Frustrated Lewis pairs: Design and reactivity

The interaction of a Lewis acid with a Lewis base results in the formation of a Lewis acid base adduct. Understanding Lewis acids and bases is central to conceptualizing chemical interactions and constitutes a major portion of metal ligand chemistry. Sterically encumbered/constrained Lewis pairs cannot form acid-base adducts, but such `Frustrated Lewis Pairs' (FLPs), with their unquenched electronic demands can be elegantly used to simultaneously react with a third species, resulting in unusual reactivity of small molecules. Such unusual reactions, explored only in the last few years, have found several applications, e.g., heterolytic splitting of H-2, activation of small molecules (CO2, N2O, etc.). FLPs have opened new opportunities in synthetic chemistry, covering organic, main group as well as transition metal chemistry. The design strategies adopted for FLP systems and their unique reactivity are discussed here.

A predictive approach to CVD of crystalline layers of TMDs: the case of MoS2

Layered transition metal dichalcogenides (TMDs), such as MoS2, are candidate materials for next generation 2-D electronic and optoelectronic devices. The ability to grow uniform, crystalline, atomic layers over large areas is the key to developing such technology. We report a chemical vapor deposition (CVD) technique which yields n-layered MoS2 on a variety of substrates. A generic approach suitable to all TMDs, involving thermodynamic modeling to identify the appropriate CVD process window, and quantitative control of the vapor phase supersaturation, is demonstrated. All reactant sources in our method are outside the growth chamber, a significant improvement over vapor-based methods for atomic layers reported to date. The as-deposited layers are p-type, due to Mo deficiency, with field effect and Hall hole mobilities of up to 2.4 cm(2) V-1 s(-1) and 44 cm(2) V-1 s(-1) respectively. These are among the best reported yet for CVD MoS2.

Structural modification and enhanced magnetic properties with two phonon modes in Ca-Co codoped BiFeO3 nanoparticles

Bi1-xCaxFe1-xCoxO3 nanoparticles with x=0.0, 0.05, 0.10 and 0.15 were successfully synthesized by cost effective tartaric acid based sol gel route. The alkali earth metal Ca2+ ions and transition metal Co3+ ions codoping at A and B-sites of BiFeO3 results in structural distortion and phase transformation. Rietveld refinement of XRD patterns suggested the coexistence of rhombohedral and orthorhombic phases in codoped BiFeO3 samples. Both XRD and Raman scattering studies showed the compressive lattice distortion in the samples induced by codoping of Ca2+ and Co3+ ions. Two-phonon Raman spectra exhibited the improvement of magnetization in these samples. X-ray photoelectron spectroscopy (XPS) showed the dominancy of Fe3+ and Co3+ oxidation states along with the shifting of the binding energy of Bi 4f orbital which confirms the substitution Ca2+ at Bi-site. The magnetic study showed the enhancement in room temperature ferromagnetic behavior with co-substitution consistent with Rama analysis. The gradual change in line shape of electron spin resonance spectra indicated the local distortion induced by codoping. (C) 2015 Published by Elsevier Ltd and Techna Group S.r.l.

Copper oxide nanoparticles: an antidermatophytic agent for Trichophyton spp.

Copper oxide (CuO) is one of the most important transition metal oxides due to its unique properties. It is used in various technological applications such as high critical temperature, superconductors, gas sensors, in photoconductive applications and so on. Recently, it has been used as an antimicrobial agent against various pathogenic bacteria. In the present investigation, we studied the structural and antidermatophytic properties of CuO nanoparticles (NPs) synthesized by a precipitation technique. Copper sulfate was used as a precursor and sodium hydroxide as a reducing agent. Scanning electron microscopy (SEM) showed flower-shaped CuO NPs and X-ray diffraction (XRD) pattern showed the crystalline nature of CuO NPs. These NPs were evaluated against two prevalent species of dermatophytes, i.e. Trichophyton rubrum and T. mentagrophytes by using the broth microdilution technique. Further, the NPs activity was also compared with synthetic sertaconazole. Although better antidermatophytic activity was exhibited with sertaconazole as compared to NPs, being synthetic, sertaconazole may not be preferred, as it shows different adverse effects. Trichophyton mentagrophytes is more susceptible to NPs than T. rubrum. A phylogenetic approach was applied for predicting differences in susceptibility of pathogens.

