The Catalytic Role of D-block Elements and Their Compounds for Improving Sorption Kinetics of Hydride Materials: A Review

The goal of finding efficient and safe hydrogen storage material motivated researchers to develop several materials to fulfil the demand of the U.S. Department of Energy (DOE). In the past few years, several metal hydrides, complex hydrides such as borohydrides and alanates, have been researched and found efficient due to their high gravimetric and volumetric density. However, the development of these materials is still limited by their high thermodynamic stability and sluggish kinetics. One of the methods to improve the kinetics is to use catalysts. Among the known catalysts for this purpose, transition metals and their compounds are known as the leading contender. The present article reviews the d-block transition metals including Ni, Co, V, Ti, Fe and Nb as catalysts to boost up the kinetics of several hydride systems. Various binary and ternary metal oxides, halides and their combinations, porous structured hybrid designs and metal-based Mxenes have been discussed as catalysts to enhance the de/rehydrogenation kinetics and cycling performance of hydrogen storage systems.

Low-temperature ammonia synthesis on electron-rich [RuH6] catalytic centers

Ammonia is a central vector in sustainable global growth, but the usage of fossil feedstocks and centralized Haber-Bosch synthesis conditions causes >1.4% of the global anthropogenic CO2 emissions. While nitrogenase enzymes convert atmospheric N2 to ammonia at ambient conditions, even the most active manmade inorganic catalysts fail due to low activity and parasitic hydrogen evolution at low temperatures. Here, we show the [RuH6] catalytic center in ternary ruthenium complex hydrides (Li4RuH6 and Ba2RuH6) activate N2 preferentially and avoid hydrogen over-saturation at low temperatures and near ambient pressure by delicately balancing H2 chemisorption and N2 activation. The active [RuH6] catalytic center is capable of achieving an unprecedented yield at low temperatures via a shift in the rate-determining reaction intermediates and transition states, where the reaction orders in hydrogen and ammonia change dramatically. Temperature-dependent atomic-scale understanding of this unique mechanism is obtained with synchronized experimental and density functional theory investigations.

Enhancement of the Hydrogenation and Dehydrogenation Characteristics of Mg by Adding Small Amounts of Nickel and Titanium

We compared the hydrogenation and dehydrogenation properties of Mg-based alloys to which small amounts of transition elements (Ni and Ti), halides (TaF5 and VCl3), and complex hydrides (LiBH4 and NaAlH4) were added through grinding in a hydrogen atmosphere (reactive milling). Mg-1.25Ni-1.25Ti is one of the samples compared, having a composition of 97.5 wt.% Mg + 1.25 wt.% Ni and 1.25 wt.% Ti. Even though Mg-1.25Ni-1.25Ti did not have the highest initial hydrogenation rate, it had the largest quantities of hydrogen absorbed and released for 60 min and the highest initial dehydrogenation rate. In addition, Mg-1.25Ni-1.25Ti did not show the incubation period in the dehydrogenation. We thus investigated the hydrogenation and dehydrogenation properties of Mg-1.25Ni-1.25Ti in more detail. Activated Mg-1.25Ni-1.25Ti absorbed 5.91 wt.% H in 12 bar H2 and released 5.80 wt.% H in 1.0 bar H2 at 593 K for 60 min at n = 3. For 5 wt.% hydrogen absorption by Mg-1.25Ni-1.25Ti, 18.7 min was required at 593 K in 12 bar H2 at n = 3. Although only small amounts of Ni and Ti were added, the hydrogenation and dehydrogenation properties of Mg were greatly improved. Ni and Ti-added Mg had a higher initial dehydrogenation rate and a larger Hd (60 min) than only Ni-added Mg, suggesting that the TiH1.924 and NiTi formed in Mg-1.25Ni-1.25Ti play roles in the increases in the initial dehydrogenation rate and Hd (60 min), probably acting as active sites for the nucleation of the Mg-H solid solution phase.

