Novel Mn-/Co-Nx Moieties Captured in N-Doped Carbon Nanotubes for Enhanced Oxygen Reduction Activity and Stability in Acidic and Alkaline Media.

Fe-N-C-based electrocatalysts have been developed as an encouraging substitute compared to their expensive Pt-containing equivalents for the oxygen reduction reaction (ORR). However, they still face major durability challenges from the in- situ production of Fenton radicals. Therefore, the synthesis of Fe-free ORR catalysts is among the emerging concerns. Herein, we have precisely applied a multistep heating strategy to produce mesoporous N-doped carbon nanostructures with Mn-/Co-Nx dual moieties from mixed-metal zeolitic imidazolate frameworks (ZIFs). It is found that their unique structure, with dual-metallic active sites, not only offers a high electrochemical performance for the ORR (E1/2 = 0.83 V vs reversible hydrogen electrode (RHE) in acid media), but also enhances the operational durability of the catalyst after 20 000 cycles with 97% of retention and very low H2O2 production (<5%) in 0.1 M HClO4. In addition, the catalyst performs well toward the ORR also in alkaline solution (exhibiting E1/2 = 0.90 V and 30 000 cyclic stability).

[1]  Zhengchun Peng,et al.  A metal free electrocatalyst for high-performance zinc-air battery applications with good resistance towards poisoning species , 2020 .

[2]  Shuqin Song,et al.  Recent advances on oxygen reduction electrocatalysis: Correlating the characteristic properties of metal organic frameworks and the derived nanomaterials , 2020 .

[3]  Y. Tong,et al.  Iron oxide@graphitic carbon core-shell nanoparticles embedded in ordered mesoporous N-doped carbon matrix as an efficient cathode catalyst for PEMFC , 2020, Applied Catalysis B: Environmental.

[4]  M. Aslam,et al.  Nano-engineered directed growth of Mn3O4 quasi-nanocubes on N-doped polyhedrons: Efficient electrocatalyst for oxygen reduction reaction , 2020 .

[5]  Jing Xu,et al.  A new insight into the effect of scan rate and mass transport from Pt rotating disk electrode on the electrochemical oxidation process of methanol , 2020 .

[6]  Xiaodong Zhuang,et al.  Boosting Oxygen Reduction of Single Iron Active Sites via Geometric and Electronic Engineering: Nitrogen and Phosphorus Dual-Coordination. , 2020, Journal of the American Chemical Society.

[7]  L. Du,et al.  Metal-organic framework derived carbon materials for electrocatalytic oxygen reactions: Recent progress and future perspectives , 2020 .

[8]  S. Shah,et al.  Electron penetration from metal core to metal species attached skin in nitrogen-doped core-shell catalyst for enhancing oxygen evolution reaction , 2019 .

[9]  P. Tsiakaras,et al.  Molybdenum-modified and vertex-reinforced quaternary hexapod nano-skeletons as efficient electrocatalysts for methanol oxidation and oxygen reduction reaction , 2019 .

[10]  Zidong Wei,et al.  Enhancing by nano-engineering: Hierarchical architectures as oxygen reduction/ evolution reactions for zinc-air batteries , 2019, Journal of Power Sources.

[11]  Yun Chan Kang,et al.  Yolk–shell-structured manganese oxide/nitride composite powders comprising cobalt-nanoparticle-embedded nitrogen-doped carbon nanotubes as cathode catalysts for long-life-cycle lithium–oxygen batteries , 2019, Chemical Engineering Journal.

[12]  Shibin Yin,et al.  Oxygen Reduction Reaction over PtFeM (M = Mo, V, W) Alloy Electrocatalysts: Role of the Compressive Strain Effect on Pt , 2019, ACS Sustainable Chemistry & Engineering.

[13]  Pei Kang Shen,et al.  Facile synthesis of bimetallic Pt-Pd symmetry-broken concave nanocubes and their enhanced activity toward oxygen reduction reaction , 2019, Applied Catalysis B: Environmental.

[14]  S. Shah,et al.  Role of P-doping in Antipoisoning: Efficient MOF-Derived 3D Hierarchical Architectures for the Oxygen Reduction Reaction , 2019, The Journal of Physical Chemistry C.

[15]  Shuqin Song,et al.  Bimetallic−organic framework-derived hierarchically porous Co-Zn-N-C as efficient catalyst for acidic oxygen reduction reaction , 2019, Applied Catalysis B: Environmental.

