Tuning the Properties of Pd Nanoclusters by Ligand Coatings: Electronic Structure Computations on Phosphine, Thiol, and Mixed PhosphineThiol Ligand Shells
Fresch, Barbara; Remacle, Françoise
2014 • In Journal of Physical Chemistry. C, Nanomaterials and interfaces
[en] Tuning the properties of Palladium nanoparticles using different protecting ligand shells is an important step toward the application-orientated design of nanoparticles for nano-electronics and catalysis. We present a density functional theoretical characterization of Pd13 and Pd55 metal cores protected by only-thiol, only-phosphine and mixed phosphine-thiol ligand shells. We analyze the ligand contributions to the frontier orbitals and the charge redistribution between the ligand shell and the metal core and show that these properties control the values of the charging energy and the catalytic activity. The charge transfer character of the metal-ligand interaction is influenced by the presence of other ligands in the capping system indicating a cooperative effect in the ligand induced charge redistribution. Because of the interplay between the stabilization of the frontier orbital due to the contribution of the sulfur and the charge donation by the phosphine, the charging energy of the mixed phosphine-thiol protected cluster is larger than that of the only-phosphine and the only-thiol systems. The complementary point of view is adopted for rationalizing the catalytic properties of the clusters by analyzing the effect of the interaction with the metallic core on the properties of the ligand. The impact of solvation on the electronic structure of the ligand capped Pd13 cluster is investigated by including explicitly a layer of water molecules in the model system.
Disciplines :
Chemistry
Author, co-author :
Fresch, Barbara ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Remacle, Françoise ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Language :
English
Title :
Tuning the Properties of Pd Nanoclusters by Ligand Coatings: Electronic Structure Computations on Phosphine, Thiol, and Mixed PhosphineThiol Ligand Shells
Publication date :
2014
Journal title :
Journal of Physical Chemistry. C, Nanomaterials and interfaces
ISSN :
1932-7447
eISSN :
1932-7455
Publisher :
American Chemical Society, Washington, United States - District of Columbia
Watt, J.; Cheong, S.; Toney, M. F.; Ingham, B.; Cookson, J.; Bishop, P. T.; Tilley, R. D. Ultrafast Growth of Highly Branched Palladium Nanostructures for Catalysis ACS Nano 2009, 4, 396-402
Bell, A. T. The Impact of Nanoscience on Heterogeneous Catalysis Science 2003, 299, 1688-1691
Li, L.; Larsen, A. H.; Romero, N. A.; Morozov, V. A.; Glinsvad, C.; Abild-Pedersen, F.; Greeley, J.; Jacobsen, K. W.; Nørskov, J. K. Investigation of Catalytic Finite-Size-Effects of Platinum Metal Clusters J. Phys. Chem. Lett. 2012, 4, 222-226
Gavia, D. J.; Shon, Y.-S. Controlling Surface Ligand Density and Core Size of Alkanethiolate-Capped Pd Nanoparticles and Their Effects on Catalysis Langmuir 2012, 28, 14502-14508
