Metal-organic framework crystal-glass composites

The majority of research into metal-organic frameworks (MOFs) focuses on their crystalline nature. Recent research has revealed solid-liquid transitions within the family, which we use here to create a class of functional, stable and porous composite materials. Described herein is the design, synthesis, and characterisation of MOF crystal-glass composites, formed by dispersing crystalline MOFs within a MOF-glass matrix. The coordinative bonding and chemical structure of a MIL-53 crystalline phase are preserved within the ZIF-62 glass matrix. Whilst separated phases, the interfacial interactions between the closely contacted microdomains improve the mechanical properties of the composite glass. More significantly, the high temperature open pore phase of MIL-53, which spontaneously transforms to a narrow pore upon cooling in the presence of water, is stabilised at room temperature in the crystal-glass composite. This leads to a significant improvement of CO2 adsorption capacity.

Metal–organic frameworks (MOFs) are a class of hybrid materials, composed of metal nodes and coordinating organic linkers. The arrangement of these components in highly regular motifs often leads to materials exhibiting ultra-high surface areas1. Applications are therefore proposed which utilise this porosity for reversible host–guest behaviour, for example, in gas storage, catalysis and drug delivery2,3,4,5,6. Several MOF-based products have been commercialised, such as for delaying the over-ripening of fruit, and for harmful gas storage (e.g., PH3) within the semiconductor industry7.

The main body of MOF research typically focuses on the discovery of new materials and expanding the library of available crystalline MOFs, which currently stands at over 70,0008. Attempts have been made to develop existing MOFs and explore new applications using known functionalities, and introducing flexibility, defects and stimuli responsive behaviour9,10. Whilst crystalline MOFs have shown exceptional properties, a number of industrial practicability issues remain. One barrier is the inherent difficulties in processing and shaping MOF microcrystalline powders into mechanically robust macroscale morphologies11,12. Conventionally, high pressure pelletisation or binders are used in the shaping of MOF powders but these treatments have been shown to significantly decrease material efficacy13.

The formation of composites by combining MOFs with more processable materials such as polymers, not only engages with the theme of new materials discovery, but also offers solutions to the aforementioned problems in manufacturing robust bulk structures. These include core–shell structures, in which a MOF outer layer is grown on an inner sphere of another material14,15. Amongst these macroscale architectures, membranes and thin films are particularly important given the requirements for continuous, defect free coverage and flexibility under pressure16. Mixed matrix membranes (MMMs) are a prototypical case of such materials17. Here, a crystalline MOF filler is typically dispersed in an organic polymer18. The disordered nature of the polymeric organic component within MMMs provides both structural stability and facilitates shaping. Significant penalties are incurred however, including pore blocking by the matrix, aggregation of the filler and poor adhesion between the two components, which prevents high loading capacities19. Therefore, the synthesis and characterisation of composite MOF materials without these disadvantages is of great importance to bridge the divide between advanced MOF material synthesis and practical device fabrication.

Structural disorder is an emerging topic in the MOF field. In particular, solid–liquid transitions upon heating in both the phosphonate coordination polymer and the zeolitic imidazolate framework (ZIF) families are of interest20,21. The latter family contains tetrahedral metal ions, linked by imidazolate (Im – C3H3N2−) derived bidentate ligands. Studies of the ZIF-zni [Zn(Im)2] structure show that at ca. 550 °C, rapid dissociation-association of the imidazolate linker around Zn2+ centres occurs, leading to formation of a viscous liquid of identical chemical composition22.

The porous glasses formed upon quenching these high temperature liquid ZIFs has been modelled by continuous random network topologies, analogous to amorphous silica. Here, we exploit the disordered MOF state as an analogue for the organic matrix component of MOF–organic composites and create a class of materials comprising crystalline MOFs embedded in a host MOF–glass matrix. These composites, which we term MOF crystal–glass composites (CGCs), might be expected to display better interfacial binding between filler and matrix components than their MMM counterparts, given their greater degree of chemical compatibility. They may also, importantly, exhibit a diverse array of mechanical and structural properties different to those of either parent phase.

ZIF-62 [Zn(Im)1.75(bIm)0.25] (bIm = benzimidazolate, C7H5N2−) was selected as the MOF–glass matrix due to a relatively low temperature of melting (Tm = 430 °C) and a large temperature range over which the resultant liquid is stable before decomposing (at ca. 550 °C). The glass, here referred to as agZIF-62, which is formed upon cooling the ZIF-62 liquid, is also extremely stable against crystallisation, which is ascribed to the high viscosity of the liquid phase23.

The two key requirements for the crystalline component in such a composite, are that the temperature of decomposition (Td) should exceed the glass-forming matrix Tm, and that the chemical (in)compatibility is such that no flux melting occurs24. The two frameworks we chose, MIL-53(Al) [Al(OH)(O2C-C6H4-CO2)] and UiO-66 [Zr6O4(OH)4(O2C-C6H4-CO2)6] both fulfil these criteria25,26. MIL-53(Al) is an aluminium 1,4-benzenedicarboxylate (BDC) based MOF (referred to as MIL-53 hereafter), with a 3D framework structure built with trans chains of corner-sharing AlO4(OH)2 octahedra27,28. The as-synthesised (MIL-53-as) structure contains unreacted H2BDC within the framework. The removal of these guest molecules by thermal treatment leads to an open-pore structure (MIL-53-lp)29. Physisorption of water by MIL-53-lp causes a transition to a closed pore structure (MIL-53-np), due to formation of framework-guest (water molecule) interactions (Fig. 1a). UiO-66, on the other hand, consists of Zr-centred secondary building units connected to (in a perfect crystal) 12 BDC linkers. The crystal structure of UiO-66 is rigid with high thermal and mechanical stability, due to the strong Zr–O bonds and a close-packed structure30.