Adhesion Energies of Solvent Films to Pt(111) and Ni(111) Surfaces by Adsorption Calorimetry

Rumptz, John R.; Campbell, Charles T.

doi:10.1021/acscatal.9b03591

Title: Adhesion Energies of Solvent Films to Pt(111) and Ni(111) Surfaces by Adsorption Calorimetry

Full Record
Other Related Research

Abstract

Solvent/metal adhesion energies are vital to understanding solvent effects on adsorption energies, which are, in turn, central to understanding liquid-phase catalysis, electrocatalysis, and many other technologies such as adsorption-based separations and chemical sensors. Differences in reactant adsorption energies in different solvents are dominated by differences in their solvent/metal adhesion energies. Here, the adhesion energies of five liquid solvents to clean Pt(111) and Ni(111) surfaces have been estimated using ultrahigh vacuum calorimetric measurements of heats of adsorption versus coverage integrated from zero coverage up to thick (bulk-like) multilayer solid films. The adhesion energies are found to vary from 0.15 to 0.60 J/m², increasing in the trend CH₃OH < HCOOH < H₂O < benzene ≈ phenol. This trend suggests that solvents with higher heats of adsorption per unit area in the first adsorbed layer have higher adhesion energies to a given metal surface. The adhesion energies to Ni(111) are generally larger than to Pt(111) (on average by 0.09 J/m²). This is due to the 24% higher number of metal atoms per unit area on Ni(111) than on Pt(111) and, with oxygen-containing solvents, the greater oxophilicity of Ni compared to that of Pt.

Authors:

Rumptz, John R. ^[1];

^[1]

Univ. of Washington, Seattle, WA (United States)

Publication Date:: Thu Oct 31 00:00:00 EDT 2019

Research Org.:: Univ. of Washington, Seattle, WA (United States)

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

OSTI Identifier:: 1597966

Grant/Contract Number:: FG02-96ER14630; CHE-1665077

Resource Type:: Accepted Manuscript

Journal Name:: ACS Catalysis

Additional Journal Information:: Journal Volume: 9; Journal Issue: 12; 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; solvent effects; adhesion energy; liquid / solid interface; adsorption in liquids; catalysis

Citation Formats


                    Rumptz, John R., and Campbell, Charles T. Adhesion Energies of Solvent Films to Pt(111) and Ni(111) Surfaces by Adsorption Calorimetry.  United States: N. p., 2019. 
Web.  doi:10.1021/acscatal.9b03591.

Copy to clipboard


                    Rumptz, John R., & Campbell, Charles T. Adhesion Energies of Solvent Films to Pt(111) and Ni(111) Surfaces by Adsorption Calorimetry.  United States.  https://doi.org/10.1021/acscatal.9b03591

Copy to clipboard


                    Rumptz, John R., and Campbell, Charles T. Thu .  
"Adhesion Energies of Solvent Films to Pt(111) and Ni(111) Surfaces by Adsorption Calorimetry".  United States.  https://doi.org/10.1021/acscatal.9b03591.  https://www.osti.gov/servlets/purl/1597966.

Copy to clipboard


                    
@article{osti_1597966,

  title        = {Adhesion Energies of Solvent Films to Pt(111) and Ni(111) Surfaces by Adsorption Calorimetry},

  author       = {Rumptz, John R. and Campbell, Charles T.},

  abstractNote = {Solvent/metal adhesion energies are vital to understanding solvent effects on adsorption energies, which are, in turn, central to understanding liquid-phase catalysis, electrocatalysis, and many other technologies such as adsorption-based separations and chemical sensors. Differences in reactant adsorption energies in different solvents are dominated by differences in their solvent/metal adhesion energies. Here, the adhesion energies of five liquid solvents to clean Pt(111) and Ni(111) surfaces have been estimated using ultrahigh vacuum calorimetric measurements of heats of adsorption versus coverage integrated from zero coverage up to thick (bulk-like) multilayer solid films. The adhesion energies are found to vary from 0.15 to 0.60 J/m2, increasing in the trend CH3OH < HCOOH < H2O < benzene ≈ phenol. This trend suggests that solvents with higher heats of adsorption per unit area in the first adsorbed layer have higher adhesion energies to a given metal surface. The adhesion energies to Ni(111) are generally larger than to Pt(111) (on average by 0.09 J/m2). This is due to the 24% higher number of metal atoms per unit area on Ni(111) than on Pt(111) and, with oxygen-containing solvents, the greater oxophilicity of Ni compared to that of Pt.},

  doi          = {10.1021/acscatal.9b03591},

  journal      = {ACS Catalysis},

  number       = 12,

  volume       = 9,

  place        = {United States},

  year         = {Thu Oct 31 00:00:00 EDT 2019},

  month        = {Thu Oct 31 00:00:00 EDT 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acscatal.9b03591