[16]  Edward F. Holby,et al.  Experimental and Theoretical Trends of PGM-Free Electrocatalysts for the Oxygen Reduction Reaction with Different Transition Metals , 2019, Journal of The Electrochemical Society.

[17]  Edward F. Holby,et al.  Progress in the Development of Fe‐Based PGM‐Free Electrocatalysts for the Oxygen Reduction Reaction , 2019, Advanced materials.

[18]  S. Shah,et al.  An Efficient Anti-poisoning Catalyst against SOx , NOx , and POx : P, N-Doped Carbon for Oxygen Reduction in Acidic Media. , 2018, Angewandte Chemie.

[19]  Zheng Hu,et al.  Co nanoparticle embedded in atomically-dispersed Co-N-C nanofibers for oxygen reduction with high activity and remarkable durability , 2018, Nano Energy.

[20]  Ling Zhang,et al.  Exploring Fe-Nx for Peroxide Reduction: Template-Free Synthesis of Fe-Nx Traumatized Mesoporous Carbon Nanotubes as an ORR Catalyst in Acidic and Alkaline Solutions. , 2018, Chemistry.

[21]  Lishan Peng,et al.  Design and synthesis of conductive carbon polyhedrons enriched with Mn-Oxide active-centres for oxygen reduction reaction , 2018 .

[22]  Jianchuang Wang,et al.  Understanding the Roles of Nitrogen Configurations in Hydrogen Evolution: Trace Atomic Cobalt Boosts the Activity of Planar Nitrogen-Doped Graphene , 2018 .

[23]  Shuxiang Wu,et al.  The relation of magnetic properties and anomalous Hall behaviors in Mn4N (200) epitaxial films , 2018 .

[24]  Yuyan Shao,et al.  Nitrogen‐Coordinated Single Cobalt Atom Catalysts for Oxygen Reduction in Proton Exchange Membrane Fuel Cells , 2018, Advanced materials.

[25]  Shuqin Song,et al.  Enhancement of oxygen reduction reaction performance: The characteristic role of FeN coordinations , 2018 .

[26]  Deborah J. Jones,et al.  Stabilization of Iron-Based Fuel Cell Catalysts by Non-Catalytic Platinum , 2018 .

[27]  P. Tsiakaras,et al.  Highly effective oxygen reduction reaction electrocatalysis: Nitrogen-doped hierarchically mesoporous carbon derived from interpenetrated nonporous metal-organic frameworks , 2017 .

[28]  Zihan Meng,et al.  3D Co-N-doped hollow carbon spheres as excellent bifunctional electrocatalysts for oxygen reduction reaction and oxygen evolution reaction , 2017 .

[29]  Lirong Zheng,et al.  Hollow N-Doped Carbon Spheres with Isolated Cobalt Single Atomic Sites: Superior Electrocatalysts for Oxygen Reduction. , 2017, Journal of the American Chemical Society.

[30]  X. Qi,et al.  Monodispersed Co in Mesoporous Polyhedrons: Fine-tuning of ZIF-8 Structure with Enhanced Oxygen Reduction Activity , 2017 .

[31]  Yuyan Shao,et al.  Single Atomic Iron Catalysts for Oxygen Reduction in Acidic Media: Particle Size Control and Thermal Activation. , 2017, Journal of the American Chemical Society.

[32]  Karren L. More,et al.  Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst , 2017, Science.

[33]  P. Tsiakaras,et al.  2D nitrogen-doped hierarchically porous carbon: Key role of low dimensional structure in favoring electrocatalysis and mass transfer for oxygen reduction reaction , 2017 .

[34]  Arumugam Manthiram,et al.  “Wiring” Fe‐Nx‐Embedded Porous Carbon Framework onto 1D Nanotubes for Efficient Oxygen Reduction Reaction in Alkaline and Acidic Media , 2017, Advanced materials.

[35]  Dongyuan Zhao,et al.  General Oriented Formation of Carbon Nanotubes from Metal-Organic Frameworks. , 2017, Journal of the American Chemical Society.

[36]  C. Santoro,et al.  Air Breathing Cathodes for Microbial Fuel Cell using Mn-, Fe-, Co- and Ni-containing Platinum Group Metal-free Catalysts , 2017, Electrochimica acta.

[37]  Chao Zhang,et al.  Networking Pyrolyzed Zeolitic Imidazolate Frameworks by Carbon Nanotubes Improves Conductivity and Enhances Oxygen‐Reduction Performance in Polymer‐Electrolyte‐Membrane Fuel Cells , 2017, Advanced materials.

