ABSTRACT
Postsynthetic exchange (PSE) is a method that is widely used to change the composition of metal-organic frameworks (MOFs) by replacing connecting linkers or metal nodes after the framework has been synthesized. However, few techniques can probe the nature and distribution of exchanged species following PSE. Herein, we show that X-ray photoelectron spectroscopy can be used to compare the relative concentrations of exchanged ligands at the surface and interior regions of MOF particles. Specifically, PSE of iodobenzene dicarboxylate ligands results in a gradient distribution from surface to bulk in UiO-66 nanoparticles that depends on PSE time. X-ray photoelectron spectroscopy also reveals differences between the surface chemistry of the PSE product and that of the direct synthesis product.
ABSTRACT
Solid-state NMR has been used to study mixed-matrix membranes (MMMs) prepared with a metal-organic framework (MOF, UiO-66) and two different high molecular weight polymers (PEO and PVDF). 13C and 1H NMR data provide overwhelming evidence that most UiO-66 organic linkers are within 1 nm of PEO, which indicates that PEO is homogeneously distributed throughout the MOF. Systematic changes in MOF 13C NMR peak positions and 1H NMR line widths, as well as dramatic reductions in the MOF 1H T1ρ relaxation times, are observed as the PEO content increases, and when the pores have been filled, a further increase in PEO results in the formation of semicrystalline PEO outside the UiO-66 particles. In contrast, similar studies on PVDF MMMs show that the polymer contacts only a small fraction (<20%) of the MOF linkers. Simulations confirm that PEO penetrates into UiO-66 more easily than does PVDF. These studies are among the first to provide experimental insights into MOF-polymer interactions in an MMM.
ABSTRACT
Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer-Emmett-Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro- and mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already-measured raw adsorption isotherms were provided to sixty-one labs, who were asked to calculate the corresponding BET areas. This round-robin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called "BET surface identification" (BETSI), expands on the well-known Rouquerol criteria and makes an unambiguous BET area assignment possible.
Subject(s)
Reproducibility of Results , Adsorption , PorosityABSTRACT
A series of styrene/butadiene polymers were combined with up to 90 wt% UiO-66 to form mixed-matrix membranes with varying physical properties. Notably, polystyrene-block-polybutadiene (SBS) membranes retained much of the processability and flexibility of the native polymer component and the porosity, chemical tunability, and adsorption of the native MOF.