S, N Dual-Doped Graphene-like Carbon Nanosheets as Efficient Oxygen Reduction Reaction Electrocatalysts.

Replacement of rare and precious metal catalysts with low-cost and earth-abundant ones is currently among the major goals of sustainable chemistry. Herein, we report the synthesis of S, N dual-doped graphene-like carbon nanosheets via a simple pyrolysis of a mixture of melamine and dibenzyl sulfide as efficient metal-free electrocatalysts for oxygen reduction reaction (ORR). The S, N dual-doped graphene-like carbon nanosheets show enhanced activity toward ORR as compared with mono-doped counterparts, and excellent durability in contrast to the conventional Pt/C electrocatalyst in both alkaline and acidic media. A high content of graphitic-N and pyridinic-N is necessary for ORR electrocatalysis in the graphene-like carbon nanosheets, but an appropriate amount of S atoms further contributes to the improvement of ORR activity. Superior ORR performance from the as-prepared S, N dual-doped graphene-like carbon nanosheets implies great promises in practical applications in energy devices.

[1]  Gang Wu.  Oxygen Reduction Reaction , 2018 .

[2]  Rui Li,et al.  Cornstalk-Derived Nitrogen-Doped Partly Graphitized Carbon as Efficient Metal-Free Catalyst for Oxygen Reduction Reaction in Microbial Fuel Cells. , 2016, ACS applied materials & interfaces.

[3]  W. Mai,et al.  The influence of nitrogen source and doping sequence on the electrocatalytic activity for oxygen reduction reaction of nitrogen doped carbon materials , 2016 .

[4]  P. Ajayan,et al.  Tuning the Electrochemical Reactivity of Boron‐ and Nitrogen‐Substituted Graphene , 2016, Advanced materials.

[5]  Yi Luo,et al.  Conversion of Dinitrogen to Ammonia by FeN3-Embedded Graphene. , 2016, Journal of the American Chemical Society.

[6]  C. Tung,et al.  Nitrogen‐Doped Porous Carbon Nanosheets Templated from g‐C3N4 as Metal‐Free Electrocatalysts for Efficient Oxygen Reduction Reaction , 2016, Advanced materials.

[7]  Kwang Soo Kim,et al.  Covalent versus Charge Transfer Modification of Graphene/Carbon-Nanotubes with Vitamin B1: Co/N/S-C Catalyst toward Excellent Oxygen Reduction. , 2016, ACS applied materials & interfaces.

[8]  Hongxia Wang,et al.  Nitrogen-doped graphenes as efficient electrocatalysts for the selective reduction of carbon dioxide to formate in aqueous solution , 2016 .

[9]  Fenglin Yang,et al.  Potentiodynamic Uniform Anchoring of Platinum Nanoparticles on N‐Doped Graphene with Improved Mass Activity for the Electrooxidation of Ammonia , 2016 .

[10]  Yi Luo,et al.  Unraveling the formation mechanism of graphitic nitrogen-doping in thermally treated graphene with ammonia , 2016, Scientific Reports.

[11]  B. Rezaei,et al.  Pyridine-functionalized graphene oxide, an efficient metal free electrocatalyst for oxygen reduction reaction , 2016 .

[12]  Xijiang Han,et al.  Bifunctional Nitrogen-Doped Microporous Carbon Microspheres Derived from Poly(o-methylaniline) for Oxygen Reduction and Supercapacitors. , 2016, ACS Applied Materials and Interfaces.

[13]  Zhengtang Luo,et al.  Essential roles of defects in pure graphene/Cu2O photocatalyst , 2016 .

[14]  Deli Wang,et al.  Microporous Organic Polymers Derived Microporous Carbon Supported Pd Catalysts for Oxygen Reduction Reaction: Impact of Framework and Heteroatom , 2016 .

[15]  T. Kondo,et al.  Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts , 2016, Science.

[16]  Jing Pan,et al.  Aminothiazole-derived N,S,Fe-doped graphene nanosheets as high performance electrocatalysts for oxygen reduction. , 2015, Chemical communications.

[17]  Zhenhai Xia,et al.  Design Principles for Heteroatom‐Doped Carbon Nanomaterials as Highly Efficient Catalysts for Fuel Cells and Metal–Air Batteries , 2015, Advanced materials.

[18]  Porun Liu,et al.  Thiourea sole doping reagent approach for controllable N, S co-doping of pre-synthesized large-sized carbon nanospheres as electrocatalyst for oxygen reduction reaction , 2015 .

[19]  L. Gu,et al.  Direct Transformation from Graphitic C3N4 to Nitrogen-Doped Graphene: An Efficient Metal-Free Electrocatalyst for Oxygen Reduction Reaction. , 2015, ACS applied materials & interfaces.

[20]  Y. Nie,et al.  Recent Advancements in Pt and Pt‐Free Catalysts for Oxygen Reduction Reaction , 2015 .

[21]  Takahiro Ishizaki,et al.  Simple one-step synthesis of fluorine-doped carbon nanoparticles as potential alternative metal-free electrocatalysts for oxygen reduction reaction , 2015 .

[22]  L. Dai,et al.  Sulfur-doped graphene derived from cycled lithium-sulfur batteries as a metal-free electrocatalyst for the oxygen reduction reaction. , 2015, Angewandte Chemie.

[23]  L. Nazar,et al.  Electrospun porous nanorod perovskite oxide/nitrogen-doped graphene composite as a bi-functional catalyst for metal air batteries , 2014 .

[24]  Song Jin,et al.  Earth-abundant inorganic electrocatalysts and their nanostructures for energy conversion applications , 2014 .

