Water dissociative adsorption on NiO(111): Energetics and structure of the hydroxylated surface

Zhao, Wei; Bajdich, Michal; Carey, Spencer; Vojvodic, Aleksandra; Nørskov, Jens K.; Campbell, Charles T.

doi:10.1021/acscatal.6b01997

Title: Water dissociative adsorption on NiO(111): Energetics and structure of the hydroxylated surface

Abstract

The energetics of the reactions of water with metal oxide surfaces are of tremendous interest for catalysis, electrocatalysis, and geochemistry, yet the energy for the dissociative adsorption of water was only previously measured on one well-defined oxide surface, iron oxide. In the present paper, the enthalpy of the dissociative adsorption of water is measured on NiO(111)-2 × 2 at 300 K using single-crystal adsorption calorimetry. The differential heat of dissociative adsorption decreases with coverage from 170 to 117 kJ/mol in the first 0.25 ML of coverage. Water adsorbs molecularly on top of that, with a heat of ~92 kJ/mol. Density functional theory (DFT) calculations reproduce the measured energies well (all within 17 kJ/mol) and provide insight into the atomic-level structure of the surfaces studied experimentally. They show that the oxygen-terminated O-octo(2 × 2) structure is the most stable NiO(111)-2 × 2 termination and gives reaction energies with water that are more consistent with the calorimetry results than the metal-terminated surface. They show that water adsorbs dissociatively on this (2 × 2)-O-octo surface to produce a hydroxyl-covered surface with a heat of adsorption of 171 ± 5 kJ/mol in the low-coverage limit (very close to 170 kJ/mol experimentally) and an integralmore »« less

Authors:

Zhao, Wei ^[1]; Bajdich, Michal ^[2]; Carey, Spencer ^[1]; Vojvodic, Aleksandra ^[2]; Nørskov, Jens K. ^[2]; Campbell, Charles T. ^[1]

Univ. of Washington, Seattle, WA (United States)
Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)

Publication Date:: Mon Sep 19 00:00:00 EDT 2016

Research Org.:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1348873

Grant/Contract Number:: AC02-76SF00515

Resource Type:: Accepted Manuscript

Journal Name:: ACS Catalysis

Additional Journal Information:: Journal Volume: 6; Journal Issue: 11; Journal ID: ISSN 2155-5435

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; adsorption calorimetry; benchmark; density functional theory; heat of adsorption; nickel oxide; surface hydroxyl; water dissociation

Citation Formats


                    Zhao, Wei, Bajdich, Michal, Carey, Spencer, Vojvodic, Aleksandra, Nørskov, Jens K., and Campbell, Charles T. Water dissociative adsorption on NiO(111): Energetics and structure of the hydroxylated surface.  United States: N. p., 2016. 
Web.  doi:10.1021/acscatal.6b01997.

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                    Zhao, Wei, Bajdich, Michal, Carey, Spencer, Vojvodic, Aleksandra, Nørskov, Jens K., & Campbell, Charles T. Water dissociative adsorption on NiO(111): Energetics and structure of the hydroxylated surface.  United States.  https://doi.org/10.1021/acscatal.6b01997

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                    Zhao, Wei, Bajdich, Michal, Carey, Spencer, Vojvodic, Aleksandra, Nørskov, Jens K., and Campbell, Charles T. Mon .  
"Water dissociative adsorption on NiO(111): Energetics and structure of the hydroxylated surface".  United States.  https://doi.org/10.1021/acscatal.6b01997.  https://www.osti.gov/servlets/purl/1348873.

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@article{osti_1348873,

  title        = {Water dissociative adsorption on NiO(111): Energetics and structure of the hydroxylated surface},

  author       = {Zhao, Wei and Bajdich, Michal and Carey, Spencer and Vojvodic, Aleksandra and Nørskov, Jens K. and Campbell, Charles T.},

