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Colloid Science of Metal Nanoparticle Catalysts in 2D and 3D Structures. Challenges of Nucleation, Growth, Composition, Particle Shape, Size Control and their Influence on Activity and Selectivity

Description: Recent breakthroughs in synthesis in nanosciences have achieved control of size and shapes of nanoparticles that are relevant for catalyst design. In this article, we review the advance of synthesis of nanoparticles, fabrication of two and three dimensional model catalyst system, characterization, and studies of activity and selectivity. The ability to synthesize monodispersed platinum and rhodium nanoparticles in the 1-10 nm range permitted us to study the influence of composition, structure, and dynamic properties of monodispersed metal nanoparticle on chemical reactivity and selectivity. We review the importance of size and shape of nanoparticles to determine the reaction selectivity in multi-path reactions. The influence of metal-support interaction has been studied by probing the hot electron flows through the metal-oxide interface in catalytic nanodiodes. Novel designs of nanoparticle catalytic systems are discussed.
Date: February 13, 2008
Creator: Somorjai, Gabor A. & Park, Jeong Y.
Partner: UNT Libraries Government Documents Department

The Effects of Oxygen Plasma on the Chemical Composition and Morphology of the Ru Capping Layer of the Extreme Ultraviolet (EUV) Mask Blanks

Description: Contamination removal from extreme ultraviolet (EUV) mask surfaces is one of the most important aspects to improve reliability for the next generation of EUV lithography. We report chemical and morphological changes of the ruthenium (Ru) mask surface after oxygen plasma treatment using surface sensitive analytical methods: X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and transmission electron microscopy (TEM). Chemical analysis of the EUV masks shows an increase in the subsurface oxygen concentration, Ru oxidation and surface roughness. XPS spectra at various photoelectron takeoff angles suggest that the EUV mask surface was covered with chemisorbed oxygen after oxygen plasma treatment. It is proposed that the Kirkendall effect is the most plausible mechanism that explains the Ru surface oxidation. The etching rate of the Ru capping layer by oxygen plasma was estimated to be 1.5 {+-} 0.2 {angstrom}/min, based on TEM cross sectional analysis.
Date: June 7, 2008
Creator: Belau, Leonid; Park, Jeong Y.; Liang, Ted & Somorjai, Gabor A.
Partner: UNT Libraries Government Documents Department

Molecular Components of Catalytic Selectivity

Description: Selectivity, that is, to produce one molecule out of many other thermodynamically feasible product molecules, is the key concept to develop 'clean manufacturing' processes that do not produce byproducts (green chemistry). Small differences in potential energy barriers for elementary reaction steps control which reaction channel is more likely to yield the desired product molecule (selectivity), instead of the overall activation energy for the reaction that controls turnover rates (activity). Recent studies have demonstrated the atomic- or molecular-level tailoring of parameters such as the surface structures of active sites that give rise to nanoparticle size and shape dependence of turnover rates and reaction selectivities. Here, we highlight seven molecular components that influence reaction selectivities. These include: surface structure, adsorbate-induced restructuring, adsorbate mobility, reaction intermediates, surface composition, charge transport, and oxidation states for model metal single crystal and colloid nanoparticle catalysts. We show examples of their functioning and describe in-situ instruments that permit us to investigate their roles in surface reactions.
Date: July 2, 2008
Creator: Somorjai, Gabor A. & Park, Jeong Y.
Partner: UNT Libraries Government Documents Department

Molecular Surface Chemistry by Metal Single Crystals and Nanoparticles from Vacuum to High Pressure.

Description: Model systems for studying molecular surface chemistry have evolved from single crystal surfaces at low pressure to colloidal nanoparticles at high pressure. Low pressure surface structure studies of platinum single crystals using molecular beam surface scattering and low energy electron diffraction techniques probe the unique activity of defects, steps and kinks at the surface for dissociation reactions (H-H, C-H, C-C, O{double_bond}O bonds). High-pressure investigations of platinum single crystals using sum frequency generation vibrational spectroscopy have revealed the presence and the nature of reaction intermediates. High pressure scanning tunneling microscopy of platinum single crystal surfaces showed adsorbate mobility during a catalytic reaction. Nanoparticle systems are used to determine the role of metal-oxide interfaces, site blocking and the role of surface structures in reactive surface chemistry. The size, shape and composition of nanoparticles play important roles in determining reaction activity and selectivity.
Date: April 5, 2008
Creator: Somorjai, Gabor A. & Park, Jeong Y.
Partner: UNT Libraries Government Documents Department

Probing Hot Electron Flow Generated on Pt Nanoparticles with Au/TiO2 Schottky Diodes during Catalytic CO Oxidation

