Direct Synthesis of Tertiary Phosphines via Alkoxide-Mediated Deborylative Phosphination of Organoboronates.

The direct transformation of alkylboron has emerged as a versatile and powerful methodology for creating carbon-carbon and carbon-heteroatom bonds. However, its potential application in the formation of carbon and phosphorus remains unexplored. In this study, we present an alkoxide base-promoted reaction system that enables deborylative phosphination of benzylic organoboronates and geminal bis(boronates) via selective C-B bond cleavage. This approach allows for the synthesis of valuable tertiary phosphines in good yields under mild conditions. The practicality and industrial potential of this approach are underscored by the operational simplicity, broad substrate scope, and easy scalability.

Facile preparation of organosilanes from benzylboronates and gem-diborylalkanes mediated by KOtBu.

Methods to efficiently synthesize organosilanes are valuable in the fields of synthetic chemistry and materials science. During the past decades, boron conversion has become a generic and powerful approach for constructing carbon-carbon and other carbon-heteroatom bonds, but its potential application in forming carbon-silicon remains unexplored. Herein, we describe an alkoxide base-promoted deborylative silylation of benzylic organoboronates, geminal bis(boronates) or alkyltriboronates, allowing for straightforward access to synthetically valuable organosilanes. This selective deborylative methodology exhibits operational simplicity, broad substrate scope, excellent functional group compatibility and convenient scalability, providing an effective and complementary platform for the generation of diversified benzyl silanes and silylboronates. Detailed experimental results and calculated studies revealed an unusual mechanistic feature of this C-Si bond formation.

Effect of potato flour on quality and staling properties of wheat-potato flour bread.

To elucidate the impact of potato flour (PF) on quality changes and staling characteristics of the composite bread from wheat-potato flour (WPF), the physicochemical (specific volume, colority, sensory value, texture, and viscosity) properties, and staling (X-ray diffraction and water migration) properties of bread were investigated. The quality of composite bread was comparable to wheat bread when addition level of PF at 20%, but decreased when the addition level increased to 30% or more, and became unacceptable at 50%. A chewy mouthfeel and an elastic and none-crumbly texture were observed on composite bread, which had higher hardness than wheat bread, and could keep on both longer linear distance and higher linear force during compression test. It indicated that such new parameters other than hardness should be introduced to coordinate with the texture quality of composite bread. During storage, the higher addition level of PF significantly decreased crystallinity of composite bread and slowed water migration rate from the crumb to crust, suggesting that PF had antistaling effect on composite bread, which was further emphasized by the fact that the setback value of the WPF decreased with the increase of PF addition.

The effects of extruded corn flour on rheological properties of wheat-based composite dough and the bread quality.

The effects of extruded corn flour (ECF) on the rheological properties of the wheat-based composite dough and quality of the bread were investigated. The RVA results of the composite flour with ECF showed weak thermal viscosity and resistance to starch retrogradation. Mixolab tests revealed that the water absorption capacity increased with the increasing amount of ECF, while dough development time (DT) and dough stability (ST) showed a downward trend, and the composite dough became more resistant to retrogradation. The microstructure of the composite dough showed that the presence of both ECF and unextruded corn flour (UECF) resulted in a more broken gluten matrix. The breads made from the composite flour with ECF had significantly softer texture, lower hardening percentage with storage time, darker crust color, larger specific volume, and higher sensory scores than the UECF ones. It is concluded that the extrusion of corn flour is an effective way to improve the quality of the composite bread and retard staling during storage.

Electron-Enhanced Atomic Layer Deposition of Boron Nitride Thin Films at Room Temperature and 100 °C.