  abstractNote = {The energetics of the reactions of water with metal oxide surfaces are of tremendous interest for catalysis, electrocatalysis, and geochemistry, yet the energy for the dissociative adsorption of water was only previously measured on one well-defined oxide surface, iron oxide. In the present paper, the enthalpy of the dissociative adsorption of water is measured on NiO(111)-2 × 2 at 300 K using single-crystal adsorption calorimetry. The differential heat of dissociative adsorption decreases with coverage from 170 to 117 kJ/mol in the first 0.25 ML of coverage. Water adsorbs molecularly on top of that, with a heat of ~92 kJ/mol. Density functional theory (DFT) calculations reproduce the measured energies well (all within 17 kJ/mol) and provide insight into the atomic-level structure of the surfaces studied experimentally. They show that the oxygen-terminated O-octo(2 × 2) structure is the most stable NiO(111)-2 × 2 termination and gives reaction energies with water that are more consistent with the calorimetry results than the metal-terminated surface. They show that water adsorbs dissociatively on this (2 × 2)-O-octo surface to produce a hydroxyl-covered surface with a heat of adsorption of 171 ± 5 kJ/mol in the low-coverage limit (very close to 170 kJ/mol experimentally) and an integral heat that decreases by 14 kJ/mol up to saturation (compared to ~30 kJ/mol experimentally). As a result, sensitivity of this reaction’s energy to choice of DFT method is tested using a variety of different exchange correlation functionals, including HSE06, and found to be quite weak.},

  doi          = {10.1021/acscatal.6b01997},

  journal      = {ACS Catalysis},

  number       = 11,

  volume       = 6,

  place        = {United States},

  year         = {Mon Sep 19 00:00:00 EDT 2016},

  month        = {Mon Sep 19 00:00:00 EDT 2016}

}

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Carbon doping switching on the hydrogen adsorption activity of NiO for hydrogen evolution reaction
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Kou, Tianyi; Chen, Mingpeng; Wu, Feng
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Carbon doping switching on the hydrogen adsorption activity of NiO for hydrogen evolution reaction
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Kou, Tianyi; Chen, Mingpeng; Wu, Feng
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DOI: 10.1038/s41467-020-14462-2

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Title: Water dissociative adsorption on NiO(111): Energetics and structure of the hydroxylated surface

Abstract

Citation Formats

Enthalpies and Entropies of Adsorption on Well-Defined Oxide Surfaces: Experimental Measurements journal, December 2012

Interaction of water with the (1×1) and (2×1) surfaces of α-Fe2O3(012) journal, November 1998

Water Interaction with Iron Oxides journal, October 2015

The oxidative chemistry of methane over supported nickel catalysts journal, November 1998

Catalytic partial oxidation of methane to synthesis gas over Ni–CeO2 journal, February 2001

Catalytic activities of nickel-containing catalysts for ethylene dimerization and butene isomerization and their relationship to acidic properties journal, April 2002

Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis journal, August 2014

Hydroxyl groups on oxide surfaces: NiO(100), NiO(111) and Cr2O3(111) journal, November 1993

Surface hydroxylation and local structure of NiO thin films formed on Ni(111) journal, June 1998

Molecular adsorption on the surface of strongly correlated transition-metal oxides: A case study for CO/NiO(100) journal, February 2004

Density functional study of CO and NO adsorption on Ni-doped MgO(100) journal, March 2010

Why the case for clean surfaces does not hold water: Structure and morphology of hydroxylated nickel oxide (111) journal, January 2010

First-principles study of the reconstruction and hydroxylation of the polar NiO(111) surface journal, July 2011

Calorimeter for adsorption energies of larger molecules on single crystal surfaces journal, November 2004

Improved pyroelectric detectors for single crystal adsorption calorimetry from 100 to 350 K journal, February 2010

Stabilization of NiO(111) Thin Films by Surface Hydroxyls journal, March 1995

A photoemission study of the interaction of Ni(100), (110) and (111) surfaces with oxygen journal, June 1977

Oxidation kinetics for Ni ( 111 ) and the structure of the oxide layers journal, January 2007

Molecular beam investigation of adsorption kinetics on bulk metal targets: Nitrogen on tungsten journal, February 1972

Energetics of Cyclohexene Adsorption and Reaction on Pt(111) by Low-Temperature Microcalorimetry journal, August 2008

The Energy of Adsorbed Hydroxyl on Pt(111) by Microcalorimetry journal, May 2011

Surface chemistry of polar oxide surfaces: formic acid on NiO (111) journal, January 1995

Energy of Molecularly Adsorbed Water on Clean Pt(111) and Pt(111) with Coadsorbed Oxygen by Calorimetry journal, April 2011

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal, July 1996

Ab initiomolecular dynamics for liquid metals journal, January 1993

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

Generalized Gradient Approximation Made Simple journal, October 1996

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal, January 1998

Oxidation energies of transition metal oxides within the GGA + U framework journal, May 2006

Lattice parameter, microstrains and non-stoichiometry in NiO. Comparison between mosaic microcrystals and quasi-perfect single microcrystals journal, August 1979

Photoemission and inverse photoemission spectroscopy of NiO journal, December 1984

