Hydrogen Diffusion on, into and in Magnesium Probed by DFT: A Review

Hydrogen is an energy carrier that can be a sustainable solution for alternative energy with zero greenhouse gas emissions. Hydrogen storage is a key point for hydrogen energy. Metals provide an access for safe, controlled and reversible hydrogen storage and release. Magnesium, due to its outstanding hydrogen storage capacity, high natural abundance, low cost and non-toxicity is one of the most attractive materials for hydrogen storage. The economic efficiency of Mg as a hydrogen accumulator is limited by its sluggish hydrogen sorption kinetics and high stability of its hydride MgH2. Many attempts have been made to overcome these shortcomings. On a microscopic level, hydrogen absorption by metal is a complex multistep process that is impossible to survey experimentally. Theoretical studies help to elucidate this process and focus experimental efforts on the design of new effective Mg-based materials for hydrogen storage. This review reports on the results obtained within a density functional theory approach to studying hydrogen interactions with magnesium surfaces, diffusion on Mg surfaces, into and in bulk Mg, as well as hydrogen induced phase transformations in MgHx and hydrogen desorption from MgH2 surfaces

Ion Exchange in Natural Clinoptilolite: Aspects Related to Its Structure and Applications

Clinoptilolite is one of the most common, widespread and abundant zeolites in nature. Its availability, low cost, and outstanding ion exchange properties make clinoptilolite an excellent candidate for both direct use and various modifications to create new low-cost functional materials for sustainable development. Specific applications in which clinoptilolite is already being used include water treatment and heavy metal ion removal, agricultural purposes, storage and conversion of unwanted gaseous emissions into the atmosphere, production of catalysts and photocatalysts, bioactive materials, and a number of others. Unlike some other zeolites, clinoptilolite is difficult to synthesize, which is why most publications refer to this zeolite in its natural form, either directly from the deposit or after applying various processes to this mineral to improve its properties. Among the modification methods used, ion exchange stands out. This review is devoted to the study of ion exchange processes in natural clinoptilolite with two goals: first, as its strategic property for use in processes in which cation exchange is fundamentally necessary; second, as a way to modify it to create composite materials with predetermined desired properties

Bimetallic Copper-Silver Systems Supported on Natural Clinoptilolite: Long-Term Changes in Nanospecies’ Composition and Stability

Long-term changes in species of copper-silver bimetallic systems on natural clinoptilolite obtained by ion exchange of Cu2+ and Ag+ and then reduced at different temperatures were studied. Even after storage under ambient conditions, XRD and UV-Vis diffuse reflectance spectra indicate the presence of nanospecies and larger particles of reduced copper and silver. Scanning electron microscopy of aged bimetallic samples, reduced at the highest temperature (450 °C) and the pristine sample for their preparation, also aged, showed the presence of silver particles with a size of about 100 nm. They are formed in the initial ion-exchanged sample (without reduction) due to the degradation of Ag+ ions. The particles in the reduced sample are larger; in both samples they are evenly distributed over the surface. The presence of silver affects the stability and the mechanism of decomposition/oxidation of reduced copper species, and this stability is higher in bimetallic systems. The decomposition pattern of recently reduced species includes the formation of smaller nanoparticles and few-atomic clusters. This can occur, preceding the complete oxidation of Cu to ions. Quasicolloidal silver, which is present in fresh bimetallic samples reduced at lower temperatures, transforms after aging into Ag8 clusters, which indicates the stability of these nanospecies on natural clinoptilolite

Bimetallic Copper-Silver Systems Supported on Natural Clinoptilolite: Long-Term Changes in Nanospecies’ Composition and Stability

Long-term changes in species of copper-silver bimetallic systems on natural clinoptilolite obtained by ion exchange of Cu2+ and Ag+ and then reduced at different temperatures were studied. Even after storage under ambient conditions, XRD and UV-Vis diffuse reflectance spectra indicate the presence of nanospecies and larger particles of reduced copper and silver. Scanning electron microscopy of aged bimetallic samples, reduced at the highest temperature (450 °C) and the pristine sample for their preparation, also aged, showed the presence of silver particles with a size of about 100 nm. They are formed in the initial ion-exchanged sample (without reduction) due to the degradation of Ag+ ions. The particles in the reduced sample are larger; in both samples they are evenly distributed over the surface. The presence of silver affects the stability and the mechanism of decomposition/oxidation of reduced copper species, and this stability is higher in bimetallic systems. The decomposition pattern of recently reduced species includes the formation of smaller nanoparticles and few-atomic clusters. This can occur, preceding the complete oxidation of Cu to ions. Quasicolloidal silver, which is present in fresh bimetallic samples reduced at lower temperatures, transforms after aging into Ag8 clusters, which indicates the stability of these nanospecies on natural clinoptilolite

