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Title: Novel Hybrid Catalyst for the Oxidation of Organic Acids: Pd Nanoparticles Supported on Mn-N-3D-Graphene Nanosheets

Abstract

This paper reports the fabrication and electrochemical performance of a hybrid catalyst composed of Pd nanoparticles and atomically dispersed Mn active centers integrated into the nitrogen-doped three-dimensional graphene nanosheets (Pd/Mn-N-3D-GNS). Our results show that the synergistic integration of both Pd nanoparticles and atomically dispersed Mn can be used to enhance the activity toward the electrochemical oxidation of organic acids at biologically relevant pH values. The hybrid catalyst (Pd/Mn-N-3D-GNS) showed increased maximum currents toward the oxidation of oxalic acid when compared to its individual catalysts, namely, Pd/3D-GNS and Mn N-3D-GNS catalysts. The hybrid also showed a decreased onset potential for oxidation of mesoxalic acid as compared to Mn-N-3D-GNS and decreased onset potentials for the oxidation of glyoxalic acid when compared to both of its constituent catalysts. Oxidation of formic acid was also tested and the hybrid was shown to catalyze both dehydration and dehydrogenation mechanisms of formic acid electro-oxidation. Using density functional theory calculations, it was elucidated that a two-site catalysis most likely promotes dehydrogenation reaction for formic acid oxidation, which can explain the selectivity of Pd nanoparticles and atomically dispersed Mn towards the dehydrogenation/ dehydration pathway.

Authors:
 [1];  [1];  [2];  [1];  [1];  [1];  [1]
  1. Univ. of New Mexico, Albuquerque, NM (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of New Mexico, Albuquerque, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1396121
Alternate Identifier(s):
OSTI ID: 1389887
Report Number(s):
LA-UR-17-21295
Journal ID: ISSN 2196-0216
Grant/Contract Number:  
AC52-06NA25396; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ChemElectroChem
Additional Journal Information:
Journal Volume: 4; Journal Issue: 9; Journal ID: ISSN 2196-0216
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Material Science

Citation Formats

Perry, Albert, Kabir, Sadia, Matanovic, Ivana, Chavez, Madelaine Seow, Artyushkova, Kateryna, Serov, Alexey, and Atanassov, Plamen. Novel Hybrid Catalyst for the Oxidation of Organic Acids: Pd Nanoparticles Supported on Mn-N-3D-Graphene Nanosheets. United States: N. p., 2017. Web. doi:10.1002/celc.201700285.
Perry, Albert, Kabir, Sadia, Matanovic, Ivana, Chavez, Madelaine Seow, Artyushkova, Kateryna, Serov, Alexey, & Atanassov, Plamen. Novel Hybrid Catalyst for the Oxidation of Organic Acids: Pd Nanoparticles Supported on Mn-N-3D-Graphene Nanosheets. United States. doi:10.1002/celc.201700285.
Perry, Albert, Kabir, Sadia, Matanovic, Ivana, Chavez, Madelaine Seow, Artyushkova, Kateryna, Serov, Alexey, and Atanassov, Plamen. Fri . "Novel Hybrid Catalyst for the Oxidation of Organic Acids: Pd Nanoparticles Supported on Mn-N-3D-Graphene Nanosheets". United States. doi:10.1002/celc.201700285. https://www.osti.gov/servlets/purl/1396121.
@article{osti_1396121,
title = {Novel Hybrid Catalyst for the Oxidation of Organic Acids: Pd Nanoparticles Supported on Mn-N-3D-Graphene Nanosheets},
author = {Perry, Albert and Kabir, Sadia and Matanovic, Ivana and Chavez, Madelaine Seow and Artyushkova, Kateryna and Serov, Alexey and Atanassov, Plamen},
abstractNote = {This paper reports the fabrication and electrochemical performance of a hybrid catalyst composed of Pd nanoparticles and atomically dispersed Mn active centers integrated into the nitrogen-doped three-dimensional graphene nanosheets (Pd/Mn-N-3D-GNS). Our results show that the synergistic integration of both Pd nanoparticles and atomically dispersed Mn can be used to enhance the activity toward the electrochemical oxidation of organic acids at biologically relevant pH values. The hybrid catalyst (Pd/Mn-N-3D-GNS) showed increased maximum currents toward the oxidation of oxalic acid when compared to its individual catalysts, namely, Pd/3D-GNS and Mn N-3D-GNS catalysts. The hybrid also showed a decreased onset potential for oxidation of mesoxalic acid as compared to Mn-N-3D-GNS and decreased onset potentials for the oxidation of glyoxalic acid when compared to both of its constituent catalysts. Oxidation of formic acid was also tested and the hybrid was shown to catalyze both dehydration and dehydrogenation mechanisms of formic acid electro-oxidation. Using density functional theory calculations, it was elucidated that a two-site catalysis most likely promotes dehydrogenation reaction for formic acid oxidation, which can explain the selectivity of Pd nanoparticles and atomically dispersed Mn towards the dehydrogenation/ dehydration pathway.},
doi = {10.1002/celc.201700285},
journal = {ChemElectroChem},
number = 9,
volume = 4,
place = {United States},
year = {2017},
month = {6}
}

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