Surface thermodynamics and Lewis acid-base properties of metal-organic framework Crystals by Inverse gas chromatography at infinite dilution

In this study, the surface thermodynamic properties and more particularly, the dispersive component γsd of the surface energy of crystals of a Zr-based MOF, UiO-66 (Zr6O4(OH)4(BDC)6; BDC = benzene 1,4-dicarboxylic acid), the specific interactions, and their acid-base constants were determined by using different molecular models and inverse gas chromatography methods. The determination of γsd of the UiO-66 surface was obtained by using several models such as Dorris-Gray and those based on the Fowkes relation by applying the various molecular models giving the surface areas of n-alkanes and polar organic molecules. Six models were used: Kiselev, spherical, geometric, Van der Waals, Redlich-Kwong, and cylindrical models. The obtained results were corrected by using our model taking into account the thermal effect on the surface areas of molecules. A linear equation was obtained between γsd and the temperature. The specific free energy, enthalpy and entropy of adsorption of polar molecules, as well as the acid and base constants of UiO-66 particles were determined with an excellent precision. It was also proved that the UiO-66 surface exhibited an amphoteric acid-base character with stronger acidity. The linear variations of the specific free energy of interaction as a function of the temperature allowed to obtain the specific surface enthalpy and entropy of adsorption, as well as the acid and base constants of UiO-66 by using ten different models and methods. The best results were obtained by using our model that gave the more precise values of the acid constant KA=0.57, the base constant KD=0.18 of the MOF particles and the ratio KA/KD = 3.14 clearly proving a strong acid character of the UiO-66 surface

Efficient biofuel production by MTV-UiO-66 based catalysts

In this study, highly defected and functionalized metal-organic framework (MOF) structures are developed and exploited as catalysts for an esterification reaction for biofuel production. Two systems of multivariate UiO-66 series, namely MTV-UiO-66(COOH)2 and MTV-UiO-66(OH)2 incorporating dicarboxylate and dihydroxy groups, respectively, along with the single component structures, are thus explored for butyl butyrate production. Ratios of functionalized linkers to terephthalic acid are varied and a modulation synthesis approach is employed allowing for high levels of structural defects. The synthesized MOF structures are fully characterized using Powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), proton nuclear magnetic resonance (1H NMR), Brunauer–Emmett–Teller (BET), and scanning electron microscopy (SEM), and the results confirmed the homogeneous incorporation of the functionalized linkers in the structures. The combination of multivariate approach along with modulation synthesis yields structures with catalytic activity higher than those of highly defective fully functionalized structures and close to the homogeneous conventional catalyst used in esterification reactions. Moreover, the ratio of functionalized linkers to terephthalic acid is shown to be very important since not all MTV-UiO-66 performed better than the single-component structure which can be attributed to a combination of factors related to the density of active sites and their accessibility. The most active MTV-UiO-66(OH)2 member, incorporating 52% of functionalized linkers, a defects number of 1.9, and a surface area of 761 m2/g, yielded 92% conversion to butyl butyrate, compared to 95% for H2SO4, and its activity and stability is maintained over 4 consecutive cycles. Furthermore, by using the data of 33 different UiO-66 based catalysts for butyl butyrate production, a weighted linear regression model is suggested to predict the conversion based on the parameters that are concluded to mostly govern the catalytic activity of MOF catalysts. These parameters include the surface area, the catalytic loading, the defects number, and the level of incorporation of BDC, and the functionalized linkers. The weights calculated for each of these parameters indicate that there is a more pronounced effect of active sites density on the conversion when compared to the surface area or the catalyst loading. These conclusions help pave the way for the engineering of MOF-based catalysts in the path of bridging the gap between homogeneous and heterogeneous catalysis for efficient biofuel production

Enhanced removal of ultratrace levels of gold from wastewater using sulfur-rich covalent organic frameworks

In view of the increasing global demand and consumption of gold, there is a growing need and effort to extract gold from alternative sources besides conventional mining, e.g., from water. This drive is mainly due to the potential benefits for the economy and the environment as these sources contain large quantities of the precious metal that can be utilized. Wastewater is one of these valuable sources in which the gold concentration can be in the ppb range. However, the effective selective recovery and recycling of ultratrace amounts of this metal remain a challenge. In this article, we describe the development of a covalent imine based organic framework with pores containing thioanisole functional groups (TTASDFPs) formed by the condensation of a triazine-based triamine and an aromatic dialdehyde. The sulfur-functionalized pores served as effective chelating agents to bind Au3+ ions, as evidenced by the uptake of more than 99% of the 9 ppm Au3+ solution within 2 min. This is relatively fast kinetics compared with other adsorbents reported for gold adsorption. TTASDFP also showed a high removal capacity of 245 mg·g−1 and a clear selectivity toward gold ions. More importantly, the material can capture gold at concentrations as low as 1 ppb.This work was supported by New York University Abu Dhabi and the NYUAD Water Research Center, funded by Tamkeen under the NYUAD Research Institute Award (Project CG007). We thank NYUAD for their generous support for the research program. We also thank Sandooq Al Watan (Grant No. SWARD-S22-014; Project ID, PRJ-SWARD-628) for their generous support. The research work was carried out by using the Core Technology Platform resources at NYUAD. We acknowledge Graphic Designer Aisha Jrad, who made the abstract and Table of Contents (TOC) artwork of the manuscript ([email protected])