Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts

Tough core-shell catalysts One approach for increasing the activity of precious metals in catalysis is to coat them onto less expensive earth-abundant transition metal cores such as nickel, but often these structures alloy and deactivate during reactions. Hunt et al. synthesized several types of transition metal carbide nanoparticles coated with atomically thin precious-metal shells. Titanium-doped tungsten carbide nanoparticles with platinum-ruthenium shells were highly active for methanol electrooxidation, stable over 10,000 cycles, and resistant to CO deactivation. Science, this issue p. 974 Transition metal carbide nanoparticles coated with noble metal monolayers resist CO poisoning during catalysis. We demonstrated the self-assembly of transition metal carbide nanoparticles coated with atomically thin noble metal monolayers by carburizing mixtures of noble metal salts and transition metal oxides encapsulated in removable silica templates. This approach allows for control of the final core-shell architecture, including particle size, monolayer coverage, and heterometallic composition. Carbon-supported Ti0.1W0.9C nanoparticles coated with Pt or bimetallic PtRu monolayers exhibited enhanced resistance to sintering and CO poisoning, achieving an order of magnitude increase in specific activity over commercial catalysts for methanol electrooxidation after 10,000 cycles. These core-shell materials provide a new direction to reduce the loading, enhance the activity, and increase the stability of noble metal catalysts.

[1]  Xiaoge Xu,et al.  Trends in Electrochemical Stability of Transition Metal Carbides and Their Potential Use As Supports for Low-Cost Electrocatalysts , 2014 .

[2]  Irene J. Hsu,et al.  Atomic layer deposition synthesis of platinum-tungsten carbide core-shell catalysts for the hydrogen evolution reaction. , 2012, Chemical communications.

[3]  Jason W. Zack,et al.  Oxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode Technique II. Influence of Ink Formulation, Catalyst Layer Uniformity and Thickness , 2015 .

[4]  Yuriy Román‐Leshkov,et al.  Alloying Tungsten Carbide Nanoparticles with Tantalum: Impact on Electrochemical Oxidation Resistance and Hydrogen Evolution Activity , 2015 .

[5]  W. Schottky Über spontane Stromschwankungen in verschiedenen Elektrizitätsleitern , 1918 .

[6]  Feng Tao,et al.  Reaction-Driven Restructuring of Rh-Pd and Pt-Pd Core-Shell Nanoparticles , 2008, Science.

[7]  A. Walsh,et al.  Surface Sensitivity in Lithium-Doping of MgO: A Density Functional Theory Study with Correction for on-Site Coulomb Interactions , 2007 .

[8]  T. Kikegawa,et al.  A high-pressure and high-temperature synthesis of platinum carbide , 2005 .

[9]  Qiang Xu,et al.  Synergistic Catalysis over Bimetallic Alloy Nanoparticles , 2013 .

[10]  Yuriy Román-Leshkov,et al.  Engineering non-sintered, metal-terminated tungsten carbide nanoparticles for catalysis. , 2014, Angewandte Chemie.

[11]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[12]  R. E. Watson,et al.  Electronic Structure and Catalytic Behavior of Tungsten Carbide , 1974, Science.

[13]  Manos Mavrikakis,et al.  Ru-Pt core-shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen. , 2008, Nature materials.

[14]  A. Bell The Impact of Nanoscience on Heterogeneous Catalysis , 2003, Science.

[15]  Jason W. Zack,et al.  Oxygen Reduction Reaction Measurements on Platinum Electrocatalysts Utilizing Rotating Disk Electrode Technique I. Impact of Impurities, Measurement Protocols and Applied Corrections , 2015 .

[16]  Lin Gan,et al.  Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis. , 2013, Nature materials.

[17]  Karren L. More,et al.  Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces , 2014, Science.

[18]  R. Kötz,et al.  Determination of the Electrochemically Active Surface Area of Metal-Oxide Supported Platinum Catalyst , 2014 .

[19]  Hong Yang,et al.  Platinum-based electrocatalysts with core-shell nanostructures. , 2011, Angewandte Chemie.

[20]  Ib Chorkendorff,et al.  Understanding the electrocatalysis of oxygen reduction on platinum and its alloys , 2012 .

[21]  G. Jackson,et al.  PtSn intermetallic, core-shell, and alloy nanoparticles as CO-tolerant electrocatalysts for H2 oxidation. , 2010, Angewandte Chemie.

[22]  S. Oyama,et al.  The Chemistry of Transition Metal Carbides and Nitrides , 1996 .

[23]  Andrew J. Medford,et al.  Departures from the Adsorption Energy Scaling Relations for Metal Carbide Catalysts , 2014 .

[24]  Jingguang G. Chen,et al.  Comparison of O−H, C−H, and C−O Bond Scission Sequence of Methanol on Tungsten Carbide Surfaces Modified by Ni, Rh, and Au , 2011 .

[25]  Charles C. L. McCrory,et al.  Benchmarking hydrogen evolving reaction and oxygen evolving reaction electrocatalysts for solar water splitting devices. , 2015, Journal of the American Chemical Society.

