Generation of hydrogen by hydroheterogeneous compositions based on aluminum and alkali metals

The process of hydrogen formation and the associated risk of combustion and explosion is a complex problem concerned with the hydrogen and radiation safety of nuclear reactors. Lithium, potassium and sodium hydroxides are used in VVER reactors as corrective additives for keeping the hydrogen potential of the water coolant with boric acid at a controlled level of 5.8 to 10.3. In the process of investigating the interaction of aqueous solutions of the above hydroxides with aluminum, the most chemically active of these is lithium hydroxide; this reaction proceeds with hydrogen formed at a high rate at room temperature (in an exothermic mode). The processes of hydrogen generation in hydroheterogeneous compositions with potassium and sodium hydroxides proceed at an acceptable rate with heating to ~ 60 °C. The kinetics of hydrogen generation depends in a complex way on the content of boric acid, namely, the hydrogen yield is at a level of ~ 1000 ml at a low concentration of 0.01 to 0.05 g/l, and there is no hydrogen formation at a concentration of 0.6 g/l. According to the coolant quality standards, in the hot state of a VVER-1000 unit or in the reactor state at the minimum controlled power level, the total concentration of alkali metals is about 1 mg/dm3, i.e. two to three orders of magnitude as less as in the investigated compositions. The discovery of the influence of alkali metal hydroxides on the formation of hydrogen with the participation of structural materials based on the example of aluminum makes it possible to suggest that the hydroxides of these metals contained in the coolant in a small amount can also take part in the hydroheterogeneous process of formation of minor hydrogen amounts. The potential for hydrogen formation in such a way needs to be taken into account during long-term operation of nuclear reactors, and during accidents and incidents at NPPs

A Density Functional Theory Investigation of the Reaction of Water with Ce2O-

Cerium suboxide clusters are a recent catalyst class that has received interest for the generation of H₂ from water. Using density functional theory calculations, this work examines the reaction of Ce₂O^– clusters with H₂O. It is shown that the reaction can proceed along both doublet and quartet pathways. In both cases, hydrogen formation is facilitated by intermediate structures featuring bridging hydride and hydroxide ligands. Interestingly, it is shown that metal d electrons facilitate the reduction of water. This work provides new understanding of this reaction and provides new insight into the reactivity of small lanthanide-based clusters with water.<br>

The Role of the Molecular Hydrogen Formation in the Process of Metal-Ion Reduction on Multicrystalline Silicon in a Hydrofluoric Acid Matrix

Metal deposition on silicon in hydrofluoric acid (HF) solutions is a well-established process for the surface patterning of silicon. The reactions behind this process, especially the formation or the absence of molecular hydrogen (H2), are controversially discussed in the literature. In this study, several batch experiments with Ag+, Cu2+, AuCl4– and PtCl62– in HF matrix and multicrystalline silicon were performed. The stoichiometric amounts of the metal depositions, the silicon dissolution and the molecular hydrogen formation were determined analytically. Based on these data and theoretical considerations of the valence transfer, four reasons for the formation of H2 could be identified. First, H2 is generated in a consecutive reaction after a monovalent hole transfer (h+) to a Si–Si bond. Second, H2 is produced due to a monovalent hole transfer to the Si–H bonds. Third, H2 occurs if Si–Si back bonds of the hydrogen-terminated silicon are attacked by Cu2+ reduction resulting in the intermediate species HSiF3, which is further degraded to H2 and SiF62–. The fourth H2-forming reaction reduces oxonium ions (H3O+) on the silver/, copper/ and gold/silicon contacts via monovalent hole transfer to silicon. In the case of (cumulative) even-numbered valence transfers to silicon, no H2 is produced. The formation of H2 also fails to appear if the equilibrium potential of the 2H3O+/H2 half-cell does not reach the energetic level of the valence bands of the bulk or hydrogen-terminated silicon. Non-hydrogen-forming reactions in silver, copper and gold deposition always occur with at least one H2-forming process. The PtCl62– reduction to Pt proceeds exclusively via even-numbered valence transfers to silicon. This also applies to the reaction of H3O+ at the platinum/silicon contact. Consequently, no H2 is formed during platinum deposition.

Selective hydrogenation of furfural using a membrane reactor

Electrocatalytic palladium membrane reactors (ePMRs) use electricity and water to drive hydrogenation reactions without ever forming H2 gas. In these reactors, a palladium membrane physically separates electrochemical hydrogen formation in...

Electrochemical Hydrogen Formation Catalysed by a Pd8 String

The linear Pd8 complex supported by tetraphosphines reacted with HBF4 to give an unprecedented linear tetrapalladium complex with a terminal hydride, which promoted electrocatalytic hydrogen formation from HBF4 in acetonitrile....