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

Abstract

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 N 2- and O 2-saturated solutions after 2000 cycles, demonstrating the highest ORR activity and stability reported to date for GN-based electrocatalysts in acidic media.

Authors:
 [1];  [2];  [3];  [4];  [1];  [1];  [5];  [4];  [6];  [6];  [7];  [1];  [1];  [1];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Materials Physics and Applications Division
  2. 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
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Materials Science and Technology Division
  4. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemical and Biological Engineering
  5. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Chemistry Division
  6. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division. Center for Nanophase Materials Sciences
  7. Rutgers Univ., Piscataway, NJ (United States). Science and Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
OSTI Identifier:
1261296
Grant/Contract Number:  
AC05-00OR22725; AC52-06NA25396; AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 2; Journal Issue: 3; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; electrocatalysts; intercalated water; graphene oxide; oxygen reduction

Citation Formats

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., and Gupta, Gautam. Critical role of intercalated water for electrocatalytically active nitrogen-doped graphitic systems. United States: N. p., 2016. Web. doi:10.1126/sciadv.1501178.
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. Critical role of intercalated water for electrocatalytically active nitrogen-doped graphitic systems. United States. https://doi.org/10.1126/sciadv.1501178
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., and Gupta, Gautam. Fri . "Critical role of intercalated water for electrocatalytically active nitrogen-doped graphitic systems". United States. https://doi.org/10.1126/sciadv.1501178. https://www.osti.gov/servlets/purl/1261296.
@article{osti_1261296,
title = {Critical role of intercalated water for electrocatalytically active nitrogen-doped graphitic systems},
author = {Martinez, Ulises and Dumont, Joseph H. and Holby, Edward F. and Artyushkova, Kateryna and Purdy, Geraldine M. and Singh, Akhilesh and Mack, Nathan H. and Atanassov, Plamen and Cullen, David A. and More, Karren L. and Chhowalla, Manish and Zelenay, Piotr and Dattelbaum, Andrew M. and Mohite, Aditya D. and Gupta, Gautam},
abstractNote = {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 (E½) of 0.71 V, and a selectivity for four-electron reduction of >95%. Finally and further, durability testing showed E½ 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.},
doi = {10.1126/sciadv.1501178},
url = {https://www.osti.gov/biblio/1261296}, journal = {Science Advances},
issn = {2375-2548},
number = 3,
volume = 2,
place = {United States},
year = {2016},
month = {3}
}

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Works referenced in this record:

Graphene-based nanomaterials for energy storage
journal, January 2011


Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage
journal, January 2015


An oxygen reduction electrocatalyst based on carbon nanotube–graphene complexes
journal, May 2012


A carbon-nanotube-supported graphene-rich non-precious metal oxygen reduction catalyst with enhanced performance durability
journal, January 2013


Graphene-based materials for catalysis
journal, January 2012


Graphene-based electrochemical energy conversion and storage: fuel cells, supercapacitors and lithium ion batteries
journal, January 2011


The role of graphene for electrochemical energy storage
journal, December 2014


Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs
journal, March 2005


Carbon as catalyst and support for electrochemical energy conversion
journal, August 2014


A class of non-precious metal composite catalysts for fuel cells
journal, September 2006


High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt
journal, April 2011


Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells
journal, August 2011


Graphene-based materials in electrochemistry
journal, January 2010


Recent advances in non-precious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuelcells
journal, January 2011


A review on non-precious metal electrocatalysts for PEM fuel cells
journal, January 2011


Nitrogen-Doped Graphene as Efficient Metal-Free Electrocatalyst for Oxygen Reduction in Fuel Cells
journal, February 2010


Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction
journal, January 2012


The Role of Intercalated Water in Multilayered Graphene Oxide
journal, October 2010


Graphene-based macroscopic assemblies and architectures: an emerging material system
journal, January 2014


A review of graphene and graphene oxide sponge: material synthesis and applications to energy and the environment
journal, January 2014


Scalable enhancement of graphene oxide properties by thermally driven phase transformation
journal, December 2013


ReaxFF- l g: Correction of the ReaxFF Reactive Force Field for London Dispersion, with Applications to the Equations of State for Energetic Materials
journal, October 2011


Hydrogen Bond Networks in Graphene Oxide Composite Paper: Structure and Mechanical Properties
journal, March 2010


Chemically reduced graphene contains inherent metallic impurities present in parent natural and synthetic graphite
journal, July 2012


Pristine Graphite Oxide
journal, January 2012


PACKMOL: A package for building initial configurations for molecular dynamics simulations
journal, October 2009


Packing optimization for automated generation of complex system's initial configurations for molecular dynamics and docking
journal, May 2003


Direct visualization of reversible dynamics in a Si6 cluster embedded in a graphene pore
journal, April 2013


    Works referencing / citing this record:

    Nanocarbon for Oxygen Reduction Electrocatalysis: Dopants, Edges, and Defects
    journal, January 2017


    Active Sites and Mechanism of Oxygen Reduction Reaction Electrocatalysis on Nitrogen-Doped Carbon Materials
    journal, October 2018


    Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts
    journal, December 2016


    The critical role of hydroxyl groups in water vapor sensing of graphene oxide
    journal, January 2019


    Progress in the Development of Fe‐Based PGM‐Free Electrocatalysts for the Oxygen Reduction Reaction
    journal, December 2018