A Systematic Study on Bond Activation Energies of NO, N2, and O2 on Hexamers of Eight Transition Metals

Catalytic bond activation pathways of diatomic molecules on small metal clusters have been studied by density functional theory calculations. The focus of this study is dissociation of NO, N2, and O2 on hexamers of eight transition metals (Ni, Cu, Rh, Pd, Ag, Ir, Pt, and Au). For all the 24 cases, the lowest energy structures at the molecular‐adsorption state, bond dissociation transition state (TS), and dissociative‐adsorption state were identified by a systematic procedure. At TS of 20 cases, the transition metal hexamer moiety took a different shape from bare transition metal hexamers. The results support the importance of metastable cluster structures in catalytic activity, recently proposed in several catalytic systems. Furthermore, using the obtained dataset, a simple linear regression analysis was made to explore the applicability of the Brønsted‐Evans‐Polanyi principle to flexible metal cluster catalysts.

[1]  E. Jimenez-Izal,et al.  Computational Design of Clusters for Catalysis. , 2018, Annual review of physical chemistry.

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

[3]  Geng Sun,et al.  Metastable Structures in Cluster Catalysis from First-Principles: Structural Ensemble in Reaction Conditions and Metastability Triggered Reactivity. , 2018, Journal of the American Chemical Society.

[4]  Yosuke Sumiya,et al.  Implementation and performance of the artificial force induced reaction method in the GRRM17 program , 2017, J. Comput. Chem..

[5]  J. L. D. Da Silva,et al.  Evolution of the structural, energetic, and electronic properties of the 3d, 4d, and 5d transition-metal clusters (30 TMn systems for n = 2-15): a density functional theory investigation. , 2017, Physical chemistry chemical physics : PCCP.

[6]  S. Anderson,et al.  Ethylene Dehydrogenation on Pt4,7,8 Clusters on Al2O3: Strong Cluster Size Dependence Linked to Preferred Catalyst Morphologies , 2017 .

[7]  A. Alexandrova,et al.  Fluxionality of Catalytic Clusters: When It Matters and How to Address It , 2017 .

[8]  U. Landman,et al.  Structure sensitivity in the nonscalable regime explored via catalysed ethylene hydrogenation on supported platinum nanoclusters , 2016, Nature Communications.

[9]  Š. Vajda,et al.  Catalysis Applications of Size-Selected Cluster Deposition , 2015 .

[10]  K. Morokuma,et al.  Intrinsic reaction coordinate: Calculation, bifurcation, and automated search , 2015 .

[11]  Giannis Mpourmpakis,et al.  Understanding the Stability and Electronic and Adsorption Properties of Subnanometer Group XI Monometallic and Bimetallic Catalysts , 2014 .

[12]  T. Taketsugu,et al.  Application of Automated Reaction Path Search Methods to a Systematic Search of Single-Bond Activation Pathways Catalyzed by Small Metal Clusters: A Case Study on H-H Activation by Gold. , 2014, Journal of chemical theory and computation.

[13]  K. Koyasu,et al.  Nonscalable oxidation catalysis of gold clusters. , 2014, Accounts of chemical research.

[14]  T. Bligaard,et al.  On the Structure Sensitivity of Direct NO Decomposition over Low-Index Transition Metal Facets , 2014, Topics in Catalysis.

[15]  Jonathan E. Sutton,et al.  Brønsted–Evans–Polanyi and Transition State Scaling Relations of Furan Derivatives on Pd(111) and Their Relation to Those of Small Molecules , 2014 .

[16]  Š. Vajda,et al.  A first-principles theoretical approach to heterogeneous nanocatalysis. , 2012, Nanoscale.

[17]  J. Nørskov,et al.  Universal transition state scaling relations for (de)hydrogenation over transition metals. , 2011, Physical chemistry chemical physics : PCCP.

[18]  J. Nørskov,et al.  Universal Brønsted-Evans-Polanyi Relations for C–C, C–O, C–N, N–O, N–N, and O–O Dissociation Reactions , 2011 .

[19]  Thomas Bligaard,et al.  Density functional theory in surface chemistry and catalysis , 2011, Proceedings of the National Academy of Sciences.

[20]  Matthew Neurock,et al.  Reactivity theory of transition-metal surfaces: a Brønsted-Evans-Polanyi linear activation energy-free-energy analysis. , 2010, Chemical reviews.

[21]  L. Curtiss,et al.  Density Functional Studies of Methanol Decomposition on Subnanometer Pd Clusters , 2009 .

[22]  A. Baiker,et al.  Fluxionality of gold nanoparticles investigated by Born-Oppenheimer molecular dynamics , 2009 .

[23]  P. Sautet,et al.  Fast prediction of selectivity in heterogeneous catalysis from extended Brønsted-Evans-Polanyi relations: a theoretical insight. , 2009, Angewandte Chemie.

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

[25]  L. Curtiss,et al.  Subnanometre platinum clusters as highly active and selective catalysts for the oxidative dehydrogenation of propane. , 2009, Nature materials.

[26]  Britta Redlich,et al.  Structures of Neutral Au7, Au19, and Au20 Clusters in the Gas Phase , 2008, Science.

[27]  A. Corma,et al.  On the activation of molecular hydrogen by gold: a theoretical approximation to the nature of potential active sites. , 2007, Chemical communications.

[28]  J. Fierro,et al.  A density functional theory study of the dissociation of H2 on gold clusters: importance of fluxionality and ensemble effects. , 2006, The Journal of chemical physics.

[29]  T. Walsh,et al.  Structural isomers and reactivity for Rh6 and Rh6+. , 2006, The journal of physical chemistry. B.

[30]  Hansong Cheng,et al.  Rate constants for dissociative chemisorption of hydrogen molecules on copper clusters , 2006 .

[31]  F. Weigend,et al.  Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. , 2005, Physical chemistry chemical physics : PCCP.

[32]  Hansong Cheng,et al.  Evolution of small copper clusters and dissociative chemisorption of hydrogen. , 2005, Physical review letters.

[33]  Thomas Bligaard,et al.  The Brønsted–Evans–Polanyi relation and the volcano curve in heterogeneous catalysis , 2004 .

[34]  Masatake Haruta,et al.  When gold is not noble: catalysis by nanoparticles. , 2003, Chemical record.

[35]  J. Nørskov,et al.  Universality in Heterogeneous Catalysis , 2002 .

[36]  P. Calaminici,et al.  Structure and stability of small copper clusters , 2002 .

[37]  Søren Dahl,et al.  The Brønsted-Evans-Polanyi relation and the volcano plot for ammonia synthesis over transition metal catalysts , 2001 .

[38]  M. Neurock,et al.  Electronic Factors Governing Ethylene Hydrogenation and Dehydrogenation Activity of Pseudomorphic PdML/Re(0001), PdML/Ru(0001), Pd(111), and PdML/Au(111) Surfaces , 2000 .

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

[40]  R. Bell,et al.  The Theory of Reactions Involving Proton Transfers , 1936 .

[41]  J. Brønsted.  Acid and Basic Catalysis. , 1928 .

[42]  J. Onuchic,et al.  Theory of protein folding: the energy landscape perspective. , 1997, Annual review of physical chemistry.

[43]  Ron Elber,et al.  Reaction path study of helix formation in tetrapeptides: Effect of side chains , 1991 .

[44]  M. G. Evans,et al.  Inertia and driving force of chemical reactions , 1938 .