Enhanced oxygen reduction with single-atomic-site iron catalysts for a zinc-air battery and hydrogen-air fuel cell

Efficient, durable and inexpensive electrocatalysts that accelerate sluggish oxygen reduction reaction kinetics and achieve high-performance are highly desirable. Here we develop a strategy to fabricate a catalyst comprised of single iron atomic sites supported on a nitrogen, phosphorus and sulfur co-doped hollow carbon polyhedron from a metal-organic framework@polymer composite. The polymer-based coating facilitates the construction of a hollow structure via the Kirkendall effect and electronic modulation of an active metal center by long-range interaction with sulfur and phosphorus. Benefiting from structure functionalities and electronic control of a single-atom iron active center, the catalyst shows a remarkable performance with enhanced kinetics and activity for oxygen reduction in both alkaline and acid media. Moreover, the catalyst shows promise for substitution of expensive platinum to drive the cathodic oxygen reduction reaction in zinc-air batteries and hydrogen-air fuel cells.Development of fuel cells and metal-air batteries is hindered by electrocatalyst performance, which can be enhanced with uniform and atomically dispersed active sites. Here the authors report an iron-based electrocatalyst for oxygen reduction in cathodes for a zinc-air battery and a hydrogen-air fuel cell.

[1]  Yadong Li,et al.  Isolated Single Iron Atoms Anchored on N-Doped Porous Carbon as an Efficient Electrocatalyst for the Oxygen Reduction Reaction. , 2017, Angewandte Chemie.

[2]  A. Roßberg,et al.  Wavelet analysis of extended x-ray absorption fine structure data , 2005 .

[3]  Md. Ariful Hoque,et al.  Highly active and porous graphene encapsulating carbon nanotubes as a non-precious oxygen reduction electrocatalyst for hydrogen-air fuel cells , 2016 .

[4]  L. Gu,et al.  Interfacial electronic effects control the reaction selectivity of platinum catalysts. , 2016, Nature materials.

[5]  Jens K Nørskov,et al.  Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. , 2006, Angewandte Chemie.

[6]  Mato Knez,et al.  Monocrystalline spinel nanotube fabrication based on the Kirkendall effect , 2006, Nature materials.

[7]  Frédéric Jaouen,et al.  Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. , 2015, Nature materials.

[8]  Yadong Li,et al.  50 ppm of Pd dispersed on Ni(OH)2 nanosheets catalyzing semi-hydrogenation of acetylene with high activity and selectivity , 2018, Nano Research.

[9]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[10]  Hui Xie,et al.  Atomically Dispersed Iron-Nitrogen Species as Electrocatalysts for Bifunctional Oxygen Evolution and Reduction Reactions. , 2017, Angewandte Chemie.

[11]  Wavelet analysis of extended x-ray absorption fine structure data , 2005 .

[12]  Si Zhou,et al.  Metal–Organic‐Framework‐Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution , 2017, Advanced materials.

[13]  Mu Pan,et al.  Porosity-graded micro-porous layers for polymer electrolyte membrane fuel cells , 2007 .

[14]  Jun Yang,et al.  Hollow MOx-RuO2 (M = Co, Cu, Fe, Ni, CuNi) nanostructures as highly efficient electrodes for supercapacitors , 2016, Science China Materials.

[15]  Michael J. Workman,et al.  PGM-free Fe-N-C catalysts for oxygen reduction reaction: Catalyst layer design , 2016 .

[16]  J. Baek,et al.  Defect-Free Encapsulation of Fe0 in 2D Fused Organic Networks as a Durable Oxygen Reduction Electrocatalyst. , 2018, Journal of the American Chemical Society.

[17]  X. Lou,et al.  Carbon-Incorporated Nickel-Cobalt Mixed Metal Phosphide Nanoboxes with Enhanced Electrocatalytic Activity for Oxygen Evolution. , 2017, Angewandte Chemie.

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

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

[20]  L. Gu,et al.  A Polymer Encapsulation Strategy to Synthesize Porous Nitrogen‐Doped Carbon‐Nanosphere‐Supported Metal Isolated‐Single‐Atomic‐Site Catalysts , 2018, Advanced materials.

[21]  J. Hofkens,et al.  Dopant-induced electron localization drives CO2 reduction to C2 hydrocarbons , 2018, Nature Chemistry.

