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@article{osti_1787859,

  title        = {Conversion of Formic Acid on Single- and Nano-Crystalline Anatase TiO2(101)},

  author       = {Petrik, Nikolay G. and Wang, Yang and Wen, Bo and Wu, Yiqing and Ma, Runze and Dahal, Arjun P. and Gao, Feng and Rousseau, Roger J. and Wang, Yong and Kimmel, Gregory A. and Selloni, Annabella and Dohnálek, Zdenek},

  abstractNote = {Understanding thermochemical transformations of formic acid (FA) on metal oxide surfaces is important for many catalytical reactions. Here we study thermally induced reactions of FA on a single-crystalline and nanocrystalline anatase TiO2(101). We employ a combination of scanning tunneling microscopy (STM), temperature-programmed desorption (TPD), infrared reflection absorption spectroscopy (IRAS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and density functional theory (DFT) to follow the FA surface intermediates and reaction products above room temperature. We find that the primary reaction products desorbing at about 300, 480, and 515 K are molecular water, carbon monoxide, and formaldehyde, respectively. Bidentate (BD) formate and bridging hydroxyl (HOb) are identified as central intermediates in the FA transformations. Bridging oxygen vacancies (VO) are also likely participants despite their low stability at the surface. In conclusion, the parallel studies on single crystals and faceted TiO2(101) nanoparticles reveal the spectroscopic commonalities of surface species and of the thermal conversion of molecular and deprotonated forms of FA.},

  doi          = {10.1021/acs.jpcc.1c00571},

  journal      = {Journal of Physical Chemistry. C},

  number       = 14,

  volume       = 125,

  place        = {United States},

  year         = {Mon Apr 05 00:00:00 EDT 2021},

  month        = {Mon Apr 05 00:00:00 EDT 2021}

}

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Title: Conversion of Formic Acid on Single- and Nano-Crystalline Anatase TiO2(101)

Abstract

Citation Formats

On the catalytic decomposition of formic acid. I. The activation energies for oxide catalysis journal, March 1998

Ab initio quantum-chemical study of the unimolecular pyrolysis mechanisms of formic acid journal, February 1986

Electrochemical Photolysis of Water at a Semiconductor Electrode journal, July 1972

The Catalytic Decomposition of Formic Acid Vapor journal, January 1928

New reaction route of HCOOH catalytic decomposition journal, October 2005

(Sub)Surface Mobility of Oxygen Vacancies at the TiO 2 Anatase (101) Surface journal, September 2012

Elementary steps and site requirements in formic acid dehydration reactions on anatase and rutile TiO2 surfaces journal, March 2020

A surface science perspective on TiO2 photocatalysis journal, June 2011

Synthesis of anatase TiO2 nanocrystals with {101}, {001} or {010} single facets of 90% level exposure and liquid-phase photocatalytic reduction and oxidation activity orders journal, January 2013

Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides journal, July 2001

Switchover of Reaction Mechanism for the Catalytic Decomposition of HCOOH on a TiO 2 (110) Surface journal, November 2007

Nonthermal Water Splitting on Rutile TiO 2 : Electron-Stimulated Production of H 2 and O 2 in Amorphous Solid Water Films on TiO 2 (110) journal, February 2009

Structural Sensitivity in the Dissociation of Water on TiO 2 Single-Crystal Surfaces journal, January 1996

Infrared spectroscopy study of adsorption and photodecomposition of formic acid on reduced and defective rutile TiO 2 (110) surfaces journal, November 2014

Formation of Metastable Water Chains on Anatase TiO 2 (101) journal, September 2017

Single-Molecule Vibrational Spectroscopy of H 2 O on Anatase TiO 2 (101) journal, January 2017

Adsorption of formic acid on rutile TiO 2 (110) revisited: An infrared reflection-absorption spectroscopy and density functional theory study journal, January 2014

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

Formic acid adsorption and decomposition on TiO 2 (1 1 0) and on Pd/TiO 2 (1 1 0) model catalysts journal, June 2002

Dissociation of formic acid on anatase TiO2(101) probed by vibrational spectroscopy journal, March 2012