Effect of Different Amounts of TiF3 on the Reversible Hydrogen Storage Properties of 2LiBH4–Li3AlH6 Composite

Hydrogen is a potential green alternative to conventional energy carriers such as oil and coal. Compared with the storage of hydrogen in gaseous or liquid phases, the chemical storage of hydrogen in solid complex hydrides is safer and more effective. In this study, the complex hydride composite 2LiBH4–Li3AlH6 with different amounts of TiF3 was prepared by simple ball-milling and its hydrogen storage properties were investigated. Temperature programmed desorption and differential scanning calorimetry were used to characterize the de/rehydrogenation performance, and X-ray diffraction and scanning electron microscopy (SEM) were used to explore the phase structure and surface topography of the materials. The dehydrogenation temperature decreased by 48°C in 2LiBH4–Li3AlH6 with 15 wt% TiF3 composites compared to the composite without additives while the reaction kinetics was accelerated by 20%. In addition, the influence of hydrogen back pressure on the 2LiBH4–Li3AlH6 with 5 wt% TiF3 composite was also investigated. The results show that hydrogen back pressure between 2.5 and 3.5 bar can improve the reversible performance of the composite to some extent. With a back pressure of 3.5 bar, the second dehydrogenation capacity increased to 4.6 wt% from the 3.3 wt% in the 2LiBH4–Li3AlH6 composite without hydrogen back pressure. However, the dehydrogenation kinetics was hindered. About 150 h, which is 100 times the time required without back pressure, was needed to release 8.7 wt% of hydrogen at 3.5 bar hydrogen back pressure. The SEM results show that aluminum was aggregated after the second cycle of dehydrogenation at the hydrogen back pressure of 3 bar, resulting in the partial reversibility of the 5 wt% TiF3-added 2LiBH4–Li3AlH6 composite.

Light Weight Complex Metal Hydrides for Reversible Hydrogen Storage

We have investigated the complex metal hydrides involving light weight elements or compounds for the reversible hydrogen storage. The complex hydrides are prepared via an inexpensive solid state mechanochemical process under reactive atmosphere at ambient temperatures. The complex metal hydride, LiBH4 with different mole concentrations of ZnCl2 were characterized for the new phase formation and hydrogen decomposition characteristics of Zn(BH4)2. Furthermore, the complex metal hydride is destabilized using the addition of nano MgH2 for the reversible hydrogen storage characteristics. The structural, microstructural, surface, and other physicochemical behaviors of these lightweight complex metal hydrides have been studied via various metrological tools such as x-ray diffraction, Fourier transform infrared spectroscopy, thermal programed desorption, and PCT hydrogen absorption methods.

Can nitrogen-based complex hydrides be a hydrogen isotope separation material?

The nitrogen-based complex hydride Li–N–H has positive thermodynamic isotope effects with a separation factor of 1.42.

Ternary Ruthenium Complex Hydrides for Ammonia Synthesis

Ammonia is the feedstock for nitrogen fertilizers and a potential carbon-free energy carrier, but the current production emits more CO₂ than any other chemical producing reaction in the world. The demand for decarbonizing the ammonia industry by using renewable energy has renewed research interests into catalyst development for effective N₂ reduction under mild conditions, a grand scientific challenge. Conventional heterogeneous catalysts based on metallic Fe or Ru mediate dinitrogen dissociation and hydrogenation through a relatively energy-costing pathway. The ternary ruthenium complex hydrides Li₄RuH₆ and Ba₂RuH₆ reported in this work, on the other hand, represent an entirely new class of compound catalysts, which are composed of the electron- and H-rich [RuH₆] anionic centers for non-dissociative dinitrogen reduction, where hydridic H transports electron and proton between the centers, and the Li(Ba) cations for stabilizing N_xH_y (x: 0 to 2, y: 0 to 3) intermediates. The dynamic and synergistic involvement of all the components of the ternary complex hydrides facilitates a novel reaction mechanism with a narrow energy span and perfectly balanced kinetic barriers for the multi-step process, leading to ammonia production from N₂+H₂ with superior kinetics under mild conditions.