Synthesis of Hierarchical-Porous Fluorinated Metal-Organic Frameworks with Superior Toluene Adsorption Properties.

Constructing metal-organic frameworks (MOFs) with high volatile organic compounds (VOCs) adsorption capacity and excellent water resistance remain challenging. Herein, a monocarboxylic acid-assisted mixed ligands strategy was designed to synthesize a novel fluorinated MOFs, MIL-53 (Al). The monocarboxylic acid promoted crystallization and produced abundant crystal defects, which increased pore volume. Moreover, the competitive coordination between tetrafluoroterephthalic acid and 1,4-dicarboxybenzene was moderated by monocarboxylic modulators, significantly improving the hydrophobicity. The toluene uptake of the optimal sample reached 254.85 mg g-1 under humid conditions, increased by 33.56 % of MIL-53(Al), and the QWet /QDry (the ratio of adsorption quality under wet to adsorption quality under dry) was 0.92, remarkably surpassing that of origin MIL-53 (0.72). The recycle experiment showed superior reusability with no performance degradation after 10 recycle under RH=50 % (relative humidity). The adsorptive kinetic and thermodynamic analysis proves that the adsorption process is controlled by surface mono-layer adsorption and pore diffusion. The fluorine group affects the internal diffusion, which weakens the transfer rate. This strategy opens a new prospect of obtaining hierarchical functional MOFs for meeting the VOCs uptake under the practical application.

A metal-OH group modification strategy to prepare highly-hydrophobic MIL-53-Al for efficient acetone capture under humid conditions.

A series of highly-hydrophobic MIL-53-Al (MIL = Materials of Institut Lavoisier) frameworks synthesized via decoration of the Al-OH groups by alkyl phosphonic acid were developed as adsorbents for removing acetone from humid gas streams. The newly prepared materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), N2 adsorption-desorption and thermogravimetric analysis (TGA). Their adsorption behaviors toward acetone vapor under dry and wet conditions were studied subsequently. Results showed that alkyl phosphonic acid was successfully grafted into MIL-53-Al skeleton through coordinating interaction with Al3+ generating MIL-53-Al@Cx (x = 12, 14, 18). The MIL-53-Al@Cx exhibited similar crystal structure and thermal stability to parent MIL-53-Al. Furthermore, the modified materials showed significantly enhanced hydrophobicity. The water vapor uptake of MIL-53-Al@C14 decreased by 72.55% at 75% relative humidity (RH). Dynamic adsorption experiments demonstrated that water vapor had almost no effect on the acetone adsorption performance of MIL-53-Al@C14. Under the condition of 90% RH, the acetone adsorption capacity of MIL-53-Al@C14 was 102.98% higher than that of MIL-53-Al. Notably, MIL-53-Al@C14 presented excellent adsorption reversibility and regeneration performance in 10 adsorption-desorption cycles. Taken together, the strategy of metal-OH group modification is an attractive way to improve the acetone adsorption performance over metal-organic frameworks (MOFs) under humid conditions. Besides, MIL-53-Al@C14 would be deemed as a promising candidate for capturing acetone in high moisture environment.

Potential applications of porous organic polymers as adsorbent for the adsorption of volatile organic compounds.

Volatile organic compounds (VOCs) with high toxicity and carcinogenicity are emitted from kinds of industries, which endanger human health and the environment. Adsorption is a promising method for the treatment of VOCs due to its low cost and high efficiency. In recent years, activated carbons, zeolites, and mesoporous materials are widely used to remove VOCs because of their high specific surface area and abundant porosity. However, the hydrophilic nature and low desorption rate of those materials limit their commercial application. Furthermore, the adsorption capacities of VOCs still need to be improved. Porous organic polymers (POPs) with extremely high porosity, structural diversity, and hydrophobic have been considered as one of the most promising candidates for VOCs adsorption. This review generalized the superiority of POPs for VOCs adsorption compared to other porous materials and summarized the studies of VOCs adsorption on different types of POPs. Moreover, the mechanism of competitive adsorption between water and VOCs on the POPs was discussed. Finally, a concise outlook for utilizing POPs for VOCs adsorption was discussed, noting areas in which further work is needed to develop the next-generation POPs for practical applications.

