Electron microscopic phase analysis of BN-thin films

A series of BN films was deposited by means of r.f. magnetron sputtering of a h-BN target onto Si(1OO) surfaces. Hereby, the substrate bias voltage was varied. Special interest is focussed to the influence of the deposition parameters on the orientation of the growing hexagonal BN film with respect to the substrate. For structural investigation, cross section samples were prepared. In addition to HRTEM and diffraction investigations, especially electron energy loss spectroscopy (EELS) was applied successfully for phase identification. For negative bias voltages of U _B =–300 V and U _B =–350V, we found a phase system consisting of a first-grown 25 nm thick layer of hexagonal structure with the c axis parallel to the substrate surface followed by the cubic phase.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

2D/2D h‐BN/N‐doped MoS2 Heterostructure Catalyst with Enhanced Peroxidase‐like Performance for Visual Colorimetric Determination of H2O2

Recently, nanozymes have attracted extensive attention because of their advantages of combining nanomaterials with enzymes. Herein, hexagonal boron nitride (h‐BN) and nitride‐doped molybdenum disulfide (N?MoS₂) nano‐composites (h‐BN/N?MoS₂) were synthesized by facile and cost‐effective liquid exfoliation with a solvothermal method in nontoxic ethanol solution. The results show that h‐BN, as a co‐catalyst, can not only dope into the lattice of MoS₂ but also form a heterogeneous structure with MoS₂NSs. It expanded the layer spacing and specific surface area of MoS₂NSs, which was beneficial to the contact between the catalyst and the substrate, and resulted in a synergistic enhancement of the catalytic activity of hydrogen peroxide (H₂O₂) with MoS₂. A colorimetric determination platform of h‐BN/N?MoS₂‐TMB‐H₂O₂ was constructed. It exhibited a wide linear range of 1–1000 μM with a low limit of detection (LOD) of 0.4 μM under optimal conditions, high sensitivity and stability, as well as good reliability (99.4–110.0%) in practice, making the measurement system more widely applicable.1. Introduction     

Colloid-chemical properties of ruthenium dioxide in relation to catalysis of the photochemical generation of hydrogen

A colloid of RuO₂, prepared by thermal decomposition of RuCl₃, was characterized with respect to its colloid-chemical properties and assessed as a catalyst for photochemical production of hydrogen. The RuO₂ proved to be unstable towards coagulation, even under conditions of low electrolyte concentration and in the presence of polymers. The sol manifested the same electric double layer characteristics as many other oxide dispersions. The point of zero charge (p.z.c.) in indifferent electrolyte was positioned at pH 5.75.Adsorption of methylviologen (MV²⁺), a commonly used electron relay in photochemical systems, at the RuO₂/solution interface is mainly a result of attractive coulombic interactions (above the p.z.c. of RuO₂). No indications have been found that it adsorbs on RuO₂ under the operational conditions of hydrogen production. In the hydrogen production system, the mass transfer of methylviologen radicals (MV⁺) is a rate-limiting factor. As a function of the methylviologen concentration, the catalytic production of hydrogen passes through a maximum.Dedicated to Professor Dr. Dr. h. c. Armin Weiss on the occasion of his 60th birthday.     

Determination of the stoichiometry and the Yb2+/Yb3+ ratio in YbF x optical IAD films by RBS and in situ XPS analysis

Thin films of YbF₃ are interesting as a possible component in antireflection coatings matching the CO₂ laser radiation. Ion assisted deposition (IAD) techniques for producing high density films were applied to this material and proved to be most successful in optimising the figures of merit for this purpose (low absorption values, high damage thresholds). Our XPS and RBS measurements, however, reveal a deficiency of fluorine in these IAD films that becomes more pronounced with increasing ion bombardment. The deficiency correlates with an increasing Yb²⁺/Yb³⁺ ratio determined by XPS. It can be concluded that the fluorine deficiency is well compensated by a valence state transition of the Yb ion and the formation of a corresponding amount of YbF₂ in the film. This process appears to be essential for avoiding metallic precipitation and achieving good optical film properties. By applying an in situ XPS technique, results have been obtained that are representative for the bulk of the films as has been confirmed by RBS.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Production and characterization of nitrided CVD-SiC films

Silicon Carbide (SiC) and SiC with free silicon [SiC(Si)] thin films were prepared by chemical vapor deposition (CVD) using a CH₃SiCl₃-H₂-Ar gas mixture at a temperature of 1223 K. Afterwards these layers were gas nitrided in an ammonia-hydrogen-argon mixture at 1273 K. The solid product is an extremely thin film of silicon nitride on SiC or SiC(Si)-basic layers. These ultra thin silicon nitride films were investigated by glow discharge optical spectroscopy (GDOS) and x-ray photoelectron spectroscopy (XPS). The thickness of the layers was determined to a maximum value of 30 nm.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

