SPECIFIC STRUCTURE OF EFFECTIVE MEMBRANE ALLOYS BASED ON NIOBIUM, VANADIUM AND ZIRCONIUM

Аморфные, нанокристаллические мембранные сплавы на основе элементов V группы с уникальными механическими и функциональными свойствами и с матричной дуплексной микроструктурой активно способствуют развитию водородной энергетики. Имеются еще не вполне разрешенные проблемы для этих новых сплавов -их низкая термическая стабильность, недосточная механическая прочность (пластичность, твердость), а также охрупчивание интерметаллидное и гидридное. Для эффективного применения разрабатываются сплавы с тройным составом - в которые помимо элементов V группы входят и легирующие металлы никель и титан. Получают не только аморфные и нанокристаллические сплавы, применимые в электронике и электроэнергетике, а также мембранные сплавы с дуплексной матричной структурой, объединяющей аморфные, так нано- и квазикристаллические дендритно упрочняющие фазы, как упрочняющие аморфную матрицу. В специализируемых мембранных тройных сплавах формируются соединения NiTi и NiTi, стабилизирующие и предохраняющие нано- и кристаллические мембраны от хрупкого разрушения. Установлено, что интенсивное образование гидридов в этих альтернативных мембранных сплавах столь же не желательно, как и для традиционных сплавов на основе палладия. Рассматриваемые сплавы действительно позволяют получить газообразный водород высокой чистоты с применением новых составов взамен дорогостоящих мембран на основе сплавов Pd - Au / Ag / Cu. With unique mechanical and functional properties, amorphous, nanocrystalline and matrix duplex microstructure membrane alloys based on group V elements actively contribute to the development of hydrogen energy. There are still not completely resolved problems for these new alloys - their low thermal stability, insufficient mechanical strength (plasticity, hardness), and intermetallic and hydride embrittlement. For effective use, alloys with a triple composition are being developed - which, in addition to the elements of group V, also include nickel and titanium as alloying metals. Not only amorphous and nanocrystalline alloys are obtained that are applicable in electronics and power engineering, as well as membrane alloys with a duplex matrix structure that combines amorphous, nano-and quasicrystalline dendritic-hardening phases strengthening the amorphous matrix. In specialized membrane ternary alloys, NiTi and NiTi compounds are formed, which stabilize and protect nano-and crystalline membranes from brittle destruction. It has been found that the intense formation of hydrides in these alternative membrane alloys is as undesirable as for palladium-based compounds. The alloys under consideration actually make it possible to obtain high-purity gaseous hydrogen using new compositions instead of expensive membranes based on Pd - Au / Ag / Cu alloys.

Applicability of Nickel-Based Catalytic Systems for Hydrodehalogenation of Recalcitrant Halogenated Aromatic Compounds

This review summarizes recent applications of nickel as a nonprecious metal catalyst in hydrodehalogenation (HDH) reactions of halogenated aromatic compounds (Ar–Xs). Nickel-based HDH catalysts were developed for reductive treatment of both waste containing concentrated Ar–Xs (mainly polychlorinated benzenes) and for wastewater contaminated with Ar–Xs. Ni-catalyzed HDH enables the production of corresponding nonhalogenated aromatic products (Ar–Hs), which are principally further applicable/recyclable and/or Ar–Hs, which are much more biodegradable and can be mineralized during aerobic wastewater treatment. Developed HDH methods enable the utilization of both gaseous hydrogen via the direct HDH process or other chemical reductants as a source of hydrogen utilized in the transfer of the hydrodehalogenation process. This review highlights recent and major developments in Ni-catalyzed hydrodehalogenation topic since 1990.