Other availability

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Size-Dependent Adsorption and Adhesion Energetics of Ag Nanoparticles on Graphene Films on Ni(111) by Calorimetry

Journal Article Rumptz, John R. ; Mao, Zhongtian ; Campbell, Charles T. - ACS Catalysis

Interest in the use of carbon supports for late transition metal nanoparticle catalysts has expanded rapidly due to the increasing importance of electrocatalysts for clean energy and environmental technologies and the use and storage of renewable electricity. Compared to oxide supports, almost nothing is known about the effect of metal nanoparticle size on the energies of the metal atoms within carbon-supported nanoparticles, yet these energies are crucial for understanding their surface reactivity and sintering kinetics. Here, the growth morphology and adsorption energetics of vapor-deposited Ag onto clean graphene/Ni(111) surfaces have been studied using a combination of single-crystal adsorption calorimetry (SCAC)more »« less
https://doi.org/10.1021/acscatal.1c05589

Full Text Available
Trends in Adhesion Energies of Metal Nanoparticles on Oxide Surfaces: Understanding Support Effects in Catalysis and Nanotechnology

Journal Article Hemmingson, Stephanie L. ; Campbell, Charles T. - ACS Nano

Nanoparticles on surfaces are ubiquitous in nanotechnologies, especially in catalysis, where metal nanoparticles anchored to oxide supports are widely used to produce and use fuels and chemicals, and in pollution abatement. Here we show that for hemispherical metal particles of the same diameter, D, the chemical potentials of the metal atoms in the particles (μ_M) differ between two supports by approximately –2(E_adh,A – E_adh,B)V_m/D, where E_ad,i is the adhesion energy between the metal and support i, and V_m is the molar volume of the bulk metal. This is consistent with calorimetric measurements of metal vapor adsorption energies onto clean oxidemore »« less
Cited by 114
https://doi.org/10.1021/acsnano.6b07502

Full Text Available
Size-Dependent Energy of Ni Nanoparticles on Graphene Films on Ni(111) and Adhesion Energetics by Adsorption Calorimetry

Journal Article Rumptz, John R. ; Zhao, Kun ; Mayo, Jackson ; ... - ACS Catalysis

The use of carbon supports for late transition-metal nanoparticle catalysts has grown substantially in recent years due to efforts to develop electrocatalysts for clean energy applications and catalysts for new aqueous-phase biomass-related conversions and due to the evolution of new carbon materials with unique properties (e.g., graphene, carbon nanotubes, and so forth). However, much less is known about the bonding energetics of catalytic metal nanoparticles on carbon supports in comparison with oxide supports, which are more common for thermal catalysis. Here, we report the growth morphology and heats of adsorption of Ni vapor deposited onto graphene/Ni(111) at 300 K andmore »« less
https://doi.org/10.1021/acscatal.2c02765

Full Text Available
Size-Dependent Energy and Adhesion of Pd Nanoparticles on Graphene on Ni(111) by Pd Vapor Adsorption Calorimetry

Journal Article Zhao, Kun ; Janulaitis, Nida ; Rumptz, John R. ; ... - ACS Catalysis

Carbon-supported late transition-metal nanoparticles are promising catalysts and electrocatalysts for wide-ranging applications. However, experimental investigations of the bonding energetics of metal nanoparticles on carbon supports are very limited. Here, in this work, we report heats of adsorption of Pd vapor deposited onto single-layer graphene(0001) supported on Ni(111) at 100 and 300 K as Pd grows particles of well-defined size in the range from three atom clusters to 6 nm diameter. Sizes were determined from He⁺ low-energy ion scattering (LEIS). In this size range, the differential heat of Pd adsorption increases from 228 kJ/mol to within 10 kJ/mol of the heatmore »« less
https://doi.org/10.1021/acscatal.2c06343

Full Text Available
Calorimetric measurement of adsorption and adhesion energies of Cu on Pt(111)

Journal Article James, Trevor E. ; Hemmingson, Stephanie L. ; Sellers, Jason R. V. ; ... - Surface Science

The adsorption energies of submonolayer amounts of one metal on the surface of another metal have been measured for decades by temperature programmed desorption. However, that method fails for metals that alloy. We report here the first measurement of the adsorption energy for any such metal-on-metal combination that forms a bulk alloy. The adsorption and interfacial energetics of vapor deposited Cu onto Pt(111) at 300 K has been studied herein using single crystal adsorption calorimetry (SCAC) and X-ray photoelectron spectroscopy (XPS). The Cu grows as 2D pseudomorphic islands in the first layer and its heat of adsorption decreased linearly frommore »« less
Cited by 4
https://doi.org/10.1016/j.susc.2016.10.012

Full Text Available

Similar Records