Mo2C@C nanofibers film as durable self-supported electrode for efficient electrocatalytic hydrogen evolution

Self-supported electrocatalytic thin films consist 3D conducting network and well-embedded electrocatalysts, which endows the advantage in mass flow kinetics and durability for large-scale water splitting. Synthesis of such self-supported electrode still remains a big challenge due to the difficulty in the control over the 3D conducting network and the simultaneous growth of catalyst with well attachment on the conducting fibers. Herein, a self-supported Mo2C@carbon nanofibers (Mo2C@C NF) film has been successfully fabricated with outstanding electrocatalytic performance under optimized pyrolysis temperature and precursors mass ratio conditions. During the carbonation process, the Mo2C nanoparticles (~16 nm) are simultaneously grown and well dispersed on the inter-connected carbon nanofibers, which form 3D conducting network. The as-formed 3D carbon network is strong enough to support direct electrocatalytic application without additional ink or supporting substrates. This particular electrode structure facilitates easy access to the active catalytic sites, electron transfer, and hydrogen diffusion, resulting in the high hydrogen evolution reaction (HER) activity. A low overpotential of 86 mV is needed to achieve 10 mA cm-2 current density with outstanding kinetics metric (Tafel 43 mV dec-1) in 1M KOH. Additionally, the self-supported Mo2C@C NF film, a binder-free electrode, exhibits extraordinary stability of more than 340 h.

Modeling the Hydrogen Redistribution at the Grain Boundary of Misoriented Bicrystals in Austenite Stainless Steel

Hydrogen embrittlement, as one of the major concerns for austenitic stainless steel, is closely linked to the diffusion of hydrogen through the grain boundary of materials. The phenomenon is still not well understood yet, especially the full interaction between hydrogen diffusion and the misorientation of the grains. This work aimed at the development of a robust numerical strategy to model the full coupling of the hydrogen diffusion and the anisotropic behavior of crystals in 316 stainless steel. A constitutive model, which allows easy incorporation of crystal orientation, various loading conditions, and arbitrary model geometries, was established by using the finite element package ABAQUS. The study focuses on three different bicrystal models composed of misoriented crystals, and the results indicate that the redistribution of hydrogen is significant closely to the grain boundary, and the redistribution is driven by the hydrostatic pressure caused by the misorientation of two neighboring grains. A higher elastic modulus ratio along the tensile direction will lead to a higher hydrogen concentration difference in the two grains equidistant from the grain boundary. The hydrogen concentration shows a high value in the crystal along the direction with stiff elastic modulus. Moreover, there exists a large hydrogen concentration gradient in a narrow region very close to the grain boundary to balance the concentration difference of the neighboring grains.