Magnitude and Origin of the Band Gap in NiO journal, December 1984

Island growth kinetics during vapor deposition of Cu onto the Zn-terminated ZnO(0001) surface journal, September 1999

Magnetic ordering and exchange effects in the antiferromagnetic solid solutions Mn x Ni 1 − x O journal, June 1983

Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation journal, June 2012

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces journal, April 2008

Hybrid functionals based on a screened Coulomb potential journal, May 2003

Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)] journal, June 2006

Linear response approach to the calculation of the effective interaction parameters in the LDA + U method journal, January 2005

Accurate adsorption energies of small molecules on oxide surfaces: CO–MgO(001) journal, January 2013

Kinetic energy effects on the oxidation of Ni(111) using O2 molecular beams journal, November 1998

Reconstruction of NaCl surfaces from a dipolar solution to the Madelung problem journal, June 1992

Hydroxy1 driven reconstruction of the polar NiO(111) surface journal, August 1994

Stable reconstruction of the polar (111) surface of NiO on Au(111) journal, February 1994

Structural investigation of the dynamics of the NiO(111) surface by GIXS journal, August 1999

Adsorption and reaction of formic acid on NiO(100) films on Mo(100): Temperature programmed desorption and high resolution electron energy loss spectroscopy studies journal, December 1992

Application of HREEL spectroscopy to characterize adsorbates on insulating metal oxide surfaces: carboxylates on MgO(100) journal, December 1991

Dimerization Induced Deprotonation of Water on RuO 2 (110) journal, September 2014

Adsorption of Water on a PdO(101) Thin Film: Evidence of an Adsorbed HO−H 2 O Complex journal, January 2009

Molecular adsorption of NO on NiO(100): DFT and DFT + U calculations journal, January 2005

Importance of Correlation in Determining Electrocatalytic Oxygen Evolution Activity on Cobalt Oxides journal, September 2012

Femtomole Adsorption Calorimetry on Single-Crystal Surfaces journal, April 1998

A benchmark database for adsorption bond energies to transition metal surfaces and comparison to selected DFT functionals journal, October 2015

Carbon doping switching on the hydrogen adsorption activity of NiO for hydrogen evolution reaction journal, January 2020

Pinpointing the active sites and reaction mechanism of CO oxidation on NiO journal, January 2019

Water Interaction with Sputter-Deposited Nickel Oxide on n-Si Photoanode: Cryo Photoelectron Spectroscopy on Adsorbed Water in the Frozen Electrolyte Approach journal, January 2018

N-Modified NiO Surface for Superior Alkaline Hydrogen Evolution journal, February 2018

Ultrathin Fe-N-C Nanosheets Coordinated Fe-Doped CoNi Alloy Nanoparticles for Electrochemical Water Splitting journal, September 2018

Structural motifs of water on metal oxide surfaces journal, January 2017

Theoretical Insights to Bulk Activity Towards Oxygen Evolution in Oxyhydroxides journal, April 2017

Carbon doping switching on the hydrogen adsorption activity of NiO for hydrogen evolution reaction journal, January 2020

Enthalpies and Entropies of Adsorption on Well-Defined Oxide Surfaces: Experimental Measurements
journal, December 2012

Interaction of water with the (1×1) and (2×1) surfaces of α-Fe2O3(012)
journal, November 1998

Water Interaction with Iron Oxides
journal, October 2015

The oxidative chemistry of methane over supported nickel catalysts
journal, November 1998

Catalytic partial oxidation of methane to synthesis gas over Ni–CeO2
journal, February 2001

Catalytic activities of nickel-containing catalysts for ethylene dimerization and butene isomerization and their relationship to acidic properties
journal, April 2002

Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis
journal, August 2014

Hydroxyl groups on oxide surfaces: NiO(100), NiO(111) and Cr2O3(111)
journal, November 1993

Surface hydroxylation and local structure of NiO thin films formed on Ni(111)
journal, June 1998

Molecular adsorption on the surface of strongly correlated transition-metal oxides: A case study for CO/NiO(100)
journal, February 2004

Density functional study of CO and NO adsorption on Ni-doped MgO(100)
journal, March 2010

Why the case for clean surfaces does not hold water: Structure and morphology of hydroxylated nickel oxide (111)
journal, January 2010

First-principles study of the reconstruction and hydroxylation of the polar NiO(111) surface
journal, July 2011

Calorimeter for adsorption energies of larger molecules on single crystal surfaces
journal, November 2004

Improved pyroelectric detectors for single crystal adsorption calorimetry from 100 to 350 K
journal, February 2010

