Coadsorption of Formic Acid and Hydrazine on Cu(110) Single-Crystal Surfaces

Yao, Yunxi; Guerrero-Sánchez, Jonathan; Takeuchi, Noboru; Zaera, Francisco

doi:10.1021/acs.jpcc.8b01804

Title: Coadsorption of Formic Acid and Hydrazine on Cu(110) Single-Crystal Surfaces

Abstract

The chemistry of coadsorbed formic acid and hydrazine on Cu(110) surfaces was characterized both experimentally, by temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS), and theoretically, via density functional theory (DFT) calculations. It was found that the two reactants interact with each other via hydrogen bonds, and that this modifies their individual thermal chemistry on the surface in two main ways: by stabilizing a HCOOH:N₂H₄ adduct, which desorbs molecularly at around 240 K, and by slightly delaying the decomposition of the hydrazine to higher temperatures and shifting the selectivity of that step from dehydrogenation and formation of N₂H_x(ads) species to scission of the N–N bond and ammonia production. The coadsorbed formic acid was determined to react at higher temperatures than hydrazine, in chemistry not affected by the latter, which is no longer present on the surface at that stage. One interesting aspect of this chemistry revealed by the DFT calculations is that formic acid may preferentially H-bond on top of adsorbed hydrazine rather than directly attach to the copper surface. The implications of these results to atomic layer deposition (ALD) processes are discussed.

Authors:

Yao, Yunxi ^[1]; Guerrero-Sánchez, Jonathan ^[2]; Takeuchi, Noboru ^[3];

^[1]

Univ. of California, Riverside, CA (United States). Dept. of Chemistry
Nacional Autonoma de Mexico (UNAM), Baja California (Mexico). Centro de Nanociencias y Nanotecnología
Univ. of California, Riverside, CA (United States); Nacional Autonoma de Mexico (UNAM), Baja California (Mexico). Centro de Nanociencias y Nanotecnología

Publication Date:: 2018-05-14

Research Org.:: Univ. of California, Riverside, CA (United States)

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

OSTI Identifier:: 1593408

Grant/Contract Number:: SC0001839

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 123; Journal Issue: 13; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Yao, Yunxi, Guerrero-Sánchez, Jonathan, Takeuchi, Noboru, and Zaera, Francisco. Coadsorption of Formic Acid and Hydrazine on Cu(110) Single-Crystal Surfaces.  United States: N. p., 2018. 
        Web.  doi:10.1021/acs.jpcc.8b01804.

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                    Yao, Yunxi, Guerrero-Sánchez, Jonathan, Takeuchi, Noboru, & Zaera, Francisco. Coadsorption of Formic Acid and Hydrazine on Cu(110) Single-Crystal Surfaces.  United States.  doi:https://doi.org/10.1021/acs.jpcc.8b01804

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                    Yao, Yunxi, Guerrero-Sánchez, Jonathan, Takeuchi, Noboru, and Zaera, Francisco. Mon .  
        "Coadsorption of Formic Acid and Hydrazine on Cu(110) Single-Crystal Surfaces".  United States.  doi:https://doi.org/10.1021/acs.jpcc.8b01804.  https://www.osti.gov/servlets/purl/1593408.

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@article{osti_1593408,

  title        = {Coadsorption of Formic Acid and Hydrazine on Cu(110) Single-Crystal Surfaces},

  author       = {Yao, Yunxi and Guerrero-Sánchez, Jonathan and Takeuchi, Noboru and Zaera, Francisco},

  abstractNote = {The chemistry of coadsorbed formic acid and hydrazine on Cu(110) surfaces was characterized both experimentally, by temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS), and theoretically, via density functional theory (DFT) calculations. It was found that the two reactants interact with each other via hydrogen bonds, and that this modifies their individual thermal chemistry on the surface in two main ways: by stabilizing a HCOOH:N2H4 adduct, which desorbs molecularly at around 240 K, and by slightly delaying the decomposition of the hydrazine to higher temperatures and shifting the selectivity of that step from dehydrogenation and formation of N2Hx(ads) species to scission of the N–N bond and ammonia production. The coadsorbed formic acid was determined to react at higher temperatures than hydrazine, in chemistry not affected by the latter, which is no longer present on the surface at that stage. One interesting aspect of this chemistry revealed by the DFT calculations is that formic acid may preferentially H-bond on top of adsorbed hydrazine rather than directly attach to the copper surface. The implications of these results to atomic layer deposition (ALD) processes are discussed.},

  doi          = {10.1021/acs.jpcc.8b01804},

  journal      = {Journal of Physical Chemistry. C},

  number       = 13,

  volume       = 123,

  place        = {United States},

  year         = {2018},

  month        = {5}

}

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DOI: https://doi.org/10.1021/acs.jpcc.8b01804