INFLUENCE OF ALLOYING Ti, Mo AND W ON THE KINETIC AND STRENGTH CHARACTERISTICS OF MEMBRANE ALLOYS BASED ON Nb AND V

Проведен анализ влияния Ti, Mo и W на характер аморфной нано- и кристаллической структуры на прочностные и кинетические характеристики - диффузии D и проницаемости Ф водорода в мембранных сплавах, созданных на основе бинарных Ni - Nb и V - Ni. Легирование сплавов Ni - V титаном, молибденом и вольфрамом ведет к постепенному замещению ими ниобия и ванадия и способствует образованию нескольких второстепенных фаз хотя и действующих как барьеры для диффузии водорода, но способствующих снижению процессов гидридообразования. Выявлена строгая зависимость кинетики водорода не только от термодинамических параметров -температуры и давления, но и от наличия свободного объема в формируемых аморфных, нано-кристаллических и кристаллических сплавов. Установлено, что процессы селективности, динамика водорода - его поток J, определяемый произведением диффузии и проницаемости (J = D×Ф), зависят от базового состава, выбора легирующих элементов (Ti,Mo и W ), а также формируемых структур - аморфной, нанокристаллической и полифазной дуплексной кристаллической микроструктурой. Установлено, что тщательно подобранный состав определяет производительность селективного процесса и способствует выделению высокочистого водорода с последующими его приложениями для зеленой энергетики. An analysis was carried out of influence of Ti, Mo and W on the nature of the amorphous nano- and crystalline structures on the strength and kinetic characteristics - diffusion D and permeability Ф of hydrogen in membrane alloys based on binary Nb - Ni, V - Ni. Doping with Nb - V alloys, titanium, molybdenum and tungsten leads to the gradual replacement of niobium and vanadium, and promotes the formation of several minor phases while acting as barriers for hydrogen diffusion, but contributing hydride reduction processes. A close dependence of the hydrogen kinetics was revealed not only on thermodynamic parameters - temperature and pressure, but also on the presence of free volume in the formed amorphous, nanocrystalline and crystalline alloys. So, the processes of selectivity, the dynamics of hydrogen - its flux J determined by the product of diffusion D and permeability Ф, J = D×Ф depend on the basic composition and the choice of alloying elements (Ti,Mo and W ), as well as the formed structures - amorphous, nanocrystalline and duplex, represented by multiphase crystalline microstructures. It was found that a carefully selected composition determines the productivity of the selective process and promotes the release of high-purity hydrogen with its subsequent applications for green energy.

Hydrogen Diffusion and Adsorption on WO3 (001) based on First Principles Calculation

Hydrogen reduction of tungsten oxide is currently the most widely applied ultrafine tungsten powder production process. The process has the advantage of short, pollution free and simple production equipment. But it is difficult to effectively control the morphology and particle size of the tungsten powder because of lacking in-depth understanding of the dynamic mechanism of the process. The first-principles calculations are carried out to explore the diffusion and internal adsorption of hydrogen on the WO-terminated surface of WO3 based on the density functional theory. The results show that hydrogen can diffuse from the WO terminal surface to the inside of WO3, the activation energy of diffusion is 46.682 Kcal/mol. It’s preferable for hydrogen to diffuse from the surface to the inside than diffuse within the WO3 lattice. The adsorption energy of hydrogen on the WO termination surface of WO3 is 15.093 Kcal/mol, the adsorption energy of hydrogen inside the WO termination surface of WO3 is 14.116 Kcal/mol, which means the hydrogen is easier to adsorb inside the WO3 lattice.

Investigation of hydrogen diffusion behavior in 12Cr2Mo1R(H) steel by electrochemical tests and first-principles calculation

Purpose This paper aims to study the mechanism of hydrogen embrittlement in 12Cr2Mo1R(H) steel, which will help to provide valuable information for the subsequent hydrogen embrittlement research of this kind of steel, so as to optimize the processing technology and take more appropriate measures to prevent hydrogen damage. Design/methodology/approach The hydrogen diffusion coefficient of 12Cr2Mo1R(H) steel was measured by the hydrogen permeation technique of double electrolytic cells. Moreover, the influence of hydrogen traps in the material and experimental temperature on hydrogen diffusion behavior was discussed. The first-principles calculations based on density functional theory were used to study the occupancy of H atoms in the bcc-Fe cell, the diffusion path and the interaction with vacancy defects. Findings The results revealed that the logarithm of the hydrogen diffusion coefficient of the material has a linear relationship with the reciprocal of temperature and the activation energy of hydrogen atom diffusion in 12Cr2Mo1R(H) steel is 23.47 kJ/mol. H atoms stably exist in the nearly octahedral interstices in the crystal cell with vacancies. In addition, the solution of Cr/Mo alloy atom does not change the lowest energy path of H atom, but increases the diffusion activation energy of hydrogen atom, thus hindering the diffusion of hydrogen atom. Cr/Mo and vacancy have a synergistic effect on inhibiting the diffusion of H atoms in α-Fe. Originality/value This article combines experiments with first-principles calculations to explore the diffusion behavior of hydrogen in 12Cr2Mo1R(H) steel from the macroscopic and microscopic perspectives, which will help to establish a calculation model with complex defects in the future.