Electrochemical Kinetics and X-ray Absorption Spectroscopic Investigations of Oxygen Reduction on Chalcogen-Modified Ruthenium Catalysts in Alkaline Media

doi:https://doi.org/10.1021/jp201841j

Title: Electrochemical Kinetics and X-ray Absorption Spectroscopic Investigations of Oxygen Reduction on Chalcogen-Modified Ruthenium Catalysts in Alkaline Media

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Abstract

The oxygen reduction reaction (ORR) in alkaline media has been investigated on chalcogen-modified ruthenium nanoparticles (Ru/C, Se/Ru/C, Se/RuMo/C, S/Ru/C, S/RuMo/C) synthesized in-house via aqueous routes. In acidic medium, it is well known that modification by a chalcogen prevents the oxidation of the underlying transition-metal (Ru) surface, thereby promoting direct molecular O{sub 2} adsorption on the Ru metal. On an unmodified Ru catalyst in alkaline media, the surface oxides on Ru mediate the 2e{sup -} reduction of molecular O{sub 2} to a stable peroxide anion (HO{sub 2}{sup -}) intermediate via an outer-sphere electron-transfer mechanism. This increases the activity of HO{sub 2}{sup -} near the electrode surface and decreases the overpotential for ORR by effectively carrying out the reduction of HO{sub 2}{sup -} to OH{sup -} at the oxide-free ruthenium metal site. An increase in ORR activity of Ru is observed by modification with a chalcogen; however, the increase is not as significant as observed in acidic media. Ternary additives, such as Mo, were found to significantly improve the stability of the chalcogen-modified catalysts. Detailed investigations of the ORR activity of this class of catalyst have been carried out in alkaline media along with comparisons to acidic media wherever necessary. A combinationmore »« less

Authors:: Ramaswamy, N; Allen, R; Mukerjee, S; Y,

Publication Date:: 2011-12-31

Research Org.:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Org.:: USDOE SC OFFICE OF SCIENCE (SC)

OSTI Identifier:: 1042216

Report Number(s):: BNL-97894-2012-JA
Journal ID: ISSN 1932-7447; TRN: US201212%%627

DOE Contract Number:: DE-AC02-98CH10886

Resource Type:: Journal Article

Journal Name:: Journal of Physical Chemistry C

Additional Journal Information:: Journal Volume: 115; Journal Issue: 25; Journal ID: ISSN 1932-7447

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; ADDITIVES; ADSORPTION; ANIONS; CATALYSTS; ELECTRODES; ELECTROLYTES; ELECTRON TRANSFER; KINETICS; MODIFICATIONS; OXIDATION; OXIDES; OXYGEN; PEROXIDES; RUTHENIUM; STABILITY

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                    Ramaswamy, N, Allen, R, Mukerjee, S, and Y,. Electrochemical Kinetics and X-ray Absorption Spectroscopic Investigations of Oxygen Reduction on Chalcogen-Modified Ruthenium Catalysts in Alkaline Media.  United States: N. p., 2011. 
        Web.  doi:10.1021/jp201841j.

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                    Ramaswamy, N, Allen, R, Mukerjee, S, & Y,. Electrochemical Kinetics and X-ray Absorption Spectroscopic Investigations of Oxygen Reduction on Chalcogen-Modified Ruthenium Catalysts in Alkaline Media.  United States.  https://doi.org/10.1021/jp201841j

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                    Ramaswamy, N, Allen, R, Mukerjee, S, and Y,. Sat .  
        "Electrochemical Kinetics and X-ray Absorption Spectroscopic Investigations of Oxygen Reduction on Chalcogen-Modified Ruthenium Catalysts in Alkaline Media".  United States.  https://doi.org/10.1021/jp201841j.

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@article{osti_1042216,

  title        = {Electrochemical Kinetics and X-ray Absorption Spectroscopic Investigations of Oxygen Reduction on Chalcogen-Modified Ruthenium Catalysts in Alkaline Media},

  author       = {Ramaswamy, N and Allen, R and Mukerjee, S and Y,},

  abstractNote = {The oxygen reduction reaction (ORR) in alkaline media has been investigated on chalcogen-modified ruthenium nanoparticles (Ru/C, Se/Ru/C, Se/RuMo/C, S/Ru/C, S/RuMo/C) synthesized in-house via aqueous routes. In acidic medium, it is well known that modification by a chalcogen prevents the oxidation of the underlying transition-metal (Ru) surface, thereby promoting direct molecular O{sub 2} adsorption on the Ru metal. On an unmodified Ru catalyst in alkaline media, the surface oxides on Ru mediate the 2e{sup -} reduction of molecular O{sub 2} to a stable peroxide anion (HO{sub 2}{sup -}) intermediate via an outer-sphere electron-transfer mechanism. This increases the activity of HO{sub 2}{sup -} near the electrode surface and decreases the overpotential for ORR by effectively carrying out the reduction of HO{sub 2}{sup -} to OH{sup -} at the oxide-free ruthenium metal site. An increase in ORR activity of Ru is observed by modification with a chalcogen; however, the increase is not as significant as observed in acidic media. Ternary additives, such as Mo, were found to significantly improve the stability of the chalcogen-modified catalysts. Detailed investigations of the ORR activity of this class of catalyst have been carried out in alkaline media along with comparisons to acidic media wherever necessary. A combination of electrochemical and X-ray absorption spectroscopic (EXAFS, XANES, {Delta}{mu}) studies has been performed in order to understand the structure/property relationships of these catalysts within the context of ORR in alkaline electrolytes.},

  doi          = {10.1021/jp201841j},

  url          = {https://www.osti.gov/biblio/1042216},
  journal      = {Journal of Physical Chemistry C},

  issn         = {1932-7447},

  number       = 25,

  volume       = 115,

  place        = {United States},

  year         = {2011},

  month        = {12}

}

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