Pelzer, A. W.; Jellinek, J.; Jackson, K. A. H2 Reactions on Palladium Clusters J. Phys. Chem. A 2013, 117, 10407-10415
Gubin, S. P.; Yu, V. G.; Khomutov, G. B.; Kislov, V. V.; Kolesov, V. V.; Soldatov, E. S.; Sulaimankulov, K. S.; Trifonov, A. S. Molecular Clusters as Building Blocks for Nanoelectronics: The First Demonstration of a Cluster Single-Electron Tunnelling Transistor at Room Temperature Nanotechnology 2002, 13, 185
Carducci, T. M.; Murray, R. W. Kinetics and Low Temperature Studies of Electron Transfers in Films of Small (<2 nm) Au Monolayer Protected Clusters J. Am. Chem. Soc. 2013, 135, 11351-11356
Muroski, M. E.; Kogot, J. M.; Strouse, G. F. Bimodal Gold Nanoparticle Therapeutics for Manipulating Exogenous and Endogenous Protein Levels in Mammalian Cells J. Am. Chem. Soc. 2012, 134, 19722-19730
Yusop, R. M.; Unciti-Broceta, A.; Johansson, E. M. V.; Sánchez-Martín, R. M.; Bradley, M. Palladium-Mediated Intracellular Chemistry Nat. Chem. 2011, 3, 239-243
Chen, S.; Ingram, R. S.; Hostetler, M. J.; Pietron, J. J.; Murray, R. W.; Schaaff, T. G.; Khoury, J. T.; Alvarez, M. M.; Whetten, R. L. Gold Nanoelectrodes of Varied Size: Transition to Molecule-Like Charging Science 1998, 280, 2098-2101
Andres, R. P.; Bein, T.; Dorogi, M.; Feng, S.; Henderson, J. I.; Kubiak, C. P.; Mahoney, W.; Osifchin, R. G.; Reifenberger, R. Coulomb Staircase at Room Temperature in a Self-Assembled Molecular Nanostructure Science 1996, 272, 1323-1325
Klein, D. L.; Roth, R.; Lim, A. K. L.; Alivisatos, A. P.; McEuen, P. L. A Single-Electron Transistor Made from a Cadmium Selenide Nanocrystal Nature 1997, 389, 699-701
Quinn, B. M.; Liljeroth, P.; Ruiz, V.; Laaksonen, T.; Kontturi, K. Electrochemical Resolution of 15 Oxidation States for Monolayer Protected Gold Nanoparticles J. Am. Chem. Soc. 2003, 125, 6644-6645
Javey, A.; Dai, H. Regular Arrays of 2 Nm Metal Nanoparticles for Deterministic Synthesis of Nanomaterials J. Am. Chem. Soc. 2005, 127, 11942-11943
Sharma, J.; Chhabra, R.; Andersen, C. S.; Gothelf, K. V.; Yan, H.; Liu, Y. Toward Reliable Gold Nanoparticle Patterning on Self-Assembled DNA Nanoscaffold J. Am. Chem. Soc. 2008, 130, 7820-7821
Fendler, J. H. Chemical Self-Assembly for Electronic Applications Chem. Mater. 2001, 13, 3196-3210
L. Feldheim, D.; D. Keating, C. Self-Assembly of Single Electron Transistors and Related Devices Chem. Soc. Rev. 1998, 27, 1-12
Li, Z.; Liu, Y.; Mertens, S. F. L.; Pobelov, I. V.; Wandlowski, T. From Redox Gating to Quantized Charging J. Am. Chem. Soc. 2010, 132, 8187-8193
Kibata, T.; Mitsudome, T.; Mizugaki, T.; Jitsukawa, K.; Kaneda, K. Investigation of Size-Dependent Properties of Sub-Nanometer Palladium Clusters Encapsulated within a Polyamine Dendrimer Chem. Commun. 2013, 49, 167-169
Herzing, A. A.; Kiely, C. J.; Carley, A. F.; Landon, P.; Hutchings, G. J. Identification of Active Gold Nanoclusters on Iron Oxide Supports for Co Oxidation Science 2008, 321, 1331-1335
