MOF Catalysis

MOFs are promising materials for heterogeneous catalysis and our research team is investigating how particular structural motifs can be incorporated into the design of MOFs to develop new or more efficient catalysts.  This work extends from garnering new fundamental insight into MOF-supported molecular catalysts, through new MOF catalysts and finally using MOFs as templates for catalysis. Techniques such as post-synthetic metalation (see our review of this area) are important to preparing new catalysts and we have purpose-built catalytic testing facilities for examining gas phase catalysis.

SCXRD studies of catalysts - reactive species and reaction intermediates

Through our work on flexible MOFs we discovered a material capable of undergoing quantitative post-synthetic metalation with retention of single crystallinity. As such, this materials enables structural insight to be readily garnered into metal centred reactions occurring int the protective pore environment of the material. This has allowed us to study catalytic reactions in the MOF and to trap unusual or reactive species. These insights can help with the design of other MOF or heterogeneous catalysts.

The original report of this work is:

• Capturing snapshots of post-synthetic metallation chemistry in metal-organic frameworks, Nature Chemistry, 2014, 6, 906-912.

Some recent contributions include:

• Mapping-out catalytic processes in a metal-organic framework with single-crystal X-ray crystallography. Angewandte Chemie - International Edition, 2017, 56, 8412-8416.

• Protecting-group-free site-selective reactions in a metal-organic framework reaction vessel. Journal of the American Chemical Society, 2018, 140, 6416-6425.

MOF catalysts

Due to having a modular approach to construction, the structures and functionality of MOFs can be systematically modified. This chemical mutability, in conjunction with large pore volumes and high surface areas, has particularly earmarked MOFs as promising materials for heterogeneous catalysis. We have directed much of our efforts to heterogenising known homogenous catalysts by designing MOFs with diols, cyclometalation sites, and heterocyclic donors, with potential for post-synthetic or concommitant metalation.

Some contributions include:

• Control of framework interpenetration for in situ modified hydroxyl functionalised IRMOFs, Chemical Communications, 2012, 48, 10328-10330.

• A 3-D diamondoid MOF catalyst based on in situ generated [Cu(L)2] N-heterocyclic carbene (NHC) linkers: hydroboration of CO₂, Chemical Communications, 2014, 50, 11760-11763.

• Influence of nanoscale structuralisation on the catalytic performance of ZIF-8: a cautionary surface catalysis study. CrystEngComm, 2018, 20, 4926-4934.

MOF-derived materials as catalysts

The chemical mutability and structural diversity of MOFs allows the preparation of materials with precise composition and spatial arrangements. These MOF materials can serve as templates to synthesise catalysts with unique morphologies.

A recent contribution is:

• Highly active catalyst for CO₂ methanation derived from a metal organic framework template. Journal of Materials Chemistry A, 2017, 5, 12990-12997.