Metal–Organic Framework-Induced Synthesis of Ultrasmall Encased NiFe Nanoparticles Coupling with Graphene as an Efficient Oxygen Electrode for a Rechargeable Zn–Air Battery

Rational design of electrocatalysts to replace the noble-metal-based materials for oxygen reactions is highly desirable but challenging for rechargeable metal–air batteries. Herein, we demonstrate a unique two stage encapsulation strategy to regulate the structure and performance of catalysts featured with thin graphene nanosheets coupling with full encapsulated ultrafine and high-loaded (∼25 wt %) transition metal nanoparticles (TMs@NCX) for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). By optimizing the electronic modulation effect from suitable metal cores, the best NiFe@NCX catalyst exhibits high stability and activity with an onset potential of 1.03 V for ORR and an overpotential of only 0.23 V at 10 mA cm–2 for OER, which is superior to commercial Pt/C and IrO2 catalysts. Rechargeable Zn–air battery using NiFe@NCX catalyst exhibited an unprecedented small charge–discharge overpotential of 0.78 V at 50 mA cm–2, high reversibility, and stability, holding great promise for the pr...

[1]  Cheng-gong Sun,et al.  Preparation of spherical activated carbon with hierarchical porous texture , 2009 .

[2]  Fei Zhang,et al.  Nitrogen‐Enriched Core‐Shell Structured Fe/Fe3C‐C Nanorods as Advanced Electrocatalysts for Oxygen Reduction Reaction , 2012, Advanced materials.

[3]  H. Fei,et al.  Cobalt nanoparticles embedded in nitrogen-doped carbon for the hydrogen evolution reaction. , 2015, ACS applied materials & interfaces.

[4]  Yufan Zhang,et al.  Dicobalt phosphide nanoparticles encased in boron and nitrogen co-doped graphitic layers as novel non-precious metal oxygen reduction electrocatalysts in alkaline media. , 2015, Chemical communications.

[5]  L. Gu,et al.  Yolk–shell structured iron carbide/N-doped carbon composite as highly efficient and stable oxygen reduction reaction electrocatalyst , 2015 .

[6]  P. Bruce,et al.  A Reversible and Higher-Rate Li-O2 Battery , 2012, Science.

[7]  Jun Chen,et al.  Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts. , 2012, Chemical Society reviews.

[8]  Zhaolin Liu,et al.  Mn and Co co-substituted Fe3O4 nanoparticles on nitrogen-doped reduced graphene oxide for oxygen electrocatalysis in alkaline solution , 2014 .

[9]  John B Goodenough,et al.  Evolution of strategies for modern rechargeable batteries. , 2013, Accounts of chemical research.

[10]  D. Portehault,et al.  High N-content holey few-layered graphene electrocatalysts: scalable solvent-less production , 2015 .

[11]  Wei Zhang,et al.  Hollow spheres of iron carbide nanoparticles encased in graphitic layers as oxygen reduction catalysts. , 2014, Angewandte Chemie.

[12]  Z. Zou,et al.  Photodegradation performance of g-C3N4 fabricated by directly heating melamine. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[13]  Dan Xu,et al.  Oxygen electrocatalysts in metal-air batteries: from aqueous to nonaqueous electrolytes. , 2014, Chemical Society reviews.

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

[15]  Jun Chen,et al.  Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis , 2015, Nature Communications.

[16]  Yong Wang,et al.  In situ cobalt-cobalt oxide/N-doped carbon hybrids as superior bifunctional electrocatalysts for hydrogen and oxygen evolution. , 2015, Journal of the American Chemical Society.

[17]  Piotr Zelenay,et al.  Recent advances in non-precious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuel cells , 2011 .

[18]  Mietek Jaroniec,et al.  Nitrogen and Oxygen Dual‐Doped Carbon Hydrogel Film as a Substrate‐Free Electrode for Highly Efficient Oxygen Evolution Reaction , 2014, Advanced materials.

[19]  J. St-Pierre,et al.  Growth mechanism and active site probing of Fe3C@N-doped carbon nanotubes/C catalysts: guidance for building highly efficient oxygen reduction electrocatalysts , 2015 .

[20]  S. Bent,et al.  Active MnOx Electrocatalysts Prepared by Atomic Layer Deposition for Oxygen Evolution and Oxygen Reduction Reactions , 2012 .

[21]  Jun Chen,et al.  Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts. , 2011, Nature chemistry.