Organic-inorganic hybrid PtCo nanoparticle with high electrocatalytic activity and durability for oxygen reduction

In Pt-transition metal (TM) alloy catalysts, the electron transfer from the TM to Pt is retarded owing to the inevitable oxidation of the TM surface by oxygen. In addition, acidic electrolytes such as those employed in fuel cells accelerate the dissolution of the surface TM oxide, which leads to catalyst degradation. Herein, we propose a novel synthesis strategy that selectively modifies the electronic structure of surface Co atoms with N-containing polymers, resulting in highly active and durable PtCo nanoparticle catalysts useful for the oxygen reduction reaction (ORR). The polymer, which is functionalized on carbon black, selectively interacts with the Co precursor, resulting in Co-N bond formation on the PtCo nanoparticle surface. Electron transfer from Co to Pt in the PtCo nanoparticles modified by the polymer is enhanced by the increase in the difference in electronegativity between Pt and Co compared with that in bare PtCo nanoparticles with the TM surface oxides. In addition, the dissolution of Co and Pt is prevented by the selective passivation of surface Co atoms and the decrease in the O-binding energy of surface Pt atoms. As a result, the catalytic activity and durability of PtCo nanoparticles for the ORR are significantly improved by the electronic ensemble effects. The proposed organic/inorganic hybrid concept will provide new insights into the tuning of nanomaterials consisting of heterogeneous metallic elements for various electrochemical and chemical applications.

Optical-Phonon-Limited High-Field Transport in Layered Materials

An optical-phonon-limited velocity model has been employed to investigate high-field transport in a selection of layered 2-D materials for both, low-power logic switches with scaled supply voltages, and high-power, high-frequency transistors. Drain currents, effective electron velocities, and intrinsic cutoff frequencies as a function of carrier density have been predicted, thus providing a benchmark for the optical-phonon-limited high-field performance limits of these materials. The optical-phonon-limited carrier velocities for a selection of multi-layers of transition metal dichalcogenides and black phosphorus are found to be modest compared to their n-channel silicon counterparts, questioning the utility of biasing these devices in the source-injection dominated regime. h-BN, at the other end of the spectrum, is shown to be a very promising material for high-frequency, high-power devices, subject to the experimental realization of high carrier densities, primarily due to its large optical-phonon energy. Experimentally extracted saturation velocities from few-layer MoS2 devices show reasonable qualitative and quantitative agreement with the predicted values. The temperature dependence of the measured v(sat) is discussed and compared with the theoretically predicted dependence over a range of temperatures.

Characterization of silver-kaolinite (AgK): an adsorbent for long-lived I-129 species

Bentonite is a preferred buffer and backfill material for deep geological disposal of high-level nuclear waste (HLW). Bentonite does not retain anions by virtue of its negatively charged basal surface. Imparting anion retention ability to bentonite is important to enable the expansive clay to retain long-lived I-129 (iodine-129; half-life = 16 million years) species that may escape from the HLW geological repository. Silver-kaolinite (AgK) material is prepared as an additive to improve the iodide retention capacity of bentonite. The AgK is prepared by heating kaolinite-silver nitrate mix at 400 degrees C to study the kaolinite influence on the transition metal ion when reacting at its dehydroxylation temperature. Thermo gravimetric-Evolved Gas Detection analysis, X-ray diffraction analysis, X-ray photo electron spectroscopy and electron probe micro analysis indicated that silver occurs as AgO/Ag2O surface coating on thermally reacting kaolinite with silver nitrate at 400 degrees C.

NH3 adsorption on PtM (Fe, Co, Ni) surfaces: Cooperating effects of charge transfer, magnetic ordering and lattice strain

Adsorption of a molecule or group with an atom which is less electronegative than oxygen (0) and directly interacting with the surface is very relevant to development of PtM (M = 3d-transition metal) catalysts with high activity. Here, we present theoretical analysis of the adsorption of NH3 molecule (N being less electronegative than 0) on (111) surfaces of PtM (Fe, Co, Ni) alloys using the first principles density functional approach. We find that, while NH3-Pt interaction is stronger than that of NH3 with the elemental M-surfaces, it is weaker than the strength of interaction of NH3 with M-site on the surface of PtM alloy. (C) 2016 Published by Elsevier B.V.

