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Binding Energy and Diffusion Barrier of Formic Acid on Pd(111)

[Image: see text] Velocity-resolved kinetics is used to measure the thermal rate of formic acid desorption from Pd(111) between 228 and 273 K for four isotopologues: HCOOH, HCOOD, DCOOH, DCOOD. Upon molecular adsorption, formic acid undergoes decomposition to CO(2) and H(2) and thermal desorption. T...

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Autores principales: Fingerhut, Jan, Lecroart, Loïc, Borodin, Dmitriy, Schwarzer, Michael, Hörandl, Stefan, Kandratsenka, Alexander, Auerbach, Daniel J., Wodtke, Alec M., Kitsopoulos, Theofanis N.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9841570/
https://www.ncbi.nlm.nih.gov/pubmed/36583672
http://dx.doi.org/10.1021/acs.jpca.2c07414
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author Fingerhut, Jan
Lecroart, Loïc
Borodin, Dmitriy
Schwarzer, Michael
Hörandl, Stefan
Kandratsenka, Alexander
Auerbach, Daniel J.
Wodtke, Alec M.
Kitsopoulos, Theofanis N.
author_facet Fingerhut, Jan
Lecroart, Loïc
Borodin, Dmitriy
Schwarzer, Michael
Hörandl, Stefan
Kandratsenka, Alexander
Auerbach, Daniel J.
Wodtke, Alec M.
Kitsopoulos, Theofanis N.
author_sort Fingerhut, Jan
collection PubMed
description [Image: see text] Velocity-resolved kinetics is used to measure the thermal rate of formic acid desorption from Pd(111) between 228 and 273 K for four isotopologues: HCOOH, HCOOD, DCOOH, DCOOD. Upon molecular adsorption, formic acid undergoes decomposition to CO(2) and H(2) and thermal desorption. To disentangle the contributions of individual processes, we implement a mass-balance-based calibration procedure from which the branching ratio between desorption and decomposition for formic acid is determined. From experimentally derived elementary desorption rate constants, we obtain the binding energy 639 ± 8 meV and the diffusion barrier 370 ± 130 meV using the detailed balance rate model (DBRM). The DBRM explains the observed kinetic isotope effects.
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spelling pubmed-98415702023-01-17 Binding Energy and Diffusion Barrier of Formic Acid on Pd(111) Fingerhut, Jan Lecroart, Loïc Borodin, Dmitriy Schwarzer, Michael Hörandl, Stefan Kandratsenka, Alexander Auerbach, Daniel J. Wodtke, Alec M. Kitsopoulos, Theofanis N. J Phys Chem A [Image: see text] Velocity-resolved kinetics is used to measure the thermal rate of formic acid desorption from Pd(111) between 228 and 273 K for four isotopologues: HCOOH, HCOOD, DCOOH, DCOOD. Upon molecular adsorption, formic acid undergoes decomposition to CO(2) and H(2) and thermal desorption. To disentangle the contributions of individual processes, we implement a mass-balance-based calibration procedure from which the branching ratio between desorption and decomposition for formic acid is determined. From experimentally derived elementary desorption rate constants, we obtain the binding energy 639 ± 8 meV and the diffusion barrier 370 ± 130 meV using the detailed balance rate model (DBRM). The DBRM explains the observed kinetic isotope effects. American Chemical Society 2022-12-30 /pmc/articles/PMC9841570/ /pubmed/36583672 http://dx.doi.org/10.1021/acs.jpca.2c07414 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Fingerhut, Jan
Lecroart, Loïc
Borodin, Dmitriy
Schwarzer, Michael
Hörandl, Stefan
Kandratsenka, Alexander
Auerbach, Daniel J.
Wodtke, Alec M.
Kitsopoulos, Theofanis N.
Binding Energy and Diffusion Barrier of Formic Acid on Pd(111)
title Binding Energy and Diffusion Barrier of Formic Acid on Pd(111)
title_full Binding Energy and Diffusion Barrier of Formic Acid on Pd(111)
title_fullStr Binding Energy and Diffusion Barrier of Formic Acid on Pd(111)
title_full_unstemmed Binding Energy and Diffusion Barrier of Formic Acid on Pd(111)
title_short Binding Energy and Diffusion Barrier of Formic Acid on Pd(111)
title_sort binding energy and diffusion barrier of formic acid on pd(111)
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9841570/
https://www.ncbi.nlm.nih.gov/pubmed/36583672
http://dx.doi.org/10.1021/acs.jpca.2c07414
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