Proton relaxation and hydrogen mobility in Ti–V–Cr alloys: Improved exchange model

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Short-Range Structure of Ti0.63V0.27Fe0.10D1.73 from Neutron Total Scattering and Reverse Monte Carlo Modelling

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Short-Range Structure of Ti0.63V0.27Fe0.10D1.73 from Neutron Total Scattering and Reverse Monte Carlo Modelling

Ti-V-based body-centered cubic (BCC) alloys have potential for large-scale hydrogen storage if expensive vanadium is substituted with much cheaper Fe-containing ferrovanadium. Use of ferrovanadium reduces the alloys’ hydrogen storage capacity. This is puzzling since the amount of Fe is low and hydrogen atoms are accommodated in interstitial sites which are partly coordinated by Fe in many intermetallic compounds. The present work is aimed at finding a structural explanation for Fe-induced capacity loss in Ti-V alloys. Since such alloys and their hydrides are highly disordered without long-range occupational order of the different metal species, it was necessary to employ a technique which is sensitive to local structure. Neutron total scattering coupled with reverse Monte Carlo modelling was thus employed to elucidate short-range atomic correlations in Ti0.63V0.27Fe0.10D1.73 from the pair distribution function. It was found that Fe atoms form clusters and that the majority of the vacant interstitial sites are within these clusters. These clusters take the same face-centered cubic structure as the Ti-V matrix in the deuteride and thus they are not simply unreacted Fe which has a BCC structure. The presence of Fe clusters is confirmed by transmission electron microscopy. Density functional theory calculations indicate that the clustering is driven by thermodynamics

NMR Study of Intercalates and Grafted Organic Derivatives of H2La2Ti3O10

The protonated perovskite-like titanate H2La2Ti3O10 has been used to produce organic-inorganic hybrids with simple organic molecules: methylamine, methanol, monoethanolamine, and n-butylamine. The optimal pathways for the preparation of such hybrids are summarized. Solid-state NMR, combined with thermal analysis, Raman, and IR spectroscopy, has been applied to determine the bonding type in the obtained organic-inorganic hybrids. It has been found that, in the methanolic hybrid, the organic residues are covalently bound to the inorganic matrix. In contrast, in the methylamine and n-butylamine hybrids, the organic molecules are intercalated into the inorganic matrix in cationic forms. The structure of the monoethanolamine hybrid is composite and includes both the covalently bound and intercalated organic species

Magnetic resonance and its applications

The book provides a basic understanding of the underlying theory, fundamentals and applications of magnetic resonance The book implies a few levels of the consideration (from simple to complex) of phenomena, that can be useful for different groups of readers The introductory chapter provides the necessary underpinning knowledge for newcomers to the methods The exposition of theoretical materials goes from initial to final formulas through detailed intermediate expressions

Active Sites in H-Mordenite Catalysts Probed by NMR and FTIR

Mordenites are widely used in catalysis and environmental protection. The catalytic properties of mordenite are largely determined by the composition of its crystal framework, i.e., the SiO2/Al2O3 molar ratio (MR), and the cationic form. In H-mordenites, the most important characteristic becomes the structure and distribution of acid sites, which depends on the number and distribution of Al tetrahedra in the framework. In the present work, the local structure of these centers in H-mordenite catalysts with a nominal MR varied from 9.9 to 19.8 was studied in detail using a combination of magic angle spinning nuclear magnetic resonance (MAS NMR) and Fourier transform infrared spectroscopy (FTIR). 27Al MAS NMR indicates the presence of extra-framework Al in most of the studied samples that results in a higher real MR of the zeolitic framework compared to the nominal value. Concentrations of Lewis and Brønsted acid sites, as well as of silanol groups were estimated by elemental analysis, NMR, and FTIR spectroscopy. The values of site concentrations obtained from band intensities of adsorbed CO and those of OH groups are compared with the amount of framework and extra-framework aluminum. The advantages and restrictions of different methods of active site characterization are discussed