Activity of Pdn (n = 1–5) Clusters on Alumina Film on Ni3Al(111) for CO Oxidation: A Molecular Beam Study

Single atom catalyst (SAC) is a vivid new area of research in catalysis. However, the activity in CO oxidation of isolated Pt or Pd atoms, generally supported on an oxide powder, is still controversial. Furthermore, the steady state activity of few atoms clusters is still not yet quantitatively known. In this work we study, by molecular beam reactive scattering (MBRS), the activity of Pdn (n= 1-5) clusters, grown on a nanostructured alumina films on a Ni3Al(111) surface. It is shown that the single atoms are not active at 473 K but they diffuse and coalesce at 533K forming larger clusters. The activity of a cluster is proportional to the number of atoms it contains (n=2-5). At 533 K, the activity per (surface-) atom, which is the turnover frequency (TOF), is constant. Its value is close to those obtained for large clusters of 181±13 atoms and Pd (111) extended surfaces, in the same experimental conditions.

[1]  R. Jinnouchi,et al.  CO oxidation activity of non-reducible oxide-supported mass-selected few-atom Pt single-clusters , 2020, Nature Communications.

[2]  C. Henry,et al.  Particle size effect on the Langmuir-Hinshelwood barrier for CO oxidation on regular arrays of Pd clusters supported on ultrathin alumina films. , 2019, Journal of Chemical Physics.

[3]  B. D. Kay,et al.  Low-Temperature Oxidation of Methanol to Formaldehyde on a Model Single-Atom Catalyst: Pd Atoms on Fe3O4(001) , 2019, ACS Catalysis.

[4]  A. Corma,et al.  Determination of the Evolution of Heterogeneous Single Metal Atoms and Nanoclusters under Reaction Conditions: Which Are the Working Catalytic Sites? , 2019, ACS catalysis.

[5]  C. Papp,et al.  Growth and stability of Pt nanoclusters from 1 to 50 atoms on h-BN/Rh(111). , 2019, Physical chemistry chemical physics : PCCP.

[6]  C. Henry,et al.  Regular Arrays of Pt Clusters on Alumina: A New Superstructure on Al2O3/Ni3Al(111) , 2019, The Journal of Physical Chemistry C.

[7]  P. Afanasiev,et al.  Dynamics of Single Pt Atoms on Alumina during CO Oxidation Monitored by Operando X-ray and Infrared Spectroscopies , 2019, ACS Catalysis.

[8]  Gianfranco Pacchioni,et al.  Structural evolution of atomically dispersed Pt catalysts dictates reactivity , 2019, Nature Materials.

[9]  Angelica D. Benavidez,et al.  CO oxidation by Pd supported on CeO2(100) and CeO2(111) facets , 2019, Applied Catalysis B: Environmental.

[10]  B. Bourguignon,et al.  Probing Nanoparticle Geometry down to Subnanometer Size: The Benefits of Vibrational Spectroscopy. , 2019, The journal of physical chemistry letters.

[11]  M. Pivetta,et al.  Direct capture and electrostatic repulsion in the self-assembly of rare-earth atom superlattices on graphene , 2018, Physical Review B.

[12]  U. Heiz,et al.  A Microscopy Approach to Investigating the Energetics of Small Supported Metal Clusters , 2018, The Journal of Physical Chemistry C.

[13]  T. Michely,et al.  A Monolayer of Hexagonal Boron Nitride on Ir(111) as a Template for Cluster Superlattices. , 2018, ACS nano.

[14]  Avelino Corma,et al.  Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles , 2018, Chemical reviews.

[15]  Rongming Wang,et al.  Stability investigation of a high number density Pt1/Fe2O3 single-atom catalyst under different gas environments by HAADF-STEM , 2018, Nanotechnology.

[16]  Xiaoqing Pan,et al.  Catalyst Architecture for Stable Single Atom Dispersion Enables Site-Specific Spectroscopic and Reactivity Measurements of CO Adsorbed to Pt Atoms, Oxidized Pt Clusters, and Metallic Pt Clusters on TiO2. , 2017, Journal of the American Chemical Society.