[38]  Gaixia Zhang,et al.  Is iron involved in the lack of stability of Fe/N/C electrocatalysts used to reduce oxygen at the cathode of PEM fuel cells? , 2016 .

[39]  Mingmei Wu,et al.  Efficient Pt-free electrocatalyst for oxygen reduction reaction: Highly ordered mesoporous N and S co-doped carbon with saccharin as single-source molecular precursor , 2016 .

[40]  Lauren R. Grabstanowicz,et al.  Investigation of Oxygen Reduction Activity of Catalysts Derived from Co and Co/Zn Methyl‐Imidazolate Frameworks in Proton Exchange Membrane Fuel Cells , 2016 .

[41]  B. Geng,et al.  Porous Mn2 O3 : A Low-Cost Electrocatalyst for Oxygen Reduction Reaction in Alkaline Media with Comparable Activity to Pt/C. , 2016, Chemistry.

[42]  K. Tadanaga,et al.  Nitrogen-Rich Manganese Oxynitrides with Enhanced Catalytic Activity in the Oxygen Reduction Reaction. , 2016, Angewandte Chemie.

[43]  Feng Wang,et al.  Composition-dependent electro-catalytic activities of covalent carbon-LaMnO3 hybrids as synergistic catalysts for oxygen reduction reaction , 2016 .

[44]  C. Tung,et al.  Well‐Dispersed ZIF‐Derived Co,N‐Co‐doped Carbon Nanoframes through Mesoporous‐Silica‐Protected Calcination as Efficient Oxygen Reduction Electrocatalysts , 2016, Advanced materials.

[45]  Nitrogen‐Doped Carbon Electrocatalysts Decorated with Transition Metals for the Oxygen Reduction Reaction , 2015 .

[46]  Linjie Zhang,et al.  Structural Evolution from Metal–Organic Framework to Hybrids of Nitrogen-Doped Porous Carbon and Carbon Nanotubes for Enhanced Oxygen Reduction Activity , 2015 .

[47]  K. Mayrhofer,et al.  Stability of Fe-N-C Catalysts in Acidic Medium Studied by Operando Spectroscopy. , 2015, Angewandte Chemie.

[48]  Dustin Banham,et al.  A review of the stability and durability of non-precious metal catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells , 2015 .

[49]  L. Du,et al.  Nitrogen-doped ordered mesoporous carbon: synthesis and active sites for electrocatalysis of oxygen reduction reaction , 2015 .

[50]  Xizhang Wang,et al.  Alloyed Co–Mo Nitride as High-Performance Electrocatalyst for Oxygen Reduction in Acidic Medium , 2015 .

[51]  Y. Shan,et al.  Ordered mesoporous Fe (or Co)–N–graphitic carbons as excellent non-precious-metal electrocatalysts for oxygen reduction , 2014 .

[52]  Stanislaus S. Wong,et al.  Probing Ultrathin One-Dimensional Pd–Ni Nanostructures As Oxygen Reduction Reaction Catalysts , 2014 .

[53]  Jyhfu Lee,et al.  Effects of structures of pyrolyzed corrin, corrole and porphyrin on oxygen reduction reaction , 2014 .

[54]  D. Schmeißer,et al.  Correlations between mass activity and physicochemical properties of Fe/N/C catalysts for the ORR in PEM fuel cell via 57Fe Mössbauer spectroscopy and other techniques. , 2014, Journal of the American Chemical Society.

[55]  Stanislaus S. Wong,et al.  Designing Enhanced One-Dimensional Electrocatalysts for the Oxygen Reduction Reaction: Probing Size- and Composition-Dependent Electrocatalytic Behavior in Noble Metal Nanowires , 2012 .

[56]  S. Mukerjee,et al.  Structure of the catalytic sites in Fe/N/C-catalysts for O2-reduction in PEM fuel cells. , 2012, Physical chemistry chemical physics : PCCP.

[57]  K. Artyushkova,et al.  Multitechnique Characterization of a Polyaniline–Iron–Carbon Oxygen Reduction Catalyst , 2012 .

[58]  Stanislaus S. Wong,et al.  Size- and Composition-Dependent Enhancement of Electrocatalytic Oxygen Reduction Performance in Ultrathin Palladium–Gold (Pd1–xAux) Nanowires , 2012 .

[59]  Stanislaus S. Wong,et al.  Highly enhanced electrocatalytic oxygen reduction performance observed in bimetallic palladium-based nanowires prepared under ambient, surfactantless conditions. , 2012, Nano letters.

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