Nanostructured materials for solid-state hydrogen storage: A review of the achievement of COST Action MP1103

In the framework of the European Cooperation in Science and Technology (COST) Action MP1103 Nanostructured Materials for Solid-State Hydrogen Storage were synthesized, characterized and modeled. This Action dealt with the state of the art of energy storage and set up a competitive and coordinated network capable to define new and unexplored ways for Solid State Hydrogen Storage by innovative and interdisciplinary research within the European Research Area. An important number of new compounds have been synthesized: metal hydrides, complex hydrides, metal halide ammines and amidoboranes. Tuning the structure from bulk to thin film, nanoparticles and nanoconfined composites improved the hydrogen sorption properties and opened the perspective to new technological applications. Direct imaging of the hydrogenation reactions and in situ measurements under operando conditions have been carried out in these studies. Computational screening methods allowed the prediction of suitable compounds for hydrogen storage and the modeling of the hydrogen sorption reactions on mono-, bi-, and three-dimensional systems. This manuscript presents a review of the main achievements of this Action. (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Surface Reactions are Crucial for Energy Storage

Elsa Callini, Shunsuke Kato, Philippe Mauron

Reactions between gas molecules, e.g. H-2 and CO2 and solids take place at the surface. The electronic states and the local geometry of the atomic arrangement determine the energy of the adsorbate, i.e. the initial molecule and the transition state. Here we review our research to identify the surface species, their chemical state and orientation, the interaction with the neighbouring molecules and the mobility of the adsorbed species and complement the experimental results with thermodynamic modelling. The role of the Ti was found to be a bridge between the charged species preventing the individual movement of the ions including charge separation. The Ti has no catalytic effect on the hydrogen sorption reaction in borohydrides. The physisorption of molecular hydrogen is too weak at ambient temperature to reach a significant hydrogen storage density. The addition of a hydrogen dissociation catalyst to a nanoporous material with a large specific surface area may potentially enable the spillover of hydrogen atoms from the metal catalyst to the surface of the porous material and chemisorb on specific sites with a much higher binding energy compared to physisorption. The intercalation of alkali metals in C-60 fullerenes increases the interaction energy of hydrogen with the so-called metal fullerides significantly. Sterical diffusion barriers by partial oxidation of the surface of borohydrides turned out to redirect the reaction path towards pure hydrogen desorption and suppress the formation of diborane, a by-product of the hydrogen evolution reaction from borohydrides previously undetected. The combination of a newly developed gas controlling system with microreactors allows us to investigate complex reactions with small quantities of nano designed new catalytic materials. Furthermore, tip-enhanced Raman spectroscopy (TERS) will allow the investigation of the reactions locally on the surface of the catalyst and the near ambient pressure photoelectron spectroscopy enables analysis of the surfaces in ultra-high vacuum and in situ interaction with the adsorbates i.e. while the reaction takes place. This brings us in a unique position for the investigation of the heterogeneous reactive systems. The mechanism of the Ti catalysed hydrogen sorption reactions in alanates was recently established based on spectroscopic investigations combined with thermodynamic analysis of the transition states.

Schweizerische Chemische Gesellschaft2015

Complex and liquid hydrides for energy storage

Elsa Callini

The research on complex hydrides for hydrogen storage was initiated by the discovery of Ti as a hydrogen sorption catalyst in NaAlH4 by Boris Bogdanovic in 1996. A large number of new complex hydride materials in various forms and combinations have been synthesized and characterized, and the knowledge regarding the properties of complex hydrides and the synthesis methods has grown enormously since then. A significant portion of the research groups active in the field of complex hydrides is collaborators in the International Energy Agreement Task 32. This paper reports about the important issues in the field of complex hydride research, i.e. the synthesis of borohydrides, the thermodynamics of complex hydrides, the effects of size and confinement, the hydrogen sorption mechanism and the complex hydride composites as well as the properties of liquid complex hydrides. This paper is the result of the collaboration of several groups and is an excellent summary of the recent achievements.

Springer2016

Decreasing the Stability of Borohydride with Ionic Liquids for Hydrogen Storage and Carbon Dioxide Conversion

Loris Giovanni Lombardo

The world needs to move from a fossil fuel to a renewable energy based society. With the increasing electricity production from wind and PV, short and long term energy storage are becoming one of challenge of the 21st century. While batteries are the preferred method for short term storage, another technology is required for seasonal storage. Hydrogen is a valuable energy carrier owning its high energy density (122 kJ/g). However, compact and safe storage of H2 is challenging. The current solution is to compress hydrogen up to 700 bar for mobile application (fuel cell cars), and metal hydrides for stationary application. Material-based H2 storage avoids using high-pressure cylinder. Complex hydrides are especially attractive for solid-state H2 storage due to their high gravimetric and volumetric hydrogen density. Sodium borohydride (NaBH4) contains 10.6 mass% of H2, but high temperatures are needed to release H2 (505 Â°C) and the reaction is not reversible under moderate conditions. To apply complex hydrides in real applications, they must be modified to improve the kinetics and thermodynamics of H2 desorption. Several possibilities exist such as confinement into scaffolds, catalyst addition, or combination of several hydrides to modify the dehydrogenation pathway. The stability of complex hydrides is determined by the localization of the charge on the central atom of the complex. Therefore, in this thesis the interaction of highly polar or ionic compounds with complex hydrides were investigated. We combine NaBH4 with a special class of organic salts: ionic liquids (IL). Considering their chemical and thermal stability, IL are attractive additive. Using organic additives instead of expensive metal catalysts is another advantage. Two different techniques were employed to combine the IL and NaBH4. The first one consists of mechanochemically milling them to create an interaction between BH4- and IL. The second one is to directly synthesized IL borohydrides ([IL][BH4]) by metathesis reaction. Different ILs, such as vinylbenzyltrimethylammonium chloride ([VBTMA][Cl]), 1-butyl-3-methylimidazolium chloride ([bmim][Cl]), and 1-ethyl-1-methylpyrrolidinium bromide ([EMPY][Br]) were tested. [bmim][BH4] was able to release H2 below 100 Â°C. The hydrogen content ranges between 2.4 mass% and 2.9 mass%. The second challenge of this century is the CO2 problematic. Atmospheric CO2 concentration linearly increases, leading to greenhouse effect. Carbon capture and sequestration (CCS) and utilization (CCU) are primordial research topic to stabilize the CO2 emission. Hydrides are primary reducing agents, thus reduction of CO2 can be accomplished with them. Direct CO2 reduction at ambient conditions is challenging for classical borohydrides. With our [IL][BH4], gaseous CO2 can be captured and reduced under ambient conditions (1 bar, RT). Three CO2 bounds with boron to give triformatoborohydride ([HB(OCHO)3]â. Dilute CO2 (6 vol%) can be used as well. The reaction was followed in real time with a magnetic suspended balance (MSB). Further, CO2 reduction happened when air is used as a carbon dioxide source. Formic acid can be obtained by adding HCl. Thus, ionic liquid borohydrides have great potential as a CO2 absorber and reducer to alternative fuels. In short, we applied ionic liquid to destabilized borohydrides. The resulting materials exhibited potential for solid-state hydrogen storage, as well as CO2 capture and transformation.