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

Albert Perry; Sadia Kabir; Ivana Matanovic; Madelaine Seow Chavez; Kateryna Artyushkova; Alexey Serov; Plamen Atanassov

doi:10.1002/celc.201700285

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

Albert Perry, Sadia Kabir, Ivana Matanovic, Madelaine Seow Chavez, Kateryna Artyushkova, Alexey Serov, Plamen Atanassov

Research output: Contribution to journal › Article › peer-review

4 Scopus citations

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.

Original language	English
Pages (from-to)	2336-2344
Number of pages	9
Journal	ChemElectroChem
Volume	4
Issue number	9
DOIs	https://doi.org/10.1002/celc.201700285
State	Published - Sep 2017
Externally published	Yes

Funding

This work was supported by US DOD, ARO-Multidisciplinary University Research Initiative Grant W911NF-14-1-0263 to University of Utah. VASP license was provided by Theoretical division, LANL, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC52-06NA25396. Computational work was performed using the computational resources of EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory, NERSC, supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, and CNMS, sponsored at Oak Ridge National Laboratory by the Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy. This paper has been designated LA-UR-17-21295.

Funders	Funder number
Scientific User Facilities Division
US DOD	W911NF-14-1-0263
U.S. Department of Energy	DE-AC52-06NA25396
Office of Science
Basic Energy Sciences	LA-UR-17-21295
Biological and Environmental Research	DE-AC02-05CH11231
Oak Ridge National Laboratory
University of Utah

Keywords

electrochemical catalysis
hybrid catalysis
inorganic electrocatalysts
neutral media catalysts
organic substrate oxidation

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10.1002/celc.201700285

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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.",

keywords = "electrochemical catalysis, hybrid catalysis, inorganic electrocatalysts, neutral media catalysts, organic substrate oxidation",

author = "Albert Perry and Sadia Kabir and Ivana Matanovic and Chavez, {Madelaine Seow} and Kateryna Artyushkova and Alexey Serov and Plamen Atanassov",

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AU - Kabir, Sadia

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AU - Chavez, Madelaine Seow

AU - Artyushkova, Kateryna

AU - Serov, Alexey

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AB - 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.

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

Abstract

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Keywords

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