Description: Hot electron flow generated on colloid platinum nanoparticles during exothermic catalytic carbon monoxide oxidation was directly detected with Au/TiO{sub 2} diodes. Although Au/TiO{sub 2} diodes are not catalytically active, platinum nanoparticles on Au/TiO{sub 2} exhibit both chemicurrent and catalytic turnover rate. Hot electrons are generated on the surface of the metal nanoparticles and go over the Schottky energy barrier between Au and TiO{sub 2}. The continuous Au layer ensures that the metal nanoparticles are electrically connected to the device. The overall thickness of the metal assembly (nanoparticles and Au thin film) is comparable to the mean free path of hot electrons, resulting in ballistic transport through the metal. The chemicurrent and chemical reactivity of nanoparticles with citrate, hexadecylamine, hexadecylthiol, and TTAB (Tetradecyltrimethylammonium Bromide) capping agents were measured during catalytic CO oxidation at pressures of 100 Torr O{sub 2} and 40 Torr CO at 373-513 K. We found that chemicurrent yield varies with each capping agent, but always decreases with increasing temperature. We suggest that this inverse temperature dependence is associated with the influence of charging effects due to the organic capping layer during hot electron transport through the metal-oxide interface.
Date: May 1, 2008
Creator: Park, Jeong Y.; Lee, Hyunjoo; Renzas, J. Russell; Zhang, Yawen & Somorjai, G.A.
Partner: UNT Libraries Government Documents Department

Sensing Current and Forces with SPM

Description: Atomic force microscopy (AFM) and scanning tunneling microscopy (STM) are well established techniques to image surfaces and to probe material properties at the atomic and molecular scale. In this review, we show hybrid combinations of AFM and STM that bring together the best of two worlds: the simultaneous detection of atomic scale forces and conduction properties. We illustrate with several examples how the detection of forces during STM and the detection of currents during AFM can give valuable additional information of the nanoscale material properties.
Date: July 2, 2010
Creator: Park, Jeong Y.; Maier, Sabine; Hendriksen, Bas & Salmeron, Miquel
Partner: UNT Libraries Government Documents Department

Evolution of the Surface Science of Catalysis from Single Crystals to Metal Nanoparticles under Pressure

Description: Vacuum studies of metal single crystal surfaces using electron and molecular beam scattering revealed that the surface atoms relocate when the surface is clean (reconstruction) and when it is covered by adsorbates (adsorbate induced restructuring). It was also discovered that atomic steps and other low coordination surface sites are active for breaking chemical bonds (H-H, O=O, C-H, C=O and C-C) with high reaction probability. Investigations at high reactant pressures using sum frequency generation (SFG)--vibrational spectroscopy and high pressure scanning tunneling microscopy (HPSTM) revealed bond breaking at low reaction probability sites on the adsorbate-covered metal surface, and the need for adsorbate mobility for continued turnover. Since most catalysts (heterogeneous, enzyme and homogeneous) are nanoparticles, colloid synthesis methods were developed to produce monodispersed metal nanoparticles in the 1-10 nm range and controlled shapes to use them as new model catalyst systems in two-dimensional thin film form or deposited in mesoporous three-dimensional oxides. Studies of reaction selectivity in multipath reactions (hydrogenation of benzene, cyclohexene and crotonaldehyde) showed that reaction selectivity depends on both nanoparticle size and shape. The oxide-metal nanoparticle interface was found to be an important catalytic site because of the hot electron flow induced by exothermic reactions like carbon monoxide oxidation.
Date: March 6, 2008
Creator: Somorjai, Gabor A. & Park, Jeong Y.
Partner: UNT Libraries Government Documents Department

Hydrogen Oxidation-Driven Hot Electron Flow Detected by Catalytic Nanodiodes

Description: Hydrogen oxidation on platinum is shown to be a surface catalytic chemical reaction that generates a steady state flux of hot (>1 eV) conduction electrons. These hot electrons are detected as a steady-state chemicurrent across Pt/TiO{sub 2} Schottky diodes whose Pt surface is exposed to hydrogen and oxygen. Kinetic studies establish that the chemicurrent is proportional to turnover frequency for temperatures ranging from 298 to 373 K for P{sub H2} between 1 and 8 Torr and P{sub O2} at 760 Torr. Both chemicurrent and turnover frequency exhibit a first order dependence on P{sub H2}.
Date: July 20, 2009
Creator: Hervier, Antoine; Renzas, J. Russell; Park, Jeong Y. & Somorjai, Gabor A.
Partner: UNT Libraries Government Documents Department

The Role of Organic Capping Layers of Platinum Nanoparticles in Catalytic Activity of CO Oxidation