β-Ga2O3 nanowires sheathed with boron nitrogen

A new synthetic route was developed to obtain β-Ga₂O₃ nanowires by heating mixed B and Ga₂O₃ powder precursor at 1600 °C under Ar atmosphere. The nanowires have widths of 30–60 nm and perfect crystallinity. When the heating of B and Ga₂O₃ powder precursor was carried out in N₂ atmosphere, β-Ga₂O₃ nanowires sheathed with BN layers (3–5 nm) were yielded. The structure and composition of the products were characterized. The growth scenario for the β-Ga₂O₃ nanowires as well as the formation of outer BN sheaths was also discussed.     

Amperometric hydrogen peroxide biosensor based on a glassy carbon electrode modified with polythionine and gold nanoparticles

We report on a novel hydrogen peroxide biosensor that was fabricated by the layer-by-layer deposition method. Thionine was first deposited on a glassy carbon electrode by two-step electropolymerization to form a positively charged surface. The negatively charged gold nanoparticles and positively charged horseradish peroxidase were then immobilized onto the electrode via electrostatic adsorption. The sequential deposition process was characterized using electrochemical impedance spectroscopy by monitoring the impedance change of the electrode surface during the construction process. The electrochemical behaviour of the modified electrode and its response to hydrogen peroxide were studied by cyclic voltammetry. The effects of the experimental variables on the amperometric determination of H₂O₂ such as solution pH and applied potential were investigated for optimum analytical performance. Under the optimized conditions, the biosensor exhibited linear response to H₂O₂ in the concentration ranges from 0.20 to 1.6?mM and 1.6 to 4.0?mM, with a detection limit of 0.067?mM (at an S/N of 3). In addition, the stability and reproducibility of this biosensor was also evaluated and gave satisfactory results.

Structure of Ir-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> coatings obtained by chemical vapor deposition in the hydrogen atmosphere

Chemical vapor deposition is used to obtain Ir and Ir-Al₂O₃ coatings with a thickness of up to 5 μm and growth rate of 2.5 μm/h on steel substrates previously covered with an alumina layer. Tris-acetylacetonates of Ir(III) and Al(III) are used as precursors. The deposition process is carried out at the atmospheric pressure in the presence of hydrogen. The coatings obtained are studied by X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. A dependence of the structure and composition of coatings on their preparation conditions is found.     

An Analysis of Low Frequency Discharge in a CH3SiCl3-Ar-H2 Mixture by Optical Emission Spectroscopy and Actinometry

Low frequency (100 kHz) discharge in Ar-H₂ and CH₃SiCl₃-Ar-H₂ mixtures was studied to obtain information on the processes involved in plasma deposition of Si_xC_y:H films from CH₃SiCl₃-Ar-H₂ plasma once the properties of Ar-H₂ plasma are known. The plasmas were studied using optical emission spectroscopy. The addition of small amounts of nitrogen to the plasma mixtures also permitted the use of an actinometry technique. First, plasma parameters (electron density and temperature) and actinometric concentrations of atomic hydrogen in an argon–hydrogen plasma were investigated as a function of the hydrogen content in the feed. Second, the emission intensities of Si, Si⁺, CH, H, Ar and Ar⁺ species produced in the CH₃SiCl₃-Ar-H₂ discharge were analysed as a function of time following the introduction of CH₃SiCl₃ (methyltrichlorosilane, MTCS) to the argon–hydrogen plasmas with various proportions of the feed gasses. The results reveal a rapid decay of the Si-excited state number density versus time, while those of Si⁺ and CH fell off more slowly. The emission of atomic silicon was believed to be a result of electron impact dissociative and excitation processes occurring in the bulk of the discharge, whereas the Si⁺ and CH seemed to originate mainly from products of sputtering of the growing film surface. The fragmentation of the MTCS associated with HCl formation and enhanced atomic hydrogen production as a result of HCl dissociation are proposed. Variations in the radical densities of H and CH₃ were determined using an actinometry technique. The results indicate a significant role for H₂ in gas-phase reactions occurring in the CH₃SiCl₃-Ar-H₂ plasma, as well as in gas-surface interactions, leading to competition between deposition and chemical sputtering of already deposited material.     