Recent Achievements in Microalgal Photobiological Hydrogen Production

It is well known that over the last 60 years the trend of long-lived greenhouse gas emissions have shown a strong acceleration. There is an increasing concern and a mounting opposition by public opinion to continue with the use of fossil energy. Western countries are presently involved in a so-called energy transition with the objective of abandoning fossil energy for renewable sources. In this connection, hydrogen can play a central role. One of the sustainable ways to produce hydrogen is the use of microalgae which possess two important natural catalysts: photosystem II and hydrogenase, used to split water and to combine protons and electrons to generate gaseous hydrogen, respectively. For about 20 years of study on photobiological hydrogen production, our scientific hopes were based on the application of the sulfur protocol, which indisputably represented a very important advancement in the field of hydrogen production biotechnology. However, as reported in this review, there is increasing evidence that this strategy is not economically viable. Therefore, a change of paradigm for the photobiological production of hydrogen based on microalgae seems mandatory. This review points out that an increasing number of microalgal strains other than Chlamydomonas reinhardtii are being tested and are able to produce sustainable amount of hydrogen without nutrient starvation and to fulfill this goal including the application of co-cultures.

Effect of Working Process Adjustable Parameters on the Formation of Nitrogen Oxides in a Hydrogen Diesel Engine

The article considers formation of nitrogen oxides in a hydrogen diesel engine with direct injection of gaseous hydrogen depending on the adjustable parameters of the working process: excess air ratio, cyclic hydrogen supply, advance angle and duration of hydrogen injection. It was found that in a number of cases the effect of these parameters on the working process and the emission of nitrogen oxides leads to results that differ significantly from those in traditional diesel engines running on hydrocarbon fuel. It is shown that by varying the specified controlled parameters, it is possible to minimize the concentration of nitrogen oxides in the exhaust gases of a hydrogen diesel engine.

Bromine speciation in volcanic plumes: new in situ derivatization LC-MS method for the determination of gaseous hydrogen bromide by gas diffusion denuder sampling

The chemical characterization of volcanic gas emissions gives insights into the interior of volcanoes. Bromine species have been correlated with changes in the activity of a volcano. In order to exploit the volcanic bromine gases, we need to understand what happens to them after they are outgassed into the atmosphere. This study aims to shed light on the conversion of bromospecies after degassing. The method presented here allows for the specific analysis of gaseous hydrogen bromide (HBr) in volcanic environments. HBr is immobilized by reaction with 5,6-epoxy-5,6-dihydro-[1,10]-phenanthroline (EP), which acts as an inner coating inside of diffusion denuder tubes (in situ derivatization). The derivative is analyzed by high-performance liquid chromatography coupled to electrospray ionization mass spectrometry (HPLC-ESI-MS). The collection efficiency for HBr (99.5 %), the collection efficiency for HBr alongside HCl (98.1 %), and the relative standard deviation of comparable samples (8 %) have been investigated. The comparison of the new denuder-based method and Raschig tubes as alkaline traps resulted on average in a relative bias between both methods of 10 ± 6 %. The denuder sampling setup was applied in the plume of Masaya (Nicaragua) in 2016. HBr concentrations in the range between 0.44 and 1.97 ppb were measured with limits of detection and quantification below 0.1 and 0.3 ppb respectively. The relative contribution of HBr as a fraction of total bromine decreased from 75 ± 11 % at the Santiago crater (214 m distance to the volcanic emission source) to 36 ± 8 % on the Nindiri rim (740 m distance). A comparison between our data and the previously calculated HBr, based on the CAABA/MECCA box model, showed a slightly higher trend for the HBr fraction on average than expected from the model. Data gained from this new method can further refine model runs in the future.

Photo-Driven Dehydrogenative Homo-Coupling of Benzylic C–H Bonds Forming Strained C–C Bonds

A photoinduced dehydrogenative homo-coupling reaction of alkylarenes is reported. Gaseous hydrogen is evolved as the sole byproduct and neither oxidants nor hydrogen acceptors are required. The present reaction offers an environmentally benign and atom-economical means for forming sterically strained C–C single bonds. It also gives a remarkable example of photo-driven reactions overcoming a considerable rise in energy.