Molecular Water Adsorption and Reactions on α-Al 2 O 3 (0001) and α-Alumina Particles journal, April 2018

Probing Acid–Base Properties of Anatase TiO 2 Nanoparticles with Dominant {001} and {101} Facets Using Methanol Chemisorption and Surface Reactions journal, February 2021

A climbing image nudged elastic band method for finding saddle points and minimum energy paths journal, December 2000

Surface preparation of TiO2 anatase (101): Pitfalls and how to avoid them journal, August 2014

The surface science of titanium dioxide journal, January 2003

Observation of Molecular Hydrogen Produced from Bridging Hydroxyls on Anatase TiO 2 (101) journal, October 2020

Oxygen Vacancy Promoting Catalytic Dehydration of Formic Acid on TiO 2 (110) by in Situ Scanning Tunneling Microscopic Observation journal, October 2005

Formic Acid on TiO 2– x (110): Dissociation, Motion, and Vacancy Healing journal, June 2014

Nobel Prize in chemistry 1912 to Sabatier: Organic chemistry or catalysis? journal, December 2013

Strongly Constrained and Appropriately Normed Semilocal Density Functional journal, July 2015

Evidence for oxygen adatoms on TiO2(110) resulting from O2 dissociation at vacancy sites journal, September 1998

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

Acetone and Water on TiO 2 (110): H/D Exchange journal, March 2005

Steps on anatase TiO2(101) journal, July 2006

Structure–activity relationship of surface hydroxyl groups during NO 2 adsorption and transformation on TiO 2 nanoparticles journal, January 2017

Efficient Photochemical Water Splitting by a Chemically Modified n-TiO2 journal, September 2002

Structure Determination of Formic Acid Reaction Products on TiO 2 (110) † journal, September 2004

Site-dependent electron-stimulated reactions in water films on TiO2(110) journal, December 2007

Techniques for attainment, control, and calibration of cryogenic temperatures at small single‐crystal samples under ultrahigh vacuum journal, July 1993

Fourier Transform Reflection−Absorption IR Spectroscopy Study of Formate Adsorption on TiO 2 (110) journal, January 1999

Adsorption and decomposition mechanism of formic acid on the Ga 2 O 3 surface by first principle studies journal, February 2017

Production of CO-Free H2 by Formic Acid Decomposition over Mo2C/Carbon Catalysts journal, June 2010

First-Principles Theoretical Study and Scanning Tunneling Microscopic Observation of Dehydration Process of Formic Acid on a TiO 2 (110) Surface † journal, September 2004

Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results journal, May 1995

Reaction Kinetics of Water Molecules with Oxygen Vacancies on Rutile TiO 2 (110) journal, September 2015

Bridging Hydroxyls on Anatase TiO 2 (101) by Water Dissociation in Oxygen Vacancies journal, October 2017

Complexity in the Decomposition of Formic Acid on the TiO 2 (110) Surface journal, January 1997

Probing equilibrium of molecular and deprotonated water on TiO 2 (110) journal, February 2017

Unimolecular Decomposition of Formic Acid in the Gas PhaseOn the Ratio of the Competing Reaction Channels journal, June 2005

Adsorption and Reaction of Methanol on Anatase TiO 2 (101) Single Crystals and Faceted Nanoparticles journal, September 2019

Formic Acid Dehydration Rates and Elementary Steps on Lewis Acid–Base Site Pairs at Anatase and Rutile TiO 2 Surfaces journal, September 2020

Separable dual-space Gaussian pseudopotentials journal, July 1996

Inhomogeneous Electron Gas journal, November 1964

Hydrogen interaction with the anatase TiO2(101) surface journal, January 2012

THE CATALYTIC DECOMPOSITION OF FORMIC ACID IN ACETIC ANHYDRIDE 1 journal, February 1923

Binding of Formic Acid on Anatase TiO 2 (101) journal, August 2020

Pathways for carboxylic acid decomposition on titania journal, July 1988

Frequencies and Thermal Stability of Isolated Surface Hydroxyls on Pyrogenic TiO 2 Nanoparticles journal, September 2019

Chemical Reactivity of Reduced TiO 2 (110): The Dominant Role of Surface Defects in Oxygen Chemisorption journal, June 2009

