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Title: Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces

Journal Article · · Science
 [1];  [2];  [3];  [3];  [3];  [4];  [2];  [2];  [5];  [5];  [6];  [6];  [7];  [2];  [3];  [8];  [2]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Tsinghua Univ., Beijing (China)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Univ. of Wisconsin, Madison, WI (United States)
  6. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  7. Tsinghua Univ., Beijing (China)
  8. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); King Abdulaziz Univ., Jeddah (Saudia Arabia)

Control of structure at the atomic level can precisely and effectively tune catalytic properties of materials, enabling enhancement in both activity and durability. We synthesized a highly active and durable class of electrocatalysts by exploiting the structural evolution of platinum-nickel (Pt-Ni) bimetallic nanocrystals. The starting material, crystalline PtNi3 polyhedra, transforms in solution by interior erosion into Pt3Ni nanoframes with surfaces that offer three-dimensional molecular accessibility. The edges of the Pt-rich PtNi3 polyhedra are maintained in the final Pt3Ni nanoframes. Both the interior and exterior catalytic surfaces of this open-framework structure are composed of the nanosegregated Pt-skin structure, which exhibits enhanced oxygen reduction reaction (ORR) activity. The Pt3Ni nanoframe catalysts achieved a factor of 36 enhancement in mass activity and a factor of 22 enhancement in specific activity, respectively, for this reaction (relative to state-of-the-art platinum-carbon catalysts) during prolonged exposure to reaction conditions.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1227053
Journal Information:
Science, Vol. 343, Issue 6177; ISSN 0036-8075
Publisher:
AAAS
Country of Publication:
United States
Language:
English