[25]  Sreekumar Kurungot,et al.  Layer-separated distribution of nitrogen doped graphene by wrapping on carbon nitride tetrapods for enhanced oxygen reduction reactions in acidic medium. , 2014, Chemical communications.

[26]  M. Chhowalla,et al.  N-, O-, and S-tridoped nanoporous carbons as selective catalysts for oxygen reduction and alcohol oxidation reactions. , 2014, Journal of the American Chemical Society.

[27]  Klaus Müllen,et al.  Hierarchically porous carbons with optimized nitrogen doping as highly active electrocatalysts for oxygen reduction , 2014, Nature Communications.

[28]  Hua Zhang,et al.  Nitrogen and Sulfur Codoped Graphene: Multifunctional Electrode Materials for High‐Performance Li‐Ion Batteries and Oxygen Reduction Reaction , 2014, Advanced materials.

[29]  Ja-Yeon Choi,et al.  Oxygen Reduction on Graphene−Carbon Nanotube Composites Doped Sequentially with Nitrogen and Sulfur , 2014 .

[30]  Daniel Gunzelmann,et al.  Observation of active sites for oxygen reduction reaction on nitrogen-doped multilayer graphene. , 2014, ACS nano.

[31]  Jiujun Zhang,et al.  A Review of Graphene‐Based Nanostructural Materials for Both Catalyst Supports and Metal‐Free Catalysts in PEM Fuel Cell Oxygen Reduction Reactions , 2014 .

[32]  Jaephil Cho,et al.  Graphene/Graphene‐Tube Nanocomposites Templated from Cage‐Containing Metal‐Organic Frameworks for Oxygen Reduction in Li–O2 Batteries , 2014, Advanced materials.

[33]  Lipeng Zhang,et al.  Catalytic Mechanisms of Sulfur-Doped Graphene as Efficient Oxygen Reduction Reaction Catalysts for Fuel Cells , 2014 .

[34]  Dang Sheng Su,et al.  Heterogeneous nanocarbon materials for oxygen reduction reaction , 2014 .

[35]  Yi Zhao,et al.  Sulfur- and nitrogen-doped, ferrocene-derived mesoporous carbons with efficient electrochemical reduction of oxygen. , 2013, ACS applied materials & interfaces.

[36]  K. Müllen,et al.  Mesoporous metal-nitrogen-doped carbon electrocatalysts for highly efficient oxygen reduction reaction. , 2013, Journal of the American Chemical Society.

[37]  Xiaodong Zhuang,et al.  Low-temperature synthesis of nitrogen/sulfur co-doped three-dimensional graphene frameworks as efficient metal-free electrocatalyst for oxygen reduction reaction , 2013 .

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

[39]  Y. Yoon,et al.  Synthesis of highly n-type graphene by using an ionic liquid. , 2012, Chemistry.

[40]  L. Dai,et al.  Vertically Aligned Carbon Nanotube Arrays Co-doped with Phosphorus and Nitrogen as Efficient Metal-Free Electrocatalysts for Oxygen Reduction. , 2012, The journal of physical chemistry letters.

[41]  D. Bhattacharjya,et al.  Phosphorus-doped ordered mesoporous carbons with different lengths as efficient metal-free electrocatalysts for oxygen reduction reaction in alkaline media. , 2012, Journal of the American Chemical Society.

[42]  M. Antonietti,et al.  Synthesis of monolayer-patched graphene from glucose. , 2012, Angewandte Chemie.

[43]  K. Müllen,et al.  Efficient Synthesis of Heteroatom (N or S)‐Doped Graphene Based on Ultrathin Graphene Oxide‐Porous Silica Sheets for Oxygen Reduction Reactions , 2012 .

[44]  Meilin Liu,et al.  Facile Synthesis of Nitrogen‐Doped Graphene via Pyrolysis of Graphene Oxide and Urea, and its Electrocatalytic Activity toward the Oxygen‐Reduction Reaction , 2012 .

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

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

[47]  T. Maiyalagan,et al.  Review on Recent Progress in Nitrogen-Doped Graphene: Synthesis, Characterization, and Its Potential Applications , 2012 .

[48]  L. Niu,et al.  Wet chemical synthesis of nitrogen-doped graphene towards oxygen reduction electrocatalysts without high-temperature pyrolysis , 2012 .

[49]  H. Dai,et al.  Covalent hybrid of spinel manganese-cobalt oxide and graphene as advanced oxygen reduction electrocatalysts. , 2012, Journal of the American Chemical Society.

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

[51]  Liangti Qu,et al.  Nitrogen-doped graphene quantum dots with oxygen-rich functional groups. , 2012, Journal of the American Chemical Society.

[52]  L. Dai,et al.  Vertically aligned BCN nanotubes as efficient metal-free electrocatalysts for the oxygen reduction reaction: a synergetic effect by co-doping with boron and nitrogen. , 2011, Angewandte Chemie.

[53]  Sean C. Smith,et al.  Nanoporous graphitic-C3N4@carbon metal-free electrocatalysts for highly efficient oxygen reduction. , 2011, Journal of the American Chemical Society.

[54]  H. Dai,et al.  Co₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. , 2011, Nature materials.

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

[56]  A S Bondarenko,et al.  Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. , 2009, Nature chemistry.

[57]  Lei Zhang,et al.  Progress in preparation of non-noble electrocatalysts for PEM fuel cell reactions , 2006 .

[58]  B. Steele,et al.  Materials for fuel-cell technologies , 2001, Nature.

[59]  J. Robertson,et al.  Interpretation of Raman spectra of disordered and amorphous carbon , 2000 .

[60]  R. Car,et al.  Raman spectra of graphite oxide and functionalized graphene sheets. , 2008, Nano letters.