Intermetallic Alloys as CO Electroreduction Catalysts—Role of Isolated Active Sites

One of the main challenges associated with the electrochemical CO or CO2 reduction is poor selectivity toward energetically rich products. In order to promote selectivity toward hydrocarbons and alcohols, most notably, the hydrogen evolution reaction (HER) should be suppressed. To achieve this goal, we studied intermetallic compounds consisting of transition metal (TM) elements that can reduce CO (Ru, Co, Rh, Ir, Ni, Pd, Pt, and Cu) separated by TM and post transition metal elements (Ag, Au, Cd, Zn, Hg, In, Sn, Pb, Sb, and Bi) that are very poor HER catalysts. In total, 34 different stable binary bulk alloys forming from these elements have been investigated using density functional theory calculations. The electronic and geometric properties of the catalyst surface can be tuned by varying the size of the active centers and the elements forming them. We have identified six different potentially selective intermetallic surfaces on which CO can be reduced to methanol at potentials comparable to or even slig...

[1]  Andrew A. Peterson,et al.  Activity Descriptors for CO2 Electroreduction to Methane on Transition-Metal Catalysts , 2012 .

[2]  Matthew W Kanan,et al.  CO2 reduction at low overpotential on Cu electrodes resulting from the reduction of thick Cu2O films. , 2012, Journal of the American Chemical Society.

[3]  H. Gasteiger,et al.  On the reaction pathway for methanol and carbon monoxide electrooxidation on Pt-Sn alloy versus Pt-Ru alloy surfaces , 1996 .

[4]  Jens K Nørskov,et al.  Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. , 2006, Angewandte Chemie.

[5]  Philip N. Ross,et al.  TEMPERATURE-DEPENDENT HYDROGEN ELECTROCHEMISTRY ON PLATINUM LOW-INDEX SINGLE-CRYSTAL SURFACES IN ACID SOLUTIONS , 1997 .

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

[7]  Anne C. Co,et al.  A review of the aqueous electrochemical reduction of CO2 to hydrocarbons at copper , 2006 .

[8]  A. Rappe,et al.  First-principles extrapolation method for accurate CO adsorption energies on metal surfaces , 2003, cond-mat/0310688.

[9]  R. Behm,et al.  The Role of Atomic Ensembles in the Reactivity of Bimetallic Electrocatalysts , 2001, Science.

[10]  Jens K. Nørskov,et al.  Monte Carlo simulations of adsorption-induced segregation , 2002 .

[11]  Manos Mavrikakis,et al.  Reactivity descriptors for direct methanol fuel cell anode catalysts , 2008 .

[12]  K. Jacobsen,et al.  Real-space grid implementation of the projector augmented wave method , 2004, cond-mat/0411218.

[13]  M. Koper,et al.  Electrochemical reduction of carbon dioxide on copper electrodes , 2017 .

[14]  Itai Panas,et al.  Single atom hot-spots at Au-Pd nanoalloys for electrocatalytic H2O2 production. , 2011, Journal of the American Chemical Society.

[15]  F. Abild‐Pedersen,et al.  CO adsorption energies on metals with correction for high coordination adsorption sites – A density functional study , 2007 .

[16]  Perspectives on the first principles elucidation and the design of active sites , 2003 .

[17]  P. Ross,et al.  Surface science studies of model fuel cell electrocatalysts , 2002 .

[18]  Ib Chorkendorff,et al.  Adsorption-driven surface segregation of the less reactive alloy component. , 2009, Journal of the American Chemical Society.

[19]  J Rossmeisl,et al.  Estimations of electric field effects on the oxygen reduction reaction based on the density functional theory. , 2007, Physical chemistry chemical physics : PCCP.

[20]  Jens K Nørskov,et al.  Understanding Trends in the Electrocatalytic Activity of Metals and Enzymes for CO2 Reduction to CO. , 2013, The journal of physical chemistry letters.

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

[22]  Ib Chorkendorff,et al.  Enabling direct H2O2 production through rational electrocatalyst design. , 2013, Nature materials.

[23]  Daniel L DuBois,et al.  Development of molecular electrocatalysts for CO2 reduction and H2 production/oxidation. , 2009, Accounts of chemical research.