Description: We report the catalytic activity of colloid platinum nanoparticles synthesized with different organic capping layers. On the molecular scale, the porous organic layers have open spaces that permit the reactant and product molecules to reach the metal surface. We carried out CO oxidation on several platinum nanoparticle systems capped with various organic molecules to investigate the role of the capping agent on catalytic activity. Platinum colloid nanoparticles with four types of capping layer have been used: TTAB (Tetradecyltrimethylammonium Bromide), HDA (hexadecylamine), HDT (hexadecylthiol), and PVP (poly(vinylpyrrolidone)). The reactivity of the Pt nanoparticles varied by 30%, with higher activity on TTAB coated nanoparticles and lower activity on HDT, while the activation energy remained between 27-28 kcal/mol. In separate experiments, the organic capping layers were partially removed using ultraviolet light-ozone generation techniques, which resulted in increased catalytic activity due to the removal of some of the organic layers. These results indicate that the nature of chemical bonding between organic capping layers and nanoparticle surfaces plays a role in determining the catalytic activity of platinum colloid nanoparticles for carbon monoxide oxidation.
Date: December 17, 2008
Creator: Park, Jeong Y.; Aliaga, Cesar; Renzas, J. Russell; Lee, Hyunjoo & Somorjai, Gabor A.
Partner: UNT Libraries Government Documents Department

Chemical Effect of Dry and Wet Cleaning of the Ru Protective Layer of the Extreme ultraviolet (EUV) Lithography Reflector

Description: The authors report the chemical influence of cleaning of the Ru capping layer on the extreme ultraviolet (EUV) reflector surface. The cleaning of EUV reflector to remove the contamination particles has two requirements: to prevent corrosion and etching of the reflector surface and to maintain the reflectivity functionality of the reflector after the corrosive cleaning processes. Two main approaches for EUV reflector cleaning, wet chemical treatments [sulfuric acid and hydrogen peroxide mixture (SPM), ozonated water, and ozonated hydrogen peroxide] and dry cleaning (oxygen plasma and UV/ozone treatment), were tested. The changes in surface morphology and roughness were characterized using scanning electron microscopy and atomic force microscopy, while the surface etching and change of oxidation states were probed with x-ray photoelectron spectroscopy. Significant surface oxidation of the Ru capping layer was observed after oxygen plasma and UV/ozone treatment, while the oxidation is unnoticeable after SPM treatment. Based on these surface studies, the authors found that SPM treatment exhibits the minimal corrosive interactions with Ru capping layer. They address the molecular mechanism of corrosive gas and liquid-phase chemical interaction with the surface of Ru capping layer on the EUV reflector.
Date: April 10, 2009
Creator: Belau, Leonid; Park, Jeong Y.; Liang, Ted; Seo, Hyungtak & Somorjai, Gabor A.
Partner: UNT Libraries Government Documents Department

Influence of Reaction with XeF2 on Surface Adhesion of Al and Al2O3 Surfaces

Description: The change of surface adhesion after fluorination of Al and Al{sub 2}O{sub 3} surfaces using XeF{sub 2} was investigated with atomic force microscopy. The chemical interaction between XeF{sub 2} and Al and Al{sub 2}O{sub 3} surfaces was studied by in situ x-ray photoelectron spectroscopy. Fresh Al and Al{sub 2}O{sub 3} surfaces were obtained by etching top silicon layers of Si/Al and Si/Al{sub 2}O{sub 3} with XeF{sub 2}. The surface adhesion and chemical composition were measured as a function of time after the exposure to air or annealing (at 200 C under vauum). The correlation between the adhesion force increase and presence of AlF{sub 3} on the surface was revealed.
Date: July 28, 2008
Creator: Zhang, Tianfu; Park, Jeong Y.; Huang, Wenyu & Somorjai, Gabor A.
Partner: UNT Libraries Government Documents Department

Size Effect of Ruthenium Nanoparticles in Catalytic Carbon Monoxide Oxidation

Description: Carbon monoxide oxidation over ruthenium catalysts has shown an unusual catalytic behavior. Here we report a particle size effect on CO oxidation over Ru nanoparticle (NP) catalysts. Uniform Ru NPs with a tunable particle size from 2 to 6 nm were synthesized by a polyol reduction of Ru(acac){sub 3} precursor in the presence of poly(vinylpyrrolidone) stabilizer. The measurement of catalytic activity of CO oxidation over two-dimensional Ru NPs arrays under oxidizing reaction conditions (40 Torr CO and 100 Torr O{sub 2}) showed an activity dependence on the Ru NP size. The CO oxidation activity increases with NP size, and the 6 nm Ru NP catalyst shows 8-fold higher activity than the 2 nm catalysts. The results gained from this study will provide the scientific basis for future design of Ru-based oxidation catalysts.
Date: April 4, 2010
Creator: Joo, Sang Hoon; Park, Jeong Y.; Renzas, J. Russell; Butcher, Derek R.; Huang, Wenyu & Somorjai, Gabor A.
Partner: UNT Libraries Government Documents Department

Sum frequency generation and catalytic reaction studies of the removal of the organic capping agents from Pt nanoparticles by UV-ozone treatment

