Functionalised metal-organic frameworks: a novel approach to stabilising single metal atoms

We have investigated the potential of metal-organic frameworks for immobilising single atoms of transition metals using a model system of Pd supported on NH2-MIL-101(Cr). Our Transmission Electron Microscopy and in-situ Raman spectroscopy results give evidence for the first time that functionalised metal-organic frameworks may support, isolate and stabilise single atoms of palladium. Using Thermal Desorption Spectroscopy we were able to evaluate the proportion of single Pd atoms. Furthermore, in a combined theoretical-experimental approach, we show that the H-H bonds in a H2 molecule elongate by over 15% through the formation of a complex with single atoms of Pd. Such deformation would affect any hydrogenation reaction and thus the single atoms supported on metal-organic frameworks may become promising single atom catalysts in the future

How to functionalise metal–organic frameworks to enable guest nanocluster embedment

We report on the development and verification of an enhanced computational model capable of robust predictions and yielding a single descriptor to the successful embedding of guest nanoclusters into the pores of functionalised metal-organic frameworks. Using the predictions of this model, we have been able to embed Pd nanoclusters in the pores of Br-UiO-66 and show that the embedding of Pd nanoclusters in both (OH)2-UiO-66 and (Cl)2-UiO-66 is not successful. Also, using various independent methods, we identified the strong host-guest interactions that anchor the guest nanoclusters inside the Br-UiO-66 framework which result in the surface modification of said nanoclusters. We demonstrated that the level of this surface modification is a direct function of the framework functional groups. This new approach for the rational design of nanocluster-metal-organic framework systems, and a demonstrated tool box for their characterisation, will promote the exploitation of surface modification of nanoclusters via their embedding into functionalised metal-organic framework pores

Developments in the Ni–Nb–Zr amorphous alloy membranes

Most of the global H2 production is derived from hydrocarbon-based fuels, and efficient H2/CO2 separation is necessary to deliver a high-purity H2 product. Hydrogen-selective alloy membranes are emerging as a viable alternative to traditional pressure swing adsorption processes as a means for H2/CO2 separation. These membranes can be formed from a wide range of alloys, and those based on Pd are the closest to commercial deployment. The high cost of Pd (USD *31,000 kg-1) is driving the development of less-expensive alternatives, including inexpensive amorphous (Ni60Nb40)100-xZrx alloys. Amorphous alloy membranes can be fabricated directly from the molten state into continuous ribbons via melt spinning and depending on the composition can exhibit relatively high hydrogen permeability between 473 and 673 K. Here we review recent developments in these low-cost membrane materials, especially with respect to permeation behavior, electrical transport properties, and understanding of local atomic order. To further understand the nature of these solids, atom probe tomography has been performed, revealing amorphous Nb-rich and Zr-rich clusters embedded in majority Ni matrix whose compositions deviated from the nominal overall composition of the membrane

Interplay of Linker Functionalization and Hydrogen Adsorption in the Metal–Organic Framework MIL-101

Functionalization of metal–organic frameworks results in higher hydrogen uptakes owing to stronger hydrogen–host interactions. However, it has not been studied whether a given functional group acts on existing adsorption sites (linker or metal) or introduces new ones. In this work, the effect of two types of functional groups on MIL-101 (Cr) is analyzed. Thermal-desorption spectroscopy reveals that the −Br ligand increases the secondary building unit’s hydrogen affinity, while the −NH2 functional group introduces new hydrogen adsorption sites. In addition, a subsequent introduction of −Br and −NH2 ligands on the linker results in the highest hydrogen-store interaction energy on the cationic nodes. The latter is attributed to a push-and-pull effect of the linkers

Fundamentals of hydrogen storage in nanoporous materials

Physisorption of hydrogen in nanoporous materials offers an efficient and competitive alternative for hydrogen storage. At low temperatures (e.g. 77 K) and moderate pressures (below 100 bar) molecular H2 adsorbs reversibly, with very fast kinetics, at high density on the inner surfaces of materials such as zeolites, activated carbons and metal–organic frameworks (MOFs). This review, by experts of Task 40 ‘Energy Storage and Conversion based on Hydrogen’ of the Hydrogen Technology Collaboration Programme of the International Energy Agency, covers the fundamentals of H2 adsorption in nanoporous materials and assessment of their storage performance. The discussion includes recent work on H2 adsorption at both low temperature and high pressure, new findings on the assessment of the hydrogen storage performance of materials, the correlation of volumetric and gravimetric H2 storage capacities, usable capacity, and optimum operating temperature. The application of neutron scattering as an ideal tool for characterising H2 adsorption is summarised and state-of-the-art computational methods, such as machine learning, are considered for the discovery of new MOFs for H2 storage applications, as well as the modelling of flexible porous networks for optimised H2 delivery. The discussion focuses moreover on additional important issues, such as sustainable materials synthesis and improved reproducibility of experimental H2 adsorption isotherm data by interlaboratory exercises and reference materials

Metal hydride hydrogen storage and compression systems for energy storage technologies

Along with a brief overview of literature data on energy storage technologies utilising hydrogen and metal hydrides, this article presents results of the related R&D activities carried out by the authors. The focus is put on proper selection of metal hydride materials on the basis of AB5- and AB2-type intermetallic compounds for hydrogen storage and compression applications, based on the analysis of PCT properties of the materials in systems with H2 gas. The article also presents features of integrated energy storage systems utilising metal hydride hydrogen storage and compression, as well as their metal hydride based components developed at IPCP and HySA Systems

Materials for hydrogen-based energy storage - past, recent progress and future outlook

Globally, the accelerating use of renewable energy sources, enabled by increased efficiencies and reduced costs, and driven by the need to mitigate the effects of climate change, has significantly increased research in the areas of renewable energy production, storage, distribution and end-use. Central to this discussion is the use of hydrogen, as a clean, efficient energy vector for energy storage. This review, by experts of Task 32, “Hydrogen-based Energy Storage” of the International Energy Agency, Hydrogen TCP, reports on the development over the last 6 years of hydrogen storage materials, methods and techniques, including electrochemical and thermal storage systems. An overview is given on the background to the various methods, the current state of development and the future prospects. The following areas are covered; porous materials, liquid hydrogen carriers, complex hydrides, intermetallic hydrides, electrochemical storage of energy, thermal energy storage, hydrogen energy systems and an outlook is presented for future prospects and research on hydrogen-based energy storage