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Title: Controlling the Active Sites of Sulfur-Doped Carbon Nanotube-Graphene Nanolobes for Highly Efficient Oxygen Evolution and Reduction Catalysis

Abstract

Controlling active sites of metal-free catalysts is an important strategy to enhance activity of the oxygen evolution reaction (OER). We made many attempts have been made to develop metal-free catalysts, but the lack of understanding of active-sites at the atomic-level has slowed the design of highly active and stable metal-free catalysts. We also developed a sequential two-step strategy to dope sulfur into carbon nanotube–graphene nanolobes. This bidoping strategy introduces stable sulfur–carbon active-sites. Fluorescence emission of the sulfur K-edge by X-ray absorption near edge spectroscopy (XANES) and scanning transmission electron microscopy electron energy loss spectroscopy (STEM-EELS) mapping and spectra confirm that increasing the incorporation of heterocyclic sulfur into the carbon ring of CNTs not only enhances OER activity with an overpotential of 350 mV at a current density of 10 mA cm -2, but also retains 100% of stability after 75 h. Furthermore, the bidoped sulfur carbon nanotube–graphene nanolobes behave like the state-of-the-art catalysts for OER but outperform those systems in terms of turnover frequency (TOF) which is two orders of magnitude greater than (20% Ir/C) at 400 mV overpotential with very high mass activity 1000 mA cm -2 at 570 mV. Moreover, the sulfur bidoping strategy shows high catalytic activitymore » for the oxygen reduction reaction (ORR). Stable bifunctional (ORR and OER) catalysts are low cost, and light-weight bidoped sulfur carbon nanotubes are potential candidates for next-generation metal-free regenerative fuel cells.« less

Authors:
 [1];  [2];  [3];  [4];  [5];  [4];  [6];  [7]
  1. Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemistry and Inst. of Materials Science; Tanta Univ. (Egypt). Dept. of Chemistry
  2. Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemistry; Tanta Univ. (Egypt). Dept. of Chemistry
  3. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton NY 11973 USA; Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials
  4. Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemistry
  5. Photon Science Directorate, Brookhaven National Laboratory, Upton NY 11973 USA; Brookhaven National Lab. (BNL), Upton, NY (United States)
  6. Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemistry and Inst. of Materials Science
  7. Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemistry and Inst. of Materials Science and Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1336156
Report Number(s):
BNL-112670-2016-JA
Journal ID: ISSN 1614-6832; KC0403020
Grant/Contract Number:  
SC00112704; FG02-86ER13622.A000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 6; Journal Issue: 5; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Sulfur-Doped Carbon; oxygen reduction; Center for Functional Nanomaterials

Citation Formats

El-Sawy, Abdelhamid M., Mosa, Islam M., Su, Dong, Guild, Curtis J., Khalid, Syed, Joesten, Raymond, Rusling, James F., and Suib, Steven L. Controlling the Active Sites of Sulfur-Doped Carbon Nanotube-Graphene Nanolobes for Highly Efficient Oxygen Evolution and Reduction Catalysis. United States: N. p., 2015. Web. doi:10.1002/aenm.201501966.
El-Sawy, Abdelhamid M., Mosa, Islam M., Su, Dong, Guild, Curtis J., Khalid, Syed, Joesten, Raymond, Rusling, James F., & Suib, Steven L. Controlling the Active Sites of Sulfur-Doped Carbon Nanotube-Graphene Nanolobes for Highly Efficient Oxygen Evolution and Reduction Catalysis. United States. https://doi.org/10.1002/aenm.201501966
El-Sawy, Abdelhamid M., Mosa, Islam M., Su, Dong, Guild, Curtis J., Khalid, Syed, Joesten, Raymond, Rusling, James F., and Suib, Steven L. Thu . "Controlling the Active Sites of Sulfur-Doped Carbon Nanotube-Graphene Nanolobes for Highly Efficient Oxygen Evolution and Reduction Catalysis". United States. https://doi.org/10.1002/aenm.201501966. https://www.osti.gov/servlets/purl/1336156.
@article{osti_1336156,
title = {Controlling the Active Sites of Sulfur-Doped Carbon Nanotube-Graphene Nanolobes for Highly Efficient Oxygen Evolution and Reduction Catalysis},
author = {El-Sawy, Abdelhamid M. and Mosa, Islam M. and Su, Dong and Guild, Curtis J. and Khalid, Syed and Joesten, Raymond and Rusling, James F. and Suib, Steven L.},
abstractNote = {Controlling active sites of metal-free catalysts is an important strategy to enhance activity of the oxygen evolution reaction (OER). We made many attempts have been made to develop metal-free catalysts, but the lack of understanding of active-sites at the atomic-level has slowed the design of highly active and stable metal-free catalysts. We also developed a sequential two-step strategy to dope sulfur into carbon nanotube–graphene nanolobes. This bidoping strategy introduces stable sulfur–carbon active-sites. Fluorescence emission of the sulfur K-edge by X-ray absorption near edge spectroscopy (XANES) and scanning transmission electron microscopy electron energy loss spectroscopy (STEM-EELS) mapping and spectra confirm that increasing the incorporation of heterocyclic sulfur into the carbon ring of CNTs not only enhances OER activity with an overpotential of 350 mV at a current density of 10 mA cm-2, but also retains 100% of stability after 75 h. Furthermore, the bidoped sulfur carbon nanotube–graphene nanolobes behave like the state-of-the-art catalysts for OER but outperform those systems in terms of turnover frequency (TOF) which is two orders of magnitude greater than (20% Ir/C) at 400 mV overpotential with very high mass activity 1000 mA cm-2 at 570 mV. Moreover, the sulfur bidoping strategy shows high catalytic activity for the oxygen reduction reaction (ORR). Stable bifunctional (ORR and OER) catalysts are low cost, and light-weight bidoped sulfur carbon nanotubes are potential candidates for next-generation metal-free regenerative fuel cells.},
doi = {10.1002/aenm.201501966},
url = {https://www.osti.gov/biblio/1336156}, journal = {Advanced Energy Materials},
issn = {1614-6832},
number = 5,
volume = 6,
place = {United States},
year = {2015},
month = {12}
}

