Adsorption and oxidation of formaldehyde on a polycrystalline Pt film electrode: An in situ IR spectroscopy search for adsorbed reaction intermediates

As part of a mechanistic study of the electrooxidation of C1 molecules we have systematically investigated the dissociative adsorption/oxidation of formaldehyde on a polycrystalline Pt film electrode under experimental conditions optimizing the chance for detecting weakly adsorbed reaction intermedi...

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Main Authors: Zenonas Jusys, R. Jürgen Behm
Format: Article
Language:English
Published: Beilstein-Institut 2014-05-01
Series:Beilstein Journal of Nanotechnology
Subjects:
Online Access:https://doi.org/10.3762/bjnano.5.87
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author Zenonas Jusys
R. Jürgen Behm
author_facet Zenonas Jusys
R. Jürgen Behm
author_sort Zenonas Jusys
collection DOAJ
description As part of a mechanistic study of the electrooxidation of C1 molecules we have systematically investigated the dissociative adsorption/oxidation of formaldehyde on a polycrystalline Pt film electrode under experimental conditions optimizing the chance for detecting weakly adsorbed reaction intermediates. Employing in situ IR spectroscopy in an attenuated total reflection configuration (ATR-FTIRS) with p-polarized IR radiation to further improve the signal-to-noise ratio, and using low reaction temperatures (3 °C) and deuterium substitution to slow down the reaction kinetics and to stabilize weakly adsorbed reaction intermediates, we could detect an IR absorption band at 1660 cm−1 characteristic for adsorbed formyl intermediates. This assignment is supported by an isotope shift in wave number. Effects of temperature, potential and deuterium substitution on the formation and disappearance of different adsorbed species (COad, adsorbed formate, adsorbed formyl), are monitored and quantified. Consequences on the mechanism for dissociative adsorption and oxidation of formaldehyde are discussed.
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spelling doaj.art-c8c602ec6ede4ea6a1c0e5050b3d1e722022-12-21T23:50:58ZengBeilstein-InstitutBeilstein Journal of Nanotechnology2190-42862014-05-015174775910.3762/bjnano.5.872190-4286-5-87Adsorption and oxidation of formaldehyde on a polycrystalline Pt film electrode: An in situ IR spectroscopy search for adsorbed reaction intermediatesZenonas Jusys0R. Jürgen Behm1Institute of Surface Chemistry and Catalysis, Ulm University, Albert-Einstein-Allee 47, D-89081 Ulm, GermanyInstitute of Surface Chemistry and Catalysis, Ulm University, Albert-Einstein-Allee 47, D-89081 Ulm, GermanyAs part of a mechanistic study of the electrooxidation of C1 molecules we have systematically investigated the dissociative adsorption/oxidation of formaldehyde on a polycrystalline Pt film electrode under experimental conditions optimizing the chance for detecting weakly adsorbed reaction intermediates. Employing in situ IR spectroscopy in an attenuated total reflection configuration (ATR-FTIRS) with p-polarized IR radiation to further improve the signal-to-noise ratio, and using low reaction temperatures (3 °C) and deuterium substitution to slow down the reaction kinetics and to stabilize weakly adsorbed reaction intermediates, we could detect an IR absorption band at 1660 cm−1 characteristic for adsorbed formyl intermediates. This assignment is supported by an isotope shift in wave number. Effects of temperature, potential and deuterium substitution on the formation and disappearance of different adsorbed species (COad, adsorbed formate, adsorbed formyl), are monitored and quantified. Consequences on the mechanism for dissociative adsorption and oxidation of formaldehyde are discussed.https://doi.org/10.3762/bjnano.5.87electrocatalysisformaldehyde adsorptionformyl intermediatein situ spectro-electrochemistryPt
spellingShingle Zenonas Jusys
R. Jürgen Behm
Adsorption and oxidation of formaldehyde on a polycrystalline Pt film electrode: An in situ IR spectroscopy search for adsorbed reaction intermediates
Beilstein Journal of Nanotechnology
electrocatalysis
formaldehyde adsorption
formyl intermediate
in situ spectro-electrochemistry
Pt
title Adsorption and oxidation of formaldehyde on a polycrystalline Pt film electrode: An in situ IR spectroscopy search for adsorbed reaction intermediates
title_full Adsorption and oxidation of formaldehyde on a polycrystalline Pt film electrode: An in situ IR spectroscopy search for adsorbed reaction intermediates
title_fullStr Adsorption and oxidation of formaldehyde on a polycrystalline Pt film electrode: An in situ IR spectroscopy search for adsorbed reaction intermediates
title_full_unstemmed Adsorption and oxidation of formaldehyde on a polycrystalline Pt film electrode: An in situ IR spectroscopy search for adsorbed reaction intermediates
title_short Adsorption and oxidation of formaldehyde on a polycrystalline Pt film electrode: An in situ IR spectroscopy search for adsorbed reaction intermediates
title_sort adsorption and oxidation of formaldehyde on a polycrystalline pt film electrode an in situ ir spectroscopy search for adsorbed reaction intermediates
topic electrocatalysis
formaldehyde adsorption
formyl intermediate
in situ spectro-electrochemistry
Pt
url https://doi.org/10.3762/bjnano.5.87
work_keys_str_mv AT zenonasjusys adsorptionandoxidationofformaldehydeonapolycrystallineptfilmelectrodeaninsituirspectroscopysearchforadsorbedreactionintermediates
AT rjurgenbehm adsorptionandoxidationofformaldehydeonapolycrystallineptfilmelectrodeaninsituirspectroscopysearchforadsorbedreactionintermediates