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A unique method for synthesizing a surface modifier for metallic hydrogen permeable membranes based on non-classic bimetallic pentagonally structured Pd-Pt nanoparticles was developed. It was found that nanoparticles had unique hollow structures. This significantly reduced the cost of their production due to the economical use of metal. According to the results of electrochemical studies, a synthesized bimetallic Pd-Pt/Pd-Ag modifier showed excellent catalytic activity (up to 60.72 mA cm-2), long-term stability, and resistance to COads poisoning in the alkaline oxidation reaction of methanol. The membrane with the pentagonally structured Pd-Pt/Pd-Ag modifier showed the highest hydrogen permeation flux density, up to 27.3 mmol s-1 m-2. The obtained hydrogen flux density was two times higher than that for membranes with a classic Pdblack/Pd-Ag modifier and an order of magnitude higher than that for an unmodified membrane. Since the rate of transcrystalline hydrogen transfer through a membrane increased, while the speed of transfer through defects remained unchanged, a one and a half times rise in selectivity of the developed Pd-Pt/Pd-Ag membranes was recorded, and it amounted to 3514. The achieved results were due to both the synergistic effect of the combination of Pd and Pt metals in the modifier composition and the large number of available catalytically active centers, which were present as a result of non-classic morphology with high-index facets. The specific faceting, defect structure, and unusual properties provide great opportunities for the application of nanoparticles in the areas of membrane reactors, electrocatalysis, and the petrochemical and hydrogen industries.

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We doped carbon into a TiZrN coating to reduce hydrogen permeability, and investigated the phase formation, bonding state, microstructure, and surface roughness of the carbon-doped TiZrN. The laser output for laser carburization was limited to a range of 20-50%. The grain size of the TiZrN coatings decreased from 26.49 nm before carburization to 18.31 nm after carburization. For XPS analysis, the sp2/sp3 ratio was 1.23 at 20% laser output, but it showed 2.64 at 40% laser output, which means that amorphous carbon was formed. As the grain size decreased with the formation of amorphous carbon, the surface microstructure of the carbon-doped TiZrN coatings transitioned to an intergranular structure, indicating the creation of amorphous carbon-embedded (Ti, Zr)(C, N) in the coating. The surface roughness (Ra) of the carbon-doped TiZrN coating was decreased to a maximum of 7.12 nm, and the hydrogen permeability correspondingly decreased by 78% at 573 K.

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The precise liquidus projection of the V-Ti-Fe system are crucial for designing high-performance hydrogen permeation alloys, but there are still many controversies in the research of this system. To this end, this article first uses the CALPHAD (CALculation of PHAse Diagrams) method to reconstruct the alloy phase diagram and compares and analyses existing experimental data, confirming that the newly constructed phase diagram in this article has good reliability and accuracy. Second, this obtained phase diagram was applied to the subsequent development process of hydrogen permeation alloys, and the (Ti65Fe35)100-xVx (x = 0, 2.5, 5, 10, 15, 25) alloys with dual-phase {bcc-(V, Ti) + TiFe} structure were successfully explored. In particular, the alloys with x values equal to 2.5 at.% and 5 at.% exhibit relatively high hydrogen permeability. Third, to further increase the H2 flux permeation through the alloys, a 500-mm-long tubular (Ti65Fe35)95V5 membrane for hydrogen permeation was prepared for the first time. Hydrogen permeation testing showed that this membrane had a very high H2 flux (4.06 mL min-1), which is ca. 6.7 times greater than the plate-like counterpart (0.61 mL min-1) under the same test conditions. This work not only indicates the reliability of the obtained V-Ti-Fe phase diagram in developing new hydrogen permeation alloys, but also demonstrates that preparing tubular membranes is one of the most important means of improving H2 flux.

