Electrocatalytic Oxygen Reduction Reaction by the Pd/Fe-N-C Catalyst and Application in a Zn–Air Battery

Developing a non-platinum catalyst that effectively catalyzes the oxygen reduction reaction (ORR) is highly significant for metal–air batteries. Metal and nitrogen co-doped carbons (M-N-Cs) have emerged as alternative candidates to platinum. In this work, dual-metal Pd/Fe-N-C electrocatalysts were synthesized by the one-step pyrolysis of phytic acid, melamine, and Pd/Fe-based salts. The Pd/Fe-N-C catalyst exhibited a good catalytic ability during the ORR process and outperformed the commercial Pt/C catalyst as regards mass activity, catalytic stability, and methanol tolerance. It was found that Pd-Nx is the active center, and the synergistic effect from the Fe component introduction endowed the Pd/Fe-N-C with an excellent catalytic performance towards the ORR. When assembled into a Zn–air battery, its specific capacity was ~775 mAh gZn−1. Meanwhile, the peak power density could reach 3.85 W mgPd−1, i.e., 3.4 times that of the commercial Pt/C catalyst (1.13 W mgPt−1). This implies that the Pd/Fe-N-C catalyst has potential applications in metal–air batteries.

[1]  S. Dou,et al.  Electrocatalytic Oxygen Reduction to Produce Hydrogen Peroxide: Rational Design from Single-Atom Catalysts to Devices , 2022, Electrochemical Energy Reviews.

[2]  P. Dong,et al.  Vanadium Nitride Supported on N-Doped Carbon as High-Performance ORR Catalysts for Zn–Air Batteries , 2022, Catalysts.

[3]  Haiou Song,et al.  Single-atom palladium anchored N-doped carbon towards oxygen electrocatalysis for rechargeable Zn-air batteries. , 2022, Dalton transactions.

[4]  Chao Feng,et al.  A doping-adsorption-pyrolysis strategy for constructing atomically dispersed cobalt sites anchored on a N-doped carbon framework as an efficient bifunctional electrocatalyst for hydrogen evolution and oxygen reduction , 2022, RSC advances.

[5]  Chenxiang Sun,et al.  Understanding the active sites of Fe–N–C materials and their properties in the ORR catalysis system , 2022, RSC advances.

[6]  Jeong‐Gil Kim,et al.  Hierarchical porous single-wall carbon nanohorns with atomic-level designed single-atom Co sites toward oxygen reduction reaction , 2022, Nano Energy.

[7]  Huolin L. Xin,et al.  Altering Ligand Fields in Single-Atom Sites through Second-Shell Anion Modulation Boosts the Oxygen Reduction Reaction. , 2022, Journal of the American Chemical Society.

[8]  Yinghan Wang,et al.  Recent Advances in ZIF-Derived Atomic Metal-N-C Electrocatalysts for Oxygen Reduction Reaction: Synthetic Strategies, Active Centers, and Stabilities. , 2022, Small.

[9]  Xundao Liu,et al.  Fe/Co/N–C/graphene derived from Fe/ZIF-67/graphene oxide three dimensional frameworks as a remarkably efficient and stable catalyst for the oxygen reduction reaction , 2022, RSC advances.

[10]  Hanxue Sun,et al.  Synthesis and electrocatalytic properties of M (Fe, Co),N co-doped porous carbon frameworks for efficient oxygen reduction reaction , 2022, International Journal of Hydrogen Energy.

[11]  Hongyan Xi,et al.  Research Progress of Asymmetrically Coordinated Single-Atom Catalysts for Electrocatalytic Reactions , 2022, Journal of Materials Chemistry A.

[12]  Chang-feng Yan,et al.  Three-Dimensional Ordered Honeycomb Nanostructure Anchored with Pt-N Active Sites via Self-Assembly of Block Copolymer: An Efficient Electrocatalyst towards Oxygen Reduction Reaction in Fuel Cells , 2022, Journal of Materials Chemistry A.

[13]  Jiye Fang,et al.  Nanoscale Design of Pd‐Based Electrocatalysts for Oxygen Reduction Reaction Enhancement in Alkaline Media , 2021, Small Structures.

[14]  Ming Liu,et al.  A “Pre‐Constrained Metal Twins” Strategy to Prepare Efficient Dual‐Metal‐Atom Catalysts for Cooperative Oxygen Electrocatalysis , 2021, Advanced materials.

[15]  Jiahao Wu,et al.  Enhanced oxygen reduction with carbon-polyhedron-supported discrete cobalt-nitrogen sites for Zn-air batteries , 2021, Chemical Engineering Journal.

[16]  Zhenxing Feng,et al.  Improving Pd–N–C fuel cell electrocatalysts through fluorination-driven rearrangements of local coordination environment , 2021, Nature Energy.

[17]  Xiangcun Li,et al.  Well-defined Fe–Cu diatomic sites for efficient catalysis of CO2 electroreduction , 2021, Journal of Materials Chemistry A.

[18]  Yuxiang Chen,et al.  Interfacing spinel NiCo2O4 and NiCo alloy derived N-doped carbon nanotubes for enhanced oxygen electrocatalysis , 2021 .

[19]  Xiyou Li,et al.  The cobalt carbide/bimetallic CoFe phosphide dispersed on carbon nanospheres as advanced bifunctional electrocatalysts for the ORR, OER, and rechargeable Zn-air batteries. , 2021, Journal of colloid and interface science.