Lei, Y. Increased Silver Activity for Direct Propylene Epoxidation Via Subnanometer Size Effects Science 2010, 328, 224-228
Bertorelle, F.; Hamouda, R.; Rayane, D.; Broyer, M.; Antoine, R.; Dugourd, P.; Gell, L.; Kulesza, A.; Mitric, R.; Bonacic-Koutecky, V. Synthesis, Characterization and Optical Properties of Low Nuclearity Liganded Silver Clusters: Ag31(Sg)19 and Ag15(Sg)11 Nanoscale 2013, 5, 5637-5643
Bonacic-Koutecky, V. Silver Cluster-Biomolecule Hybrids: From Basics Towards Sensors Phys. Chem. Chem. Phys. 2012, 14, 9282-9290
Costa, N. J. S.; Rossi, L. M. Synthesis of Supported Metal Nanoparticle Catalysts Using Ligand Assisted Methods Nanoscale 2012, 4, 5826-5834
Montalti, M.; Zaccheroni, N.; Prodi, L.; OReilly, N.; James, S. L. Enhanced Sensitized Nir Luminescence from Gold Nanoparticles Via Energy Transfer from Surface-Bound Fluorophores J. Am. Chem. Soc. 2007, 129, 2418-2419
Gell, L.; Kulesza, A.; Petersen, J.; Röhr, M. I. S.; Mitrić, R.; Bonačić-Koutecký, V. Tuning Structural and Optical Properties of Thiolate-Protected Silver Clusters by Formation of a Silver Core with Confined Electrons J. Phys. Chem. C 2013, 117, 14824-14831
Milette, J.; Toader, V.; Reven, L.; Lennox, R. B. Tuning the Miscibility of Gold Nanoparticles Dispersed in Liquid Crystals Via the Thiol-for-Dmap Reaction J. Mater. Chem. 2011, 21, 9043-9050
Kuna, J. J.; Voitchovsky, K.; Singh, C.; Jiang, H.; Mwenifumbo, S.; Ghorai, P. K.; Stevens, M. M.; Glotzer, S. C.; Stellacci, F. The Effect of Nanometre-Scale Structure on Interfacial Energy Nat. Mater. 2009, 8, 837-842
Moreno, M.; Ibanez, F. J.; Jasinski, J. B.; Zamborini, F. P. Hydrogen Reactivity of Palladium Nanoparticles Coated with Mixed Monolayers of Alkyl Thiols and Alkyl Amines for Sensing and Catalysis Applications J. Am. Chem. Soc. 2011, 133, 4389-4397
Litrán, R.; Sampedro, B.; Rojas, T. C.; Multigner, M.; Sánchez-López, J. C.; Crespo, P.; López-Cartes, C.; García, M. A.; Hernando, A.; Fernández, A. Magnetic and Microstructural Analysis of Palladium Nanoparticles with Different Capping Systems Phys. Rev. B 2006, 73, 054404
Cookson, J. The Preparation of Palladium Nanoparticles Platinum Met. Rev. 2012, 56, 83-98
Azcárate, J. C.; Corthey, G.; Pensa, E.; Vericat, C.; Fonticelli, M. H.; Salvarezza, R. C.; Carro, P. Understanding the Surface Chemistry of Thiolate-Protected Metallic Nanoparticles J. Phys. Chem. Lett. 2013, 3127-3138
Corthey, G. New Insights into the Chemistry of Thiolate-Protected Palladium Nanoparticles J. Phys. Chem. C 2012, 116, 9830-9837
Woehrle, G. H.; Warner, M. G.; Hutchison, J. E. Ligand Exchange Reactions Yield Subnanometer, Thiol-Stabilized Gold Particles with Defined Optical Transitions J. Phys. Chem. B 2002, 106, 9979-9981
Woehrle, G. H.; Brown, L. O.; Hutchison, J. E. Thiol-Functionalized, 1.5-nm Gold Nanoparticles through Ligand Exchange Reactions: Scope and Mechanism of Ligand Exchange J. Am. Chem. Soc. 2005, 127, 2172-2183