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As a commonly used liner material for fully reinforced, carbon-fiber-composite hydrogen storage cylinders, polyamide 6 (PA6) needs to meet the required hydrogen permeation index during use; otherwise, it may adversely affect the safe use of hydrogen storage cylinders. The hydrogen permeability of PA6 under different temperatures and pressures was tested, and the variations in its hydrogen permeability were investigated. Additionally, the hydrogen permeability of PA6, polyamide 11 (PA11), and high-density polyethylene (HDPE) at a temperature of 288 K and a pressure of 70 MPa was tested, and the differences in hydrogen permeability among these commonly used liner materials for type IV on-board hydrogen storage cylinders were studied. The results reported herein indicate that both the hydrogen permeability and diffusion coefficient of PA6 increase with rising test temperature but decrease with increasing pressure. The solubility coefficient of PA6 shows no significant change with varying test temperatures and pressures. At a test temperature of 288 K and a pressure of 70 MPa, among the three materials, PA6 has slightly stronger hydrogen permeation resistance than PA11, while HDPE has the least resistance. These research findings can serve as valuable reference data for evaluating the hydrogen permeability of liner materials.

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Thin Pd-40%Cu films were obtained via the classical melting and rolling method, magnetron sputtering, and modified with nanostructured functional coatings to intensify the process of hydrogen transportation. The films were modified by electrodeposition, according to the classical method of obtaining palladium black and "Pd-Au nanoflowers" with spherical and pentagonal particles, respectively. The experiment results demonstrated the highest catalytic activity (89.47 mA cm-2), good resistance to CO poisoning and long-term stability of Pd-40%Cu films with a pentagonal structured coating. The investigation of the developed membranes in the hydrogen transport processes in the temperature range of 25-300 °C also demonstrated high and stable fluxes of up to 475.28 mmol s-1 m-2 (deposited membranes) and 59.41 mmol s-1 m-2 (dense metal membranes), which were up to 1.5 higher, compared with membrane materials with classic niello. For all-metal modified membranes, the increase in flux was up to sevenfold, compared with a smooth membrane made of pure palladium, and for deposited films, this difference was manyfold. The membrane materials' selectivity was also high, up to 4419. The developed strategy for modifying membrane materials with functional coatings of a fundamentally new complex geometry can shed new light on the development and fabrication of durable and highly selective palladium-based membranes for gas steam reformers.

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In order to investigate the type IV hydrogen storage bottle with better hydrogen storage capacity, the polymer lining of the hydrogen storage bottle was further developed. In this paper, the molecular dynamics method was used to simulate the helium adsorption and diffusion processes within a modified montmorillonite (OMMT)-filled polyamide 6 (PA6) system. The effects of the barrier properties of the composites were investigated at different filler contents (3%, 4%, 5%, 6% and 7%), different temperatures (288 K and 328 K) and different pressures (0.1 MPa, 41.6 MPa, 52 MPa and 60 MPa) for certain contents. It was found that when the filler content was 5%, the permeability coefficient of the material was lower than 2 × 10-13 cm3∙cm/(cm2∙s∙Pa) and the barrier performance was the best. The modified filler with 5% OMMT/PA6 at 328 K still had the strongest barrier performance. When the pressure increased, the permeability coefficient of the modified material first decreased and then increased. In addition to this, the effect of the fractional free volume on the barrier properties of the materials was also investigated. This study provides a basis and reference for the selection and preparation of polymer linings for high-barrier hydrogen storage cylinders.

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The hydrogen/deuterium sorption properties of Ni33Ti39Nb28 synthesized by the vacuum induction melting technique were measured between 400 and 495 °C for pressure lower than 3 bar. The Sieverts law is valid up to H(D)/M < 0.2 in its ideal form; the absolute values of the hydrogenation/deuteration enthalpy are ΔH(H2) = 85 ± 5 kJ/mol and ΔH(D2) = 84 ± 4 kJ/mol. From the kinetics of absorption, the diffusion coefficient was derived, and an Arrhenius dependence from the temperature was obtained, with Ea,d = 12 ± 1 kJ/mol for both hydrogen isotopes. The values of the alloy permeability, obtained by combining the solubility and the diffusion coefficient, were of the order of 10-9 mol m-1 s-1 Pa-0.5, a value which is one order of magnitude lower than that of Ni41Ti42Nb17, until now the best Ni-Ti-Nb alloy for hydrogen purification. In view of the simplicity of the technique here proposed to calculate the permeability, this method could be used for the preliminary screening of new alloys.