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Works referenced in this record:

Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts
journal, May 2012


A comprehensive review on PEM water electrolysis
journal, April 2013


A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles
journal, October 2011


Nanoporous BiVO4 Photoanodes with Dual-Layer Oxygen Evolution Catalysts for Solar Water Splitting
journal, February 2014


A Fast Soluble Carbon-Free Molecular Water Oxidation Catalyst Based on Abundant Metals
journal, March 2010


Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution
journal, September 2013


Size-Dependent Activity of Co 3 O 4 Nanoparticle Anodes for Alkaline Water Electrolysis
journal, July 2009


Spinel-type lithium cobalt oxide as a bifunctional electrocatalyst for the oxygen evolution and oxygen reduction reactions
journal, May 2014


Hierarchical Zn x Co 3– x O 4 Nanoarrays with High Activity for Electrocatalytic Oxygen Evolution
journal, February 2014


Water Oxidation Catalysis using Amorphous Manganese Oxides, Octahedral Molecular Sieves (OMS-2), and Octahedral Layered (OL-1) Manganese Oxide Structures
journal, February 2012


The “Best Catalyst” for Water Oxidation Depends on the Oxidation Method Employed: A Case Study of Manganese Oxides
journal, June 2015


X-ray Absorption Spectroscopic Study of a Highly Thermally Stable Manganese Oxide Octahedral Molecular Sieve (OMS-2) with High Oxygen Reduction Reaction Activity
journal, September 2014


Understanding Interactions between Manganese Oxide and Gold That Lead to Enhanced Activity for Electrocatalytic Water Oxidation
journal, March 2014


Understanding the Role of Gold Nanoparticles in Enhancing the Catalytic Activity of Manganese Oxides in Water Oxidation Reactions
journal, October 2014


Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction
journal, February 2009


Sulfur and Nitrogen Dual-Doped Mesoporous Graphene Electrocatalyst for Oxygen Reduction with Synergistically Enhanced Performance
journal, October 2012


Sulfur-Doped Graphene as an Efficient Metal-free Cathode Catalyst for Oxygen Reduction
journal, December 2011


Two-Step Boron and Nitrogen Doping in Graphene for Enhanced Synergistic Catalysis
journal, January 2013


Nitrogen and Oxygen Dual-Doped Carbon Hydrogel Film as a Substrate-Free Electrode for Highly Efficient Oxygen Evolution Reaction
journal, February 2014


Nitrogen-doped carbon nanomaterials as non-metal electrocatalysts for water oxidation
journal, August 2013


Graphitic Carbon Nitride Nanosheet-Carbon Nanotube Three-Dimensional Porous Composites as High-Performance Oxygen Evolution Electrocatalysts
journal, June 2014


