A metal-free ORR/OER bifunctional electrocatalyst derived from metal-organic frameworks for rechargeable Zn-Air batteries

Abstract Rechargeable Zn-air batteries are under intensive studies because of their high-energy density, low cost, and safety. However, their wide application is prevented by several remaining technical issues, one of which is the lack of suitable bifunctional cathodic catalysts for oxygen reduction reaction (ORR) during discharging and oxygen evolution reaction (OER) during charging. Due to low material cost and wide distribution, carbon-based materials may serve as promising electrocatalysts, while doping heteroatoms such as nitrogen or boron can effectively enhance their catalytic activity. Herein, we pyrolyze a metal-organic framework containing Zn, N, and B as the precursor to synthesize dual-doped and metal-free porous carbon materials as efficient ORR/OER bifunctional electrocatalysts. The surface area of obtained carbon materials can be greatly enhanced by pyrolysis under H 2 -containing atmosphere. In addition, N and B are evenly distributed within the carbon materials due to the crystalline MOF precursor. The resultant carbon materials exhibit high ORR and OER catalytic activities in both half-cell and single-cell battery measurements. Our study has demonstrated for the first time that MOFs can be used as precursors to synthesize metal-free ORR/OER bifunctional cathodic electrocatalysts with great potential in rechargeable Zn-air batteries.

[1]  M. P. Kumar,et al.  Bifunctional Electrocatalytic Activity of Boron‐Doped Graphene Derived from Boron Carbide , 2015 .

[2]  P. Fulvio,et al.  Nitrogen-enriched ordered mesoporous carbons through direct pyrolysis in ammonia with enhanced capacitive performance , 2013 .

[3]  C. Shi,et al.  Study of Mg powder as catalyst carrier for the carbon nanotube growth by CVD , 2011 .

[4]  G. Hu,et al.  Formation of active sites for oxygen reduction reactions by transformation of nitrogen functionalities in nitrogen-doped carbon nanotubes. , 2012, ACS nano.

[5]  P. Feng,et al.  Porous metal carboxylate boron imidazolate frameworks. , 2010, Angewandte Chemie.

[6]  B. Liu,et al.  Two-dimensional metal-organic framework with wide channels and responsive turn-on fluorescence for the chemical sensing of volatile organic compounds. , 2014, Journal of the American Chemical Society.

[7]  S. Woo,et al.  Additional doping of phosphorus and/or sulfur into nitrogen-doped carbon for efficient oxygen reduction reaction in acidic media. , 2013, Physical chemistry chemical physics : PCCP.

[8]  Mietek Jaroniec,et al.  Graphitic carbon nitride nanosheet-carbon nanotube three-dimensional porous composites as high-performance oxygen evolution electrocatalysts. , 2014, Angewandte Chemie.

[9]  J. Nørskov,et al.  Atomic-scale imaging of carbon nanofibre growth , 2004, Nature.

[10]  Xi‐Wen Du,et al.  N‐Doped Graphene Natively Grown on Hierarchical Ordered Porous Carbon for Enhanced Oxygen Reduction , 2013, Advanced materials.

[11]  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 .

[12]  Lei Zhu,et al.  Boron-doped carbon nanotubes as metal-free electrocatalysts for the oxygen reduction reaction. , 2011, Angewandte Chemie.

[13]  Tomoki Akita,et al.  From metal-organic framework to nanoporous carbon: toward a very high surface area and hydrogen uptake. , 2011, Journal of the American Chemical Society.

[14]  A. Manthiram,et al.  Performance and stability of Pd–Pt–Ni nanoalloy electrocatalysts in proton exchange membrane fuel cells , 2011 .

[15]  Shengqian Ma,et al.  Heat-treatment of metal–organic frameworks for green energy applications , 2015 .

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

[17]  Hui Li,et al.  Highly active and durable core-corona structured bifunctional catalyst for rechargeable metal-air battery application. , 2011, Nano letters.

[18]  Freek Kapteijn,et al.  Visualizing MOF Mixed Matrix Membranes at the Nanoscale: Towards Structure‐Performance Relationships in CO2/CH4 Separation Over NH2‐MIL‐53(Al)@PI , 2014 .

[19]  Xizhang Wang,et al.  Can boron and nitrogen co-doping improve oxygen reduction reaction activity of carbon nanotubes? , 2013, Journal of the American Chemical Society.

[20]  Min Han,et al.  Nitrogen-doped Fe/Fe3C@graphitic layer/carbon nanotube hybrids derived from MOFs: efficient bifunctional electrocatalysts for ORR and OER. , 2015, Chemical communications.

[21]  Wei Xia,et al.  Metal–organic frameworks and their derived nanostructures for electrochemical energy storage and conversion , 2015 .

[22]  X. Lou,et al.  Porous Fe2O3 nanocubes derived from MOFs for highly reversible lithium storage , 2013 .

[23]  Yayuan Liu,et al.  Mesoporous Metal–Organic Frameworks with Size‐, Shape‐, and Space‐Distribution‐Controlled Pore Structure , 2015, Advanced materials.

[24]  L. Ferrighi,et al.  Boosting Graphene Reactivity with Oxygen by Boron Doping: Density Functional Theory Modeling of the Reaction Path. , 2014 .