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A controlled strategy for the electrochemical synthesis of mono- and bimetallic nanoparticles with a unique and complex morphology has been developed. The investigation of the effect of changing the surfactant concentration and current density regulating the medium pH has revealed the fundamental patterns of nanoparticle growth. The developed method has allowed to synthesis of nanoparticles with a controlled pentabranched structure for the monometallic palladium as well as for favorable combinations of metals-Pd-Ag and Pd-Pt. The obtained nanoparticles were investigated in alkaline methanol oxidation. The results demonstrated quite high catalytic activity up to 83.51 mA cm-2 and long-term stability, which are caused by the increase in electrochemically active surface area by increasing the active center's number. This was made possible due to the creation of unusual nanoparticle morphology, namely the presence of high-energy high-index facets. The developed nanoparticles were also studied as a modifying coating for hydrogen-permeable membranes in the processes of hydrogen transport. The membranes coated with the nanoparticles demonstrated sufficiently high hydrogen flux up to 11.33 mmol s-1 m-2 and high H2/N2 selectivity up to 2254. Such results can be explained by the obvious acceleration of surface processes through the application of the developed nanoparticles. The novel synthesis strategy can potentially be extended to other metal nanoparticle systems. Thus it can be an effective way to solve relevant problems of design of controlled synthetic methods allowing the nanoparticle morphology tuning according to the required functional properties.

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Hydrogen separation membranes are one of the most promising technologies for hydrogen purification. The development of high-entropy alloys (HEAs) for hydrogen separation membranes is driven by a "cocktail effect" of elements with different hydrogen affinities to prevent hydride formation and retain high permeability due to the single-phase BCC structure. In this paper, equimolar and non-equimolar Nb-Ni-Ti-Zr-Co high entropy alloys were fabricated by arc melting. The microstructure and phase composition of the alloys were analyzed by scanning electron microscopy and X-ray diffraction, respectively. The hydrogen permeation experiments were performed at 300-500 °C and a hydrogen pressure of 4 bar. In order to estimate the effect of composition and lattice structure on hydrogen location and diffusivity in Nb-Ni-Ti-Zr-Co alloy, ab initio calculations of hydrogen binding energy were performed using virtual crystal approximation. It was found that Nb-enriched and near equimolar BCC phases were formed in Nb20Ni20Ti20Zr20Co20 HEA while Nb-enriched BCC and B2-Ni(Ti, Zr) were formed in Nb40Ni25Ti18Zr12Co5 alloy. Hydrogen permeability tests showed that Nb20Ni20Ti20Zr20Co20 HEA shows lower activation energy and higher permeability at lower temperatures as well as higher resistance to hydrogen embrittlement compared to Nb40Ni25Ti18Zr12Co5 alloy. The effect of composition, microstructure and hydrogen binding energies on permeability of the fabricated alloys was discussed.

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The interaction of hydrogen with specimens of 316L steel and Inconel 718 alloy processed by selective laser melting (SLM) was studied. The effect of hydrogen on the mechanical properties of SLM materials, hydrogen permeability, and microstructure was investigated; besides, these values were compared with the properties of conventionally produced materials. It was shown that SLM can be successfully used to produce parts for operation in hydrogen environments at high pressure at room temperature.

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Hydrogen (H2) sensors that can be produced en masse with cost-effective manufacturing tools are critical for enabling safety in the emerging hydrogen economy. The use of melt-processed nanocomposites in this context would allow the combination of the advantages of plasmonic hydrogen detection with polymer technology; an approach which is held back by the slow diffusion of H2 through the polymer matrix. Here, we show that the use of an amorphous fluorinated polymer, compounded with colloidal Pd nanoparticles prepared by highly scalable continuous flow synthesis, results in nanocomposites that display a high H2 diffusion coefficient in the order of 10-5 cm2 s-1. As a result, plasmonic optical hydrogen detection with melt-pressed fluorinated polymer nanocomposites is no longer limited by the diffusion of the H2 analyte to the Pd nanoparticle transducer elements, despite a thickness of up to 100 µm, thereby enabling response times as short as 2.5 s at 100 mbar (≡10 vol. %) H2. Evidently, plasmonic sensors with a fast response time can be fabricated with thick, melt-processed nanocomposites, which paves the way for a new generation of robust H2 sensors.

