Curved Porous PdCu Metallene as a High-Efficiency Bifunctional Electrocatalyst for Oxygen Reduction and Formic Acid Oxidation.

Designing high-efficiency and newly developed Pd-based bifunctional catalytic materials still faces tremendous challenges for oxygen reduction reaction (ORR) and formic acid oxidation reaction (FAO). Metallene materials with unique structural features are considered strong candidates for enhancing the catalytic performance. In this work, we synthesized copper-doped two-dimensional curved porous Pd metallene nanomaterials via a simplistic one-pot solvothermal method. The updated catalysts served as sturdy bifunctional electrocatalysts for cathodal ORR and anodic FAO. In particular, the developed PdCu metallene exhibits excellent half-wave potential (0.943 V vs RHE) and mass activity (MA) (1.227 A mgPt-1) in alkaline solutions, which are 1.09 and 6.26 times higher than those of commercial Pt/C, respectively, indicating that the nanomaterials have abundant active sites, displaying surpassing catalytic performance for oxygen reduction. Furthermore, in an acidic formic acid electrolyte, PdCu metallene exhibits prominent MA with a value of 0.905 A mgPd-1, which is 2.76 times that of commercial Pd/C. The remarkable bifunctional catalytic performance of metallene materials can be attributed to the special structure and electronic effects. This work shows that metallene materials with curved and porous properties provide a scientific idea for the development and design of efficient and steady electrocatalysts.

[1]  Ziqiang Wang,et al.  Interfacial Polarization in Metal-Organic Framework Reconstructed Cu/Pd/CuOx Multi-Phase Heterostructures for Electrocatalytic Nitrate Reduction to Ammonia , 2022, Applied Catalysis B: Environmental.

[2]  J. Saleem,et al.  Recent Advances in Anode Electrocatalysts for Direct Formic Acid Fuel Cells – Part I – Fundamentals and Pd Based Catalysts , 2022, Chemical record.

[3]  Ying Zhang,et al.  Recent progress in low-dimensional palladium-based nanostructures for electrocatalysis and beyond , 2022, Coordination Chemistry Reviews.

[4]  Qinghua Zhang,et al.  Local Coordination Regulation through Tuning Atomic‐Scale Cavities of Pd Metallene toward Efficient Oxygen Reduction Electrocatalysis , 2022, Advanced materials.

[5]  M. Koper,et al.  How palladium inhibits CO poisoning during electrocatalytic formic acid oxidation and carbon dioxide reduction , 2022, Nature communications.

[6]  Mingliang Du,et al.  Sublayer Stable Fe Dopant in Porous Pd Metallene Boosts Oxygen Reduction Reaction. , 2021, ACS nano.

[7]  Shaojun Guo,et al.  Structural Regulation of Pd‐Based Nanoalloys for Advanced Electrocatalysis , 2021, Small Science.

[8]  W. Cao,et al.  Pd-based intermetallic nanocrystals: From precise synthesis to electrocatalytic applications in fuel cells , 2021 .

[9]  Xianwei Fu,et al.  Descriptors for the Evaluation of Electrocatalytic Reactions: d‐Band Theory and Beyond , 2021, Advanced Functional Materials.

[10]  Younan Xia,et al.  Facile Synthesis of Palladium‐Based Nanocrystals with Different Crystal Phases and a Comparison of Their Catalytic Properties , 2021, Advanced materials.

[11]  Mingliang Du,et al.  Hyper-dendritic PdZn nanocrystals as highly stable and efficient bifunctional electrocatalysts towards oxygen reduction and ethanol oxidation , 2021 .

[12]  T. Gemming,et al.  In Situ Fabrication of Freestanding Single‐Atom‐Thick 2D Metal/Metallene and 2D Metal/ Metallene Oxide Membranes: Recent Developments , 2021, Advanced science.

[13]  Zhigang Geng,et al.  Doping regulation in transition metal compounds for electrocatalysis. , 2021, Chemical Society reviews.

[14]  A. Müller,et al.  Pulsed Laser in Liquids Made Nanomaterials for Catalysis. , 2021, Chemical reviews.

