One-pot aqueous synthesis of two-dimensional porous bimetallic PtPd alloyed nanosheets as highly active and durable electrocatalyst for boosting oxygen reduction and hydrogen evolution.

Recently, two-dimensional materials have gained increasing research attention due to their large surface area, high physical and chemical stability, and excellent electrocatalytic performances. Herein, we reported a simple and fast one-pot aqueous method for synthesis of two-dimensional porous bimetallic PtPd alloyed nanosheets (NSs) using benzyldimethylhexadecylammonium chloride (HDBAC) as the capping agent and stabilizer. The formation mechanism involved the oriented attachment and self-assembly. The PtPd NSs exhibited excellent oxygen reduction reaction (ORR) activity with the positive shift (c.a. 43 mV) of the half-wave potential in 0.1 M KOH solution, clearly outperforming that of commercial Pt/C (50 wt%). Moreover, the as-prepared catalyst displayed 2.4 times enlargement in mass activity (MA, 382.10 mA mg-1) and 3.5 times enhancement in specific activity (SA, 0.95 mA cm-2) relative to those of Pt/C at 0.80 V. Meanwhile, the as-obtained catalyst demonstrated highly boosted hydrogen evolution reaction (HER) in 0.5 M H2SO4 electrolyte, surpassing that of Pt/C. These results reveal the practical applications of the catalyst in energy storage and conversion.

[1]  S. Shahrokhian,et al.  Vertically standing Cu2O nanosheets promoted flower-like PtPd nanostructures supported on reduced graphene oxide for methanol electro-oxidation , 2018 .

[2]  Shaojun Guo,et al.  Design of Ultrathin Pt-Based Multimetallic Nanostructures for Efficient Oxygen Reduction Electrocatalysis. , 2017, Small.

[3]  Kai-Chin Wang,et al.  Synthesis of Pd@Pt3Co/C core–shell structure as catalyst for oxygen reduction reaction in proton exchange membrane fuel cell , 2017 .

[4]  Xiliang Luo,et al.  Facile synthesis of porous dendritic Pt68Ag32 nanodandelions for greatly boosting electrocatalytic activity towards oxygen reduction and hydrogen evolution , 2018 .

[5]  Junhua Yuan,et al.  One-step hydrothermal synthesis of three-dimensional nitrogen-doped reduced graphene oxide hydrogels anchored PtPd alloyed nanoparticles for ethylene glycol oxidation and hydrogen evolution reactions , 2019, Electrochimica Acta.

[6]  M. Willander,et al.  Highly catalytic active PtNiCu nanochains for hydrogen evolution reaction , 2014 .

[7]  Li Zhang,et al.  Photo-Promoted Platinum Nanoparticles Decorated MoS2@Graphene Woven Fabric Catalyst for Efficient Hydrogen Generation. , 2016, ACS applied materials & interfaces.

[8]  Hong Chen,et al.  2D WS2 nanosheet supported Pt nanoparticles for enhanced hydrogen evolution reaction , 2017 .

[9]  Yaxiang Lu,et al.  Three-dimensional catalyst electrodes based on PtPd nanodendrites for oxygen reduction reaction in PEFC applications , 2016 .

[10]  O. Park,et al.  Zigzag-Shaped Silver Nanoplates: Synthesis via Ostwald Ripening and Their Application in Highly Sensitive Strain Sensors. , 2018, ACS applied materials & interfaces.

[11]  Vishal M. Dhavale,et al.  Nitrogen-doped graphene anchored with mixed growth patterns of CuPt alloy nanoparticles as a highly efficient and durable electrocatalyst for the oxygen reduction reaction in an alkaline medium. , 2017, Nanoscale.

[12]  Zhenqin Li,et al.  Scalable preparation of PtPd/carbon nanowires in the form of membrane as highly stable electrocatalysts for oxygen reduction reaction , 2019, International Journal of Hydrogen Energy.

[13]  E. Wang,et al.  Highly efficient hydrogen evolution from seawater by a low-cost and stable CoMoP@C electrocatalyst superior to Pt/C , 2017 .

[14]  I. Sharp,et al.  Structurally Deformed MoS2 for Electrochemically Stable, Thermally Resistant, and Highly Efficient Hydrogen Evolution Reaction , 2017, Advanced materials.