Description: We report the structure of the organic capping layers of platinum colloid nanoparticles and their removal by UV-ozone exposure. Sum frequency generation vibrational spectroscopy (SFGVS) studies identify the carbon-hydrogen stretching modes on poly(vinylpyrrolidone) (PVP) and tetradecyl tributylammonium bromide (TTAB)-capped platinum nanoparticles. We found that the UV-ozone treatment technique effectively removes the capping layer on the basis of several analytical measurements including SFGVS, X-ray photoelectron spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The overall shape of the nanoparticles was preserved after the removal of capping layers, as confirmed by transmission electron microscopy (TEM). SFGVS of ethylene hydrogenation on the clean platinum nanoparticles demonstrates the existence of ethylidyne and di-{sigma}-bonded species, indicating the similarity between single-crystal and nanoparticle systems.
Date: December 10, 2009
Creator: Aliaga, Cesar; Park, Jeong Y.; Yamada, Yusuke; Lee, Hyun Sook; Tsung, Chia-Kuang; Yang, Peidong et al.
Partner: UNT Libraries Government Documents Department

Mechanical and charge transport properties of alkanethiol self-assembled monolayers on Au (111) surface: The Role of Molecular Tilt

Description: The relationship between charge transport and mechanical properties of alkanethiol self-assembled monolayers (SAM) on Au(111) films has been investigated using an atomic force microscope with a conductive tip. Molecular tilts induced by the pressure applied by the tip cause stepwise increases in film conductivity. A decay constant {beta} = 0.57 {+-} 0.03 {angstrom}{sup -1} was found for the current passing through the film as a function of tip-substrate separation due to this molecular tilt. This is significantly smaller than the value of {approx} 1 {angstrom}{sup -1} found when the separation is changed by changing the length of the alkanethiol molecules. Calculations indicate that for isolated dithiol molecules S-bonded to hollow sites, the junction conductance does not vary significantly as a function of molecular tilt. The impact of S-Au bonding on SAM conductance is discussed.
Date: November 12, 2007
Creator: Mulleregan, Alice; Qi, Yabing; Ratera, Imma; Park, Jeong Y.; Ashby, Paul D.; Quek, Su Ying et al.
Partner: UNT Libraries Government Documents Department

A Reactive Oxide Overlayer on Rh Nanoparticles during CO Oxidation and Its Size Dependence Studied by in Situ Ambient Pressure XPS

Description: CO oxidation is one of the most studied heterogeneous reactions, being scientifically and industrially important, particularly for removal of CO from exhaust streams and preferential oxidation for hydrogen purification in fuel cell applications. The precious metals Ru, Rh, Pd, Pt, and Au are most commonly used for this reaction because of their high activity and stability. Despite the wealth of experimental and theoretical data, it remains unclear what is the active surface for CO oxidation under catalytic conditions for these metals. In this communication, we utilize in situ synchrotron ambient pressure X-ray photoelectron spectroscopy (APXPS) to monitor the oxidation state at the surface of Rh nanoparticles during CO oxidation and demonstrate that the active catalyst is a surface oxide, the formation of which is dependent on particle size. The amount of oxide formed and the reaction rate both increase with decreasing particle size.
Date: September 15, 2008
Creator: Grass, Michael E.; Zhang, Yawen; Butcher, Derek R.; Park, Jeong Y.; Li, Yimin; Bluhm, Hendrik et al.
Partner: UNT Libraries Government Documents Department

Influence of molecular ordering on electrical and friction properties of omega-(trans-4-stilbene)alkylthiol self-assembled monolayers on Au (111)

Description: The electrical and friction properties of omega-(trans-4-stilbene)alkylthiol self-assembled monolayers (SAMs) on Au(111) were investigated using atomic force microscopy (AFM) and near edge x-ray absorption fine structure spectroscopy (NEXAFS). The sample surface was uniformly covered with a molecular film consisting of very small grains. Well-ordered and flat monolayer islands were formed after the sample was heated in nitrogen at 120 oC for 1 h. While lattice resolved AFM images revealed a crystalline phase in the islands, the area between islands showed no order. The islands exhibit substantial reduction (50percent) in friction, supporting the existence of good ordering. NEXAFS measurements revealed an average upright molecular orientation in the film, both before and after heating, with a narrower tilt-angle distribution for the heated fim. Conductance-AFM measurements revealed a two orders of magnitude higher conductivity on the ordered islands than on the disordered phase. We propose that the conductance enhancement is a result of a better pi-pi stacking between the trans-stilbene molecular units as a result of improved ordering in islands.
Date: April 21, 2010
Creator: Qi, Yabing; Liu, Xiaosong; Hendriksen, B.L.M.; Navarro, V.; Park, Jeong Y.; Ratera, Imma et al.
Partner: UNT Libraries Government Documents Department