A New Route to Porous Metal-Organic Framework Crystal-Glass Composites

A lower temperature route to metal–organic framework crystal–glass composites is presented. Specifically, the annealing pre-formed ZIF-62 glass with a crystalline MOF above Tg will enable formation of a greatly expanded range of materials.

Table S1.Lattice parameters of ZIF-62, ZIF-67 and UiO-66 obtained by Pawley refinement, and those reported in the literature [1,2].The starting values for the refinements were taken from the cell parameters reported in the literature.The pellet of ZIF-67 was broken after soaking for 7 days.The water uptake is calculated as follows: (1) where W a is the weight of dry sample, W b is the weight of wet sample, and ϕ is the weight fraction of MOF crystals in the dry sample.

Figure S2 .
Figure S2.Pawley refinements of CGCs with ZIF-67 and UiO-66.The signal/noise ratio is relatively poor for both lower weight loadings of the ZIF-67 composite, and the lowest weight loading of UiO-66.

Figure S8 .
Figure S8.Validation of Bragg scattering in the selected region of CGC (ZIF-67) 0.5 (ZIF-62) 0.5 tested with electron diffraction.White arrows mark some of the Bragg peaks.

Figure S11 .
Figure S11.N 2 gas isotherms at 77K of (a) CGCs with ZIF-67, and (b) CGCs with UiO-66.Solid circles represent adsorption, and hollow circles represent desorption.(c) The relative BET surface area of CGCs with different weight fraction of crystalline MOF in CGCs.The relative BET surface area is the ratio of BET surface area of the CGC to that of the pellet of pure crystalline MOF after heating at 400 C for 5 hours under Ar.

Figure S12 .
Figure S12.Thermal expansion of UiO-66 series tested by TMA.The non-physical result for the UiO-66 sample is consistent with the non-uniform nature of the sample and the presence of macroscale defects within the bulk solid (Figure3e, S4, and S7i).The deformation of the (UiO-66) 0.8 (ZIF-62) 0.2 sample, which is clear from the start of measurement, is ascribed to the dehydroxlyation of UiO-66 during the formation process.

Figure S13 .
Figure S13.Schematic diagram of chemical stability experiments.The vail containing aqueous solution and sample was kept at room temperature for 7 days.

Figure S14 .
Figure S14.XRD pattern of a g ZIF-62 before and after soaking in aqueous acid and base.

Figure S15 .
Figure S15.N 2 gas isotherms at 77K of pellets and CGCs with (a) ZIF-67 and (b) UiO-66 before and after soaking in aqueous acid at pH 5 or base at pH 12. Solid circles represent adsorption, and hollow circles represent desorption.

Figure S16 .
Figure S16.XRD pattern of pellets and CGCs with (a) ZIF-67 and (b) UiO-66 before and after soaking in aqueous acid at pH of 5 or base at pH of 12.

Figure S18 .
Figure S18.Water uptake at room temperature of pellets and CGCs with (a) ZIF-67 and (b) UiO-66.The pellet of ZIF-67 was broken after soaking for 7 days.The water uptake is calculated as follows:

Table S2 .
[1,2]ce parameters of ZIF-67 and UiO-66 obtained by Pawley refinement, and those reported in the literature[1,2].The starting values for the refinements were taken from the cell parameters reported in the literature.