Adsorption properties of M-UiO-66 (M = Zr(IV); Hf(IV) or Ce(IV)) with BDC or PDC linker.

The increasing CO2 emissions and their direct impact on climate change due to the greenhouse effect are environmental issues that must be solved as soon as possible. Metal-organic frameworks (MOFs) are one class of crystalline adsorbent materials that are thought to have enormous potential in CO2 capture applications. In this research, the effect of changing the metal center between Zr(IV), Ce(IV), and Hf(IV), and the linker between BDC and PDC has been fully studied. Thus, the six UiO-66 isoreticular derivatives have been synthesized and characterized by FTIR, PXRD, TGA, and N2 adsorption. We also report the BET surface area, CO2 adsorption capacities, kinetics, and the adsorption isosteric heat (Qst) of the UiO-66 derivatives mentioned family. The CO2 adsorption kinetics were evaluated using pseudo-first order, pseudo-second order, Avrami's kinetic models, and the rate-limiting step with Boyd's film diffusion, interparticle diffusion, and intraparticle diffusion models. The isosteric heats of CO2 adsorption using various MOFs are in the range 20-65 kJ mol-1 observing differences in adsorption capacities between 1.15 and 4.72 mmol g-1 at different temperatures due to the electrostatic interactions between CO2 and extra-framework metal ions. The isosteric heat of adsorption calculation in this report, which accounts for the unexpectedly high heat released from Zr-UiO-66-PDC, is finally represented as an increase in the interaction of CO2 with the PDC linker and an increase in Qst with defects.

Novel Hydrophobic Functionalized UiO-66 Series: Synthesis, Characterization, and Evaluation of Their Structural and Physical-Chemical Properties.

A novel set of four functionalized hydrophobic UiO-66-NHR series were synthesized through postsynthetic procedures, utilizing various benzoyl chlorides and UiO-66-NH2 as starting materials. This synthesis method was carried out by employing p- (1) and o-toluoyl (2), as well as 2- (3) and 4-fluorobenzoyl (4) substituents. The analysis of the resulting compounds was performed using conventional spectroscopic methods such as FT-IR and 1H NMR to quantify the conversion rate into amide. Furthermore, SEM and XPS techniques were employed for morphological and surface analysis. Finally, the evaluation of the chemical stability and contact angle using the sessile drop method was performed to evaluate the technological potential of these compounds for application in aqueous and acidic media (such as selective separation of different metals and wastewater recovery).