Tuning the Hierarchical Pore Structure and the Metal Site in a Metal-Organic Framework Derivative to Unravel the Mechanism for the Adsorption of Different Volatile Organic Compounds.

Volatile organic compounds (VOCs) are one of the main classes of air pollutants, and it is important to develop efficient adsorbents to remove them from the atmosphere. To do this most efficiently, we need to understand the mechanism of VOC adsorption. In this work, we described how the metal organic framework (MOF), ZIF-8, was used as a precursor to generate MOF derivatives (Zn-GC) through temperature-controlled calcination, which had adjustable metal sites and hierarchical pore structure. It was used as a model adsorbent to study the adsorption and desorption characteristics of different VOCs. Zn-GC-850 with developed pores exhibited higher adsorption performance for the benzene series, whereas Zn-GC-650 with more metal sites had a better adsorption capacity for oxygen-containing VOCs. By tuning the molecular structure of the VOCs, we revealed the adsorption mechanism of different VOCs at the molecular level. The more developed hierarchical pore structure obtained at the higher temperature facilitates the diffusion of the benzene series, and the noncovalent interaction between their methyl group(s) and the carbonized MOF derivatives improves the adsorption affinity; while the higher exposure of Zn sites obtained at lower temperature favors the adsorption of oxygen-containing VOCs by Zn-O bonds. The mass transfers of VOCs and the role of the adsorbent were simulated by multiple theoretical models. This study strengthens the basis for the design and optimization of the adsorbent and catalyst for VOCs treatment.

Effect of ligand substitution in UiO-66 metal-organic frameworks on the photocatalytic oxidation of acetaldehyde.

A series of functionalized X-UiO-66 (X = NH2, H, Br and NO2) materials were prepared using a hydrothermal method and modified with various ligands. Their photocatalytic activity was evaluated by the oxidation of acetaldehyde. Experimental results show that the introduction of different ligands significantly influences the physicochemical properties of UiO-66. Br-UiO-66 exhibited the highest photocatalytic activity and CO2 selectivity of 85.6% and 85.7%, respectively. Photochemical properties reveal that -Br functional group facilitate the separation of photogenerated electrons and holes, significantly improving their transfer and oxygen reduction. As a result, an increased number of hydroxyl and superoxide radicals can form, improving the efficiency of the photocatalytic reaction. Br-UiO-66 accumulates fewer intermediates on its surface and still shows excellent photocatalytic activity and structural stability after 24 h of dynamic reaction. This work demonstrates the excellent adsorption and catalytic oxidation performance of Br-UiO-66 towards acetaldehyde and may provide new ideas for researching catalysts in the photocatalytic degradation of pollutants.

3-D nitrogen-doped carbon cage encapsulated ultrasmall MoC nanoparticles for promoting simultaneous ZnIn2S4 photocatalytic hydrogen generation and organic wastewater degradation.

Simultaneous redox reactions on photocatalysts make it possible to use wastewater for hydrogen production. The controlled synthesis of ultrasmall metal carbides effectively enhances the photocatalytic efficiency under this system. Here, we report a new type of cocatalyst in which a three-dimensional (3-D) nitrogen-doped carbon cage (NGC) of metal-organic framework derivatives encapsulates ultrasmall MoC nanoparticles (MoC@NGC), promoting simultaneous degradation of organic pollutants and hydrogen production by ZnIn2S4 (ZIS). Characterization analyses showed that MoC accelerated the separation of the photogenerated carrier and effectively reduced the overpotential of hydrogen evolution, while NGC promoted the good dispersion of MoC particles and provided sufficient sites. The MoC@NGC/ZIS composite exhibited a high hydrogen (H2) evolution rate of 1012 µmol g-1h-1, which exceed that of ZIS loaded with platinum. In the coupled system, where the electron donor was replaced with rhodamine B (RhB), the mechanism analysis showed that RhB and the as-generated intermediates consumed holes and facilitated hydrogen evolution. In addition, we designed a combined photocatalytic anoxic and oxic sequence process to achieve the recovery of hydrogen energy during the treatment of dye wastewater. This study provides a new way for cooperation between energy development and environmental protection.

Fe-based metal organic framework derivative with enhanced Lewis acidity and hierarchical pores for excellent adsorption of oxygenated volatile organic compounds.

A series of Fe-based metal organic framework derived materials were prepared by thermal treating MIL-100(Fe) in nitrogen atmosphere for adsorption removal of oxygenated volatile organic compounds (OVOCs) such as methanol, formaldehyde and acetone under dynamic conditions. The experimental results showed that the partially carbonized M-350 material obtained by calcining MIL-100(Fe) at 350 °C exhibited the best adsorption performance and high stability. The breakthrough adsorption capacity of M-350 for methanol was 61.5% higher than that of pure MIL-100 (Fe), and it was 24.7, 6.5 and 2.6 times higher than that of commercial activated carbon, ZSM-5 and SAPO-34 adsorbents, respectively. The excellent adsorption performance was attributed to the exposure of abundant coordinatively unsaturated iron metal sites acting as Lewis acid sites through high temperature calcination, which had a strong affinity for OVOCs. Meanwhile, a hierarchical porous structure and high specific surface area further promoted the adsorption. This work provides new insights into the further development of metal organic frameworks based functional materials for VOCs removal and purification.