DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: N- and S-doped mesoporous carbon as metal-free cathode catalysts for direct biorenewable alcohol fuel cells

Abstract

Nitrogen and sulfur were simultaneously doped into the framework of mesoporous CMK-3 as metal-free catalysts for direct biorenewable alcohol fuel cells. Glucose, NH3, and thiophene were used as carbon, nitrogen and sulfur precursors, respectively, to prepare mesoporous N-S-CMK-3 with uniform mesopores and extra macropores, resulting in good O2 diffusion both in half cell and alcohol fuel cell investigations. Among all investigated CMK-3 based catalysts, N-S-CMK-3 prepared at 800 °C exhibited the highest ORR activity with the onset potential of 0.92 V vs. RHE, Tafel slope of 68 mV dec-1, and 3.96 electron transfer number per oxygen molecule in 0.1 M KOH. In addition, the alkaline membrane-based direct alcohol fuel cell (DAFC) with N-S-CMK-3 cathode displayed 88.2 mW cm-2 peak power density without obvious O2 diffusion issue, reaching 84% initial performance of that with a Pt/C cathode. The high catalyst durability and fuel-crossover tolerance led to stable performance of the N-S-CMK-3 cathode DAFC with 90.6 mW cm-2 peak power density after 2 h operation, while the Pt/C cathode-based DAFC lost 36.9% of its peak power density. In conclusion, the high ORR activity of N-S-CMK-3 can be attributed to the synergistic effect between graphitic-N and S (C–S–C structure), suggesting great potential tomore » use N-S-CMK-3 as an alternative to noble metal catalysts in the fuel cell cathode.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [2]
  1. Iowa State Univ., Ames, IA (United States). Chemical and Biological Engineering, Biorenewables Research Laboratory
  2. (United States)
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1355355
Report Number(s):
IS-J-8904
Journal ID: ISSN 2050-7488
Grant/Contract Number:  
AC02-07CH11358; CBET1159448; CBET 1501113
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 4; Journal Issue: 1; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 59 BASIC BIOLOGICAL SCIENCES

Citation Formats

Qiu, Yang, Huo, Jiajie, Jia, Fan, Shanks, Brent. H., Li, Wenzhen, and Ames Lab., Ames, IA. N- and S-doped mesoporous carbon as metal-free cathode catalysts for direct biorenewable alcohol fuel cells. United States: N. p., 2015. Web. doi:10.1039/c5ta06039g.
Qiu, Yang, Huo, Jiajie, Jia, Fan, Shanks, Brent. H., Li, Wenzhen, & Ames Lab., Ames, IA. N- and S-doped mesoporous carbon as metal-free cathode catalysts for direct biorenewable alcohol fuel cells. United States. https://doi.org/10.1039/c5ta06039g
Qiu, Yang, Huo, Jiajie, Jia, Fan, Shanks, Brent. H., Li, Wenzhen, and Ames Lab., Ames, IA. Fri . "N- and S-doped mesoporous carbon as metal-free cathode catalysts for direct biorenewable alcohol fuel cells". United States. https://doi.org/10.1039/c5ta06039g. https://www.osti.gov/servlets/purl/1355355.
@article{osti_1355355,
title = {N- and S-doped mesoporous carbon as metal-free cathode catalysts for direct biorenewable alcohol fuel cells},
author = {Qiu, Yang and Huo, Jiajie and Jia, Fan and Shanks, Brent. H. and Li, Wenzhen and Ames Lab., Ames, IA},
abstractNote = {Nitrogen and sulfur were simultaneously doped into the framework of mesoporous CMK-3 as metal-free catalysts for direct biorenewable alcohol fuel cells. Glucose, NH3, and thiophene were used as carbon, nitrogen and sulfur precursors, respectively, to prepare mesoporous N-S-CMK-3 with uniform mesopores and extra macropores, resulting in good O2 diffusion both in half cell and alcohol fuel cell investigations. Among all investigated CMK-3 based catalysts, N-S-CMK-3 prepared at 800 °C exhibited the highest ORR activity with the onset potential of 0.92 V vs. RHE, Tafel slope of 68 mV dec-1, and 3.96 electron transfer number per oxygen molecule in 0.1 M KOH. In addition, the alkaline membrane-based direct alcohol fuel cell (DAFC) with N-S-CMK-3 cathode displayed 88.2 mW cm-2 peak power density without obvious O2 diffusion issue, reaching 84% initial performance of that with a Pt/C cathode. The high catalyst durability and fuel-crossover tolerance led to stable performance of the N-S-CMK-3 cathode DAFC with 90.6 mW cm-2 peak power density after 2 h operation, while the Pt/C cathode-based DAFC lost 36.9% of its peak power density. In conclusion, the high ORR activity of N-S-CMK-3 can be attributed to the synergistic effect between graphitic-N and S (C–S–C structure), suggesting great potential to use N-S-CMK-3 as an alternative to noble metal catalysts in the fuel cell cathode.},
doi = {10.1039/c5ta06039g},
journal = {Journal of Materials Chemistry. A},
number = 1,
volume = 4,
place = {United States},
year = {Fri Nov 06 00:00:00 EST 2015},
month = {Fri Nov 06 00:00:00 EST 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 88 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