[15]  Jong‐Min Lee,et al.  Metallenes as functional materials in electrocatalysis. , 2021, Chemical Society reviews.

[16]  G. Zeng,et al.  Stabilizing Pt‐Based Electrocatalysts for Oxygen Reduction Reaction: Fundamental Understanding and Design Strategies , 2021, Advanced materials.

[17]  D. Brett,et al.  Palladium alloys used as electrocatalysts for the oxygen reduction reaction , 2021 .

[18]  Sean C. Smith,et al.  Template-Directed Rapid Synthesis of Pd-Based Ultrathin Porous Intermetallic Nanosheets for Efficient Oxygen Reduction. , 2021, Angewandte Chemie.

[19]  Xiaonian Li,et al.  Defect-Rich Porous Pd Metallene for Enhanced Alkaline Oxygen Reduction Electrocatalysis. , 2021, Angewandte Chemie.

[20]  Shahid Zaman,et al.  Progress and Perspective on Oxygen Reduction Electrocatalysts toward Practical Fuel Cells. , 2021, Angewandte Chemie.

[21]  J. Nørskov,et al.  Tuning the electronic structure of Ag-Pd alloys to enhance performance for alkaline oxygen reduction , 2021, Nature Communications.

[22]  Shahid Zaman,et al.  Advanced Platinum-Based Oxygen Reduction Electrocatalysts for Fuel Cells. , 2021, Accounts of chemical research.

[23]  Dianqing Li,et al.  Recent Progress on Rational Design of Bimetallic Pd Based Catalysts and Their Advanced Catalysis , 2020 .

[24]  Zhongying Fang,et al.  Recent advances in formic acid electro-oxidation: from the fundamental mechanism to electrocatalysts , 2020, Nanoscale advances.

[25]  Ke Chen,et al.  Recent Progress of Palladium-Based Electrocatalysts for the Formic Acid Oxidation Reaction , 2020 .

[26]  Lai Xu,et al.  Hierarchical porous Rh nanosheets for methanol oxidation reaction , 2020 .

[27]  Wei Zhang,et al.  Achieve Superior Electrocatalytic Performance by Surface Copper Vacancy Defects during Electrochemical Etching Process. , 2020, Angewandte Chemie.

[28]  Venkata Surya Kumar Choutipalli,et al.  Bifunctional Electrocatalytic Activity of Ordered Intermetallics Based on Pd and Sn , 2020, Journal of Physical Chemistry C.

[29]  Zhenxing Feng,et al.  Oxygen Reduction Electrocatalysis on Ordered Intermetallic Pd–Bi Electrodes Is Enhanced by a Low Coverage of Spectator Species , 2020 .

[30]  Qinghua Zhang,et al.  Synthesis of PdM (M=Zn, Cd, ZnCd) Nanosheets with Unconventional Face-Centered Tetragonal Phase as Highly Efficient Electrocatalysts for Ethanol Oxidation. , 2019, ACS nano.

[31]  Yi Cui,et al.  Energy storage: The future enabled by nanomaterials , 2019, Science.

[32]  X. Lou,et al.  Engineering bunched Pt-Ni alloy nanocages for efficient oxygen reduction in practical fuel cells , 2019, Science.

[33]  Zhonglong Zhao,et al.  PdMo bimetallene for oxygen reduction catalysis , 2019, Nature.

[34]  Xiaoqing Pan,et al.  PtCuNi Tetrahedra Catalysts with Tailored Surfaces for Efficient Alcohol Oxidation. , 2019, Nano letters.

[35]  Dongdong Xu,et al.  One-pot aqueous synthesis of ultrathin trimetallic PdPtCu nanosheets for the electrooxidation of alcohols , 2019, Green Chemistry.

[36]  Yaming Liu,et al.  Engineering Surface Structure of Pt Nanoshells on Pd Nanocubes to Preferentially Expose Active Surfaces for ORR by Manipulating the Growth Kinetics. , 2019, Nano letters.

[37]  Y. Li,et al.  Direct chemical synthesis of ultrathin holey iron doped cobalt oxide nanosheets on nickel foam for oxygen evolution reaction , 2018, Nano Energy.