Modeling of the Simultaneous Hydrogen Evolution and Cobalt Electrodeposition

A mathematical model of simultaneous cobalt deposition and hydrogen evolution was developed and applied to the electroreduction process of 5 mM Co²⁺ ions investigated by cyclic voltammetry (CV) technique at different hydrogen ion concentrations (pH=2, 3, 4). The kinetic parameters of such a complex process were determined, and the validity of the model and its sensitivity to changes in individual parameters were verified. The relative value of the approximate standard deviation (ASD_%) was used to determine the degree of fit of the model to the experimental data. The catalytic effect of cobalt on the hydrogen evolution process was comprehensively confirmed.     

Preparation and electrochemical hydrogen storage of boron nitride nanotubes

Boron nitride (BN) nanotubes were synthesized through chemical vapor deposition over a wafer made by a LaNi5/B mixture and nickel powder at 1473 K. Scanning electron microscopy, transmission electron microscopy, energy-dispersive spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were performed to characterize the microstructure and composition of BN nanotubes. It was found that the obtained BN nanotubes were straight with a diameter of 30-50 nm and a length of up to several microns. We first verify that the BN nanotubes can storage hydrogen by means of an electrochemical method, though its capacity is low at present. The hydrogen desorption of nonelectrochemical recombination in cyclic voltammograms, which is considered as the slow reaction at BN nanotubes, suggests the possible existence of strong chemisorption of hydrogen, and it may lead to the lower discharge capacity of BN nanotubes. It is tentatively concluded that the improvement of the electrocatalytic activity by surface modification with metal or alloy would enhance the electrochemical hydrogen storage capacity of BN nanotubes.     

Fraktometrische Analyse von Deuterium im Wasserstoffstrom

Summary A universally usable, quantitative assay for deuterium-labeling work demands a stoichiometrical transformation of all samples into elementary hydrogen. For the detector, it is the best to connect directly a fractometer, that works with a catharometer cell. Tests with several carrier gases and an attempt with a palladium-black column failed; a molecular sieve with ordinary hydrogen as carrier was appropriate. The fractogram, written by a compensograph, shows a well gaugeable peak which is linearly proportional to the deuterium content of the sample. The error at full deflection amounts to ±0,5%. Protium deuteride, HD, is acting as if it were 1/2 D₂, a fact that was confirmed by mass-spectrometric measurements.

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Für Ratschläge danken wir Herrn Dr. Kienitz, Leiter der physikalisch-analytischen Gruppe im Ammoniaklaboratorium der BASF. Herr Dr. Kraus machte die massenspektrometrischen Aufnahmen.     

铂-氢钨青铜电极的制备及对氢氧化的电催化

采用电化学还原法在表面改性的碳布上,通过改变催化剂沉积顺序及氢钨青铜沉积时间制备铂-氢钨青铜复合催化剂,所得电极作为质子交换膜燃料电池(PEMFC)阳极。利用X射线衍射(XRD)、热重分析(TG)、扫描电子显微镜(SEM)、循环伏安(CV)及单电池极化性能测试研究了催化剂的组成、沉积量、分散性及其对氢氧化的电催化活性。实验结果表明,氢钨青铜沉积时间及催化剂沉积顺序对电极催化性能有显著影响,当氢钨青铜沉积时间为10 min,先沉积氢钨青铜、后沉积铂所得Pt/HxWO3电极对氢氧化具有最佳的催化活性。适量的氢钨青铜才能与铂形成较好的协同催化效应。     

Boron Nitride Membranes with a Distinct Nanoconfinement Effect for Efficient Ethylene/Ethane Separation

A BN membrane with a distinct nanoconfinement effect toward efficient ethylene/ethane separation is presented. The horizontal and inclined self‐assembly of 2D BN nanosheets endow the BN membrane with abundant percolating nanochannels, and these nanochannels are further decorated by reactive ionic liquids (RILs) to tailor their sizes as well as to achieve nanoconfinement effect. The noncovalent interactions between RIL and BN nanosheets favor the ordered alignment of the cations and anions of RIL within BN nanochannels, which contributes to a fast and selective ethylene transport. The resultant membranes exhibit an unprecedented separation performance with superhigh C₂H₄ permeance of 138 GPU and C₂H₄/C₂H₆ selectivity of 128 as well as remarkably improved long‐term stability for 180 h, outperforming reported state‐of‐the‐art membranes.     