Shichibu, Y.; Negishi, Y.; Tsukuda, T.; Teranishi, T. Large-Scale Synthesis of Thiolated Au25 Clusters Via Ligand Exchange Reactions of Phosphine-Stabilized Au11 Clusters J. Am. Chem. Soc. 2005, 127, 13464-13465
Fresch, B.; Boyen, H. G.; Remacle, F. Magnetostructural Effects in Ligand Stabilized Pd13 Clusters: A Density Functional Theory Study Nanoscale 2012, 4, 4138-4147
Koster, A. M.; Calaminici, P.; Orgaz, E.; Roy, D. R.; Reveles, J. U.; Khanna, S. N. On the Ground State of Pd(13) J. Am. Chem. Soc. 2011, 133, 12192-12196
Moseler, M.; Häkkinen, H.; Barnett, R. N.; Landman, U. Structure and Magnetism of Neutral and Anionic Palladium Clusters Phys. Rev. Lett. 2001, 86, 2545-2548
Reveles, J. U.; Köster, A. M.; Calaminici, P.; Khanna, S. N. Structural Changes of Pd13 Upon Charging and Oxidation/Reduction J. Chem. Phys. 2012, 136, 114505
Sinfelt, J. H.; Meitzner, G. D. X-Ray Absorption Edge Studies of the Electronic Structure of Metal Catalysts Acc. Chem. Res. 1993, 26, 1-6
Carro, P.; Corthey, G. n.; Rubert, A. A.; Benitez, G. A.; Fonticelli, M. H.; Salvarezza, R. C. The Complex Thiol-Palladium Interface: A Theoretical and Experimental Study Langmuir 2010, 26, 14655-14662
Citrin, P. H.; Wertheim, G. K. Photoemission from Surface-Atom Core Levels, Surface Densities of States, and Metal-Atom Clusters: A Unified Picture Phys. Rev. B 1983, 27, 3176-3200
Becke, A. D. Density-Functional Thermochemistry. III. The Role of Exact Exchange J. Chem. Phys. 1993, 98, 5648-5652
Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields J. Phys. Chem. 1994, 98, 11623-11627
Hay, P. J.; Wadt, W. R. Ab Initio Effective Core Potentials for Molecular Calculations. Potentials for the Transition Metal Atoms Sc to Hg J. Chem. Phys. 1985, 82, 270-283
Hay, P. J.; Wadt, W. R. Ab Initio Effective Core Potentials for Molecular Calculations. Potentials for K to Au Including the Outermost Core Orbitals J. Chem. Phys. 1985, 82, 299-310
Rayon, V. M.; Valdes, H.; Diaz, N.; Suarez, D. Monoligand Zn(Ii) Complexes: Ab Initio Benchmark Calculations and Comparison with Density Functional Theory Methodologies J. Chem. Theory Comput. 2008, 4, 243-256
Mayhall, N. J.; Raghavachari, K.; Redfern, P. C.; Curtiss, L. A. Investigation of Gaussian4 Theory for Transition Metal Thermochemistry J. Phys. Chem. A 2009, 113, 5170-5175
de Jong, G. T.; Bickelhaupt, F. M. Oxidative Addition of the Chloromethane C-Cl Bond to Pd, an Ab Initio Benchmark and Dft Validation Study J. Chem. Theory Comput. 2006, 2, 322-335
Hutchison, G. R.; Ratner, M. A.; Marks, T. J. Hopping Transport in Conductive Heterocyclic Oligomers: Reorganization Energies and Substituent Effects J. Am. Chem. Soc. 2005, 127, 2339-2350
Foster, J. P.; Weinhold, F. Natural Hybrid Orbitals J. Am. Chem. Soc. 1980, 102, 7211-7218
Reed, A. E.; Curtiss, L. A.; Weinhold, F. Intermolecular Interactions from a Natural Bond Orbital, Donor-Acceptor Viewpoint Chem. Rev. 1988, 88, 899-926
Gorelsky, S. I. Aomix: Program for Molecular Orbital Analysis, Version 6.X; University of Ottawa: Ottawa, Canada, 2013.