Effects of pre-treatment and plasma enhancement on chemical vapor deposition of carbon nanotubes from ultra-thin catalyst films

We report a detailed study of surface-bound chemical vapor deposition of carbon nanotubes and nanofibers from evaporated transition metal catalysts exposed to ammonia diluted acetylene. We show that a reduction of the Fe/Co catalyst film thickness below 3 nm results into a transition from large diameter (> 40 nm), bamboo-like nanofibers to small diameter (similar to 5 nm) multi-walled carbon nanotubes. The nanostructuring of ultrathin catalyst films critically depends on the gas atmosphere, with the resulting island distribution initiating the carbon nucleation. Compared to purely thermal chemical vapor deposition, we find that, for small diameter nanotube growth, DC plasma assistance is detrimental to graphitization and sample homogeneity and cannot prevent an early catalyst poisoning. (c) 2006 Elsevier B.V. All rights reserved.

Domain structure of a Nd60Al10Fe20Co10 bulk metallic glass

Magnetic domain structure of Nd60Al10Fe20Co10 bulk metallic glass (BMG) has been studied by using magnetic-force microscopy. In the magnetic-force images it is shown that the exchange-interaction-type magnetic domains with a period of about 360 nm do exist in the BMG, which is believed to be associated with the appearance of hard-magnetic properties in this system. The existence of the large-scale domains demonstrates that the magnetic moments of a great deal of short-scale ordered atomic clusters in the BMG have been aligned by exchange coupling. Annealing at 715 K leads to partial crystallization of the BMG. However, the exchange coupling is stronger in the annealed sample, which is considered to arise from the increase of transition-metal concentration in the amorphous phase due to the precipitation of Nd crystalline phase.

Estudio de la reducción de SO2 con CH4 en presencia de O2 a altas temperaturas, sobre catalizador de Cr2O3 soportado en alúmina

Resumen: Se propone utilizar un óxido como el Cr2O3 como catalizador ya que se ha determinado anteriormente, en la primera etapa de esta investigación, (“Estudio comparativo de la retención de SO2 sobre óxidos de metales de transición soportados en alúmina”), que la retención de SO2 sobre su superficie es un proceso de quimisorción con formación de especies sulfito superficiales sobre sitios básicos y un proceso de óxido reducción del ión metálico. Apoya este mecanismo el hecho de que la cantidad de SO2 adsorbido es función de la temperatura. La mayor eficiencia del Cr2O3 puede explicarse en base a sus propiedades superficiales, lo cual ha sido utilizado en la segunda etapa de reacción de reducción, ya que se ha completado la etapa inicial de quimisorción. En la segunda etapa de esta investigación (“Estudio de la reacción de reducción de SO2 con CH4 a altas temperaturas sobre catalizador de Cr2O3 soportado en alúmina”), se apuntó al estudio de un nuevo tipo de sinergia entre propiedades ácido-base y propiedades redox en una misma superficie. Esta tercera etapa apuntó a determinar la influencia que tiene el O2 en este proceso, ya que el O2 se encuentra presente en las chimeneas industriales en las condiciones de reacción entre el SO2 y el CH4, y produce modificaciones en los parámetros de reacción. Se experimentó con diferentes masas de catalizador y flujos de los distintos gases, y se estudió la influencia de la presencia de oxígeno en la reacción y particularmente con diferentes flujos del mismo, y la posibilidad de regeneración del catalizador.

Estudio de la factibilidad de aplicación, a escala planta piloto, del catalizador Cr2O3, soportado en alúmina, en la reducción de emisión de SO2 a la atmósfera proveniente de fuentes fijas

Resumen: Se propone utilizar un óxido como el Cr2O3 como catalizador ya que se ha determinado anteriormente, en la primera etapa de esta investigación, (“Estudio comparativo de la retención de SO2 sobre óxidos de metales de transición soportados en alúmina”), que la retención de SO2 sobre su superficie es un proceso de quimisorción con formación de especies sulfito superficiales sobre sitios básicos y un proceso de óxido reducción del ión metálico. Apoya este mecanismo el hecho de que la cantidad de SO2 adsorbido es función de la temperatura. La mayor eficiencia del Cr2O3 puede explicarse en base a sus propiedades superficiales, lo cual ha sido utilizado en la segunda etapa de reacción de reducción, ya que se ha completado la etapa inicial de quimisorción. En la segunda etapa de esta investigación (“Estudio de la reacción de reducción de SO2 con CH4 a altas temperaturas sobre catalizador de Cr2O3 soportado en alúmina”), se apuntó al estudio de un nuevo tipo de sinergia entre propiedades ácido-base y propiedades redox en una misma superficie. La tercera etapa apuntó a determinar la influencia que tiene el O2 en este proceso, ya que el O2 se encuentra presente en las chimeneas industriales en las condiciones de reacción entre el SO2 y el CH4, y produce modificaciones en los parámetros de reacción. Se experimentó con diferentes masas de catalizador y flujos de los distintos gases, y se estudió la influencia de la presencia de oxígeno en la reacción y particularmente con diferentes flujos del mismo, y la posibilidad de regeneración del catalizador.En esta cuarta y última etapa se están estudiando los cambios que se producen en la reacción al pasar de escala laboratorio a planta piloto utilizando una columna de mayor diámetro construída en metal. A través de los datos experimentales se está estudiando, en conjunto con el INIFTA, la presencia de especies sulfito y sulfato sobre la superficie del soporte. Adicionalmente, por medio del programa VASP (Vienna Ab-initio Simulation Package), se analiza la interacción entre los reactivos gaseosos y el soporte.