Electron-enhanced atomic layer deposition (EE-ALD) was used to deposit boron nitride (BN) thin films at room temperature and 100 °C using sequential exposures of borazine (B3N3H6) and electrons. Electron-stimulated desorption (ESD) of hydrogen surface species and the corresponding creation of reactive dangling bonds are believed to facilitate borazine adsorption and reduce the temperature required for BN film deposition. In situ ellipsometry measurements showed that the BN film thickness increased linearly versus the number of EE-ALD cycles at room temperature. Maximum growth rates of ~3.2 Å/cycle were measured at electron energies of 80-160 eV. BN film growth was self-limiting versus borazine and electron exposures, as expected for an ALD process. The calculated average hydrogen ESD cross section was σ = 4.2 × 10-17 cm2. Ex situ spectroscopic ellipsometry measurements across the ~1 cm2 area of the BN film defined by the electron beam displayed good uniformity in thickness. Ex situ X-ray photoelectron spectroscopy and in situ Auger spectroscopy revealed high purity, slightly boron-rich BN films with C and O impurity levels <3 at. %. High-resolution transmission electron microscopy (HR-TEM) imaging revealed polycrystalline hexagonal and turbostratic BN with the basal planes approximately parallel to the substrate surface. Ex situ grazing incidence X-ray diffraction measurements observed peaks consistent with hexagonal BN with domain sizes of 1-2 nm. The BN EE-ALD growth rate of ~3.2 Å/cycle is close to the distance of 3.3 Å between BN planes in hexagonal BN. The growth rate and HR-TEM images suggest that approximately one monolayer of BN is deposited for every BN EE-ALD cycle. TEM and scanning TEM/electron energy loss spectroscopy measurements of BN EE-ALD on trenched wafers also showed preferential BN EE-ALD on the horizontal surfaces. This selective deposition on the horizontal surfaces suggests that EE-ALD may enable bottom-up filling of vias and trenches.

Coating Solution for High-Voltage Cathode: AlF3 Atomic Layer Deposition for Freestanding LiCoO2 Electrodes with High Energy Density and Excellent Flexibility.

Freestanding LiCoO2/multiwall carbon nanotube/nanocellulose fibril (LCO-MWCNT-NCF) electrodes are fabricated by a vacuum filtration technique. The electrode has a high LCO loading of 20 mg/cm2 with excellent flexibility, uniform material distribution, and low surface resistivity. When coated with 2 ALD cycles of AlF3, LCO-MWCNT-NCF has a high specific capacity of 216 mAh/g at 4.7 V. The freestanding AlF3-coated electrode preserves 75.7% of its initial capacity after 100 cycles and 70% after 160 cycles of charge discharge. In contrast, electrodes coated with 2 ALD cycles of Al2O3 cannot be cycled above 4.5 V. By elimination of the unnecessary weight of current collector, and increasing in the working voltage simultaneously, this freestanding LCO-MWCNT-NCF electrode can significantly improve the gravimetric and volumetric energy density of lithium ion batteries.

In Situ Engineering of the Electrode-Electrolyte Interface for Stabilized Overlithiated Cathodes.

The first-ever demonstration of stabilized Si/lithium-manganese-rich full cells, capable of retaining >90% energy over early cycling and >90% capacity over more than 750 cycles at the 1C rate (100% depth-of-discharge), is made through the utilization of a modified ionic-liquid electrolyte capable of forming a favorable cathode-electrolyte interface.

Electron Enhanced Growth of Crystalline Gallium Nitride Thin Films at Room Temperature and 100 °C Using Sequential Surface Reactions.

