/pdf/self-assembled-monolayers-of-thiolates-on-metals-as-a-form-1neb0hj3k4.pdf

Self-assembled monolayers of thiolates on metals as a form of nanotechnology.

The use of optical measurements to monitor electrochemical changes on the surface of nanosized metal particles is discussed within the Drude model. The absorption spectrum of a metal sol in water is shown to be strongly affected by cathodic or anodic polarization, chemisorption, metal adatom deposition, and alloying. Anion adsorption leads to strong damping of the free electron absorption. Cathodic polarization leads to anion desorption. Underpotential deposition (upd) of electropositive metal layers results in dramatic blue-shifts of the surface plasmon band of the substrate. The deposition of just 0.1 monolayer can be readily detected by eye. In some cases alloying occurs spontaneously during upd. Alloy formation can be ascertained from the optical absorption spectrum in the case of gold deposition onto silver sols. The underpotential deposition of silver adatoms onto palladium leads to the formation of a homogeneous silver shell, but the mean free path is less than predicted, due to lattice strain in t...

Surface Plasmon Spectroscopy of Nanosized Metal Particles

The development of novel materials is a fundamental focal point of chemical research; and this interest is mandated by advancements in all areas of industry and technology. A good example of the synergism between scientific discovery and technological development is the electronics industry, where discoveries of new semiconducting materials resulted in the evolution from vacuum tubes to diodes and transistors, and eventually to miniature chips. The progression of this technology led to the development * To whom correspondence should be addressed. B.L.C.: (504) 2801385 (phone); (504) 280-3185 (fax); bcushing@uno.edu (e-mail). C.J.O.: (504)280-6846(phone);(504)280-3185(fax);coconnor@uno.edu (e-mail). 3893 Chem. Rev. 2004, 104, 3893−3946

http://depa.fquim.unam.mx/amyd//archivero/FidelmarLechugaSanabria_4940.pdf

Recent advances in the liquid-phase syntheses of inorganic nanoparticles.

Reduced transition metal colloids: a novel family of reusable catalysts

Progress in preparation, processing and applications of polyaniline

On the determination of uraniumoxygen bond lengths in dioxouranium(VI) compounds by Raman spectroscopy

Mixed-ion linear actuation behaviour of polypyrrole

The Fourier transform-infrared (FT-IR) and polarized FT-Raman spectra of titanium tetraisopropoxide (tetraisopropoxytitanium, TPT), in pure and diluted forms, and of 2-propanol have been investigated in conjunction with previous assignments for related compounds to obtain a comprehensive assignment of the vibrational spectra. Evidence was obtained for the presence of both monomeric and associated species of TPT. The latter are formed by coordination expansion through bridging isopropoxy ligands. For both monomeric and associated TPT species, vibrational modes of isopropoxy ligands with ν(C−O) mode character were coupled to νs(Ti−O) and νas(Ti−O) modes (interligand coupling). The symmetrically coupled ligand modes gave rise to intense, strongly polarized bands in the Raman spectrum. The antisymmetrically coupled ligand modes gave rise to strong bands in the IR spectrum at lower wavenumbers than the corresponding Raman bands. Molecular association of TPT produced negligible shifts in the ligand modes couple...

Vibrational Spectra and Molecular Association of Titanium Tetraisopropoxide.

Electrospray mass spectrometry provides a rapid, convenient technique for characterizing and studying the chemistry of anionic metal sulfide thiolate clusters. Negative-ion electrospray mass spectra have been recorded for the thiophenolate-capped clusters [Me4N]4[E4Cd10(SPh)16] (E = S, Se), [Me4N]4[S4Zn10(SPh)16], and [Me4N]2[S4Cd17(SPh)28] and of the metal thiophenolate complexes [Me4N]2[M(SPh)4], [Me4N]2[M4(SPh)10] (M = Cd, Zn), and [Et4N]2[Cd4X4(SPh)6] (X= Cl, Br, I). The exchanges of M, E, and X which occur in various mixtures of these clusters and complexes and the fragmentation processes have been investigated. In the clusters the M−E bonds involving the sulfide or selenide core remain intact during the observed fragmentation at low cone voltages. At high cone voltages, monoions are ultimately formed by loss of charged species and neutral M(SPh)2, resulting in almost complete removal of the SPh- ligands from the cluster core. Fragmentation of the ME core unit itself occurs only at very high voltages...

Electrospray Mass Spectrometry of Thiophenolate-Capped Clusters of CdS, CdSe, and ZnS and of Cadmium and Zinc Thiophenolate Complexes: Observation of Fragmentation and Metal, Chalcogenide, and Ligand Exchange Processes.

The combined techniques of in situ Raman microscopy and scanning electron microscopy (SEM) have been used to study the selective oxidation of methanol to formaldehyde and the ethene epoxidation reaction over polycrystalline silver catalysts. The nature of the oxygen species formed on silver was found to depend critically upon the exact morphology of the catalyst studied. Bands at 640, 780 and 960 cm–1 were identified only on silver catalysts containing a significant proportion of defects. These peaks were assigned to subsurface oxygen species situated in the vicinity of surface dislocations, AgIIIO sites formed on silver atoms modified by the presence of subsurface oxygen and O2– species stabilized on subsurface oxygen-modified silver sites, respectively. The selective oxidation of methanol to formaldehyde was determined to occur at defect sites, where reaction of methanol with subsurface oxygen initially produced subsurface OH species (451 cm–1) and adsorbed methoxy species.Two distinct forms of adsorbed ethene were identified on oxidised silver sites. One of these was created on silver sites modified by the interaction of subsurface oxygen species, and the other on silver crystal planes containing a surface coverage of atomic oxygen species. The selective oxidation of ethene to ethylene oxide was achieved by the reaction between ethene adsorbed on modified silver sites and electrophilic AgIIIO species, whereas the combustion reaction was perceived to take place by the reaction of adsorbed ethene with nucleophilic surface atomic oxygen species. Defects were determined to play a critical role in the epoxidation reaction, as these sites allowed the rapid diffusion of oxygen into subsurface positions, and consequently facilitated the formation of the catalytically active AgIIIO sites.

Ralph P. Cooney

Papers

On the determination of uraniumoxygen bond lengths in dioxouranium(VI) compounds by Raman spectroscopy

Mixed-ion linear actuation behaviour of polypyrrole

Vibrational Spectra and Molecular Association of Titanium Tetraisopropoxide.

Electrospray Mass Spectrometry of Thiophenolate-Capped Clusters of CdS, CdSe, and ZnS and of Cadmium and Zinc Thiophenolate Complexes: Observation of Fragmentation and Metal, Chalcogenide, and Ligand Exchange Processes.

In situ Raman studies of the selective oxidation of methanol to formaldehyde and ethene to ethylene oxide on a polycrystalline silver catalyst