[25]  H. Zhou,et al.  Metal-organic frameworks (MOFs). , 2014, Chemical Society reviews.

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

[27]  T. Mallouk,et al.  Microporous brookite-phase titania made by replication of a metal-organic framework. , 2013, Journal of the American Chemical Society.

[28]  Jian Liu,et al.  Thermal conversion of core-shell metal-organic frameworks: a new method for selectively functionalized nanoporous hybrid carbon. , 2015, Journal of the American Chemical Society.

[29]  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.

[30]  Michael O’Keeffe,et al.  Exceptional chemical and thermal stability of zeolitic imidazolate frameworks , 2006, Proceedings of the National Academy of Sciences.

[31]  Meilin Liu,et al.  Recent Progress in Non‐Precious Catalysts for Metal‐Air Batteries , 2012 .

[32]  Xin Wang,et al.  General formation of complex tubular nanostructures of metal oxides for the oxygen reduction reaction and lithium-ion batteries. , 2013, Angewandte Chemie.

[33]  Jianguo Liu,et al.  Boron Doped Multi-walled Carbon Nanotubes as Catalysts for Oxygen Reduction Reaction and Oxygen Evolution Reactionin in Alkaline Media , 2014 .

[34]  F. Rodríguez-Reinoso,et al.  Effect of steam and carbon dioxide activation in the micropore size distribution of activated carbon , 1996 .

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

[36]  Lipeng Zhang,et al.  Mechanisms of Oxygen Reduction Reaction on Nitrogen-Doped Graphene for Fuel Cells , 2011 .

[37]  Dan Zhao,et al.  Highly efficient photocatalysts by pyrolyzing a Zn–Ti heterometallic metal–organic framework , 2016 .

[38]  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.

[39]  Dan Zhao,et al.  Metal-organic frameworks (MOFs) as precursors towards TiOx/C composites for photodegradation of organic dye , 2014 .

[40]  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.

[41]  Lauren R. Grabstanowicz,et al.  Highly efficient nonprecious metal catalyst prepared with metal–organic framework in a continuous carbon nanofibrous network , 2015, Proceedings of the National Academy of Sciences.

[42]  Michael O'Keeffe,et al.  Porous, Crystalline, Covalent Organic Frameworks , 2005, Science.

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

[44]  Y. Shao-horn,et al.  Synthesis and Activities of Rutile IrO2 and RuO2 Nanoparticles for Oxygen Evolution in Acid and Alkaline Solutions. , 2012, The journal of physical chemistry letters.

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

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

[47]  L. Burke,et al.  Mechanism of oxygen reactions at porous oxide electrodes. Part 1.—Oxygen evolution at RuO2 and RuxSn1–xO2 electrodes in alkaline solution under vigorous electrolysis conditions , 1987 .

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

[49]  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.

[50]  Ludwig Jörissen,et al.  Bifunctional oxygen/air electrodes , 2006 .

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

[52]  P. Ajayan,et al.  Design Considerations for Unconventional Electrochemical Energy Storage Architectures , 2015 .

[53]  M. Kitis,et al.  Reductive leaching of manganese and zinc from spent alkaline and zinc–carbon batteries in acidic media , 2009 .

[54]  Hao Gong,et al.  Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction , 2012 .

[55]  Jihye Park,et al.  Metal–Organic Frameworks as Biomimetic Catalysts , 2014 .

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

[57]  Shuo Chen,et al.  High-yield electrosynthesis of hydrogen peroxide from oxygen reduction by hierarchically porous carbon. , 2015, Angewandte Chemie.

[58]  Xiaopeng Zeng,et al.  Preparation of single- and few-layer graphene sheets using co deposition on SiC substrate , 2011 .

[59]  Xiulei Ji,et al.  Pyrolysis of cellulose under ammonia leads to nitrogen-doped nanoporous carbon generated through methane formation. , 2014, Nano letters.

[60]  Dan Zhao,et al.  The current status of hydrogen storage in metal–organic frameworks , 2008 .

[61]  M. Titirici,et al.  Carbon aerogels from bacterial nanocellulose as anodes for lithium ion batteries , 2014 .

[62]  Jung-Ki Park,et al.  Perfluorosulfonic acid-functionalized Pt/graphene as a high-performance oxygen reduction reaction catalyst for proton exchange membrane fuel cells , 2013, Journal of Solid State Electrochemistry.

[63]  Gengfeng Zheng,et al.  Reduced Mesoporous Co3O4 Nanowires as Efficient Water Oxidation Electrocatalysts and Supercapacitor Electrodes , 2014 .

[64]  Hongjie Dai,et al.  Recent advances in zinc-air batteries. , 2014, Chemical Society reviews.

[65]  Gengfeng Zheng,et al.  Electrocatalysis: Reduced Mesoporous Co3O4 Nanowires as Efficient Water Oxidation Electrocatalysts and Supercapacitor Electrodes (Adv. Energy Mater. 16/2014) , 2014 .

[66]  Tomoki Akita,et al.  Platinum dissolution and deposition in the polymer electrolyte membrane of a PEM fuel cell as studied by potential cycling. , 2006, Physical chemistry chemical physics : PCCP.