Attempts to Synthesize Cyclic Group 8 Metallaesters

In studying a proposed carbon monoxide reduction scheme an attempt has been made to synthesize bifunctional group 8 transition metal carbonyl complexes containing intramolecular nucleophiles. The incorporation of alkoxide nucleophiles through cyclopentadienyl ligands was hoped to encourage attack on carbonyl ligands thereby forming cyclic metallaesters. The attempts to synthesize these substituted cyclopentadienyl group 8 transition metal complexes have thus far been unsuccessful.

A Study on iron-based amorphous alloys : alloy development, thermodynamics and soft magnetism

Metallic glass has since its debut been of great research interest due to its profound scientific significance. Magnetic metallic glasses are of special interest because of their promising technological applications. In this thesis, we introduced a novel series of Fe-based alloys and offer a holistic review of the physics and properties of these alloys. A systematic alloy development and optimization method was introduced, with experimental implementation on transition metal based alloying system. A deep understanding on the influencing factors of glass forming ability was brought up and discussed, based on classical nucleation theory. Experimental data of the new Fe-based amorphous alloys were interpreted to further analyze those influencing factors, including reduced glass transition temperature, fragility, and liquid-crystal interface free energy. Various treatments (fluxing, overheating, etc.) were discussed for their impacts on the alloying systems' thermodynamics and glass forming ability. Multiple experimental characterization methods were discussed to measure the alloys' soft magnetic properties. In addition to theoretical and experimental investigation, we also gave a detailed numerical analysis on the rapid-discharge-heating-and-forming platform. It is a novel experimental system which offers extremely fast heating rate for calorimetric characterization and alloy deformation.

Functionalization of Si(111) surfaces and the formation of mixed monolayers for the covalent attachment of molecular catalysts in photoelectrochemical devices

The functionalization of silicon surfaces with molecular catalysts for proton reduction is an important part of the development of a solar-powered, water-splitting device for solar fuel formation. The covalent attachment of these catalysts to silicon without damaging the underlying electronic properties of silicon that make it a good photocathode has proven difficult. We report the formation of mixed monolayer-functionalized surfaces that incor- porate both methyl and vinylferrocenyl or vinylbipyridyl (vbpy) moieties. The silicon was functionalized using reaction conditions analogous to those of hydrosilylation, but instead of a H-terminated Si surface, a chlorine-terminated Si precursor surface was used to produce the linked vinyl-modified functional group. The functionalized surfaces were characterized by time-resolved photoconductivity decay, X-ray photoelectron spectroscopy (XPS), electro- chemical, and photoelectrochemical measurements. The functionalized Si surfaces were well passivated, exhibited high surface coverage and few remaining reactive Si atop sites, had a very low surface recombination velocity, and displayed little initial surface oxidation. The surfaces were stable toward atmospheric and electrochemical oxidation. The surface coverage of ferrocene or bipyridine was controllably varied from 0 up to 30% of a monolayer without loss of the underlying electronic properties of the silicon. Interfacial charge transfer to the attached ferrocene group was relatively rapid, and a photovoltage of 0.4 V was generated upon illumination of functionalized n-type silicon surfaces in CH₃CN. The immobilized bipyridine ligands bound transition metal ions, and thus enabled the assembly of metal complexes on the silicon surface. XPS studies demonstrated that [Cp∗Rh(vbpy)Cl]Cl, [Cp∗Ir(vbpy)Cl]Cl, and Ru(acac)₂vbpy were assembled on the surface. For the surface prepared with iridium, x-ray absorption spectroscopy at the Ir L_III edge showed an edge energy and post-edge features virtually identical to a powder sample of [Cp∗Ir(bipy)Cl]Cl (bipy is 2,2 ́-bipyridyl). Electrochemical studies on these surfaces confirmed that the assembled complexes were electrochemically active.