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Title: Coadsorption of Formic Acid and Hydrazine on Cu(110) Single-Crystal Surfaces

Abstract

Citation Formats

Structures of Glycine, Enantiopure Alanine, and Racemic Alanine Adlayers on Cu(110) and Cu(100) Surfaces journal, September 2005

Formation of Chiral Self-Assembled Structures of Amino Acids on Transition-Metal Surfaces: Alanine on Pd(111) journal, March 2014

Surface Chemistry of Alanine on Ni{111} journal, November 2015

Self-Assembly at the Liquid/Solid Interface: STM Reveals journal, March 2005

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Recent Progress in Heterogeneous Asymmetric Hydrogenation of C═O and C═C Bonds on Supported Noble Metal Catalysts journal, September 2017

Low Temperature Growth of High Purity, Low Resistivity Copper Films by Atomic Layer Deposition journal, October 2011

Thermal reactivity of metal formate hydrazinates journal, December 1983

A thermal desorption and x‐ray photoelectron spectroscopy study of the surface chemistry of iron pentacarbonyl journal, May 1989

X-ray-Initiated Metal-Promoted Thin Film Growth journal, April 2012

Effect of the nature of the substrate on the surface chemistry of atomic layer deposition precursors journal, November 2016

Kinetic measurements of hydrocarbon conversion reactions on model metal surfaces journal, January 2007

XPS, UPS and thermal desorption studies of the reactions of formaldehyde and formic acid with the Cu(110) surface journal, January 1981

Adsorption and reaction of HCOOH on doped Cu(110): coadsorption with cesium, oxygen, and Csa + Oa journal, October 1990

The oxidation of formic acid to carbonate at Cu(110) surfaces journal, April 1998

Adsorption and thermal chemistry of formic acid on clean and oxygen-predosed Cu(110) single-crystal surfaces revisited journal, April 2016

Thermal chemistry of the Cu-KI5 atomic layer deposition precursor on a copper surface journal, January 2015

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Thermal chemistry of hydrazine on clean and oxygen- and water-predosed Cu(110) single-crystal surfaces journal, August 2016

Hydrogen-Induced Subsurface Reconstruction of Cu(110) journal, November 1986

Adsorption and desorption kinetics in the systems H2/Cu(111), H2/Cu(110) and H2/Cu(100) journal, October 1989

H/Cu(110) : kinetics of reconstruction and de-reconstruction journal, April 1994

Bridging the Pressure Gap in Surface Science at the Atomic Level: H / Cu ( 110 ) journal, January 2001

On the Temperature Programmed Desorption of Hydrogen from Polycrystalline Copper journal, October 2014

Proton migrations in associates of two molecules of formic acid with one molecule of hydrazine or hydrogen peroxide journal, November 1996

Hydrogen-Bonding Interaction in Molecular Complexes and Clusters of Aerosol Nucleation Precursors journal, January 2009

Decomposition mechanism of formic acid on Cu (111) surface: A theoretical study journal, February 2017

Mechanism of Methanol Synthesis on Cu through CO 2 and CO Hydrogenation journal, February 2011

Density Functional Theory Study of the Adsorption of Hydrazine on the Perfect and Defective Copper (100), (110), and (111) Surfaces journal, October 2014

Density Functional Theory Calculations of the Interaction of Hydrazine with Low-Index Copper Surfaces journal, August 2009

Reactive scattering of small molecules from platinum crystal surfaces: D2CO, CH3OH, HCOOH, and the nonanomalous kinetics of hydrogen atom recombination journal, May 1983

Approximate Formulas for Many‐Center Integrals in the Theory of Molecules and Crystals journal, February 1953

The interaction of hydrazine with an Fe(111) surface journal, March 1979

Adsorption of hydrazine and ammonia on aluminium journal, January 1980

Hydrazine adsorption and the coadsorption of CO and D2 with nitrogen atoms on Rh(100) journal, May 1986

Effect of Coadsorbed Oxygen on the Chemistry of Ammonia over Ni(110) Single-Crystal Surfaces journal, January 2003

Surface chemistry of hydrazine on Pt(111) journal, November 1992

Atomic Layer Deposition: An Overview journal, January 2010

Mechanisms of surface reactions in thin solid film chemical deposition processes journal, December 2013

