Major Successes of Theory-and-Experiment-Combined Studies in Surface Chemistry and Heterogeneous Catalysis

Experimental discoveries followed by theoretical interpretations that pave the way of further advances by experimentalists is a developing pattern in modern surface chemistry and catalysis. The revolution of modern surface science started with the development of surface-sensitive techniques such as LEED, XPS, AES, ISS and SIMS, in which the close collaboration between experimentalists and theorists led to the quantitative determination of surface structure and composition. The experimental discovery of the chemical activity of surface defects and the trends in the reactivity of transitional metals followed by the explanations from the theoretical studies led to the molecular level understanding of active sites in catalysis. The molecular level knowledge, in turn, provided a guide for experiments to search for new generation of catalysts. These and many other examples of successes in experiment-and-theory-combined studies demonstrate the importance of the collaboration between experimentalists and theorists in the development of modern surface science

Nanoscale Advances in Catalysis and Energy Applications

In this perspective, we present an overview of nanoscience applications in catalysis, energy conversion, and energy conservation technologies. We discuss how novel physical and chemical properties of nanomaterials can be applied and engineered to meet the advanced material requirements in the new generation of chemical and energy conversion devices. We highlight some of the latest advances in these nanotechnologies and provide an outlook at the major challenges for further developments

A new scanning tunneling microscope reactor used for high-pressure and high-temperature catalysis studies

This is the published version. Copyright 2008 American Institute of PhysicsWe present the design and performance of a homebuilt high-pressure and high-temperature reactor equipped with a high-resolution scanning tunneling microscope STM for catalytic studies. In this design, the STM body, sample, and tip are placed in a small high pressure reactor 19 cm3 located within an ultrahigh vacuum UHV chamber. A sealable port on the wall of the reactor separates the high pressure environment in the reactor from the vacuum environment of the STM chamber and permits sample transfer and tip change in UHV. A combination of a sample transfer arm, wobble stick, and sample load-lock system allows fast transfer of samples and tips between the preparation chamber, high pressure reactor, and ambient environment. This STM reactor can work as a batch or flowing reactor at a pressure range of 10−13 to several bars and a temperature range of 300–700 K. Experiments performed on two samples both in vacuum and in high pressure conditions demonstrate the capability of in situ investigations of heterogeneous catalysis and surface chemistry at atomic resolution at a wide pressure range from UHV to a pressure higher than 1 atm

A new scanning tunneling microscope reactor used for high-pressure and high-temperature catalysis studies

This is the published version. Copyright 2008 American Institute of PhysicsWe present the design and performance of a homebuilt high-pressure and high-temperature reactor equipped with a high-resolution scanning tunneling microscope STM for catalytic studies. In this design, the STM body, sample, and tip are placed in a small high pressure reactor 19 cm3 located within an ultrahigh vacuum UHV chamber. A sealable port on the wall of the reactor separates the high pressure environment in the reactor from the vacuum environment of the STM chamber and permits sample transfer and tip change in UHV. A combination of a sample transfer arm, wobble stick, and sample load-lock system allows fast transfer of samples and tips between the preparation chamber, high pressure reactor, and ambient environment. This STM reactor can work as a batch or flowing reactor at a pressure range of 10−13 to several bars and a temperature range of 300–700 K. Experiments performed on two samples both in vacuum and in high pressure conditions demonstrate the capability of in situ investigations of heterogeneous catalysis and surface chemistry at atomic resolution at a wide pressure range from UHV to a pressure higher than 1 atm

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

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

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

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

John Pendry: His Contributions to the Development of LEED Surface Crystallography

In this paper we discuss the pivotal role played by Sir John Pendry in the development of Low Energy Electron Diffraction (LEED) during the past three decades; the earliest understanding on the physics of LEED to the development of sophisticated methods for the structural solution of complex surfaces

Unsaturated Ligands Seed an Order to Disorder Transition in Mixed Ligand Shells of CdSe/CdS Quantum Dots.

A phase transition within the ligand shell of core/shell quantum dots is studied in the prototypical system of colloidal CdSe/CdS quantum dots with a ligand shell composed of bound oleate (OA) and octadecylphosphonate (ODPA). The ligand shell composition is tuned using a ligand exchange procedure and quantified through proton NMR spectroscopy. Temperature-dependent photoluminescence spectroscopy reveals a signature of a phase transition within the organic ligand shell. Surprisingly, the ligand order to disorder phase transition triggers an abrupt increase in the photoluminescence quantum yield (PLQY) and full-width at half-maximum (FWHM) with increasing temperature. The temperature and width of the phase transition show a clear dependence on ligand shell composition, such that QDs with higher ODPA fractions have sharper phase transitions that occur at higher temperatures. In order to gain a molecular understanding of the changes in ligand ordering, Fourier transform infrared and vibrational sum frequency generation spectroscopies are performed. These measurements confirm that an order/disorder transition in the ligand shell tracks with the photoluminescence changes that accompany the ligand phase transition. The phase transition is simulated through a lattice model that suggests that the ligand shell is well-mixed and does not have completely segregated domains of OA and ODPA. Furthermore, we show that the unsaturated chains of OA seed disorder within the ligand shell

Dependence of Gas-Phase Crotonaldehyde Hydrogenation Selectivity and Activity on the Size of Pt Nanoparticles (1.7-7.1 nm) Supported on SBA-15

The selectivity and activity for the hydrogenation of crotonaldehyde to crotyl alcohol and butyraldehyde was studied over a series of Pt nanoparticles (diameter of 1.7, 2.9, 3.6, and 7.1 nm). The nanoparticles were synthesized by the reduction of chloroplatinic acid by alcohol in the presence of poly(vinylpyrrolidone) (PVP), followed by encapsulation into mesoporous SBA-15 silica. The rate of crotonaldehyde hydrogenation and selectivity towards crotyl alcohol both increase with increasing particle size. The selectivity towards crotyl alcohol increased from 13.7 % to 33.9 % (8 Torr crotonaldehyde, 160 Torr H{sub 2} and 353 K), while the turnover frequency increases from 2.1 x 10{sup -2} s{sup -1} to 4.8 x 10{sup -2} s{sup -1} with an increase in the particle size from 1.7 nm to 7.1 nm. The decarbonylation pathway to form propene and CO is enhanced over the higher proportion of coordinatively unsaturated sites on the smaller nanoparticles. The apparent activation energy remains constant ({approx} 16 kcal mol{sup -1} for the formation of butyraldehyde and {approx} 8 kcal mol{sup -1} for the formation of crotyl alcohol) as a function of particle size. In the presence of 130-260 mTorr CO, the reaction rate decreases for all products with a CO reaction order of -0.9 for crotyl alcohol and butyraldehyde over 7.1 nm Pt particles; over 1.7 nm Pt particles, the order in CO is -1.4 and -0.9, respectively. Hydrogen reduction at 673 K after calcination in oxygen results in increased activity and selectivity relative to reduction at either higher or lower temperature; this is discussed with regards to the incomplete removal and/or change in morphology of the polymeric surface stabilizing agent, poly(vinylpyrrolidone) used for the synthesis of the Pt nanoparticles