[22]  S. Liao,et al.  Ultra-high-performance doped carbon catalyst derived from o-phenylenediamine and the probable roles of Fe and melamine , 2014 .

[23]  A. B. Jorge,et al.  Fe-N-Doped Carbon Capsules with Outstanding Electrochemical Performance and Stability for the Oxygen Reduction Reaction in Both Acid and Alkaline Conditions. , 2016, ACS nano.

[24]  Hoon T. Chung,et al.  Active and stable carbon nanotube/nanoparticle composite electrocatalyst for oxygen reduction , 2013, Nature Communications.

[25]  G. Henkelman,et al.  A grid-based Bader analysis algorithm without lattice bias , 2009, Journal of physics. Condensed matter : an Institute of Physics journal.

[26]  Jun Chen,et al.  Defect electrocatalytic mechanism: concept, topological structure and perspective , 2018 .

[27]  J. Shui,et al.  Unveiling the high-activity origin of single-atom iron catalysts for oxygen reduction reaction , 2018, Proceedings of the National Academy of Sciences.

[28]  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.

[29]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[30]  Bin Wang,et al.  A Bimetallic Zn/Fe Polyphthalocyanine-Derived Single-Atom Fe-N4 Catalytic Site:A Superior Trifunctional Catalyst for Overall Water Splitting and Zn-Air Batteries. , 2018, Angewandte Chemie.

[31]  Xin Wang,et al.  A metal–organic framework-derived bifunctional oxygen electrocatalyst , 2016, Nature Energy.

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

[33]  H. Jónsson,et al.  Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode , 2004 .

[34]  Colin F. Dickens,et al.  Combining theory and experiment in electrocatalysis: Insights into materials design , 2017, Science.

[35]  D. R. Stull,et al.  JANAF Thermochemical Tables. Second Edition , 1971 .

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

[37]  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.

[38]  J. Behrends,et al.  On an Easy Way To Prepare Metal-Nitrogen Doped Carbon with Exclusive Presence of MeN4-type Sites Active for the ORR. , 2016, Journal of the American Chemical Society.

[39]  Chengzhou Zhu,et al.  Single-Atom Electrocatalysts. , 2017, Angewandte Chemie.

[40]  Hua Zhou,et al.  From Metal-Organic Frameworks to Single-Atom Fe Implanted N-doped Porous Carbons: Efficient Oxygen Reduction in Both Alkaline and Acidic Media. , 2018, Angewandte Chemie.

[41]  T. Hayakawa,et al.  High performance Pt-free cathode catalysts for polymer electrolyte membrane fuel cells prepared from widely available chemicals , 2014 .

[42]  M. Blume,et al.  Mössbauer Spectra in a Fluctuating Environment , 1968 .

[43]  Shuhong Yu,et al.  Nanowire-directed templating synthesis of metal-organic framework nanofibers and their derived porous doped carbon nanofibers for enhanced electrocatalysis. , 2014, Journal of the American Chemical Society.

[44]  Deborah J. Jones,et al.  Optimized synthesis of Fe/N/C cathode catalysts for PEM fuel cells: a matter of iron-ligand coordination strength. , 2013, Angewandte Chemie.

[45]  Eckert,et al.  Electron hopping in FeOCl intercalation compounds: A Mössbauer relaxation study. , 1985, Physical review. B, Condensed matter.

[46]  Yu Huang,et al.  General synthesis and definitive structural identification of MN4C4 single-atom catalysts with tunable electrocatalytic activities , 2018, Nature Catalysis.

[47]  Tao Zhang,et al.  Single-atom catalysts: a new frontier in heterogeneous catalysis. , 2013, Accounts of chemical research.

[48]  Yongping Zheng,et al.  Rational design of common transition metal-nitrogen-carbon catalysts for oxygen reduction reaction in fuel cells , 2016 .

[49]  S. Mukerjee,et al.  Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metal–nitrogen coordination , 2015, Nature Communications.

[50]  Lehui Lu,et al.  Transition metal–nitrogen–carbon nanostructured catalysts for the oxygen reduction reaction: From mechanistic insights to structural optimization , 2017, Nano Research.

