Passive Control of Indoor Formaldehyde by Mixed-Metal Oxide Latex Paints.

This work reports the incorporation of mixed-metal oxides (MMOs) such as Si/Ti and Si/Zr into latex paints in the form of thin coatings for permanent trapping of indoor formaldehyde. The formaldehyde removal performance of the surface coatings was evaluated in a lab-scale indoor air chamber, and the results were compared with those of powder analogues. Due to the pore blockage by the latex, the incorporation led to 6-30% reduction in adsorption capacity and 50-70% drop in the adsorption rate for MMO-latex paints relative to their powder MMO analogues. Under the operating conditions of concentration, temperature, and relative humidity, the Si/Zr-latex paints outperformed the Si/Ti counterparts. It was also observed that performance could decrease over excessive loading, for example, Si/Zr-latex paint with 15/1 Si/Zr weight ratio showed a 20% lower adsorption capacity than that of the Si/Zr-latex paint with 25/1 Si/Zr ratio at 5 ppmv, 25 °C, and 70% RH. While high temperature greatly reduced the adsorption rate of the MMO-latex paints, high humidity slightly promoted the rate of formaldehyde capture. In 10 L, flow-through chamber tests, 25Si/Zr-latex paint reduced 5 ppmv formaldehyde by up to 60% at 25 °C and 70% RH with an adsorption rate of 0.34 ppmv/h. Overall, this study highlights the potential of MMO-latex paints with optimized formation for the efficient abatement of indoor aldehydes.

Mixing Mg-MOF-74 with Zn-MOF-74: A Facile Pathway of Controlling the Pharmacokinetic Release Rate of Curcumin.

Recently, metal-organic frameworks (MOFs) have been widely employed as potential drug-delivery platforms; however, most studies have focused on the initial aspects of material development and have made little progress toward using MOFs as a means of controlling the pharmacokinetic rate of drug delivery. Nevertheless, it was recently determined that MOFs with highly soluble metal centers impart faster pharmacokinetic properties, so it stands to reason that combining two MOFs with different metal center solubilities could be used to control the pharmacokinetic release rate. To this end, in this study we varied the ratio of Mg-MOF-74 and Zn-MOF-74 between 80:20, 60:40, 40:60, and 20:80 wt % Mg:Zn to control the pharmacokinetic release rate of 30 wt % curcumin. The drug loading was characterized by using Fourier transform infrared spectroscopy and N2 physisorption, where it was confirmed that curcumin was impregnated successfully. More importantly, the drug delivery experiments in phosphate buffered saline from 0 to 24 h at 37.4 °C revealed that increasing the Mg-MOF-74 concentration enhanced both the raw amount of curcumin delivered and the pharmacokinetic rate of drug delivery. Specifically looking at the rate of drug delivery, drug diffusion constants of 0.17, 0.23, 0.24, and 0.26 h1/2 were calculated for the 20:80, 40:60, 60:40, and 80:20 Mg-Zn-MOF-74 samples, respectively, which indicated the profound relationship between the Mg-MOF-74 loading and the rate of curcumin delivery. In this regard, this study successfully demonstrated a potential pathway of controlling the pharmacokinetic rate of drug release from MOFs which can be considered a promising advancement in pharmacological medicine.

Novel Zeolite-5A@MOF-74 Composite Adsorbents with Core-Shell Structure for H2 Purification.