Atomic Layer Deposition of Noble Metals and Their Oxides journal, September 2013

Principles of precursor design for vapour deposition methods journal, March 2016

The Surface Chemistry of Atomic Layer Depositions of Solid Thin Films journal, May 2012

The Chemistry of Inorganic Precursors during the Chemical Deposition of Films on Solid Surfaces journal, February 2018

Thermal desorption study of formic acid decomposition on a clean Cu(110) surface journal, January 1980

Spectroscopic and kinetic studies of formic acid adsorption on Cu(110) journal, January 1996

The adsorption and decomposition of formic acid on Cu {110} journal, April 1996

Structure-Dependent Kinetics for Synthesis and Decomposition of Formate Species over Cu(111) and Cu(110) Model Catalysts journal, February 2001

Formic acid adsorption and oxidation on Cu(110) journal, May 2008

Behavior of Adsorbed Formate in the Presence of Gaseous Formic Acid on Cu(110) journal, August 2012

Advances of Ag, Cu, and Ag–Cu alloy nanoparticles synthesized via chemical reduction route journal, March 2013

Key factors in chemical reduction by hydrazine for recovery of precious metals journal, October 2002

Study of nickel nanoparticles supported on activated carbon prepared by aqueous hydrazine reduction journal, July 2006

Production of Nickel Metal Powder from a Spent Etching Solution by Solvent Extraction and Chemical Reduction journal, February 2011

Reduction crystallization of Ni, Cu, Fe and Co from a mixed metal effluent journal, May 2012

Chemical Reduction Method for Preparation of Silver Nanoparticles on a Silver Chloride Substrate for Application in Surface-Enhanced Infrared Optical Sensors journal, October 2010

Copper Nanoparticles Mediated by Chitosan: Synthesis and Characterization via Chemical Methods journal, December 2012

Preparation, characterization and catalytic activity of biomaterial-supported copper nanoparticles journal, August 2016

Copper reduction and atomic layer deposition by oxidative decomposition of formate by hydrazine journal, January 2014

Liquid-phase chemical hydrogen storage materials journal, January 2012

Role of oligomer structures in the surface chemistry of amidinate metal complexes used for atomic layer deposition of thin films journal, October 2019

Structures of Glycine, Enantiopure Alanine, and Racemic Alanine Adlayers on Cu(110) and Cu(100) Surfaces
journal, September 2005

Formation of Chiral Self-Assembled Structures of Amino Acids on Transition-Metal Surfaces: Alanine on Pd(111)
journal, March 2014

Surface Chemistry of Alanine on Ni{111}
journal, November 2015

Self-Assembly at the Liquid/Solid Interface: STM Reveals
journal, March 2005

Chirality in adsorption on solid surfaces
journal, January 2017

Frontiers of supramolecular chemistry at solid surfaces
journal, January 2017

A Generalized Two-Point H-Bonding Model for Catalytic Stereoselective Hydrogenation of Activated Ketones on Chirally Modified Platinum
journal, June 2006

Recent Progress in Heterogeneous Asymmetric Hydrogenation of C═O and C═C Bonds on Supported Noble Metal Catalysts
journal, September 2017

Low Temperature Growth of High Purity, Low Resistivity Copper Films by Atomic Layer Deposition
journal, October 2011

Thermal reactivity of metal formate hydrazinates
journal, December 1983

A thermal desorption and x‐ray photoelectron spectroscopy study of the surface chemistry of iron pentacarbonyl
journal, May 1989

X-ray-Initiated Metal-Promoted Thin Film Growth
journal, April 2012

Effect of the nature of the substrate on the surface chemistry of atomic layer deposition precursors
journal, November 2016

Kinetic measurements of hydrocarbon conversion reactions on model metal surfaces
journal, January 2007

XPS, UPS and thermal desorption studies of the reactions of formaldehyde and formic acid with the Cu(110) surface
journal, January 1981

Adsorption and reaction of HCOOH on doped Cu(110): coadsorption with cesium, oxygen, and Csa + Oa
journal, October 1990

The oxidation of formic acid to carbonate at Cu(110) surfaces
journal, April 1998

Adsorption and thermal chemistry of formic acid on clean and oxygen-predosed Cu(110) single-crystal surfaces revisited
journal, April 2016

Thermal chemistry of the Cu-KI5 atomic layer deposition precursor on a copper surface
journal, January 2015

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

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

Thermal chemistry of hydrazine on clean and oxygen- and water-predosed Cu(110) single-crystal surfaces
journal, August 2016

