Metal-organic frameworks (MOFs) have gained popularity for their diverse applications, notably as candidates for gas-storage, photocatalysts and as light harvesters.[1,2] The current status of MOF design is focused on creating large surface area materials for gas-storage, however no frameworks have been proven to have the absorption capacity, chemical stability and simplicity of synthesis to be viable replacements for pressurised gas. There have been marginally better results for MOFs as catalysts, with many examples of organic reactions being performed inside the pore, or on the framework itself. Since catalytic function is determined by the electronic structure we modify these through intelligent design of both the organic and inorganic motifs.[3]Using two prototype frameworks, MIL-125 and UiO-67, we focus on the electronic factors that influence their photocatalytic applications. MIL-125, a TiO2 based framework, has catalytic capabilities controlled by organic modifications; the valence band of MIL-125-NH2 shown, left.[4] UiO-67 is unusual as its inorganic subunit, ZrO2, is insulating thus acting as only a structural motif and does not contribute to frontier electronic states. This provides scope for intra-MOF catalysis through heterometal-coordination to bipyridine-modified UiO-67 ligands. A truncated section of UiO-67 functionalised with bypiridine is shown, right. As a result, we provide methods for both organic and inorganic electronic manipulation emphasise the importance understanding the electronic structure for application based MOF design.[1] C. H. Hendon, D. Tiana, A. Walsh, Phys. Chem. Chem. Phys., 2012, 14 , 13120.[2] C. H. Hendon, D. Tiana, T. P. Vaid, A. Walsh, J. Mater. Chem. C, 2013, 1 , 95.[3] C. H. Hendon, D. Tiana, A. T. Murray, D. R. Carbery, A. Walsh, Chem. Sci., 2013, 4 , 4278.[4] C. H. Hendon et al., J. Am. Chem. Soc., 2013, 30  , 10942.

Electronic design principles of metal-organic frameworks for photocatalysis, gas-storage and light harvesting

247th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.