[17]  L. Allard,et al.  Ab Initio Density Functional Calculations and Infra-Red Study of CO Interaction with Pd Atoms on θ-Al2O3 (010) Surface , 2017, Scientific Reports.

[18]  C. Henry,et al.  Molecular Beam Study of the Oxidation of Carbon Monoxide on a Regular Array of Palladium Clusters on Alumina , 2017 .

[19]  T. Michely,et al.  Stability and Reactivity of Graphene-Templated Nanoclusters , 2016 .

[20]  P. Blaha,et al.  Dual role of CO in the stability of subnano Pt clusters at the Fe3O4(001) surface , 2016, Proceedings of the National Academy of Sciences.

[21]  C. Henry 2D‐Arrays of Nanoparticles as Model Catalysts , 2015 .

[22]  C. Henry 2D-Arrays of Nanoparticles as Model Catalysts , 2015, Catalysis Letters.

[23]  H. Yasumatsu,et al.  Size Dependence of Low-Temperature Catalytic Activity of CO Oxidation Driven by Platinum Clusters Directly Bound to Silicon Substrate Surface , 2015 .

[24]  C. Henry,et al.  Regular arrays of Pd and PdAu clusters on ultrathin alumina films for reactivity studies. , 2014, Physical chemistry chemical physics : PCCP.

[25]  Hua Guo,et al.  Low-temperature carbon monoxide oxidation catalysed by regenerable atomically dispersed palladium on alumina , 2014, Nature Communications.

[26]  S. Anderson,et al.  Mass-selected supported cluster catalysts: Size effects on CO oxidation activity, electronic structure, and thermal stability of Pdn/alumina (n ≤ 30) model catalysts , 2014 .

[27]  G. M. Stocks,et al.  CO oxidation on supported single Pt atoms: experimental and ab initio density functional studies of CO interaction with Pt atom on θ-Al2O3(010) surface. , 2013, Journal of the American Chemical Society.

[28]  Ulrike Diebold,et al.  Carbon monoxide-induced adatom sintering in a Pd-Fe3O4 model catalyst. , 2013, Nature materials.

[29]  F. Leroy,et al.  Transition from molecule to solid state: reactivity of supported metal clusters. , 2013, Nano letters.

[30]  Ulrike Diebold,et al.  CO Induced Adatom Sintering in a Model Catalyst: Pd/Fe3O4 , 2013, 1303.0664.

[31]  Xiaofeng Yang,et al.  Single-atom catalysis of CO oxidation using Pt1/FeOx. , 2011, Nature chemistry.

[32]  C. Henry,et al.  Kinetic Monte Carlo simulation of the growth of metal clusters on regular array of defects on insulator , 2010 .

[33]  D. Goodman,et al.  New insights into catalytic CO oxidation on Pt-group metals at elevated pressures , 2009 .

[34]  M Schmid,et al.  Nanotemplate with holes: ultrathin alumina on Ni3Al(111). , 2007, Physical review letters.

[35]  M. Arenz,et al.  Cluster chemistry: size-dependent reactivity induced by reverse spill-over. , 2007, Journal of the American Chemical Society.

[36]  K. Wandelt,et al.  Surface structure of an ultrathin alumina film on Ni3Al(111): a dynamic scanning force microscopy study. , 2006, Physical review letters.

[37]  A. Rosenhahn,et al.  Al2O3-films on Ni3Al(111): a template for nanostructured cluster growth , 2002 .

[38]  U. Landman,et al.  COI oxidation on a single Pd atom supported on magnesia. , 2001, Physical review letters.

[39]  A. Sánchez,et al.  Catalytic oxidation of carbon monoxide on monodispersed platinum clusters: Each atom counts , 1999 .

[40]  Gerhard Ertl,et al.  A molecular beam investigation of the catalytic oxidation of CO on Pd (111) , 1978 .

[41]  G. Stucky,et al.  Supplementary Material for Identification of active sites in CO oxidation and water-gas shift over supported Pt catalysts , 2015 .

[42]  张涛,et al.  Single-atom catalysis of CO oxidation using Pt1 FeOx , 2011 .