Photocatalytic Activity of Bulk TiO 2 Anatase and Rutile Single Crystals Using Infrared Absorption Spectroscopy journal, March 2011

Chemisorption Geometry, Vibrational Spectra, and Thermal Desorption of Formic Acid on TiO 2 (110) journal, February 1998

Experimental Investigation of the Interaction of Water and Methanol with Anatase−TiO 2 (101) journal, March 2003

Surface infrared spectroscopy journal, May 1988

Dehydration Pathway for the Dissociation of Gas-Phase Formic Acid on Pt(111) Surface Observed via Ambient-Pressure XPS journal, January 2018

Polarization- and Azimuth-Resolved Infrared Spectroscopy of Water on TiO 2 (110): Anisotropy and the Hydrogen-Bonding Network journal, March 2012

Title: Conversion of Formic Acid on Single- and Nano-Crystalline Anatase TiO₂(101)

On the catalytic decomposition of formic acid. I. The activation energies for oxide catalysis
journal, March 1998

Ab initio quantum-chemical study of the unimolecular pyrolysis mechanisms of formic acid
journal, February 1986

Electrochemical Photolysis of Water at a Semiconductor Electrode
journal, July 1972

The Catalytic Decomposition of Formic Acid Vapor
journal, January 1928

New reaction route of HCOOH catalytic decomposition
journal, October 2005

(Sub)Surface Mobility of Oxygen Vacancies at the ${TiO}_{2}$ Anatase (101) Surface
journal, September 2012

Elementary steps and site requirements in formic acid dehydration reactions on anatase and rutile TiO2 surfaces
journal, March 2020

A surface science perspective on TiO2 photocatalysis
journal, June 2011

Synthesis of anatase TiO2 nanocrystals with {101}, {001} or {010} single facets of 90% level exposure and liquid-phase photocatalytic reduction and oxidation activity orders
journal, January 2013

Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides
journal, July 2001

Switchover of Reaction Mechanism for the Catalytic Decomposition of HCOOH on a TiO ₂ (110) Surface
journal, November 2007

Nonthermal Water Splitting on Rutile TiO ₂ : Electron-Stimulated Production of H ₂ and O ₂ in Amorphous Solid Water Films on TiO ₂ (110)
journal, February 2009

Structural Sensitivity in the Dissociation of Water on TiO ₂ Single-Crystal Surfaces
journal, January 1996

Infrared spectroscopy study of adsorption and photodecomposition of formic acid on reduced and defective rutile TiO ₂ (110) surfaces
journal, November 2014

Formation of Metastable Water Chains on Anatase TiO ₂ (101)
journal, September 2017

Single-Molecule Vibrational Spectroscopy of H ₂ O on Anatase TiO ₂ (101)
journal, January 2017

Adsorption of formic acid on rutile TiO ₂ (110) revisited: An infrared reflection-absorption spectroscopy and density functional theory study
journal, January 2014

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

Formic acid adsorption and decomposition on TiO 2 (1 1 0) and on Pd/TiO 2 (1 1 0) model catalysts
journal, June 2002

Dissociation of formic acid on anatase TiO2(101) probed by vibrational spectroscopy
journal, March 2012

Molecular Water Adsorption and Reactions on α-Al ₂ O ₃ (0001) and α-Alumina Particles
journal, April 2018

Probing Acid–Base Properties of Anatase TiO ₂ Nanoparticles with Dominant {001} and {101} Facets Using Methanol Chemisorption and Surface Reactions
journal, February 2021

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

Surface preparation of TiO2 anatase (101): Pitfalls and how to avoid them
journal, August 2014

The surface science of titanium dioxide
journal, January 2003

Observation of Molecular Hydrogen Produced from Bridging Hydroxyls on Anatase TiO ₂ (101)
journal, October 2020

Oxygen Vacancy Promoting Catalytic Dehydration of Formic Acid on TiO ₂ (110) by in Situ Scanning Tunneling Microscopic Observation
journal, October 2005

Formic Acid on TiO _{2– x} (110): Dissociation, Motion, and Vacancy Healing
journal, June 2014