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Formation of Co 3 O 4 microframes from MOFs with enhanced electrochemical performance for lithium storage and water oxidation journal January 2016
Preparation of hollow PtCu nanoparticles as high-performance electrocatalysts for oxygen reduction reaction in the absence of a surfactant journal January 2016
Highly uniform distribution of Pt nanoparticles on N-doped hollow carbon spheres with enhanced durability for oxygen reduction reaction journal January 2017
Bimetallic Cu–Pd alloy multipods and their highly electrocatalytic performance for formic acid oxidation and oxygen reduction journal January 2017
Toward rational nanoparticle synthesis: predicting surface intermixing in bimetallic alloy nanocatalysts journal January 2017
Surface and interface design for heterogeneous catalysis journal January 2019
A self-supported nanoporous PtGa film as an efficient multifunctional electrocatalyst for energy conversion journal January 2018
The OH -driven synthesis of Pt–Ni nanocatalysts with atomic segregation for alkaline hydrogen evolution reaction journal January 2019
Efficient oxygen reduction on sandwich-like metal@N–C composites with ultrafine Fe nanoparticles embedded in N-doped carbon nanotubes grafted on graphene sheets journal January 2019
Oxidatively induced exposure of active surface area during microwave assisted formation of Pt 3 Co nanoparticles for oxygen reduction reaction journal January 2019
Pt-rare earth metal alloy/metal oxide catalysts for oxygen reduction and alcohol oxidation reactions: an overview journal January 2019
Effect of surface-bound sulfide on oxygen reduction reaction on Pt: Breaking the scaling relationship and mechanistic insights journal January 2019
Catalyst design by scanning probe block copolymer lithography journal March 2018
Integration mesoporous surface and hollow cavity into PtPdRh nano-octahedra for enhanced oxygen reduction electrocatalysis journal October 2019
Tailoring Catalyst Morphology towards High Performance for Low Pt Loaded PEMFC Cathodes journal January 2018
Controlled Synthesis of PtNi Hexapods for Enhanced Oxygen Reduction Reaction journal October 2018
Monodispersed Pt3Ni Nanoparticles as a Highly Efficient Electrocatalyst for PEMFCs journal July 2019
Superaerophilic Carbon-Nanotube-Array Electrode for High-Performance Oxygen Reduction Reaction journal June 2016
Well-Dispersed ZIF-Derived Co,N-Co-doped Carbon Nanoframes through Mesoporous-Silica-Protected Calcination as Efficient Oxygen Reduction Electrocatalysts journal December 2015
One-Pot Synthesis of Highly Anisotropic Five-Fold-Twinned PtCu Nanoframes Used as a Bifunctional Electrocatalyst for Oxygen Reduction and Methanol Oxidation journal August 2016
Porous Tetrametallic PtCuBiMn Nanosheets with a High Catalytic Activity and Methanol Tolerance Limit for Oxygen Reduction Reactions journal December 2016
Confining the Nucleation of Pt to In Situ Form (Pt-Enriched Cage)@CeO 2 Core@Shell Nanostructure as Excellent Catalysts for Hydrogenation Reactions journal June 2017
Self-Templated Fabrication of MoNi 4 /MoO 3- x Nanorod Arrays with Dual Active Components for Highly Efficient Hydrogen Evolution journal August 2017
A Large-Scale Graphene-Bimetal Film Electrode with an Ultrahigh Mass Catalytic Activity for Durable Water Splitting journal May 2018
Earth-Abundant Nanomaterials for Oxygen Reduction journal December 2015
Bamboo‐Like Nitrogen‐Doped Carbon Nanotubes with Co Nanoparticles Encapsulated at the Tips: Uniform and Large‐Scale Synthesis and High‐Performance Electrocatalysts for Oxygen Reduction journal August 2015
Mesoporous PtCu Alloy Nanoparticles with Tunable Compositions and Particles Sizes Using Diblock Copolymer Micelle Templates journal November 2018
Coating Pt-Ni Octahedra with Ultrathin Pt Shells to Enhance the Durability without Compromising the Activity toward Oxygen Reduction journal July 2016
Boosting Alkaline Hydrogen Evolution Electrocatalysis over Metallic Nickel Sites through Synergistic Coupling with Vanadium Sesquioxide journal November 2019
Electrochemical Scanning Probe Microscopies in Electrocatalysis journal November 2018
Fabrication of Superior Single‐Atom Catalysts toward Diverse Electrochemical Reactions journal February 2019
Key Structural Transformations and Kinetics of Pt Nanoparticles in PEFC Pt/C Electrocatalysts by a Simultaneous Operando Time-Resolved QXAFS–XRD Technique journal April 2018
Nanostructured electrocatalysts with tunable activity and selectivity journal March 2016
Anisotropic phase segregation and migration of Pt in nanocrystals en route to nanoframe catalysts journal August 2016
Electrochemical synthesis of fractal bimetallic Cu/Ag nanodendrites for efficient surface enhanced Raman spectroscopy journal January 2016
Fluorescence enhancement mediated by high-index-faceted Pt nanocrystals: roles of crystal structures journal January 2018
Porous Pt–NiO x nanostructures with ultrasmall building blocks and enhanced electrocatalytic activity for the ethanol oxidation reaction journal January 2018
Boosting the oxygen evolution reaction performance of CoS 2 microspheres by subtle ionic liquid modification journal January 2018
Alloy-composition-dependent oxygen reduction reaction activity and electrochemical stability of Pt-based bimetallic systems: a model electrocatalyst study of Pt/Pt x Ni 100−x (111) journal January 2018
Hollow nanoparticles as emerging electrocatalysts for renewable energy conversion reactions journal January 2018
Synthesis of germanium–platinum nanoparticles as high-performance catalysts for spray-deposited large-area dye-sensitized solar cells (DSSC) and the hydrogen evolution reaction (HER) journal January 2018
Direct fabrication of bi-metallic PdRu nanorod assemblies for electrochemical ammonia synthesis journal January 2019
Carved nanoframes of cobalt–iron bimetal phosphide as a bifunctional electrocatalyst for efficient overall water splitting journal January 2019
Morphology evolution of fcc Ru nanoparticles under hydrogen atmosphere journal January 2019
Ultrasmall MoP encapsulated in nitrogen-doped carbon hybrid frameworks for highly efficient hydrogen evolution reaction in both acid and alkaline solutions journal January 2019
Rational design and synthesis of noble-metal nanoframes for catalytic and photonic applications journal September 2016
Atomic-level structure engineering of metal oxides for high-rate oxygen intercalation pseudocapacitance journal October 2018
Analysis of H 2 /Air Polarization Curves: The Influence of Low Pt Loading and Fabrication Process journal January 2018
Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles journal April 2018
Thermal Properties and Segregation Behavior of Pt Nanowires Modified with Au, Ag, and Pd Atoms: A Classical Molecular Dynamics Study journal July 2019
Atomically Resolved Anisotropic Electrochemical Shaping of Nano-electrocatalyst journal April 2019
Tuning the Electrocatalytic Performance of Ionic Liquid Modified Pt Catalysts for the Oxygen Reduction Reaction via Cationic Chain Engineering journal July 2018
On-Chip in Situ Monitoring of Competitive Interfacial Anionic Chemisorption as a Descriptor for Oxygen Reduction Kinetics journal April 2018
Dealloying of Nitrogen-Introduced Pt–Co Alloy Nanoparticles: Preferential Core–Shell Formation with Enhanced Activity for Oxygen Reduction Reaction journal December 2016
Exceptional Oxygen Reduction Reaction Activity and Durability of Platinum–Nickel Nanowires through Synthesis and Post-Treatment Optimization journal April 2017
Interfacial Structure of PtNi Surface Alloy on Pt(111) Electrode for Oxygen Reduction Reaction journal May 2017
Programming ORR Activity of Ni/NiOx@Pd Electrocatalysts via Controlling Depth of Surface-Decorated Atomic Pt Clusters journal August 2018
Facile Synthesis of PtCu Alloy/Graphene Oxide Hybrids as Improved Electrocatalysts for Alkaline Fuel Cells journal August 2018
In Situ Construction of Small Pt NPs Embedded in 3D Spherical Porous Carbon as an Electrocatalyst for Liquid Fuel Oxidation with High Performance journal December 2018
In situ inward epitaxial growth of bulk macroporous single crystals journal December 2017
A self-supporting bimetallic Au@Pt core-shell nanoparticle electrocatalyst for the synergistic enhancement of methanol oxidation journal July 2017
Recent developments of nano-structured materials as the catalysts for oxygen reduction reaction journal April 2018
Engineering Ru@Pt Core-Shell Catalysts for Enhanced Electrochemical Oxygen Reduction Mass Activity and Stability journal January 2018
Solution-Grown Dendritic Pt-Based Ternary Nanostructures for Enhanced Oxygen Reduction Reaction Functionality journal June 2018
Nanostructure Optimization of Platinum-Based Nanomaterials for Catalytic Applications journal November 2018
Direct Spectroscopy for Probing the Critical Role of Partial Covalency in Oxygen Reduction Reaction for Cobalt-Manganese Spinel Oxides journal April 2019

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