Gorelsky, S. I.; Lever, A. B. P. Electronic Structure and Spectra of Ruthenium Diimine Complexes by Density Functional Theory and Indo/S. Comparison of the Two Methods J. Organomet. Chem. 2001, 635, 187-196
Mayer, I. Charge, Bond Order and Valence in the Ab Initio Scf Theory Chem. Phys. Lett. 1983, 97, 270-274
Futschek, T.; Hafner, J.; Marsman, M. Stable Structural and Magnetic Isomers of Small Transition-Metal Clusters from the Ni Group: An Ab Initio Density-Functional Study J. Phys.: Condens. Matter 2006, 18, 9703-9748
Wang, L. L.; Johnson, D. D. Density Functional Study of Structural Trends for Late-Transition-Metal 13-Atom Clusters Phys. Rev. B 2007, 75, 235405
Karabacak, M.; Özçelik, S.; Güvenç, Z. B. Structures and Energetics of Pd21-Pd55 Clusters Surf. Sci. 2003, 532-535, 306-311
Jennison, D. R.; Schultz, P. A.; Sears, M. P. Ab Initio Calculations of Ru, Pd, and Ag Cluster Structure with 55, 135, and 140 Atoms J. Chem. Phys. 1997, 106, 1856-1862
Nava, P.; Sierka, M.; Ahlrichs, R. Density Functional Study of Palladium Clusters Phys. Chem. Chem. Phys. 2003, 5, 3372-3381
Rapps, T.; Ahlrichs, R.; Waldt, E.; Kappes, M. M.; Schooss, D. On the Structures of 55-Atom Transition-Metal Clusters and Their Relationship to the Crystalline Bulk Angew. Chem., Int. Ed. 2013, 52, 6102-6105
Rojas-cervellera, V.; Giralt, E.; Rovira, C. Staple Motifs, Initial Steps in the Formation of Thiolate-Protected Gold Nanoparticles: How Do They Form ? Inorg. Chem. 2012, 51, 11422-11429
Jiang, D.-e.; Tiago, M. L.; Luo, W.; Dai, S. The "Staple" Motif: A Key to Stability of Thiolate-Protected Gold Nanoclusters J. Am. Chem. Soc. 2008, 130, 2777-2779
Cook, S. C.; Padmos, J. D.; Zhang, P. Surface Structural Characteristics and Tunable Electronic Properties of Wet-Chemically Prepared Pd Nanoparticles J. Chem. Phys. 2008, 128, 154705
Coulthard, I.; Sham, T. K. Charge Redistribution in Pd-Ag Alloys from a Local Perspective Phys. Rev. Lett. 1996, 77, 4824-4827
Zhang, P.; Sham, T. K. Tuning the Electronic Behavior of Au Nanoparticles with Capping Molecules Appl. Phys. Lett. 2002, 81, 736-738
Wertheim, G. K.; DiCenzo, S. B.; Buchanan, D. N. E. Noble- and Transition-Metal Clusters: The D Bands of Silver and Palladium Phys. Rev. B 1986, 33, 5384-5390
Koitz, R.; Soini, T. M.; Genest, A.; Trickey, S. B.; Rosch, N. Scalable Properties of Metal Clusters: A Comparative Study of Modern Exchange-Correlation Functionals J. Chem. Phys. 2012, 137, 034102
Sham, T. K. L-Edge X-Ray-Absorption Systematics of the Noble Metals Rh, Pd, and Ag and the Main-Group Metals in and Sn: A Study of the Unoccupied Density of States in 4d Elements Phys. Rev. B 1985, 31, 1888-1902
Sham, T. K. L-Edge X-Ray-Absorption Spectra of Pdal-{3} and Pdcl-{2}: A Study of Charge Redistribution in Compounds of an Element with a Nearly Full 4d Shell Phys. Rev. B 1985, 31, 1903-1908
Larsen, A. H.; Kleis, J.; Thygesen, K. S.; Nørskov, J. K.; Jacobsen, K. W. Electronic Shell Structure and Chemisorption on Gold Nanoparticles Phys. Rev. B 2011, 84, 245429
Rodriguez, J. A.; Chaturvedi, S.; Jirsak, T. The Bonding of Sulfur to Pd Surfaces: Photoemission and Molecular-Orbital Studies Chem. Phys. Lett. 1998, 296, 421-428
Rodriguez, J. A.; Hrbek, J. Interaction of Sulfur with Well-Defined Metal and Oxide Surfaces: Unraveling the Mysteries Behind Catalyst Poisoning and Desulfurization Acc. Chem. Res. 1999, 32, 719-728
Burke, M. L.; Madix, R. J. Hydrogen on Pd(100)-S: The Effect of Sulfur on Precursor Mediated Adsorption and Desorption Surf. Sci. 1990, 237, 1-19
Wilke, S.; Scheffler, M. Mechanism of Poisoning the Catalytic Activity of Pd(100) by a Sulfur Adlayer Phys. Rev. Lett. 1996, 76, 3380-3383
Dufour, F.; Fresch, B.; Durupthy, O.; Chaneac, C.; Remacle, F. Ligand and Solvation Effects on the Structural and Electronic Properties of Small Gold Clusters J. Phys. Chem. C 2014, 118, 4362-4376