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A method for obtaining composite gas-diffusion PdCu-Nb-PdCu membranes modified with a nanostructured crystalline coating was developed to increase the performance of Nb-based membranes. A modifying functional layer with a controlled size and composition was synthesized by electrochemical deposition, which made it possible to determine a certain geometric shape for palladium nanocrystallites. Developed PdCu-Nb-PdCu membranes have demonstrated flux values up to 0.232 mmol s-1 m-2 in the processes of diffusion purification of hydrogen at 400 °C. A very significant difference in the hydrogen fluxes through the modified and non-modified composite PdCu-Nb-PdCu membranes reached 1.73 times at the lower threshold temperature of 300 °C. Cu doping of protective layer did not affect the selective properties of the membranes, which was confirmed by the obtained high selectivity values up to 1323, and made it possible to reduce the noble metal content. The research data indicate that the modification of the membrane surface significantly accelerates the hydrogen transfer process at sufficiently low temperatures due to the acceleration of dissociative-associative processes on the surface. The reported approach demonstrates new possibilities for creating productive and cost-efficient membranes based on niobium.

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The method of synthesis of bimetallic Pd-Ag pentagonally structured catalyst "nanostar" on the surface of Pd-23%Ag alloy films has been developed. The resulting catalyst was studied as a highly active functional layer for methanol oxidation reaction (MOR) in alkaline media and the intensification of hydrogen transport through the Pd-23%Ag membrane in the processes of hydrogen diffusion purification. A modifying layer with a controlled size, composition and excellent electrocatalytic activity was synthesized by electrochemical deposition at a reduced current density compared to classical methods. The low deposition rate affects the formation of pentagonally structured nanocrystallites, allowing Pd and Ag particles to form well-defined structures due to the properties of the surfactant used. Electrochemical studies have demonstrated that the catalyst synthesized by the "nanostar" method shows better electrocatalytic activity in relation to MOR and demonstrates a higher peak current (up to 17.82 µA cm-2) in comparison with one for the catalyst synthesized by the "nanoparticle" method (up to 10.66 µA cm-2) in a cyclic voltammetric study. The nanostar catalyst electrode releases the highest current density (0.25 µA cm-2) for MOR and demonstrates higher catalytic activity for the oxidation of possible intermediates such as sodium formate in MOR. In the processes of diffusion membrane purification of hydrogen, a multiple increase in the density of the penetrating flux of hydrogen through the membranes modified by the "nanostar" catalyst (up to 10.6 mmol s-1 m-2) was demonstrated in comparison with the membranes modified by the "nanoparticles" method (up to 4.49 mmol s-1 m-2). Research data may indicate that the properties of the developed pentagonally structured catalyst "nanostar" and its enhanced activity with respect to reactions involving hydrogen increase the desorption activity of the membrane, which ultimately accelerates the overall stepwise transfer of hydrogen across the membrane.

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The hydrogen permeation coefficient () is generally used as a measure to show hydrogen permeation ability through dense metallic membranes, which is the product of the Fick's diffusion coefficient (D) and the Sieverts' solubility constant (K). However, the hydrogen permeability of metal membranes cannot be analyzed consistently with this conventional description. In this paper, various methods for consistent analysis of hydrogen permeability are reviewed. The derivations of the descriptions are explained in detail and four applications of the consistent descriptions of hydrogen permeability are introduced: (1) prediction of hydrogen flux under given conditions, (2) comparability of hydrogen permeability, (3) understanding of the anomalous temperature dependence of hydrogen permeability of Pd-Ag alloy membrane, and (4) design of alloy composition of non-Pd-based alloy membranes to satisfy both high hydrogen permeability together with strong resistance to hydrogen embrittlement.

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We hypothesize that the properties of proton-exchange membranes for fuel cell applications cannot be described unambiguously unless interface effects are taken into account. In order to prove this, we first develop a thermodynamically consistent description of the transport properties in the membranes, both for a homogeneous membrane and for a homogeneous membrane with two surface layers in contact with the electrodes or holder material. For each subsystem, homogeneous membrane, and the two surface layers, we limit ourselves to four parameters as the system as a whole is considered to be isothermal. We subsequently analyze the experimental results on some standard membranes that have appeared in the literature and analyze these using the two different descriptions. This analysis yields relatively well-defined values for the homogeneous membrane parameters and estimates for those of the surface layers and hence supports our hypothesis. As demonstrated, the method used here allows for a critical evaluation of the literature values. Moreover, it allows optimization of stacked transport systems such as proton-exchange membrane fuel cell units where interfacial layers, such as that between the catalyst and membrane, are taken into account systematically.