The Path Forward for Biofuels and Biomaterials
journal, January 2006

  • Ragauskas, Arthur J.; Williams, Charlotte K.; Davison, Brian H.
  • Science, Vol. 311, Issue 5760, p. 484-489
  • DOI: 10.1126/science.1114736

Advanced Technology Paths to Global Climate Stability: Energy for a Greenhouse Planet
journal, November 2002


Materials for fuel-cell technologies
journal, November 2001

  • Steele, Brian C. H.; Heinzel, Angelika
  • Nature, Vol. 414, Issue 6861, p. 345-352
  • DOI: 10.1038/35104620

Metal–air batteries: from oxygen reduction electrochemistry to cathode catalysts
journal, January 2012

  • Cheng, Fangyi; Chen, Jun
  • Chemical Society Reviews, Vol. 41, Issue 6, p. 2172-2192
  • DOI: 10.1039/c1cs15228a

Direct oxidation alkaline fuelcells: from materials to systems
journal, January 2012

  • Yu, Eileen Hao; Wang, Xu; Krewer, Ulrike
  • Energy Environ. Sci., Vol. 5, Issue 2
  • DOI: 10.1039/C2EE02552C

Anion-exchange membranes in electrochemical energy systems
journal, January 2014

  • Varcoe, John R.; Atanassov, Plamen; Dekel, Dario R.
  • Energy & Environmental Science, Vol. 7, Issue 10, p. 3135-3191
  • DOI: 10.1039/C4EE01303D

Prospects for Alkaline Anion-Exchange Membranes in Low Temperature Fuel Cells
journal, October 2004


Nano-stuctured Pt–Fe/C as cathode catalyst in direct methanol fuel cell
journal, March 2004


Metal monolayer deposition by replacement of metal adlayers on electrode surfaces
journal, March 2001


Platinum Monolayer Fuel Cell Electrocatalysts
journal, November 2007


Tuning Nanoparticle Catalysis for the Oxygen Reduction Reaction
journal, June 2013

  • Guo, Shaojun; Zhang, Sen; Sun, Shouheng
  • Angewandte Chemie International Edition, Vol. 52, Issue 33
  • DOI: 10.1002/anie.201207186

Nanostructured Nonprecious Metal Catalysts for Oxygen Reduction Reaction
journal, April 2013

  • Wu, Gang; Zelenay, Piotr
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar400011z

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

  • Liang, Ji; Jiao, Yan; Jaroniec, Mietek
  • Angewandte Chemie International Edition, Vol. 51, Issue 46
  • DOI: 10.1002/anie.201206720

Vertically Aligned BCN Nanotubes as Efficient Metal-Free Electrocatalysts for the Oxygen Reduction Reaction: A Synergetic Effect by Co-Doping with Boron and Nitrogen
journal, October 2011

  • Wang , Shuangyin; Iyyamperumal , Eswaramoorthi; Roy, Ajit
  • Angewandte Chemie International Edition, Vol. 50, Issue 49
  • DOI: 10.1002/anie.201105204

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

  • Zhang, Jintao; Zhao, Zhenghang; Xia, Zhenhai
  • Nature Nanotechnology, Vol. 10, Issue 5
  • DOI: 10.1038/nnano.2015.48

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

  • Yang, Zhi; Yao, Zhen; Li, Guifa
  • ACS Nano, Vol. 6, Issue 1, p. 205-211
  • DOI: 10.1021/nn203393d

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


Nitrogen and Phosphorus Dual-Doped Hierarchical Porous Carbon Foams as Efficient Metal-Free Electrocatalysts for Oxygen Reduction Reactions
journal, February 2014

  • Jiang, Hongliang; Zhu, Yihua; Feng, Qian
  • Chemistry - A European Journal, Vol. 20, Issue 11
  • DOI: 10.1002/chem.201304561

Boron-Doped Carbon Nanotubes as Metal-Free Electrocatalysts for the Oxygen Reduction Reaction
journal, June 2011

  • Yang, Lijun; Jiang, Shujuan; Zhao, Yu
  • Angewandte Chemie International Edition, Vol. 50, Issue 31
  • DOI: 10.1002/anie.201101287