[26]  Jingguang G. Chen,et al.  A new class of electrocatalysts for hydrogen production from water electrolysis: metal monolayers supported on low-cost transition metal carbides. , 2012, Journal of the American Chemical Society.

[27]  Manos Mavrikakis,et al.  Alkali-Stabilized Pt-OHx Species Catalyze Low-Temperature Water-Gas Shift Reactions , 2010, Science.

[28]  Jingguang G. Chen,et al.  Low-cost hydrogen-evolution catalysts based on monolayer platinum on tungsten monocarbide substrates. , 2010, Angewandte Chemie.

[29]  X. Verykios,et al.  Renewable Hydrogen from Ethanol by Autothermal Reforming , 2004, Science.

[30]  Jens K. Nørskov,et al.  Electronic factors determining the reactivity of metal surfaces , 1995 .

[32]  Jacques Jupille,et al.  Stability of rocksalt (111) polar surfaces: beyond the octopole. , 2004, Physical review letters.

[33]  Morikawa,et al.  CO chemisorption at metal surfaces and overlayers. , 1996, Physical review letters.

[34]  A S Bondarenko,et al.  Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. , 2009, Nature chemistry.

[35]  K. Ayers,et al.  Ultralow charge-transfer resistance with ultralow Pt loading for hydrogen evolution and oxidation using Ru@Pt core-shell nanocatalysts , 2015, Scientific Reports.

[36]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[37]  Xinhua Liang,et al.  Atomic layer deposited highly dispersed platinum nanoparticles supported on non-functionalized multiwalled carbon nanotubes for the hydrogenation of xylose to xylitol , 2013, Journal of Nanoparticle Research.

[38]  Jingguang G. Chen,et al.  Monolayer platinum supported on tungsten carbides as low-cost electrocatalysts: opportunities and limitations , 2011 .

[39]  Joshua A. Schaidle,et al.  On the preparation of molybdenum carbide-supported metal catalysts , 2012 .

[40]  Michael F Toney,et al.  Lattice-strain control of the activity in dealloyed core-shell fuel cell catalysts. , 2010, Nature chemistry.

[41]  H. Gasteiger,et al.  Methanol electrooxidation on a colloidal PtRu-alloy fuel-cell catalyst , 1999 .

[42]  M. Chi,et al.  Platinum-based nanocages with subnanometer-thick walls and well-defined, controllable facets , 2015, Science.

[43]  Aron Walsh,et al.  Electronic Chemical Potentials of Porous Metal–Organic Frameworks , 2014, Journal of the American Chemical Society.

[44]  P. Shen,et al.  Nanosized tungsten carbide synthesized by a novel route at low temperature for high performance electrocatalysis , 2013, Scientific Reports.

[45]  K. Sasaki,et al.  Stabilization of Platinum Oxygen-Reduction Electrocatalysts Using Gold Clusters , 2007, Science.

[46]  R. Behm,et al.  Composition and activity of high surface area PtRu catalysts towards adsorbed CO and methanol electrooxidation: A DEMS study , 2002 .

[47]  H. Gasteiger,et al.  Characterization of High‐Surface‐Area Electrocatalysts Using a Rotating Disk Electrode Configuration , 1998 .

[48]  Yuriy Román‐Leshkov,et al.  Reverse Microemulsion-mediated Synthesis of Monometallic and Bimetallic Early Transition Metal Carbide and Nitride Nanoparticles. , 2015, Journal of visualized experiments : JoVE.

[49]  Karren L. More,et al.  Correlation Between Surface Chemistry and Electrocatalytic Properties of Monodisperse PtxNi1‐x Nanoparticles , 2011 .

[50]  Lin Gan,et al.  Comparative Study of the Electrocatalytically Active Surface Areas (ECSAs) of Pt Alloy Nanoparticles Evaluated by Hupd and CO-stripping voltammetry , 2014, Electrocatalysis.

[51]  Katherine C. Elbert,et al.  Elucidating Hydrogen Oxidation/Evolution Kinetics in Base and Acid by Enhanced Activities at the Optimized Pt Shell Thickness on the Ru Core , 2015 .

[52]  Thomas Bligaard,et al.  Trends in the exchange current for hydrogen evolution , 2005 .

[53]  Hubert A. Gasteiger,et al.  Hydrogen Oxidation and Evolution Reaction Kinetics on Carbon Supported Pt, Ir, Rh, and Pd Electrocatalysts in Acidic Media , 2015 .

[54]  Shouheng Sun,et al.  Monodisperse core/shell Ni/FePt nanoparticles and their conversion to Ni/Pt to catalyze oxygen reduction. , 2014, Journal of the American Chemical Society.

[55]  Cheng Hao Wu,et al.  Thermal Stability of Core–Shell Nanoparticles: A Combined in Situ Study by XPS and TEM , 2015 .

[56]  M. Boudart,et al.  Platinum-Like Behavior of Tungsten Carbide in Surface Catalysis , 1973, Science.