Hydrogen-Induced Subsurface Reconstruction of Cu(110)
journal, November 1986

Adsorption and desorption kinetics in the systems H2/Cu(111), H2/Cu(110) and H2/Cu(100)
journal, October 1989

H/Cu(110) : kinetics of reconstruction and de-reconstruction
journal, April 1994

Bridging the Pressure Gap in Surface Science at the Atomic Level: $H / Cu (110)$
journal, January 2001

On the Temperature Programmed Desorption of Hydrogen from Polycrystalline Copper
journal, October 2014

Proton migrations in associates of two molecules of formic acid with one molecule of hydrazine or hydrogen peroxide
journal, November 1996

Hydrogen-Bonding Interaction in Molecular Complexes and Clusters of Aerosol Nucleation Precursors
journal, January 2009

Decomposition mechanism of formic acid on Cu (111) surface: A theoretical study
journal, February 2017

Mechanism of Methanol Synthesis on Cu through CO ₂ and CO Hydrogenation
journal, February 2011

Density Functional Theory Study of the Adsorption of Hydrazine on the Perfect and Defective Copper (100), (110), and (111) Surfaces
journal, October 2014

Density Functional Theory Calculations of the Interaction of Hydrazine with Low-Index Copper Surfaces
journal, August 2009

Reactive scattering of small molecules from platinum crystal surfaces: D2CO, CH3OH, HCOOH, and the nonanomalous kinetics of hydrogen atom recombination
journal, May 1983

Approximate Formulas for Many‐Center Integrals in the Theory of Molecules and Crystals
journal, February 1953

The interaction of hydrazine with an Fe(111) surface
journal, March 1979

Adsorption of hydrazine and ammonia on aluminium
journal, January 1980

Hydrazine adsorption and the coadsorption of CO and D2 with nitrogen atoms on Rh(100)
journal, May 1986

Effect of Coadsorbed Oxygen on the Chemistry of Ammonia over Ni(110) Single-Crystal Surfaces
journal, January 2003

Surface chemistry of hydrazine on Pt(111)
journal, November 1992

Atomic Layer Deposition: An Overview
journal, January 2010

Mechanisms of surface reactions in thin solid film chemical deposition processes
journal, December 2013

Atomic Layer Deposition of Noble Metals and Their Oxides
journal, September 2013

Principles of precursor design for vapour deposition methods
journal, March 2016

The Surface Chemistry of Atomic Layer Depositions of Solid Thin Films
journal, May 2012

The Chemistry of Inorganic Precursors during the Chemical Deposition of Films on Solid Surfaces
journal, February 2018

Thermal desorption study of formic acid decomposition on a clean Cu(110) surface
journal, January 1980

Spectroscopic and kinetic studies of formic acid adsorption on Cu(110)
journal, January 1996

The adsorption and decomposition of formic acid on Cu {110}
journal, April 1996

Structure-Dependent Kinetics for Synthesis and Decomposition of Formate Species over Cu(111) and Cu(110) Model Catalysts
journal, February 2001

Formic acid adsorption and oxidation on Cu(110)
journal, May 2008

Behavior of Adsorbed Formate in the Presence of Gaseous Formic Acid on Cu(110)
journal, August 2012

Advances of Ag, Cu, and Ag–Cu alloy nanoparticles synthesized via chemical reduction route
journal, March 2013

Key factors in chemical reduction by hydrazine for recovery of precious metals
journal, October 2002

Study of nickel nanoparticles supported on activated carbon prepared by aqueous hydrazine reduction
journal, July 2006

Production of Nickel Metal Powder from a Spent Etching Solution by Solvent Extraction and Chemical Reduction
journal, February 2011

Reduction crystallization of Ni, Cu, Fe and Co from a mixed metal effluent
journal, May 2012

Chemical Reduction Method for Preparation of Silver Nanoparticles on a Silver Chloride Substrate for Application in Surface-Enhanced Infrared Optical Sensors
journal, October 2010

Copper Nanoparticles Mediated by Chitosan: Synthesis and Characterization via Chemical Methods
journal, December 2012

Preparation, characterization and catalytic activity of biomaterial-supported copper nanoparticles
journal, August 2016

Copper reduction and atomic layer deposition by oxidative decomposition of formate by hydrazine
journal, January 2014

Liquid-phase chemical hydrogen storage materials
journal, January 2012

Role of oligomer structures in the surface chemistry of amidinate metal complexes used for atomic layer deposition of thin films
journal, October 2019