Hydrogen is considered as one of the most important clean and renewable energy sources for a sustainable energy future. However, its efficient and cost-effective purification still remains challenging. In this work, we report the development of novel zeolite@metal-organic framework (MOF) composites comprised of MOF-74 and zeolite-5A with core-shell structure for efficient purification of H2. The composites were synthesized hydrothermally through the addition of zeolite particles with and without carboxyl functional groups to the MOF synthesis solution. The zeolite/MOF weight ratio was varied systematically to find the optimum composition based on the adsorption performance. The formation of zeolite@MOF composites was confirmed by various characterization techniques. Single-component adsorption isotherms of CO2, CO, CH4, N2, and H2 over composites were measured at 25 °C to determine their equilibrium adsorption capacity. It was found that the zeolite-5A@MOF-74 with weight ratio of 5:95 exhibited a similar morphology to that of pristine MOF-74, but with higher surface area and total pore volume. Moreover, this composite showed 20-30% increase in CO2, CO, CH4, and N2 uptake than the bare MOF, which could be attributed to the formation of new mesopores at the MOF-zeolite interface. The estimated selectivity values for CO2/H2, CO/H2, CH4/H2, and N2/H2 were higher than those of the zeolite and/or MOF. Our results also indicated that surface modification of zeolite prior to composite formation does not enhance the adsorption capacities of the composites. Overall, the findings of this study suggest that the zeolite-5A@MOF-74 composites with core-shell structure are promising candidates for industrial H2 purification processes.

UTSA-16 Growth within 3D-Printed Co-Kaolin Monoliths with High Selectivity for CO2/CH4, CO2/N2, and CO2/H2 Separation.

Honeycomb monoliths loaded with metal-organic frameworks (MOFs) are highly desirable adsorption contactors because of their low-pressure drop, rapid mass-transfer kinetics, and high-adsorption capacity. Moreover, three-dimensional (3D)-printing technology renders direct material modification a realistic and economic prospect. In this study, 3D printing was utilized to impregnate kaolin-based monolith with UTSA-16 metal formation precursor (Co), whereupon an internal growth was facilitated via a solvothermal synthesis approach. The cobalt weight loading in the kaolin support was varied systematically to optimize the MOF growth while retaining monolith mechanical integrity. The obtained UTSA-16 monolith with 90 wt % loading exhibited similar textural features and adsorption characteristics to its powder analogue while improving upon structural integrity. In comparison to previously developed 3D-printed UTSA-16 monoliths, the UTSA-16-kaolin monolith not only showed higher MOF loading but also higher compression stress, indicative of its robust structure. Furthermore, the 3D-printed UTSA-16-kaolin monolith displayed a comparable CO2 adsorption capacity to the UTSA-16 powder (3.1 vs 3.5 mmol/g at 25 °C and 1 bar), which was proportional to its loading. Selectivity values of 49, 238, and 3725 were obtained for CO2/CH4, CO2/N2, and CO2/H2, respectively, demonstrating good separation potential of the 3D-printed MOF monolith for various gas mixtures, as determined by both equilibrium and dynamic adsorption measurements. Overall, this study provides a novel route for the fabrication of UTSA-16-loaded monoliths, which demonstrate both high MOF loading and mechanical integrity that could be readily applied to various CO2 capture applications.

3D-Printed Metal-Organic Framework Monoliths for Gas Adsorption Processes.

Metal-organic frameworks (MOFs) have shown promising performance in separation, adsorption, reaction, and storage of various industrial gases; however, their large-scale applications have been hampered by the lack of a proper strategy to formulate them into scalable gas-solid contactors. Herein, we report the fabrication of MOF monoliths using the 3D printing technique and evaluation of their adsorptive performance in CO2 removal from air. The 3D-printed MOF-74(Ni) and UTSA-16(Co) monoliths with MOF loadings as high as 80 and 85 wt %, respectively, were developed, and their physical and structural properties were characterized and compared with those of MOF powders. Our adsorption experiments showed that, upon exposure to 5000 ppm (0.5%) CO2 at 25 °C, the MOF-74(Ni) and UTSA-16(Co) monoliths can adsorb CO2 with uptake capacities of 1.35 and 1.31 mmol/g, respectively, which are 79% and 87% of the capacities of their MOF analogues under the same conditions. Furthermore, a stable performance was obtained for self-standing 3D-printed monolithic structures with relatively good adsorption kinetics. The preliminary findings reported in this investigation highlight the advantage of the robocasting (3D printing) technique for shaping MOF materials into practical configurations that are suitable for various gas separation applications.