[22]  Zhiwei Peng,et al.  M3C (M: Fe, Co, Ni) Nanocrystals Encased in Graphene Nanoribbons: An Active and Stable Bifunctional Electrocatalyst for Oxygen Reduction and Hydrogen Evolution Reactions. , 2015, ACS nano.

[23]  Hua Zhang,et al.  Ni3S2 nanorods/Ni foam composite electrode with low overpotential for electrocatalytic oxygen evolution , 2013 .

[24]  W. Schuhmann,et al.  Mesoporous nitrogen-rich carbon materials as catalysts for the oxygen reduction reaction in alkaline solution. , 2012, ChemSusChem.

[25]  Qiang Zhang,et al.  Catalysis: Spatially Confined Hybridization of Nanometer-Sized NiFe Hydroxides into Nitrogen-Doped Graphene Frameworks Leading to Superior Oxygen Evolution Reactivity (Adv. Mater. 30/2015). , 2015, Advanced materials.

[26]  Xunyu Lu,et al.  Electrocatalytic oxygen evolution at surface-oxidized multiwall carbon nanotubes. , 2015, Journal of the American Chemical Society.

[27]  M. Nath,et al.  Nickel selenide as a high-efficiency catalyst for oxygen evolution reaction , 2015 .

[28]  Y. Liu,et al.  Multifunctional glucose biosensors from Fe3O4 nanoparticles modified chitosan/graphene nanocomposites , 2015, Scientific Reports.

[29]  G. Camino,et al.  Thermal behaviour of melamine , 1988 .

[30]  Dehui Deng,et al.  Single layer graphene encapsulating non-precious metals as high-performance electrocatalysts for water oxidation , 2016 .

[31]  Shaojun Guo,et al.  Bamboo-like carbon nanotube/Fe3C nanoparticle hybrids and their highly efficient catalysis for oxygen reduction. , 2015, Journal of the American Chemical Society.

[32]  X. Bao,et al.  Cobalt nanoparticles encapsulated in nitrogen-doped carbon as a bifunctional catalyst for water electrolysis , 2014 .

[33]  B. Dunn,et al.  Electrical Energy Storage for the Grid: A Battery of Choices , 2011, Science.

[34]  Yufan Zhang,et al.  N-doped graphitic layer encased cobalt nanoparticles as efficient oxygen reduction catalysts in alkaline media. , 2015, Nanoscale.

[35]  Guosong Hong,et al.  Advanced zinc-air batteries based on high-performance hybrid electrocatalysts , 2013, Nature Communications.

[36]  Changpeng Liu,et al.  Meso/Macroporous Nitrogen‐Doped Carbon Architectures with Iron Carbide Encapsulated in Graphitic Layers as an Efficient and Robust Catalyst for the Oxygen Reduction Reaction in Both Acidic and Alkaline Solutions , 2015, Advanced materials.

[37]  Mietek Jaroniec,et al.  Metal-organic framework derived hybrid Co3O4-carbon porous nanowire arrays as reversible oxygen evolution electrodes. , 2014, Journal of the American Chemical Society.

[38]  A. B. Fuertes,et al.  Meso/Macroporous Carbon Monoliths from Polymeric Foams , 2004 .

[39]  Shun Mao,et al.  Metal−Organic Framework‐Derived Nitrogen‐Doped Core‐Shell‐Structured Porous Fe/Fe3C@C Nanoboxes Supported on Graphene Sheets for Efficient Oxygen Reduction Reactions , 2014 .

[40]  Pingwu Du,et al.  Catalysts made of earth-abundant elements (Co, Ni, Fe) for water splitting: Recent progress and future challenges , 2012 .

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

[42]  Bing Li,et al.  Mussel-inspired one-pot synthesis of transition metal and nitrogen co-doped carbon (M/N-C) as efficient oxygen catalysts for Zn-air batteries. , 2016, Nanoscale.

[43]  Xin-bo Zhang,et al.  An efficient three-dimensional oxygen evolution electrode. , 2013, Angewandte Chemie.

[44]  Qiang Zhang,et al.  Spatially Confined Hybridization of Nanometer‐Sized NiFe Hydroxides into Nitrogen‐Doped Graphene Frameworks Leading to Superior Oxygen Evolution Reactivity , 2015, Advanced materials.

[45]  Li Jin,et al.  Iron encapsulated within pod-like carbon nanotubes for oxygen reduction reaction. , 2013, Angewandte Chemie.

[46]  Jianrong Qiu,et al.  Synthesis and luminescence mechanism of multicolor-emitting g-C3N4 nanopowders by low temperature thermal condensation of melamine , 2013, Scientific Reports.