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

[52]  Matthew Thorum,et al.  Poisoning the Oxygen Reduction Reaction on Carbon-Supported Fe and Cu Electrocatalysts: Evidence for Metal-Centered Activity , 2011 .

[53]  Liangti Qu,et al.  N,P-Codoped Carbon Networks as Efficient Metal-free Bifunctional Catalysts for Oxygen Reduction and Hydrogen Evolution Reactions. , 2016, Angewandte Chemie.

[54]  Shaojun Guo,et al.  Synergistic Effects between Atomically Dispersed Fe-N-C and C-S-C for the Oxygen Reduction Reaction in Acidic Media. , 2017, Angewandte Chemie.

[55]  Zhongwei Chen,et al.  A review on non-precious metal electrocatalysts for PEM fuel cells , 2011 .

[56]  S. Mukerjee,et al.  Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction , 2017, Nature Communications.

[57]  Weijia Zhou,et al.  Mesoporous N-doped carbons prepared with thermally removable nanoparticle templates: an efficient electrocatalyst for oxygen reduction reaction. , 2015, Journal of the American Chemical Society.

[58]  B. Wood,et al.  Graphene Defects Trap Atomic Ni Species for Hydrogen and Oxygen Evolution Reactions , 2018 .

[59]  M. Jaroniec,et al.  Origin of the Electrocatalytic Oxygen Reduction Activity of Graphene-Based Catalysts: A Roadmap to Achieve the Best Performance , 2014, Journal of the American Chemical Society.

[60]  Jing Wang,et al.  Highly doped and exposed Cu(I)–N active sites within graphene towards efficient oxygen reduction for zinc–air batteries , 2016 .

[61]  L. Wan,et al.  Understanding the High Activity of Fe-N-C Electrocatalysts in Oxygen Reduction: Fe/Fe3C Nanoparticles Boost the Activity of Fe-N(x). , 2016, Journal of the American Chemical Society.

[62]  Yao Zheng,et al.  Design of electrocatalysts for oxygen- and hydrogen-involving energy conversion reactions. , 2015, Chemical Society reviews.

[63]  Piotr Zelenay,et al.  A class of non-precious metal composite catalysts for fuel cells , 2006, Nature.

[64]  Q. Wang,et al.  S-Doping of an Fe/N/C ORR Catalyst for Polymer Electrolyte Membrane Fuel Cells with High Power Density. , 2015, Angewandte Chemie.

[65]  Yadong Li,et al.  Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts. , 2016, Angewandte Chemie.

[66]  Z. Tang,et al.  Molecular architecture of cobalt porphyrin multilayers on reduced graphene oxide sheets for high-performance oxygen reduction reaction. , 2013, Angewandte Chemie.

[67]  Yanyong Wang,et al.  N, P-dual doped carbon with trace Co and rich edge sites as highly efficient electrocatalyst for oxygen reduction reaction , 2018, Science China Materials.

[68]  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.

[69]  Richard F. W. Bader A quantum theory of molecular structure and its applications , 1991 .

[70]  Min Gyu Kim,et al.  A General Approach to Preferential Formation of Active Fe-Nx Sites in Fe-N/C Electrocatalysts for Efficient Oxygen Reduction Reaction. , 2016, Journal of the American Chemical Society.

[71]  Md. Ariful Hoque,et al.  Co-N Decorated Hierarchically Porous Graphene Aerogel for Efficient Oxygen Reduction Reaction in Acid. , 2016, ACS applied materials & interfaces.

[72]  Md. Ariful Hoque,et al.  In Situ Polymer Graphenization Ingrained with Nanoporosity in a Nitrogenous Electrocatalyst Boosting the Performance of Polymer‐Electrolyte‐Membrane Fuel Cells , 2017, Advanced materials.

[73]  P. Strasser,et al.  Nanostructured electrocatalysts with tunable activity and selectivity , 2016 .

[74]  H. Jeong,et al.  Carbon nanotubes/heteroatom-doped carbon core-sheath nanostructures as highly active, metal-free oxygen reduction electrocatalysts for alkaline fuel cells. , 2014, Angewandte Chemie.

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

[76]  M. Mavrikakis,et al.  Catalytically active Au-O(OH)x- species stabilized by alkali ions on zeolites and mesoporous oxides , 2014, Science.

[77]  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.