Critical role of intercalated water for electrocatalytically active nitrogen-doped graphitic systems

Martinez, Ulises; Dumont, Joseph H.; Holby, Edward F.; Artyushkova, Kateryna; Purdy, Geraldine M.; Singh, Akhilesh; Mack, Nathan H.; Atanassov, Plamen; Cullen, David A.; More, Karren L.; Chhowalla, Manish; Zelenay, Piotr; Dattelbaum, Andrew M.; Mohite, Aditya D.; Gupta, Gautam

doi:10.1126/sciadv.1501178

Critical role of intercalated water for electrocatalytically active nitrogen-doped graphitic systems

Journal Article · Fri Mar 18 00:00:00 EDT 2016 · Science Advances

DOI:https://doi.org/10.1126/sciadv.1501178· OSTI ID:1261296

Martinez, Ulises ^[1]; Dumont, Joseph H. ^[2]; Holby, Edward F. ^[3]; Artyushkova, Kateryna ^[4]; Purdy, Geraldine M. ^[1]; Singh, Akhilesh ^[1]; Mack, Nathan H. ^[5]; Atanassov, Plamen ^[4]; Cullen, David A. ^[6]; More, Karren L. ^[6]; Chhowalla, Manish ^[7]; Zelenay, Piotr ^[1]; Dattelbaum, Andrew M. ^[1]; Mohite, Aditya D. ^[1]; Gupta, Gautam ^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Materials Physics and Applications Division
Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Materials Physics and Applications Division; Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemical and Biological Engineering
Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Materials Science and Technology Division
Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemical and Biological Engineering
Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Chemistry Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division. Center for Nanophase Materials Sciences
Rutgers Univ., Piscataway, NJ (United States). Science and Engineering

Graphitic materials are very essential in energy conversion and storage because of their excellent chemical and electrical properties. The strategy for obtaining functional graphitic materials involves graphite oxidation and subsequent dissolution in aqueous media, forming graphene-oxide nanosheets (GNs). Restacked GNs contain substantial intercalated water that can react with heteroatom dopants or the graphene lattice during reduction. We demonstrate that removal of intercalated water using simple solvent treatments causes significant structural reorganization, substantially affecting the oxygen reduction reaction (ORR) activity and stability of nitrogen-doped graphitic systems. Amid contrasting reports describing the ORR activity of GN-based catalysts in alkaline electrolytes, we demonstrate superior activity in an acidic electrolyte with an onset potential of ~0.9 V, a half-wave potential (E_½) of 0.71 V, and a selectivity for four-electron reduction of >95%. Finally and further, durability testing showed E_½ retention >95% in N₂- and O₂-saturated solutions after 2000 cycles, demonstrating the highest ORR activity and stability reported to date for GN-based electrocatalysts in acidic media.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC04-94AL85000; AC05-00OR22725; AC52-06NA25396

OSTI ID:: 1261296

Journal Information:: Science Advances, Journal Name: Science Advances Journal Issue: 3 Vol. 2; ISSN 2375-2548

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

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36 MATERIALS SCIENCE
electrocatalysts
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intercalated water
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Critical role of intercalated water for electrocatalytically active nitrogen-doped graphitic systems

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