[15]  C. Jin,et al.  Facile synthesis of Rh-Pd alloy nanodendrites as highly active and durable electrocatalysts for oxygen reduction reaction. , 2014, Nanoscale.

[16]  S. Dong,et al.  Shape-Control of Pt-Ru Nanocrystals: Tuning Surface Structure for Enhanced Electrocatalytic Methanol Oxidation. , 2018, Journal of the American Chemical Society.

[17]  Chao Yan,et al.  Two-dimensional nanosheets for electrocatalysis in energy generation and conversion , 2017 .

[18]  Limin Wang,et al.  Phytic Acid-Assisted Formation of Hierarchical Porous CoP/C Nanoboxes for Enhanced Lithium Storage and Hydrogen Generation. , 2018, ACS nano.

[19]  G. Fu,et al.  One-Pot Water-Based Synthesis of Pt–Pd Alloy Nanoflowers and Their Superior Electrocatalytic Activity for the Oxygen Reduction Reaction and Remarkable Methanol-Tolerant Ability in Acid Media , 2013 .

[20]  K. Yuan,et al.  Synergetic Contribution of Boron and Fe–Nx Species in Porous Carbons toward Efficient Electrocatalysts for Oxygen Reduction Reaction , 2018 .

[21]  Yawen Tang,et al.  One‐Pot Synthesis of Freestanding Porous Palladium Nanosheets as Highly Efficient Electrocatalysts for Formic Acid Oxidation , 2017 .

[22]  Jianguo Wang,et al.  PtPd alloy embedded in nitrogen-rich graphene nanopores: High-performance bifunctional electrocatalysts for hydrogen evolution and oxygen reduction , 2017 .

[23]  J. Nørskov,et al.  Understanding Catalytic Activity Trends in the Oxygen Reduction Reaction. , 2018, Chemical reviews.

[24]  Kai Zhou,et al.  Core–Shell Nanocomposites Based on Gold Nanoparticle@Zinc–Iron-Embedded Porous Carbons Derived from Metal–Organic Frameworks as Efficient Dual Catalysts for Oxygen Reduction and Hydrogen Evolution Reactions , 2016 .

[25]  Zhong‐Yong Yuan,et al.  Applications of hierarchically structured porous materials from energy storage and conversion, catalysis, photocatalysis, adsorption, separation, and sensing to biomedicine. , 2016, Chemical Society reviews.

[26]  Su‐Un Lee,et al.  Ultrathin Free-Standing Ternary-Alloy Nanosheets. , 2016, Angewandte Chemie.

[27]  Shaojun Guo,et al.  Ultrathin PtPd‐Based Nanorings with Abundant Step Atoms Enhance Oxygen Catalysis , 2018, Advanced materials.

[28]  X. Lou,et al.  Formation of Single‐Holed Cobalt/N‐Doped Carbon Hollow Particles with Enhanced Electrocatalytic Activity toward Oxygen Reduction Reaction in Alkaline Media , 2017, Advanced science.

[29]  H. Gong,et al.  The synergistic effect of Ceria and Co in N-doped leaf-like carbon nanosheets derived from a 2D MOF and their enhanced performance in the oxygen reduction reaction. , 2018, Chemical communications.

[30]  S. Joo,et al.  A facet-controlled Rh3Pb2S2 nanocage as an efficient and robust electrocatalyst toward the hydrogen evolution reaction. , 2018, Nanoscale.

[31]  J. Kozlova,et al.  Oxygen Electroreduction on Electrodeposited PdAu Nanoalloys , 2014, Electrocatalysis.

[32]  Guang Yang,et al.  Halide ion-induced formation of single crystalline mesoporous PtPd bimetallic nanoparticles with hollow interiors for electrochemical methanol and ethanol oxidation reaction , 2017, Nano Research.

[33]  Qi Shao,et al.  Multicomponent Pt-Based Zigzag Nanowires as Selectivity Controllers for Selective Hydrogenation Reactions. , 2018, Journal of the American Chemical Society.

[34]  Siyi Zhou,et al.  One-pot synthesis of platinum–palladium–cobalt alloyed nanoflowers with enhanced electrocatalytic activity for ethylene glycol oxidation , 2015 .

