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

James, Trevor E.; Hemmingson, Stephanie L.; Sellers, Jason R. V.; Campbell, Charles T.

doi:10.1016/j.susc.2016.10.012

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

Journal Article · Fri Nov 04 00:00:00 EDT 2016 · Surface Science

DOI:https://doi.org/10.1016/j.susc.2016.10.012· OSTI ID:1534358

James, Trevor E. ^[1]; Hemmingson, Stephanie L. ^[2]; Sellers, Jason R. V. ^[2]; Campbell, Charles T. ^[2]

Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry; University of Washington
Univ. of Washington, Seattle, WA (United States). Dept. of Chemistry

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 from 358 to 339 kJ/mol. This is attributed to increasing lattice strain with island size, associated with the small lattice mismatch (8%). It adsorbs ~2 kJ/mol more weakly in the 2nd layer than above 3 ML, where it reaches the bulk heat of sublimation of Cu(solid), 337 kJ/mol. The adhesion energy of multilayer Cu onto Pt(111) is 3.76 J/m². The extra stability of the first Cu monolayer compared to bulk Cu measured here is ~12 kJ/mol, compared to a difference of ~83 kJ/mol for underpotential deposition of Cu on a Pt(111) electrode, with the difference attributed to stronger bonding of Cu to the solvent and double layer compared to Pt.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: FG02-96ER14630

OSTI ID:: 1534358

Alternate ID(s):: OSTI ID: 1488612

Journal Information:: Surface Science, Journal Name: Surface Science Journal Issue: C Vol. 657; ISSN 0039-6028

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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