Low energy electrons may provide mechanisms to enhance thin film growth at low temperatures. As a proof of concept, this work demonstrated the deposition of gallium nitride (GaN) films over areas of ∼5 cm2 at room temperature and 100 °C using electrons with a low energy of 50 eV from an electron flood gun. The GaN films were deposited on Si(111) wafers using a cycle of reactions similar to the sequence employed for GaN atomic layer deposition (ALD). Trimethylgallium (Ga(CH3)3, TMG), hydrogen (H) radicals and ammonia (NH3) were employed as the reactants with electron exposures included in the reaction cycle after the TMG/H and NH3 exposures. A number of ex situ techniques were then employed to analyze the GaN films. Spectroscopic ellipsometry measurements revealed that the GaN films grew linearly with the number of reaction cycles. Linear growth rates of up to 1.3 Å/ cycle were obtained from the surface areas receiving the highest electron fluxes. Grazing incidence X-ray diffraction analysis revealed polycrystalline GaN films with the wurtzite crystal structure. Transmission electron microscopy (TEM) images showed crystalline grains with diameters between 2 and 10 nm depending on the growth temperature. X-ray photoelectron spectroscopy depth-profiling displayed no oxygen contamination when the GaN films were capped with Al prior to atmospheric exposure. However, the carbon concentrations in the GaN films were 10-35 at. %. The mechanism for the low temperature GaN growth is believed to result from the electron stimulated desorption (ESD) of hydrogen. Hydrogen ESD yields dangling bonds that facilitate Ga-N bond formation. Mass spectrometry measurements performed concurrently with the reaction cycles revealed increases in the pressure of H2 and various GaN etch products during the electron beam exposures. The amount of H2 and GaN etch products increased with electron beam energy from 25 to 200 eV. These results indicate that the GaN growth occurs with competing GaN etching during the reaction cycles.

Tuning electron transport in graphene-based field-effect devices using block co-polymers.

Graphene possesses many remarkable properties and shows promise as the future material for building nanoelectronic devices. For many applications such as graphene-based field-effect transistors (GFET), it is essential to control or modulate the electronic properties by means of doping. Using spatially controlled plasma-assisted CF(4) doping, the Dirac point shift of a GFET covered with a polycrystalline PS-P4VP block co-polymer (BCP) [poly(styrene-b-4-vinylpyridine)] having a cylindrical morphology can be controlled. By changing the chemical component of the microdomain (P4VP) and the major domain (PS) with the CF(4) plasma technique, the doping effect is demonstrated. This work provides a methodology where the Dirac point can be controlled via the different sensitivities of the PS and P4VP components of the BCP subjected to plasma processing.

Activation of Metal-Organic Precursors by Electron Bombardment in the Gas Phase for Enhanced Deposition of Solid Films.

The incorporation of gas-phase electron-impact ionization and activation of metal-organic compounds into atomic layer deposition (ALD) processes is reported as a way to enhance film growth with stable precursors. Specifically, it is shown here that gas-phase activation of methylcyclopentadienylmanganese tricarbonyl, MeCpMn(CO)3, which was accomplished by using a typical nude ion gauge employed in many ultrahigh-vacuum (UHV) studies, enhances its dissociative adsorption on silicon surfaces, affording the design of ALD cycles with more extensive Mn deposition and at lower temperatures. Significantly higher Mn uptakes were demonstrated by X-ray photoelectron spectroscopy (XPS) on both silicon dioxide films and on Si(100) wafers Ar(+)-sputtered to remove their native oxide layer. The effectiveness of this electron-impact activation approach in ALD is explained in terms of the cracking patterns seen in mass spectrometry for the metal-organic precursor used.

Restructuring-induced activity of SiO(2)-supported large au nanoparticles in low-temperature CO oxidation.

Large Au nanoparticles with an average size of approximately 10 nm supported on inert SiO(2) become active in low-temperature CO oxidation after the addition of NaNO(3). The catalyst structures have been characterized in detail by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and X-ray absorption spectroscopy. The NaNO(3) additive in Au/SiO(2) catalysts does not lead to the formation of fine Au nanoparticles, which are generally considered to be inevitable in low-temperature CO oxidation catalyzed by gold, nor does it alter the electronic structure of Au. The NaNO(3)-induced restructuring of large Au nanoparticles was proposed to create low-coordinated Au sites on the surface capable of catalyzing low-temperature CO oxidation. These results experimentally prove that the activity of supported Au nanoparticles in low-temperature CO oxidation could solely arise from their geometric structure, which greatly deepens the fundamental understandings of Au nanocatalysis.