Development of a new class of stable and adaptable free-standing fibre mats with high room-temperature hydroxide-ion conductivity.

For alkaline anion-exchange membrane electrolysers and fuel cells to become a technological reality, hydroxide-ion (OH-) conducting membranes that are flexible, robust, affording high OH- conductivity, and synthesised in a low-cost and scalable way must be developed. In this paper, we engineer a stable, self-supporting, and flexible fibre mat using a low-cost ZIF-8 metal-organic framework composited with ionic liquid tetrabutylammonium hydroxide and widely used polyacrylonitrile as polymeric backbone. We obtain mats with a high intrinsic OH- conductivity for a metal-organic framework-based material already at room temperature, without added ion-conductor polymers. This approach will contribute to the development of low-cost and tuneable ion-conducting membranes.

Formation and growth characteristics of nanostructured carbon films on nascent Ag clusters during room-temperature electrochemical CO2 reduction.

Synthesis of carbon nanostructures at room temperature and under atmospheric pressure is challenging but it can provide significant impact on the development of many future advanced technologies. Here, the formation and growth characteristics of nanostructured carbon films on nascent Ag clusters during room-temperature electrochemical CO2 reduction reactions (CO2RR) are demonstrated. Under a ternary electrolyte system containing [BMIm]+[BF4]-, propylene carbonate, and water, a mixture of sp2/sp3 carbon allotropes were grown on the facets of Ag nanocrystals as building blocks. We show that (i) upon sufficient energy supplied by an electric field, (ii) the presence of negatively charged nascent Ag clusters, and (iii) as a function of how far the C-C coupling reaction of CO2RR (10-390 min) has advanced, the growth of nanostructured carbon can be divided into three stages: Stage 1: sp3-rich carbon and diamond seed formation; stage 2: diamond growth and diamond-graphite transformation; and stage 3: amorphous carbon formation. The conversion of CO2 and high selectivity for the solid carbon products (>95%) were maintained during the full CO2RR reaction length of 390 min. The results enable further design of the room-temperature production of nanostructured carbon allotropes and/or the corresponding metal-composites by a viable negative CO2 emission technology.

A facile and sustainable one-pot approach to the aqueous and low-temperature PET-to-UiO-66(Zr) upcycling.

Accelerating waste management requires the conversion of polymer waste to value-added materials through sustainable approaches. While depolymerised PET has been used as feedstock to produce metal-organic frameworks, this is the first report of the successful one-pot hydrothermal synthesis of the desirable UiO-66 topology through the judicious choice of reactants, modulators and reaction conditions.

Effect of linker functionalisation on the catalytic properties of Cu nanoclusters embedded in MOFs in direct CO and CO2 reduction by H2.

Metal-organic frameworks are promising host supporting matrices for catalytically active guests. In particular, their crystallinity renders them desirable as their pores may act as atom-precise templates for the growth of nanoparticles or nanoclusters therein. This is very advantageous for studying the fundamentals of heterogeneous catalytic processes, especially for site-selective ones, in which the catalyst particle size and shape are of import. Furthermore, metal-organic frameworks may be decorated with organic functional groups, which affect a number of the frameworks' physical and chemical properties, while remaining isotopological, i.e. having identical structural features and thus templating characteristics. Effectively, this allows for the independent tuning of the Brønsted and Lewis acidity of the substrate while the geometry of the catalytically active guest remains identical. In this study, we systematically study the effect of amino functionalisation of UiO-66(Zr) as a supporting matrix for Cu nanoclusters on the direct reduction of carbon dioxide with hydrogen. In particular, we have found that through modulation of the acidity of the inorganic nodes, framework functionalisation effectively controls the reaction selectivity.

Interactions of Hydrogen with Pd@MOF Composites.

Physisorption and chemisorption of hydrogen on solid-state materials are two fundamentally different interactions, both of which display advantages and drawbacks for hydrogen storage. It has been hypothesised that their combination by merging two classes of materials showing different sorption behaviour towards hydrogen in the same composite may synergistically combine their desirable properties. As representatives of such composites, palladium nanoparticles, nanoclusters, and single atoms have been encapsulated in a metal-organic framework matrix, embedded, or immobilised in its pores, respectively. In this minireview, we review advances on the understanding and potential applications of the combination of Pd with metal-organic framework matrices through the analysis of the nanocomposite materials' interaction with hydrogen and sorption properties.