A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions
journal, April 2015


Electrocatalytic Oxygen Evolution at Surface-Oxidized Multiwall Carbon Nanotubes
journal, February 2015


Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons
journal, April 2009


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


Quantitative analysis of sulfur functional groups in natural organic matter by XANES spectroscopy
journal, December 2012


Self-assembly of a sulphur-terminated graphene nanoribbon within a single-walled carbon nanotube
journal, August 2011


Amphiphilic Surface Modification of Hollow Carbon Nanofibers for Improved Cycle Life of Lithium Sulfur Batteries
journal, February 2013


Facile One-Pot, One-Step Synthesis of a Carbon Nanoarchitecture for an Advanced Multifunctonal Electrocatalyst
journal, May 2014


N-, O-, and S-Tridoped Nanoporous Carbons as Selective Catalysts for Oxygen Reduction and Alcohol Oxidation Reactions
journal, September 2014


On the mechanism of enhanced oxygen reduction reaction in nitrogen-doped graphene nanoribbons
journal, January 2011


Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction
journal, August 2011


Ordered mesoporous Co3O4 spinels as stable, bifunctional, noble metal-free oxygen electrocatalysts
journal, January 2013


Efficient Water Oxidation Using Nanostructured α-Nickel-Hydroxide as an Electrocatalyst
journal, May 2014


A Functionally Stable Manganese Oxide Oxygen Evolution Catalyst in Acid
journal, April 2014


    Works referencing / citing this record:

    A Review of Precious-Metal-Free Bifunctional Oxygen Electrocatalysts: Rational Design and Applications in Zn−Air Batteries
    journal, August 2018


    Borocarbonitrides as Metal‐Free Catalysts for the Hydrogen Evolution Reaction
    journal, October 2018


    Atomic Modulation and Structure Design of Carbons for Bifunctional Electrocatalysis in Metal–Air Batteries
    journal, September 2018


    Carbon‐Based Metal‐Free ORR Electrocatalysts for Fuel Cells: Past, Present, and Future
    journal, January 2019


    Fungi-Enabled Synthesis of Ultrahigh-Surface-Area Porous Carbon
    journal, December 2018


    Novel Stable 3D Stainless Steel‐Based Electrodes for Efficient Water Splitting
    journal, July 2019


    Graphdiyne: Recent Achievements in Photo- and Electrochemical Conversion
    journal, October 2018


    Polydopamine-Inspired, Dual Heteroatom-Doped Carbon Nanotubes for Highly Efficient Overall Water Splitting
    journal, December 2016


    Design of Efficient Bifunctional Oxygen Reduction/Evolution Electrocatalyst: Recent Advances and Perspectives
    journal, July 2017


    Metal-Air Batteries: From Static to Flow System
    journal, August 2018


    Oxygen Reduction Reactions on Single‐ or Few‐Atom Discrete Active Sites for Heterogeneous Catalysis
    journal, September 2019


    Bifunctional Oxygen Electrocatalysts for Lithium‐Oxygen Batteries
    journal, April 2019


    Recent Advances in Carbon‐Based Bifunctional Oxygen Catalysts for Zinc‐Air Batteries
    journal, June 2019


    Nanostructured Carbon Based Heterogeneous Electrocatalysts for Oxygen Evolution Reaction in Alkaline Media
    journal, October 2019


    Nickel-Based Bicarbonates as Bifunctional Catalysts for Oxygen Evolution and Reduction Reaction in Alkaline Media
    journal, October 2018


    Three-dimensional nitrogen and phosphorous Co-doped graphene aerogel electrocatalysts for efficient oxygen reduction reaction
    journal, February 2018


    Switching effective oxygen reduction and evolution performance by controlled graphitization of a cobalt–nitrogen–carbon framework system
    journal, January 2016


    Biomass derived carbon for energy storage devices
    journal, January 2017


    A two-volt aqueous supercapacitor from porous dehalogenated carbon
    journal, January 2017


    Graphdiyne: a superior carbon additive to boost the activity of water oxidation catalysts
    journal, January 2018


    Metal–organic frameworks: a promising platform for constructing non-noble electrocatalysts for the oxygen-reduction reaction
    journal, January 2019


    Fe 1−x S@S-doped carbon core–shell heterostructured hollow spheres as highly reversible anode materials for sodium ion batteries
    journal, January 2019


    Co Nanoparticles Encapsulated in Porous N-Doped Carbon Nanofibers as an Efficient Electrocatalyst for Hydrogen Evolution Reaction
    journal, January 2018