Stabilization of NiO(111) Thin Films by Surface Hydroxyls
journal, March 1995

A photoemission study of the interaction of Ni(100), (110) and (111) surfaces with oxygen
journal, June 1977

Oxidation kinetics for $Ni (111)$ and the structure of the oxide layers
journal, January 2007

Molecular beam investigation of adsorption kinetics on bulk metal targets: Nitrogen on tungsten
journal, February 1972

Energetics of Cyclohexene Adsorption and Reaction on Pt(111) by Low-Temperature Microcalorimetry
journal, August 2008

The Energy of Adsorbed Hydroxyl on Pt(111) by Microcalorimetry
journal, May 2011

Surface chemistry of polar oxide surfaces: formic acid on NiO (111)
journal, January 1995

Energy of Molecularly Adsorbed Water on Clean Pt(111) and Pt(111) with Coadsorbed Oxygen by Calorimetry
journal, April 2011

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Ab initiomolecular dynamics for liquid metals
journal, January 1993

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Generalized Gradient Approximation Made Simple
journal, October 1996

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

Oxidation energies of transition metal oxides within the $GGA + U$ framework
journal, May 2006

Lattice parameter, microstrains and non-stoichiometry in NiO. Comparison between mosaic microcrystals and quasi-perfect single microcrystals
journal, August 1979

Photoemission and inverse photoemission spectroscopy of NiO
journal, December 1984

Magnitude and Origin of the Band Gap in NiO
journal, December 1984

Island growth kinetics during vapor deposition of Cu onto the Zn-terminated ZnO(0001) surface
journal, September 1999

Magnetic ordering and exchange effects in the antiferromagnetic solid solutions ${Mn}_{x} {Ni}_{1 - x} O$
journal, June 1983

Density functionals for surface science: Exchange-correlation model development with Bayesian error estimation
journal, June 2012

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008

Hybrid functionals based on a screened Coulomb potential
journal, May 2003

Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
journal, June 2006

Linear response approach to the calculation of the effective interaction parameters in the $LDA + U$ method
journal, January 2005

Accurate adsorption energies of small molecules on oxide surfaces: CO–MgO(001)
journal, January 2013

Kinetic energy effects on the oxidation of Ni(111) using O2 molecular beams
journal, November 1998

Reconstruction of NaCl surfaces from a dipolar solution to the Madelung problem
journal, June 1992

Hydroxy1 driven reconstruction of the polar NiO(111) surface
journal, August 1994

Stable reconstruction of the polar (111) surface of NiO on Au(111)
journal, February 1994

Structural investigation of the dynamics of the NiO(111) surface by GIXS
journal, August 1999

Adsorption and reaction of formic acid on NiO(100) films on Mo(100): Temperature programmed desorption and high resolution electron energy loss spectroscopy studies
journal, December 1992

Application of HREEL spectroscopy to characterize adsorbates on insulating metal oxide surfaces: carboxylates on MgO(100)
journal, December 1991

Dimerization Induced Deprotonation of Water on RuO ₂ (110)
journal, September 2014

Adsorption of Water on a PdO(101) Thin Film: Evidence of an Adsorbed HO−H ₂ O Complex
journal, January 2009

Molecular adsorption of NO on NiO(100): DFT and $DFT + U$ calculations
journal, January 2005

Importance of Correlation in Determining Electrocatalytic Oxygen Evolution Activity on Cobalt Oxides
journal, September 2012

Femtomole Adsorption Calorimetry on Single-Crystal Surfaces
journal, April 1998

A benchmark database for adsorption bond energies to transition metal surfaces and comparison to selected DFT functionals
journal, October 2015

Carbon doping switching on the hydrogen adsorption activity of NiO for hydrogen evolution reaction
journal, January 2020

Pinpointing the active sites and reaction mechanism of CO oxidation on NiO
journal, January 2019

Water Interaction with Sputter-Deposited Nickel Oxide on n-Si Photoanode: Cryo Photoelectron Spectroscopy on Adsorbed Water in the Frozen Electrolyte Approach
journal, January 2018

N-Modified NiO Surface for Superior Alkaline Hydrogen Evolution
journal, February 2018

Ultrathin Fe-N-C Nanosheets Coordinated Fe-Doped CoNi Alloy Nanoparticles for Electrochemical Water Splitting
journal, September 2018

Structural motifs of water on metal oxide surfaces
journal, January 2017

Theoretical Insights to Bulk Activity Towards Oxygen Evolution in Oxyhydroxides
journal, April 2017

Carbon doping switching on the hydrogen adsorption activity of NiO for hydrogen evolution reaction
journal, January 2020