Scaling-Up Microwave-Assisted Synthesis of Highly Defective Pd@UiO-66-NH2 Catalysts for Selective Olefin Hydrogenation under Ambient Conditions.

The need to develop green and cost-effective industrial catalytic processes has led to growing interest in preparing more robust, efficient, and selective heterogeneous catalysts at a large scale. In this regard, microwave-assisted synthesis is a fast method for fabricating heterogeneous catalysts (including metal oxides, zeolites, metal-organic frameworks, and supported metal nanoparticles) with enhanced catalytic properties, enabling synthesis scale-up. Herein, the synthesis of nanosized UiO-66-NH2 was optimized via a microwave-assisted hydrothermal method to obtain defective matrices essential for the stabilization of metal nanoparticles, promoting catalytically active sites for hydrogenation reactions (760 kg·m-3·day-1 space time yield, STY). Then, this protocol was scaled up in a multimodal microwave reactor, reaching 86% yield (ca. 1 g, 1450 kg·m-3·day-1 STY) in only 30 min. Afterward, Pd nanoparticles were formed in situ decorating the nanoMOF by an effective and fast microwave-assisted hydrothermal method, resulting in the formation of Pd@UiO-66-NH2 composites. Both the localization and oxidation states of Pd nanoparticles (NPs) in the MOF were achieved using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray photoelectron spectroscopy (XPS), respectively. The optimal composite, loaded with 1.7 wt % Pd, exhibited an extraordinary catalytic activity (>95% yield, 100% selectivity) under mild conditions (1 bar H2, 25 °C, 1 h reaction time), not only in the selective hydrogenation of a variety of single alkenes (1-hexene, 1-octene, 1-tridecene, cyclohexene, and tetraphenyl ethylene) but also in the conversion of a complex mixture of alkenes (i.e., 1-hexene, 1-tridecene, and anethole). The results showed a powerful interaction and synergy between the active phase (Pd NPs) and the catalytic porous scaffold (UiO-66-NH2), which are essential for the selectivity and recyclability.

Hybrid core-shell nanoparticles for cell-specific magnetic separation and photothermal heating.

Hyperthermia, as the process of heating a malignant site above 42 °C to trigger cell death, has emerged as an effective and selective cancer therapy strategy. Various modalities of hyperthermia have been proposed, among which magnetic and photothermal hyperthermia are known to benefit from the use of nanomaterials. In this context, we introduce herein a hybrid colloidal nanostructure comprising plasmonic gold nanorods (AuNRs) covered by a silica shell, onto which iron oxide nanoparticles (IONPs) are subsequently grown. The resulting hybrid nanostructures are responsive to both external magnetic fields and near-infrared irradiation. As a result, they can be applied for the targeted magnetic separation of selected cell populations - upon targeting by antibody functionalization - as well as for photothermal heating. Through this combined functionality, the therapeutic effect of photothermal heating can be enhanced. We demonstrate both the fabrication of the hybrid system and its application for targeted photothermal hyperthermia of human glioblastoma cells.

Modifying the Stöber Process: Is the Organic Solvent Indispensable?

The Stöber method is one of the most important and fundamental processes for the synthesis of inorganic (nano)materials but has the drawback of using a large amount of organic solvent. Herein, ethanol was used as an example to explore if the organic solvent in a typical Stöber method can be omitted. It was found that ethanol increases the particle size of the obtained silica spheres and aids the formation of uniform silica particles rather than forming a gel. Nevertheless, the results indicated that an organic solvent in the initial synthesis mixture is not indispensable. An initially immiscible synthesis method was discovered, which can replace the organic solvent-based Stöber method to successfully synthesize silica particles with the same size ranges as the original Stöber process without addition of organic solvents. Moreover, this process can be of further value for the extension to synthesis processes of other materials based on the Stöber process.

Towards complete elucidation of structural factors controlling thermal stability of IL/MOF composites: Effects of ligand functionalization on MOFs.

In this work, we incorporated an ionic liquid (IL), 1-n-butyl-3-methylimidazolium methyl sulfate ([BMIM][MeSO4]) into two different metal organic frameworks (MOFs), UiO-66, and its amino-functionalized counterpart, NH2-UiO-66, to investigate the effects of ligand-functionalization on the thermal stability limits of IL/MOF composites. The as-synthesized IL/MOF composites were characterized in detail by combining X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller analysis (BET), X-ray fluorescence (XRF), infrared spectroscopies (FTIR), and their thermal stability limits were determined by thermogravimetric analysis (TGA). Characterization data confirmed the successful incorporation of the IL into each MOF and indicated the presence of direct interactions between them. A comparison of the interactions in [BMIM][MeSO4]-incorporated UiO-66 and NH2-UiO-66 with those in their 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6])-incorporated counterparts showed that the hydrophilic IL, [BMIM][MeSO4], interacts with the 1,4-benzenedicarboxylate (BDC) ligand of the UiO-66, while the hydrophobic IL, [BMIM][PF6], is interacting with the joints where zirconium metal cluster coordinates with BDC ligand. The TGA data demonstrated that the composite with the ligand-functionalized MOF, NH2-UiO-66, exhibited a lower percentage decrease in the maximum tolerable temperature compared to those of IL/UiO-66 composites. Moreover, it is discovered that when the IL is hydrophilic, its hydrogen bonding ability can be utilized to designate an interaction site on MOF's ligand structure which will lead to a lower reduction in thermal stability limits. These results provide insights for the rational design of IL/MOF composites and contribute towards the complete elucidation of structural factors controlling the thermal stability.

