New materials capable of storing hydrogen at high gravimetric and volumetric densities are required if hydrogen is to be widely employed as a clean alternative to hydrocarbon fuels in cars and other mobile applications. With exceptionally high surface areas and chemically-tunable structures, microporous metal–organic frameworks have recently emerged as some of the most promising candidate materials. In this critical review we provide an overview of the current status of hydrogen storage within such compounds. Particular emphasis is given to the relationships between structural features and the enthalpy of hydrogen adsorption, spectroscopic methods for probing framework–H2 interactions, and strategies for improving storage capacity (188 references).

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Hydrogen storage in metal–organic frameworks

Hydrogen is a promising energy carrier in future energy systems. However, storage of hydrogen is a substantial challenge, especially for applications in vehicles with fuel cells that use proton-exchange membranes (PEMs). Different methods for hydrogen storage are discussed, including high-pressure and cryogenic-liquid storage, adsorptive storage on high-surface-area adsorbents, chemical storage in metal hydrides and complex hydrides, and storage in boranes. For the latter chemical solutions, reversible options and hydrolytic release of hydrogen with off-board regeneration are both possible. Reforming of liquid hydrogen-containing compounds is also a possible means of hydrogen generation. The advantages and disadvantages of the different systems are compared.

Chemical and Physical Solutions for Hydrogen Storage

Based on the principles and metrics of green chemistry and sustainable development, biocatalysis is both a green and sustainable technology. This is largely a result of the spectacular advances in molecular biology and biotechnology achieved in the past two decades. Protein engineering has enabled the optimization of existing enzymes and the invention of entirely new biocatalytic reactions that were previously unknown in Nature. It is now eminently feasible to develop enzymatic transformations to fit predefined parameters, resulting in processes that are truly sustainable by design. This approach has successfully been applied, for example, in the industrial synthesis of active pharmaceutical ingredients. In addition to the use of protein engineering, other aspects of biocatalysis engineering, such as substrate, medium, and reactor engineering, can be utilized to improve the efficiency and cost-effectiveness and, hence, the sustainability of biocatalytic reactions. Furthermore, immobilization of an enzyme ...

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Role of Biocatalysis in Sustainable Chemistry

Gas solubility in ionic liquids.

The storage of large quantities of hydrogen at safe pressures is a key factor in establishing a hydrogen-based economy. Previous strategies--where hydrogen has been bound chemically, adsorbed in materials with permanent void space or stored in hybrid materials that combine these elements--have problems arising from either technical considerations or materials cost. A recently reported clathrate hydrate of hydrogen exhibiting two different-sized cages does seem to meet the necessary storage requirements; however, the extreme pressures (approximately 2 kbar) required to produce the material make it impractical. The synthesis pressure can be decreased by filling the larger cavity with tetrahydrofuran (THF) to stabilize the material, but the potential storage capacity of the material is compromised with this approach. Here we report that hydrogen storage capacities in THF-containing binary-clathrate hydrates can be increased to approximately 4 wt% at modest pressures by tuning their composition to allow the hydrogen guests to enter both the larger and the smaller cages, while retaining low-pressure stability. The tuning mechanism is quite general and convenient, using water-soluble hydrate promoters and various small gaseous guests.

Tuning clathrate hydrates for hydrogen storage

Thermodynamic, x-ray diffraction, and Raman and nuclear magnetic resonance spectroscopy measurements show that clusters of H2 can be stabilized and stored at low pressures in a sII binary clathrate hydrate. Clusters of H2 molecules occupy small water cages, whereas large water cages are singly occupied by tetrahydrofuran. The presence of this second guest component stabilizes the clathrate at pressures of 5 megapascals at 279.6 kelvin, versus 300 megapascals at 280 kelvin for pure H2 hydrate.

https://science.sciencemag.org/content/sci/306/5695/469.full.pdf

Stable Low-Pressure Hydrogen Clusters Stored in a Binary Clathrate Hydrate

A prototype surfactant system was developed with the unique feature that it can be switched between an aggregated, amphiphilic state and a nonaggregated, nonamphiphilic state using external stimuli. This switchable surfactant system uses the reversible formation of a dynamic covalent bond for pH- and temperature-triggered on/off self-assembly of micellar aggregates by reversible displacement of the equilibrium between nonamphiphilic building blocks and their amphiphilic counterparts. The potential for application in controlled-release systems is shown by reversible uptake and release of an organic dye in aqueous media.

Triggered self-assembly of simple dynamic covalent surfactants.

Responsive Vesicles from Dynamic Covalent Surfactants

This paper reports high-pressure phase equilibrium data on binary mixtures of carbon dioxide with dimethyl sulfoxide (DMSO) and ternary mixtures of DMSO, carbon dioxide and water. The data cover a range of temperatures between 280 and 370 K and pressures up to 15 MPa. Partial liquid miscibility was observed in the binary system DMSO + CO 2 at high CO 2 concentrations. Vapor–liquid, liquid–liquid and vapor–liquid–liquid equilibrium conditions were measured. The experimental data were modeled with a group-contribution equation of state that takes into account association effects (GCA-EOS). Self-association of water and cross-association between water and DMSO molecules were considered. A molecular group (CH 3 SOCH 3 ) was used to represent DMSO, the first member of the alkyl-sulfoxide family. Pure group and binary interaction parameters for this new molecular group have been determined. Good correlation and prediction of phase equilibrium conditions were obtained.

Louw J. Florusse

Papers

Stable Low-Pressure Hydrogen Clusters Stored in a Binary Clathrate Hydrate

Triggered self-assembly of simple dynamic covalent surfactants.

Responsive Vesicles from Dynamic Covalent Surfactants

Phase equilibria of dimethyl sulfoxide (DMSO) + carbon dioxide, and DMSO + carbon dioxide + water mixtures

The influence of Na2SO4 on the CO2 solubility in water at high pressure