[35]  T. Napporn,et al.  Facile synthesis of highly active and durable PdM/C (M = Fe, Mn) nanocatalysts for the oxygen reduction reaction in an alkaline medium , 2016 .

[36]  A. Frenkel,et al.  Hydrogen-evolution catalysts based on non-noble metal nickel-molybdenum nitride nanosheets. , 2012, Angewandte Chemie.

[37]  Y. Jiao,et al.  Emerging Two-Dimensional Nanomaterials for Electrocatalysis. , 2018, Chemical reviews.

[38]  K. Fang,et al.  One-pot surfactant-free synthesis of porous PtAu alloyed nanoflowers with enhanced electrocatalytic activity for ethanol oxidation and oxygen reduction reactions , 2016 .

[39]  Hong-Yan Chen,et al.  One-pot wet-chemical synthesis of uniform AuPtPd nanodendrites as efficient electrocatalyst for boosting hydrogen evolution and oxygen reduction reactions , 2018, International Journal of Hydrogen Energy.

[40]  Zachary D. Hood,et al.  A facile, robust and scalable method for the synthesis of Pd nanoplates with hydroxylamine as a reducing agent and mechanistic insights from kinetic analysis , 2018 .

[41]  Zhiyuan Zeng,et al.  Growth of noble metal nanoparticles on single-layer TiS2 and TaS2 nanosheets for hydrogen evolution reaction , 2014 .

[42]  Joseph M. McLellan,et al.  Kinetically controlled synthesis of triangular and hexagonal nanoplates of palladium and their SPR/SERS properties. , 2005, Journal of the American Chemical Society.

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

[44]  K. Fang,et al.  Melamine-assisted solvothermal synthesis of PtNi nanodentrites as highly efficient and durable electrocatalyst for hydrogen evolution reaction. , 2018, Journal of colloid and interface science.

[45]  E. M. Ahmed,et al.  Reduced graphene oxide nanosheets decorated with Au, Pd and Au–Pd bimetallic nanoparticles as highly efficient catalysts for electrochemical hydrogen generation , 2015 .

[46]  Fan Xu,et al.  Non‐Noble Metal‐based Carbon Composites in Hydrogen Evolution Reaction: Fundamentals to Applications , 2017, Advanced materials.

[47]  G. Jiang,et al.  Fluorographene as a Mass Spectrometry Probe for High-Throughput Identification and Screening of Emerging Chemical Contaminants in Complex Samples. , 2017, Analytical chemistry.

[48]  Jinghong Li,et al.  In Situ Coupling of CoP Polyhedrons and Carbon Nanotubes as Highly Efficient Hydrogen Evolution Reaction Electrocatalyst. , 2017, Small.

[49]  Yiqi Luo,et al.  Mesoporous Pd@Ru Core-Shell Nanorods for Hydrogen Evolution Reaction in Alkaline Solution. , 2018, ACS applied materials & interfaces.

[50]  M. Arenz,et al.  Benchmarking high surface area electrocatalysts in a gas diffusion electrode: measurement of oxygen reduction activities under realistic conditions , 2018 .

[51]  Junhua Yuan,et al.  Hollow Ag44Pt56 nanotube bundles with high electrocatalytic performances for hydrogen evolution and ethylene glycol oxidation reactions. , 2018, Journal of colloid and interface science.

[52]  Wei Chen,et al.  Graphene nanosheet-tailored PtPd concave nanocubes with enhanced electrocatalytic activity and durability for methanol oxidation. , 2014, Nanoscale.

[53]  Tadele Hunde Wondimu,et al.  High catalytic activity of oxygen-vacancy-rich tungsten oxide nanowires supported by nitrogen-doped reduced graphene oxide for the hydrogen evolution reaction , 2018 .

[54]  Victor Malgras,et al.  One-Step Synthesis of Dendritic Bimetallic PtPd Nanoparticles on Reduced Graphene Oxide and Its Electrocatalytic Properties , 2016 .

[55]  Lijuan Wang,et al.  Research advances in unsupported Pt-based catalysts for electrochemical methanol oxidation , 2017 .