Nobel Prize in chemistry 1912 to Sabatier: Organic chemistry or catalysis?
journal, December 2013

Strongly Constrained and Appropriately Normed Semilocal Density Functional
journal, July 2015

Evidence for oxygen adatoms on TiO2(110) resulting from O2 dissociation at vacancy sites
journal, September 1998

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

Acetone and Water on TiO ₂ (110): H/D Exchange
journal, March 2005

Steps on anatase TiO2(101)
journal, July 2006

Structure–activity relationship of surface hydroxyl groups during NO ₂ adsorption and transformation on TiO ₂ nanoparticles
journal, January 2017

Efficient Photochemical Water Splitting by a Chemically Modified n-TiO2
journal, September 2002

Structure Determination of Formic Acid Reaction Products on TiO ₂ (110) ^†
journal, September 2004

Site-dependent electron-stimulated reactions in water films on TiO2(110)
journal, December 2007

Techniques for attainment, control, and calibration of cryogenic temperatures at small single‐crystal samples under ultrahigh vacuum
journal, July 1993

Fourier Transform Reflection−Absorption IR Spectroscopy Study of Formate Adsorption on TiO ₂ (110)
journal, January 1999

Adsorption and decomposition mechanism of formic acid on the Ga 2 O 3 surface by first principle studies
journal, February 2017

Production of CO-Free H2 by Formic Acid Decomposition over Mo2C/Carbon Catalysts
journal, June 2010

First-Principles Theoretical Study and Scanning Tunneling Microscopic Observation of Dehydration Process of Formic Acid on a TiO ₂ (110) Surface ^†
journal, September 2004

Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results
journal, May 1995

Reaction Kinetics of Water Molecules with Oxygen Vacancies on Rutile TiO ₂ (110)
journal, September 2015

Bridging Hydroxyls on Anatase TiO ₂ (101) by Water Dissociation in Oxygen Vacancies
journal, October 2017

Complexity in the Decomposition of Formic Acid on the TiO ₂ (110) Surface
journal, January 1997

Probing equilibrium of molecular and deprotonated water on TiO ₂ (110)
journal, February 2017

Unimolecular Decomposition of Formic Acid in the Gas PhaseOn the Ratio of the Competing Reaction Channels
journal, June 2005

Adsorption and Reaction of Methanol on Anatase TiO ₂ (101) Single Crystals and Faceted Nanoparticles
journal, September 2019

Formic Acid Dehydration Rates and Elementary Steps on Lewis Acid–Base Site Pairs at Anatase and Rutile TiO ₂ Surfaces
journal, September 2020

Separable dual-space Gaussian pseudopotentials
journal, July 1996

Inhomogeneous Electron Gas
journal, November 1964

Hydrogen interaction with the anatase TiO2(101) surface
journal, January 2012

THE CATALYTIC DECOMPOSITION OF FORMIC ACID IN ACETIC ANHYDRIDE ¹
journal, February 1923

Binding of Formic Acid on Anatase TiO ₂ (101)
journal, August 2020

Pathways for carboxylic acid decomposition on titania
journal, July 1988

Frequencies and Thermal Stability of Isolated Surface Hydroxyls on Pyrogenic TiO ₂ Nanoparticles
journal, September 2019

Chemical Reactivity of Reduced TiO ₂ (110): The Dominant Role of Surface Defects in Oxygen Chemisorption
journal, June 2009

Photocatalytic Activity of Bulk ${TiO}_{2}$ Anatase and Rutile Single Crystals Using Infrared Absorption Spectroscopy
journal, March 2011

Chemisorption Geometry, Vibrational Spectra, and Thermal Desorption of Formic Acid on TiO ₂ (110)
journal, February 1998

Experimental Investigation of the Interaction of Water and Methanol with Anatase−TiO ₂ (101)
journal, March 2003

Surface infrared spectroscopy
journal, May 1988

Dehydration Pathway for the Dissociation of Gas-Phase Formic Acid on Pt(111) Surface Observed via Ambient-Pressure XPS
journal, January 2018

Polarization- and Azimuth-Resolved Infrared Spectroscopy of Water on TiO ₂ (110): Anisotropy and the Hydrogen-Bonding Network
journal, March 2012