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Title: Communication: Proton exchange in low temperature co-mixed amorphous H 2O and D 2O films: The effect of the underlying Pt(111) and graphene substrates

Abstract

Isotopic exchange reactions in mixed D 2O and H 2O amorphous solid water films were investigated using reflection absorption infrared spectroscopy. Nanoscale films composed of 5% D 2O in H 2O were deposited on Pt(111) and graphene covered Pt(111) substrates using simultaneous co-dosing using two molecular beams. At 130 K, we discover that the reaction is strongly dependent on the substrate with the H/D exchange occurring more rapidly on the Pt(111) surface than on graphene. At 140 K, the films eventually crystallize with the final products on the two substrates being primarily HOD on Pt(111) and a mixture of HOD and unreacted D 2O on graphene. We demonstrate by pre-dosing H 2 and O 2 on Pt(111) that the observed differences in reactivity on the two substrates are likely due to the formation of hydrogen ions at the Pt(111) surface that are not formed on graphene. Once formed the mobile protons move through the ASW overlayer to begin the H/D exchange reaction.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1511463
Alternate Identifier(s):
OSTI ID: 1467938
Report Number(s):
PNNL-SA-135984
Journal ID: ISSN 0021-9606
Grant/Contract Number:  
AC05-76RL01830; KC0301050-16248
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 8; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Smith, R. Scott, Petrik, Nikolay G., Kimmel, Greg A., and Kay, Bruce D. Communication: Proton exchange in low temperature co-mixed amorphous H2O and D2O films: The effect of the underlying Pt(111) and graphene substrates. United States: N. p., 2018. Web. doi:10.1063/1.5046530.
Smith, R. Scott, Petrik, Nikolay G., Kimmel, Greg A., & Kay, Bruce D. Communication: Proton exchange in low temperature co-mixed amorphous H2O and D2O films: The effect of the underlying Pt(111) and graphene substrates. United States. doi:10.1063/1.5046530.
Smith, R. Scott, Petrik, Nikolay G., Kimmel, Greg A., and Kay, Bruce D. Tue . "Communication: Proton exchange in low temperature co-mixed amorphous H2O and D2O films: The effect of the underlying Pt(111) and graphene substrates". United States. doi:10.1063/1.5046530. https://www.osti.gov/servlets/purl/1511463.
@article{osti_1511463,
title = {Communication: Proton exchange in low temperature co-mixed amorphous H2O and D2O films: The effect of the underlying Pt(111) and graphene substrates},
author = {Smith, R. Scott and Petrik, Nikolay G. and Kimmel, Greg A. and Kay, Bruce D.},
abstractNote = {Isotopic exchange reactions in mixed D2O and H2O amorphous solid water films were investigated using reflection absorption infrared spectroscopy. Nanoscale films composed of 5% D2O in H2O were deposited on Pt(111) and graphene covered Pt(111) substrates using simultaneous co-dosing using two molecular beams. At 130 K, we discover that the reaction is strongly dependent on the substrate with the H/D exchange occurring more rapidly on the Pt(111) surface than on graphene. At 140 K, the films eventually crystallize with the final products on the two substrates being primarily HOD on Pt(111) and a mixture of HOD and unreacted D2O on graphene. We demonstrate by pre-dosing H2 and O2 on Pt(111) that the observed differences in reactivity on the two substrates are likely due to the formation of hydrogen ions at the Pt(111) surface that are not formed on graphene. Once formed the mobile protons move through the ASW overlayer to begin the H/D exchange reaction.},
doi = {10.1063/1.5046530},
journal = {Journal of Chemical Physics},
number = 8,
volume = 149,
place = {United States},
year = {2018},
month = {8}
}

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Figures / Tables:

FIG. 1 FIG. 1: Time series of RAIRS spectra from ASW films created by co-dosing 5% D2O and 95% H2O. Films were deposited at 30 K and then heated to and held at 130 K. Displayed is the O–D stretching region. The insets are experimental spectra at selected times. (a) Results formore » a 100 ML thick film deposited on a Pt(111) substrate. (b) Results for a 100 ML thick film deposited on a graphene covered Pt(111) substrate.« less

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