[20]  Xuan Sun,et al.  A highly efficient bifunctional electrocatalyst (ORR/OER) derived from GO functionalized with carbonyl, hydroxyl and epoxy groups for rechargeable zinc–air batteries , 2021 .

[21]  Shingo Tanaka,et al.  Boosting the electrocatalytic activity of Pd/C by Cu alloying: Insight on Pd/Cu composition and reaction pathway. , 2020, Journal of colloid and interface science.

[22]  Evan C. Wegener,et al.  Performance enhancement and degradation mechanism identification of a single-atom Co–N–C catalyst for proton exchange membrane fuel cells , 2020, Nature Catalysis.

[23]  D. M. Fernandes,et al.  Cu and Pd nanoparticles supported on a graphitic carbon material as bifunctional HER/ORR electrocatalysts , 2020 .

[24]  Dequan Xiao,et al.  Highly active sites of low spin FeIIN4 species: The identification and the ORR performance , 2020, Nano Research.

[25]  G. Fu,et al.  Embedded PdFe@N-carbon nanoframes for oxygen reduction in acidic fuel cells , 2020 .

[26]  Yanghua He,et al.  Atomically dispersed metal-nitrogen-carbon catalysts for fuel cells: advances in catalyst design, electrode performance, and durability improvement. , 2020, Chemical Society reviews.

[27]  Mao-wen Xu,et al.  Highly efficient Fe-N-C oxygen reduction electrocatalyst engineered by sintering atmosphere , 2020 .

[28]  Daolan Liu,et al.  Recent Advances in Carbon‐Based Bifunctional Oxygen Catalysts for Zinc‐Air Batteries , 2019, Batteries & Supercaps.

[29]  Haibo Li,et al.  Pd(II)/Ni(II)-dimethylglyoxime derived Pd‒Ni‒P@N-doped carbon hybrid nanocatalysts for oxygen reduction reaction , 2019, Applied Surface Science.

[30]  R. Che,et al.  Yolk-Shell Fe/Fe4 N@Pd/C Magnetic Nanocomposite as an Efficient Recyclable ORR Electrocatalyst and SERS Substrate. , 2019, Small.

[31]  A. Aricò,et al.  Methanol-Tolerant M–N–C Catalysts for Oxygen Reduction Reactions in Acidic Media and Their Application in Direct Methanol Fuel Cells , 2018, Catalysts.

[32]  Yuhan Sun,et al.  Palladium single atoms supported by interwoven carbon nanotube and manganese oxide nanowire networks for enhanced electrocatalysis , 2018 .

[33]  Zidong Wei,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.

[34]  Wei Chen,et al.  The Marriage of the FeN4 Moiety and MXene Boosts Oxygen Reduction Catalysis: Fe 3d Electron Delocalization Matters , 2018, Advanced materials.

[35]  Zhen Liu,et al.  Oxygen Reduction Reaction and Hydrogen Evolution Reaction Catalyzed by Pd–Ru Nanoparticles Encapsulated in Porous Carbon Nanosheets , 2018, Catalysts.

[36]  Jinlong Yang,et al.  Fe, Cu‐Coordinated ZIF‐Derived Carbon Framework for Efficient Oxygen Reduction Reaction and Zinc–Air Batteries , 2018, Advanced Functional Materials.

[37]  Xiaobin Fan,et al.  Rational Design of Fe/N/S-Doped Nanoporous Carbon Catalysts from Covalent Triazine Frameworks for Efficient Oxygen Reduction. , 2018, ChemSusChem.

[38]  Jun Hu,et al.  In Situ Incorporation Strategy for Bimetallic FeCo‐Doped Carbon as Highly Efficient Bifunctional Oxygen Electrocatalysts , 2018 .

[39]  S. Jeon,et al.  The individual role of pyrrolic, pyridinic and graphitic nitrogen in the growth kinetics of Pd NPs on N-rGO followed by a comprehensive study on ORR , 2018 .

[40]  D. Su,et al.  Microporous Framework Induced Synthesis of Single-Atom Dispersed Fe-N-C Acidic ORR Catalyst and Its in Situ Reduced Fe-N4 Active Site Identification Revealed by X-ray Absorption Spectroscopy , 2018 .

[41]  W. Wu,et al.  Oxygen Reduction Reaction Catalyzed by Noble Metal Clusters , 2018 .

[42]  L. Gu,et al.  Isolated Fe and Co dual active sites on nitrogen-doped carbon for a highly efficient oxygen reduction reaction. , 2018, Chemical communications.

[43]  Chang Q. Sun,et al.  DFT Study on Intermetallic Pd–Cu Alloy with Cover Layer Pd as Efficient Catalyst for Oxygen Reduction Reaction , 2017, Materials.

[44]  Yadong Li,et al.  Design of N-Coordinated Dual-Metal Sites: A Stable and Active Pt-Free Catalyst for Acidic Oxygen Reduction Reaction. , 2017, Journal of the American Chemical Society.

[45]  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.

[46]  Shuihua Tang,et al.  High performance ORR electrocatalysts prepared via one-step pyrolysis of riboflavin , 2017 .

[47]  Shengli Chen,et al.  An Fe–N–C hybrid electrocatalyst derived from a bimetal–organic framework for efficient oxygen reduction , 2016 .

[48]  Yuanjian Zhang,et al.  Quantifying the density and utilization of active sites in non-precious metal oxygen electroreduction catalysts , 2015, Nature Communications.

[49]  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.

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

[51]  V. Gunasekar,et al.  Carbon-supported Pd–Fe electrocatalysts for oxygen reduction reaction (ORR) and their methanol tolerance , 2011 .