Oxygen Reduction on Graphene–Carbon Nanotube Composites Doped Sequentially with Nitrogen and Sulfur
journal, July 2014

  • Higgins, Drew C.; Hoque, Md Ariful; Hassan, Fathy
  • ACS Catalysis, Vol. 4, Issue 8
  • DOI: 10.1021/cs5003806

Substitutional Doping of Carbon Nanotubes with Heteroatoms and Their Chemical Applications
journal, March 2014


One-Step Pyrolytic Synthesis of Nitrogen and Sulfur Dual-Doped Porous Carbon with High Catalytic Activity and Good Accessibility to Small Biomolecules
journal, October 2014

  • Gao, Weiwei; Feng, Xun; Zhang, Tianyi
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 21
  • DOI: 10.1021/am505080r

Anion exchange membranes for alkaline fuel cells: A review
journal, July 2011

  • Merle, Géraldine; Wessling, Matthias; Nijmeijer, Kitty
  • Journal of Membrane Science, Vol. 377, Issue 1-2, p. 1-35
  • DOI: 10.1016/j.memsci.2011.04.043

Synthesis of New, Nanoporous Carbon with Hexagonally Ordered Mesostructure
journal, November 2000

  • Jun, Shinae; Joo, Sang Hoon; Ryoo, Ryong
  • Journal of the American Chemical Society, Vol. 122, Issue 43
  • DOI: 10.1021/ja002261e

Ordered nanoporous arrays of carbon supporting high dispersions of platinum nanoparticles
journal, July 2001

  • Joo, Sang Hoon; Choi, Seong Jae; Oh, Ilwhan
  • Nature, Vol. 412, Issue 6843
  • DOI: 10.1038/35084046

Mesoporous Metal–Nitrogen-Doped Carbon Electrocatalysts for Highly Efficient Oxygen Reduction Reaction
journal, October 2013

  • Liang, Hai-Wei; Wei, Wei; Wu, Zhong-Shuai
  • Journal of the American Chemical Society, Vol. 135, Issue 43
  • DOI: 10.1021/ja407552k

Sulfur- and Nitrogen-Doped, Ferrocene-Derived Mesoporous Carbons with Efficient Electrochemical Reduction of Oxygen
journal, November 2013

  • Xu, Jiaoxing; Zhao, Yi; Shen, Cai
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 23
  • DOI: 10.1021/am4039294

Nitrogen-Doped Ordered Mesoporous Graphitic Arrays with High Electrocatalytic Activity for Oxygen Reduction
journal, March 2010

  • Liu, Ruili; Wu, Dongqing; Feng, Xinliang
  • Angewandte Chemie International Edition, Vol. 49, Issue 14, p. 2565-2569
  • DOI: 10.1002/anie.200907289

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

  • Jaouen, Frédéric; Proietti, Eric; Lefèvre, Michel
  • Energy Environ. Sci., Vol. 4, Issue 1, p. 114-130
  • DOI: 10.1039/C0EE00011F

Ethylene Glycol Electrooxidation on Smooth and Nanostructured Pd Electrodes in Alkaline Media
journal, June 2010


Catalysts for direct ethanol fuel cells
journal, June 2007


Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited
journal, January 2010

  • Bozell, Joseph J.; Petersen, Gene R.
  • Green Chemistry, Vol. 12, Issue 4, p. 539-554
  • DOI: 10.1039/b922014c

Triblock Copolymer Syntheses of Mesoporous Silica with Periodic 50 to 300 Angstrom Pores
journal, January 1998


Nitrogen-doped nanoporous carbon nanosheets derived from plant biomass: an efficient catalyst for oxygen reduction reaction
journal, January 2014

  • Chen, Ping; Wang, Li-Kun; Wang, Gan
  • Energy & Environmental Science, Vol. 7, Issue 12, p. 4095-4103
  • DOI: 10.1039/C4EE02531H

Sulfur-doped ordered mesoporous carbon with high electrocatalytic activity for oxygen reduction
journal, October 2013


Nonionic Triblock and Star Diblock Copolymer and Oligomeric Surfactant Syntheses of Highly Ordered, Hydrothermally Stable, Mesoporous Silica Structures
journal, June 1998

  • Zhao, Dongyuan; Huo, Qisheng; Feng, Jianglin
  • Journal of the American Chemical Society, Vol. 120, Issue 24
  • DOI: 10.1021/ja974025i

Ionic liquid derived carbons as highly efficient oxygen reduction catalysts: first elucidation of pore size distribution dependent kinetics
journal, January 2014

  • Zhang, Zhiyong; Veith, Gabriel M.; Brown, Gilbert M.
  • Chem. Commun., Vol. 50, Issue 12
  • DOI: 10.1039/C3CC48942F

Nanocasting: A Versatile Strategy for Creating Nanostructured Porous Materials
journal, July 2006