Theoretical investigation of an acid catalyst for viable release of H2 from BN nanotubes: A local pair natural orbital coupled cluster approach

Catalytic removal of H₂ from boron-nitride (BN)-based nanomaterials at ambient conditions is of paramount importance in order to develop lightweight hydrogen storage media. Here, the DLPNO-CCSD(T) technique is used to calculate accurate relative energies and activation barriers of Brønsted acid-initiated removal of H₂ from hydrogenated BN nanotubes (HBNNTs) with six different acids. Three crucial steps are identified in the mechanism: first H₂ release, catalyst regeneration via proton transfer, and second H₂ release to ensure feasibility of the dehydrogenation proposal. Our computational studies reveal that sulfonic acids with appropriate electrophilicity can facilitate dehydrogenation of HBNNT at a low free energetic cost (∆G^‡ = 17 kcal/mol). Importantly, these findings illustrate the possibility of H₂ release from BN nanomaterials at ambient conditions and provides hope for a sustainable chemical hydrogen storage strategy.     

Monitoring Hydrogen Plasma Reduction of Oxides by Na D Lines

Out of many applications of hydrogen plasma, reduction of metal oxides is an important one. The reduction can be carried out using carbon or hydrogen. While carrying out the reduction of hematite (Fe₂O₃) in hydrogen plasma, an attempt was made to characterize the hydrogen plasma by optical emission spectroscopy. The spectroscopic results provide some new and useful information. In addition to the hydrogen emission lines, two prominent lines at 589 and 589.6 nm were observed. These two lines are confirmed to be sodium D1 and D2 (Na D lines) by comparing with a low pressure sodium vapour lamp (LPSVL). The source of the trace amount of sodium is also confirmed to be from the metal oxide sample as an impurity. These lines are found to be very sensitive to various process parameters such as gas flow rate, microwave power, and reduction chamber pressure. The temporal variation of these two Na D lines also shows a characteristic trend during metal oxide reduction in hydrogen plasma. The weight loss and the X-ray diffraction analyses of reduced Fe₂O₃ sample for different time duration provides the evidence of correlation with Na D lines’ intensity trend. This trend can be used to monitor the state and completion of hydrogen plasma based reduction reaction. In processes where Na is not associated with metal oxide, trace amount of Na in its molecular form such as NaOH can be introduced for monitoring the plasma process parameters as well as the plasma based reduction process.     

Preparation and hydrogen storage properties of an Li-Mg-N-H system

An Li-Mg-N-H system has been synthesized from Mg(NH₂)₂ and LiH in the ratio 3:8 by a ball-milling process and its dehydrogenation/rehydrogenation properties at around 190°C were investigated. XRD, FTIR and TG results showed that the system was composed of an LiH phase and an amorphous Mg(NH₂)₂ phase with a purity of 90%. A reversible hydrogen storage capacity of 4.7% was observed during the first cycle and more than 90% of the stored hydrogen was desorbed within 100 min for each cycle. However, only 4.2% and 2.9%, respectively, of hydrogen was observed during two subsequent dehydrogenation cycles. In situ GC results showed that no NH3 could be observed during the dehydrogenation process. On the basis of the SEM and XRD results, the loss in hydrogen storage capacity can be mainly attributed to agglomeration, oxidation and crystallization of the materials.     

Thermodynamic analysis of preparation processes for boron-containing films with the use of N-trimethylborazine and hydrogen

The possibilities for using a minimization program for Gibbs energy functions (G _min) in multiphase multicomponent systems are illustrated. The process of chemical vapor deposition in a B-C-N-H-O system at reduced pressure (13.3 Pa) over a wide range of synthesis temperatures (300–1300 K) with the use of an initial gas mixture of N-trimethylborazine and hydrogen is modeled thermodynamically. The possibility of obtaining films of different compositions is shown, and the boundary conditions for the deposition of coatings of the general composition BC _x N _y are determined.     

Preparation of Silicon Thin Films of Different Phase Composition from Monochlorosilane as a Precursor by RF Capacitive Plasma Discharge

Monochlorosilane/argon/hydrogen (SiH₃Cl-Ar-H₂) mixture of different ratios was investigated from the point of PECVD application. RF capacitive plasma discharge of 40.68 MHz frequency was used. The process of deposition was studied by optical emission spectroscopy. The silicon thin films of different phase composition were obtained. The thin films were characterized by Raman-spectroscopy, atomic force microscopy, and secondary ion mass spectrometry. The exhaust gas mixture was analyzed by IR-spectroscopy in outlet of the reactor during PECVD process. The chemical mechanism for the deposition process was also proposed.     

Electroless deposition and properties of Co–Re–B alloys

The data on the mechanism of electroless (catalytic) deposition of Co–Re–B coatings are obtained by determining the donor capacitance of dimethylamine borane (DMAB) (CH₃)₂HN · BH₃ reductant and the oxidation level of its hydride hydrogen. From the results of the study of isotopic composition of evolved hydrogen, it is concluded that the oxidation level of DMAB hydride hydrogen depends on the catalytic activity of the alloy. The alloys containing up to 46 at % rhenium were produced by the electroless deposition.