[24]  A. Wiȩckowski,et al.  A first principles comparison of the mechanism and site requirements for the electrocatalytic oxidation of methanol and formic acid over Pt. , 2008, Faraday discussions.

[25]  J. M. García‐Lastra,et al.  Oxygen reduction and evolution at single-metal active sites: Comparison between functionalized graphitic materials and protoporphyrins , 2013 .

[26]  Georg Kresse,et al.  Significance of single-electron energies for the description of CO on Pt(111) , 2003 .

[27]  V. Stamenkovic,et al.  Enhanced electrocatalysis of the oxygen reduction reaction based on patterning of platinum surfaces with cyanide. , 2010, Nature chemistry.

[28]  Christopher D. Taylor,et al.  Calculated phase diagrams for the electrochemical oxidation and reduction of water over Pt(111). , 2006, The journal of physical chemistry. B.

[29]  Y. Hori,et al.  Electroreduction of carbon monoxide to methane and ethylene at a copper electrode in aqueous solutions at ambient temperature and pressure , 1987 .

[30]  Y. Hori,et al.  Electrochemical reduction of carbon dioxides to carbon monoxide at a gold electrode in aqueous potassium hydrogen carbonate , 1987 .

[31]  Ib Chorkendorff,et al.  Design of an active site towards optimal electrocatalysis: overlayers, surface alloys and near-surface alloys of Cu/Pt(111). , 2012, Angewandte Chemie.

[32]  Jingguang G. Chen,et al.  Experimental and theoretical investigation of the stability of Pt-3d-Pt(111) bimetallic surfaces under oxygen environment. , 2006, The journal of physical chemistry. B.

[33]  J. Nørskov,et al.  Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals , 1999 .

[34]  Katsuhei Kikuchi,et al.  Production of CO and CH4 in electrochemical reduction of CO2 at metal electrodes in aqueous hydrogencarbonate solution. , 1985 .

[35]  N. Lewis,et al.  Powering the planet: Chemical challenges in solar energy utilization , 2006, Proceedings of the National Academy of Sciences.

[36]  Thomas Bligaard,et al.  Modeling the Electrochemical Hydrogen Oxidation and Evolution Reactions on the Basis of Density Functional Theory Calculations , 2010 .

[37]  Hui Li,et al.  Electrochemical processing of carbon dioxide. , 2008, ChemSusChem.

[38]  H. Jónsson,et al.  Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode , 2004 .

[39]  T. Bligaard,et al.  Metal Oxide‐Supported Platinum Overlayers as Proton‐Exchange Membrane Fuel Cell Cathodes , 2012 .

[40]  M. Toney,et al.  Structure of Dealloyed PtCu3 Thin Films and Catalytic Activity for Oxygen Reduction , 2010 .

[41]  A. Gross,et al.  Surface strain versus substrate interaction in heteroepitaxial metal layers: Pt on Ru(0001). , 2003, Physical review letters.

[42]  A. Cuesta,et al.  At least three contiguous atoms are necessary for CO formation during methanol electrooxidation on platinum. , 2006, Journal of the American Chemical Society.

[43]  J. Nørskov,et al.  Towards the computational design of solid catalysts. , 2009, Nature chemistry.

[44]  J. Nørskov,et al.  Computational high-throughput screening of electrocatalytic materials for hydrogen evolution , 2006, Nature materials.

[45]  J. G. Chen,et al.  Role of strain and ligand effects in the modification of the electronic and chemical properties of bimetallic surfaces. , 2004, Physical review letters.

[46]  Akira Murata,et al.  PRODUCTION OF METHANE AND ETHYLENE IN ELECTROCHEMICAL REDUCTION OF CARBON DIOXIDE AT COPPER ELECTRODE IN AQUEOUS HYDROGENCARBONATE SOLUTION , 1986 .

[47]  Toshio Tsukamoto,et al.  Electrocatalytic process of CO selectivity in electrochemical reduction of CO2 at metal electrodes in aqueous media , 1994 .

[48]  Kristian Sommer Thygesen,et al.  Electrochemical CO2 and CO reduction on metal-functionalized porphyrin-like graphene , 2013 .

[49]  Andrew A. Peterson,et al.  How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels , 2010 .