Sulfur-doped porous carbons: Synthesis and applications
journal, March 2014


Nitrogen and sulfur co-doped ordered mesoporous carbon with enhanced electrochemical capacitance performance
journal, January 2013

  • Zhang, Deyi; Hao, Yuan; Zheng, Liwen
  • Journal of Materials Chemistry A, Vol. 1, Issue 26
  • DOI: 10.1039/c3ta11208j

Noble-Metal-Free Fe–N/C Catalyst for Highly Efficient Oxygen Reduction Reaction under Both Alkaline and Acidic Conditions
journal, July 2014

  • Lin, Ling; Zhu, Qing; Xu, An-Wu
  • Journal of the American Chemical Society, Vol. 136, Issue 31
  • DOI: 10.1021/ja504696r

Phosphorus-Doped Graphitic Carbon Nitrides Grown In Situ on Carbon-Fiber Paper: Flexible and Reversible Oxygen Electrodes
journal, December 2014

  • Ma, Tian Yi; Ran, Jingrun; Dai, Sheng
  • Angewandte Chemie International Edition, Vol. 54, Issue 15
  • DOI: 10.1002/anie.201411125

Mn 3 O 4 Supported on Glassy Carbon: An Active Non-Precious Metal Catalyst for the Oxygen Reduction Reaction
journal, November 2012

  • Gorlin, Yelena; Chung, Chia-Jung; Nordlund, Dennis
  • ACS Catalysis, Vol. 2, Issue 12
  • DOI: 10.1021/cs3004352

Nanocarbon Electrocatalysts for Oxygen Reduction in Alkaline Media for Advanced Energy Conversion and Storage
journal, January 2014


High-Loading Cobalt Oxide Coupled with Nitrogen-Doped Graphene for Oxygen Reduction in Anion-Exchange-Membrane Alkaline Fuel Cells
journal, April 2013

  • He, Qinggang; Li, Qing; Khene, Samson
  • The Journal of Physical Chemistry C, Vol. 117, Issue 17
  • DOI: 10.1021/jp401814f

Catalytic Conversion of Biomass to Monofunctional Hydrocarbons and Targeted Liquid-Fuel Classes
journal, October 2008


Mechanisms of Oxygen Reduction Reaction on Nitrogen-Doped Graphene for Fuel Cells
journal, May 2011

  • Zhang, Lipeng; Xia, Zhenhai
  • The Journal of Physical Chemistry C, Vol. 115, Issue 22
  • DOI: 10.1021/jp201991j

BCN Graphene as Efficient Metal-Free Electrocatalyst for the Oxygen Reduction Reaction
journal, March 2012

  • Wang, Shuangyin; Zhang, Lipeng; Xia, Zhenhai
  • Angewandte Chemie International Edition, Vol. 51, Issue 17
  • DOI: 10.1002/anie.201109257

Electrocatalytic Oxygen Evolution over Supported Small Amorphous Ni–Fe Nanoparticles in Alkaline Electrolyte
journal, June 2014


Works referencing / citing this record:

Advanced Biomass-Derived Electrocatalysts for the Oxygen Reduction Reaction
journal, December 2017

  • Borghei, Maryam; Lehtonen, Janika; Liu, Liang
  • Advanced Materials, Vol. 30, Issue 24
  • DOI: 10.1002/adma.201703691

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


Sustainable Carbonaceous Materials Derived from Biomass as Metal‐Free Electrocatalysts
journal, December 2018

  • Zhang, Zhengping; Yang, Shaoxuan; Li, Hanyu
  • Advanced Materials, Vol. 31, Issue 13
  • DOI: 10.1002/adma.201805718

Edge Chemistry of Armchair Graphene Nanoribbons Containing Sulfur Functional Groups: Towards an Understanding of the Spin‐Dependent Electrochemistry
journal, January 2020

  • López‐Urías, Florentino; Fajardo‐Díaz, Juan L.; Cortés‐López, Alejandro J.
  • Advanced Theory and Simulations, Vol. 3, Issue 3
  • DOI: 10.1002/adts.201900219

The Role of Ruthenium on Carbon‐Supported PtRu Catalysts for Electrocatalytic Glycerol Oxidation under Acidic Conditions
journal, February 2017


Exposed N and S Active Sites: An Indicator for Oxygen Reduction on Metal-Free Yam-Derived Porous Carbons
journal, September 2017


Tuning Cobalt and Nitrogen Co‐Doped Carbon to Maximize Catalytic Sites on a Superabsorbent Resin for Efficient Oxygen Reduction
journal, September 2018


A high-performance mesoporous carbon supported nitrogen-doped carbon electrocatalyst for oxygen reduction reaction
journal, November 2017