Boron- and Nitrogen-Substituted Graphene Nanoribbons as Efficient Catalysts for Oxygen Reduction Reaction

We show that nanoribbons of boron- and nitrogen-substituted graphene can be used as efficient electrocatalysts for the oxygen reduction reaction (ORR). Optimally doped graphene nanoribbons made into three-dimensional porous constructs exhibit the highest onset and half-wave potentials among the reported metal-free catalysts for this reaction and show superior performance compared to commercial Pt/C catalyst. Furthermore, this catalyst possesses high kinetic current density and four-electron transfer pathway with low hydrogen peroxide yield during the reaction. First-principles calculations suggest that such excellent electrocatalytic properties originate from the abundant edges of boron- and nitrogen-codoped graphene nanoribbons, which significantly reduce the energy barriers of the rate-determining steps of the ORR reaction.

[1]  Yongyao Xia,et al.  Nitrogen-doped graphene nanoribbons as efficient metal-free electrocatalysts for oxygen reduction. , 2014, ACS applied materials & interfaces.

[2]  P. Ajayan,et al.  Direct chemical conversion of graphene to boron- and nitrogen- and carbon-containing atomic layers , 2014, Nature Communications.

[3]  Arne Thomas,et al.  Doping carbons beyond nitrogen: an overview of advanced heteroatom doped carbons with boron, sulphur and phosphorus for energy applications , 2013 .

[4]  Yanglong Hou,et al.  Synthesis of Phosphorus‐Doped Graphene and its Multifunctional Applications for Oxygen Reduction Reaction and Lithium Ion Batteries , 2013, Advanced materials.

[5]  J. Kuo,et al.  Oxygen reduction reaction on active sites of heteroatom-doped graphene , 2013 .

[6]  M. Jaroniec,et al.  Sulfur and nitrogen dual-doped mesoporous graphene electrocatalyst for oxygen reduction with synergistically enhanced performance. , 2012, Angewandte Chemie.

[7]  Zheng Hu,et al.  Nitrogen‐Doped Carbon Nanocages as Efficient Metal‐Free Electrocatalysts for Oxygen Reduction Reaction , 2012, Advanced materials.

[8]  Mark K. Debe,et al.  Electrocatalyst approaches and challenges for automotive fuel cells , 2012, Nature.

[9]  F. Wei,et al.  An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes. , 2012, Nature nanotechnology.

[10]  C. Su,et al.  Converting graphene oxide monolayers into boron carbonitride nanosheets by substitutional doping. , 2012, Small.

[11]  Z. Yao,et al.  Sulfur-doped graphene as an efficient metal-free cathode catalyst for oxygen reduction. , 2012, ACS nano.

[12]  S. Woo,et al.  On the mechanism of enhanced oxygen reduction reaction in nitrogen-doped graphene nanoribbons. , 2011, Physical chemistry chemical physics : PCCP.

[13]  Xiulian Pan,et al.  Oxygen reduction reaction mechanism on nitrogen-doped graphene: A density functional theory study , 2011 .

[14]  Tom Regier,et al.  Co₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. , 2011, Nature materials.

[15]  Li Zhang,et al.  Preparation of Highly Conductive Graphene Hydrogels for Fabricating Supercapacitors with High Rate Capability , 2011 .

[16]  Klaus Müllen,et al.  Graphene-based carbon nitride nanosheets as efficient metal-free electrocatalysts for oxygen reduction reactions. , 2011, Angewandte Chemie.

[17]  Gang Wu,et al.  High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt , 2011, Science.

[18]  L. Dai,et al.  Polyelectrolyte functionalized carbon nanotubes as efficient metal-free electrocatalysts for oxygen reduction. , 2011, Journal of the American Chemical Society.

[19]  F. Du,et al.  3-D carbon nanotube structures used as high performance catalyst for oxygen reduction reaction. , 2010, Journal of the American Chemical Society.

[20]  Deep Jariwala,et al.  Atomic layers of hybridized boron nitride and graphene domains. , 2010, Nature materials.

[21]  J. Tour,et al.  Lower-defect graphene oxide nanoribbons from multiwalled carbon nanotubes. , 2010, ACS nano.

[22]  Y. Liu,et al.  Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. , 2010, ACS nano.

[23]  F. Du,et al.  Nitrogen-Doped Carbon Nanotube Arrays with High Electrocatalytic Activity for Oxygen Reduction , 2009, Science.

[24]  Maria Forsyth,et al.  High Rates of Oxygen Reduction over a Vapor Phase–Polymerized PEDOT Electrode , 2008, Science.

[25]  Philip N. Ross,et al.  Improved Oxygen Reduction Activity on Pt3Ni(111) via Increased Surface Site Availability , 2007, Science.

[26]  H. Gasteiger,et al.  Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs , 2005 .

[27]  K. Stevenson,et al.  Influence of nitrogen doping on oxygen reduction electrocatalysis at carbon nanofiber electrodes. , 2005, The journal of physical chemistry. B.

[28]  A. Wokaun,et al.  Oxygen reduction on high surface area Pt-based alloy catalysts in comparison to well defined smooth bulk alloy electrodes , 2002 .

[29]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.