Highly Occupied Surface States at Deuterium-Grown Boron-Doped Diamond Interfaces for Efficient Photoelectrochemistry.

Polycrystalline boron-doped diamond is a promising material for high-power aqueous electrochemical applications in bioanalytics, catalysis, and energy storage. The chemical vapor deposition (CVD) process of diamond formation and doping is totally diversified by using high kinetic energies of deuterium substituting habitually applied hydrogen. The high concentration of deuterium in plasma induces atomic arrangements and steric hindrance during synthesis reactions, which in consequence leads to a preferential (111) texture and more effective boron incorporation into the lattice, reaching a one order of magnitude higher density of charge carriers. This provides the surface reconstruction impacting surficial populations of CC dimers, CH, CO groups, and COOH termination along with enhanced kinetics of their abstraction, as revealed by high-resolution core-level spectroscopies. A series of local densities of states were computed, showing a rich set of highly occupied and localized surface states for samples deposited in deuterium, negating the connotations of band bending. The introduction of enhanced incorporation of boron into (111) facet of diamond leads to the manifestation of surface electronic states below the Fermi level and above the bulk valence band edge. This unique electronic band structure affects the charge transfer kinetics, electron affinity, and diffusion field geometry critical for efficient electrolysis, electrocatalysis, and photoelectrochemistry.

Phase, Composition and Structure Changes of CoCrNi-Based Concentrated Alloys Resulting from High Temperature Oxidation.

In this work, CoCrNi, FeCoCrNi and CoCrFeMnNi concentrated alloys with a Y-Ti oxide particle dispersion were prepared by mechanical alloying and Spark Plasma Sintering. The alloy consists of an FCC Ni-based matrix with a Y-Ti oxide dispersion and additional phases of Cr23C6 and Cr2O3. The effect of Fe, Mn, and Y-Ti oxide particles on the formation of oxide scales and the composition of the adjacent CoCrNi and FeCoCrNi alloys was studied. It was found that alloys without Mn in their composition form a protective Cr2O3 scale. The Cr23C6 particles provide an alternative mechanism for balancing the chromium loss during the oxidation. Y and Ti from the oxide particles participate in the formation of the protective oxide scales. Fe promotes Y and especially Ti diffusion through the Cr2O3 scale, resulting in the formation of Ti-depleted regions in the alloy. The findings will serve for the further development of these new materials.

Preparation of vermiculite nanoparticles using thermal hydrogen peroxide treatment.

Powdered natural Mg-vermiculite (Letovice, Czech Republic), with the formula (Mg0.35K0.02Ca0.01) (Mg2.39Fe0.51(3+)Fe0.02(2+)Al0.08) (Si2.64Al1.33Ti0.03) O10(OH)2 x 4.97H2O and particle size < 5 microm, was used for the investigation of exfoliation after hydrogen peroxide and/or microwave treatment (600 W). A sample heated in the microwave oven for 40 min exhibits a 11% mass loss and reduction of the 001 peak intensity in the X-ray diffraction pattern. The basal 001 peak intensity of untreated Mg-vermiculite sample (/001 = 100%) drops to 35% in the microwave treated sample. Only the sample treated for 5 h at 80 degrees C fully rehydrated after 120 min at room temperature. A more pronounced reduction of the 001 peak intensity (to 8%) was observed after hydrogen peroxide treatment of the sample at 25 degrees C. The combination of a five-hour hydrogen peroxide treatment at 80 degrees C and subsequent microwave heating leads to an effective extinction of the 001 diffraction in the XRD pattern. The 001 diffraction profile becomes very diffuse with peak intensity less than 1%. The degree of reduction of the 001 diffraction intensity also depends on the time and temperature of hydrogen peroxide treatment and on the peroxide concentration. An even more pronounced reduction of the peak intensity is caused by exfoliation of particles to nano-domains coupled with a randomization of the c-axes.

Effect of surface and interlayer structure on the fluorescence of rhodamine B-montmorillonite: modeling and experiment.

The surface and interlayer structure of rhodamine B (RhB)-montmorillonite for various guest concentrations has been studied using a combination of X-ray powder diffraction and molecular modeling (molecular mechanics and molecular dynamics) in the Cerius(2) modeling environment. The joint effect of surface and interlayer structure on the fluorescence spectrum has been observed and discussed in relation to the position and orientation of RhB(+) cations with respect to the silicate layer. Structural analysis showed that the surface and interlayer structures are different as to the arrangement of RhB(+) cations, and both of them strongly depend on the guest concentration in the intercalation solution and on the method of preparation. The repeated intercalation of montmorillonite by rhodamine B used in the present work allowed obtaining RhB-montmorillonite in the maximum degree of ion exchange for every sample.

Combination of modeling and experiment in structure analysis of intercalated layer silicates.

A strategy for the structure analysis of intercalated layer silicates based on a combination of modeling (i.e. force field calculations) and experiment is presented. Modeling in conjunction with experiment enables us to analyze the disordered intercalated structures of layer silicates where conventional diffraction analysis fails. Experiment plays a key role in the modeling strategy and in corroboration of the modeling results. X-ray powder diffraction and IR spectroscopy were found to be very useful complementary experiments to molecular modeling. Molecular mechanics and molecular dynamics simulations were carried out in the Cerius2 and Materials Studio modeling environments. An overview is given of the structures of layer silicates, especially smectites intercalated with various inorganic and organic guest species. Special attention is paid to the ordering of guests in the interlayer space, as it is important for the practical applications of these intercalates, where the interlayer porosity, photofunctions, etc. must be controlled. Figure Structure of montmorillonite intercalated with octadecylamine via ion-dipole interaction with the maximum concentration of guests corresponding to the monolayer arrangement of guests with basal spacing 33.3 A. The Na cations remaining in the interlayer are visualized as pink balls

Structure analysis of montmorillonite intercalated with rhodamine B: modeling and experiment.

The intercalation process and the structure of montmorillonite intercalated with [rhodamine B]+ cations have been investigated using molecular modeling (molecular mechanics and molecular dynamics simulations), X-ray powder diffraction and IR spectroscopy. The structure of the intercalate depends strongly on the concentration of rhodamine B in the intercalation solution. The presence of two phases in the intercalated structure was revealed by modeling and X-ray powder diffraction: (i) phase with basal spacing 18 A and with bilayer arrangement of guests and (ii) phase with average basal spacing 23 A and with monolayer arrangement of guests. In both phases the monomeric and dimeric arrangement can coexist in the interlayer space. Three types of dimers in the interlayer structure have been found by modeling: (i) H-dimer (head-to-head arrangement) present in the 18 A phase, (ii) sandwich type of the head-to-tail arrangement (present in the 23 A phase) and (iii) J-dimer (head-to-tail arrangement) present in the 23 A phase. Figure Montmorillonite intercalated with rhodamine B cations. On the left: phase 18 A, bilayer dimeric arrangement of guests (H-dimers). On the right: phase 23 A, monolayer arrangement of guests prepared using intercalation solution with a low concentration of rhodamine B