Defective Ultrafine MnOx Nanoparticles Confined within a Carbon Matrix for Low-Temperature Oxidation of Volatile Organic Compounds.

The development of catalysts for volatile organic compound (VOC) treatment by catalytic oxidation is of great significance to improve the atmospheric environment. Size-effect and oxygen vacancy engineering are effective strategies for designing high-efficiency heterogeneous catalysts. Herein, we explored the in situ carbon-confinement-oxidation method to synthesize ultrafine MnOx nanoparticles with adequately exposed defects. They exhibited an outstanding catalytic performance with a T90 of 167 °C for acetone oxidation, which is 73 °C lower than that of bulk MnOx (240 °C). This excellent catalytic activity was primarily ascribed to their high surface area, rich oxygen vacancies, abundant active oxygen species, and good reducibility at low temperatures. Importantly, the synthesized ultrafine MnOx exhibited impressive stability in long-term, cycling and water-resistance tests. Moreover, the possible mechanism for acetone oxidation over MnOx-NA was revealed. In this work, we not only prepared a promising material for removing VOCs but also provided a new strategy for the rational design of ultrafine nanoparticles with abundant defects.

Synthesis of Silanol-Rich MCM-48 with Mixed Surfactants and Their Application in Acetone Adsorption: Equilibrium, Kinetic, and Thermodynamic Studies.

Mesoporous silica MCM-48 with rich silanol was prepared using polyvinylpyrrolidone (PVP) and cetyltrimethylammonium bromide (CTAB) as mixed templates, and the dynamic adsorption performance of acetone was evaluated by testing breakthrough curves. The mixed micelle formed by CTAB and PVP, as well as the hydrogen bond between the carbonyl group of PVP and silanol group affected the condensation process of Si-OH group during the formation of mesoporous structure, resulting in the increase of Si-OH group number on the surface of MCM-48. Compared with MCM-48 synthesized by single template (CTAB), the acetone adsorption capacity of MCM-48 (1:3) synthesized by mixed templates (PVP:CTAB = 1:3) improved by 23.86%, which was attributed to the increase of silanol group amount and the decrease of pore size. In addition, Bangham model had the highest goodness of fit to describe the adsorption process among four kinetic models for the adsorbents, conforming to the mechanism of pore diffusion. The Langmuir and Freundlich models were used to fit the adsorption isotherm data, and the Freundlich model could better describe the adsorption of acetone. Freundlich model fitting results showed that MCM-48 with rich silanol had a strong affinity for acetone, and the adsorption of acetone on MCM-48 belonged to multilayer adsorption. The thermodynamic results showed that the adsorption of MCM-48 for acetone was physical adsorption, and the adsorption behavior was exothermic. This work provided insight into how the inherent properties of an adsorbent and environmental factors (including initial concentration and adsorption temperature) affected the adsorption performance of ketones, thus more ideas could be provided for the accurate design of adsorbents. Furthermore, silanol-rich MCM-48 synthesized by mixed templates is expected to be a promising adsorbent for acetone removal.

Enhanced Acetone Oxidation over the CeO2/Co3O4 Catalyst Derived from Metal-Organic Frameworks.

A novel CeO2/Co3O4 catalyst with a high catalytic activity has been designed and prepared by pyrolysis of metal-organic frameworks, and its catalytic performance was evaluated by the acetone catalytic oxidation reaction. The Co3O4-M catalyst with T90 at 194 °C was prepared by pyrolysis of the MOF-71 precursor, which was 56 °C lower than that of commercial Co3O4 (250 °C). By the addition of cerium to the MOF-71 precursor, an enhanced CeO2/Co3O4 catalyst with T90 at 180 °C was prepared. Importantly, the CeO2/Co3O4 catalyst exhibited superior stability for acetone oxidation. After 10 cycle tests, the conversion could also be maintained at 97% for at least 100 h with slight activity loss. Characterization studies were used to investigate the influence of cerium doping on the property of the catalyst. The results showed that addition of cerium could facilitate the expansion of the surface area and enhance the porous structure and reducibility at low temperature. Furthermore, the surface ratio of Co3+/Co2+ and mobile oxygen obviously improved with the addition of cerium. Therefore, the metal oxides prepared by this method have potential for the elimination of acetone.