[38]  Chang Ming Li,et al.  Ir-Alloyed Ultrathin Ternary PdIrCu Nanosheet-Constructed Flower with Greatly Enhanced Catalytic Performance toward Formic Acid Electrooxidation. , 2018, ACS applied materials & interfaces.

[39]  Shichun Mu,et al.  Co2P–CoN Double Active Centers Confined in N‐Doped Carbon Nanotube: Heterostructural Engineering for Trifunctional Catalysis toward HER, ORR, OER, and Zn–Air Batteries Driven Water Splitting , 2018, Advanced Functional Materials.

[40]  Christopher L. Brown,et al.  Coordination of Atomic Co-Pt Coupling Species at Carbon Defects as Active Sites for Oxygen Reduction Reaction. , 2018, Journal of the American Chemical Society.

[41]  Ligui Li,et al.  Graphitic Nitrogen Is Responsible for Oxygen Electroreduction on Nitrogen-Doped Carbons in Alkaline Electrolytes: Insights from Activity Attenuation Studies and Theoretical Calculations , 2018, ACS Catalysis.

[42]  Lei Zhang,et al.  Synthesis of ultrathin wrinkle-free PdCu alloy nanosheets for modulating d-band electrons for efficient methanol oxidation , 2018 .

[43]  Yadong Li,et al.  Ultrathin Palladium Nanomesh for Electrocatalysis. , 2018, Angewandte Chemie.

[44]  Jonathan Hwang,et al.  Tuning Redox Transitions via Inductive Effect in Metal Oxides and Complexes, and Implications in Oxygen Electrocatalysis , 2017 .

[45]  Shaojun Guo,et al.  Strain-controlled electrocatalysis on multimetallic nanomaterials , 2017 .

[46]  Qiyuan He,et al.  Recent Advances in Ultrathin Two-Dimensional Nanomaterials. , 2017, Chemical reviews.

[47]  N. Zheng,et al.  Self-Supported 3D PdCu Alloy Nanosheets as a Bifunctional Catalyst for Electrochemical Reforming of Ethanol. , 2017, Small.

[48]  Jiujun Zhang,et al.  Nanostructured palladium catalyst poisoning depressed by cobalt phosphide in the electro-oxidation of formic acid for fuel cells , 2016 .

[49]  K. Jiang,et al.  Ordered PdCu-Based Nanoparticles as Bifunctional Oxygen-Reduction and Ethanol-Oxidation Electrocatalysts. , 2016, Angewandte Chemie.

[50]  Y. Lei,et al.  Electrospun interconnected Fe-N/C nanofiber networks as efficient electrocatalysts for oxygen reduction reaction in acidic media , 2015, Scientific Reports.

[51]  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.

[52]  Ioannis Katsounaros,et al.  Oxygen electrochemistry as a cornerstone for sustainable energy conversion. , 2014, Angewandte Chemie.

[53]  M. Osawa,et al.  Mechanism of the Electrocatalytic Oxidation of Formic Acid on Metals , 2012 .

[54]  U. B. Demirci,et al.  Theoretical means for searching bimetallic alloys as anode electrocatalysts for direct liquid-feed fuel cells , 2007 .

[55]  M. Watanabe,et al.  Electronic structures of Pt-Co and Pt-Ru alloys for CO-tolerant anode catalysts in polymer electrolyte fuel cells studied by EC-XPS. , 2006, The journal of physical chemistry. B.

[56]  Y. Park,et al.  XPS studies of superconducting Mo–Ru–Rh–Pd alloy , 2000 .

[57]  J. Nørskov,et al.  Surface electronic structure and reactivity of transition and noble metals , 1997 .

[58]  Ziqiang Wang,et al.  Phosphorus-triggered activation of PdPb nanoflowers for enhanced oxygen reduction electrocatalysis , 2022, Journal of Materials Chemistry A.

[59]  Xiaoqing Pan,et al.  Strong electrostatic adsorption approach to the synthesis of sub-three nanometer intermetallic platinum–cobalt oxygen reduction catalysts , 2021 .

[60]  Jian-Feng Li,et al.  Palladium-Coated Gold Nanoparticles with a Controlled Shell Thickness Used as Surface-Enhanced Raman Scattering Substrate , 2007 .