Enhanced Water Purification Performance of Ionic Liquid Impregnated Metal-Organic Framework: Dye Removal by [BMIM][PF6]/MIL-53(Al) Composite.

We incorporated a water-stable ionic liquid (IL), 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF6], into a water-stable metal-organic framework (MOF), MIL-53(Al), to generate the [BMIM][PF6]/MIL-53(Al) composite. This composite was examined for water purification by studying its capacity for methylene blue (MB) and methyl orange (MO) removal from aqueous solutions having either single dye or a mixture of both. Data illustrated that the removal efficiency and the maximum adsorption capacity of MIL-53(Al) were increased several times upon [BMIM][PF6] incorporation. For instance, within 1 min, 10 mg of pristine MIL-53(Al) adsorbed 23.3% MB from 10 mg/L of MB solution, while [BMIM][PF6]/MIL-53(Al) composite was adsorbed 82.3% MB in an identical solution. In the case of MO, 10 mg of pristine MIL-53(Al) achieved 27.8 and 53.6% MO removal from 10 mg/L of MO solution, while [BMIM][PF6]/MIL-53(Al) composite removed 61.4 and 99.2% within 5 min and 3 h, respectively. Moreover, upon [BMIM][PF6] incorporation, the maximum MB and MO adsorption capacities of the pristine MOF were increased from 84.5 to 44 mg/g to 204.9 to 60 mg/g, respectively. The adsorption of dyes in pristine MIL-53(Al) and [BMIM][PF6]/MIL-53(Al) followed a pseudo-second-order kinetic model and a Langmuir isotherm model. In a mixture of both dyes, the IL/MOF composite showed a doubled MB selectivity after the IL incorporation. The composite was successfully regenerated at least two times after its use in water purification to remove MB, MO, and their mixtures. Infrared (IR) spectra indicated that the MB/MO adsorption occurs on [BMIM][PF6]/MIL-53(Al) by electrostatic interactions, hydrogen bonding, and π-π interactions. These results showed that [BMIM][PF6]/MIL-53(Al) composite is a highly promising material for efficient water purification.

MIL-53(Al) as a Versatile Platform for Ionic-Liquid/MOF Composites to Enhance CO2 Selectivity over CH4 and N2.

Five different imidazolium-based ionic liquids (ILs) were incorporated into a metal-organic framework (MOF), MIL-53(Al), to investigate the effect of IL incorporation on the CO2 separation performance of MIL-53(Al). CO2 , CH4 , and N2 adsorption isotherms of the IL/MIL-53(Al) composites and pristine MIL-53(Al) were measured to evaluate the effect of the ILs on the CO2 /CH4 and CO2 /N2 selectivities of the MOF. Of the composite materials that were tested, [BMIM][PF6 ]/MIL-53(Al) exhibited the largest increase in CO2 /CH4 selectivity, 2.8-times higher than that of pristine MIL-53(Al), whilst [BMIM][MeSO4 ]/MIL-53(Al) exhibited the largest increase in CO2 /N2 selectivity, 3.3-times higher than that of pristine MIL-53(Al). A comparison of the CO2 separation potentials of the IL/MOF composites showed that the [BMIM][BF4 ]- and [BMIM][PF6 ]-incorporated MIL-53(Al) composites both showed enhanced CO2 /N2 and CO2 /CH4 selectivities at pressures of 1-5 bar compared to composites of CuBTC and ZIF-8 with the same ILs. These results demonstrate that MIL-53(Al) is a versatile platform for IL/MOF composites and could help to guide the rational design of new composites for target gas-separation applications.

Improving CO2 Separation Performance of MIL-53(Al) by Incorporating 1-n-Butyl-3-Methylimidazolium Methyl Sulfate.

1-n-Butyl-3-methylimidazolium methyl sulfate is incorporated into MIL-53(Al). Detailed characterization is done by X-ray fluorescence, Brunauer-Emmett-Teller surface area, scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, and thermogravimetric analysis. Results show that ionic liquid (IL) interacts directly with the framework, significantly modifying the electronic environment of MIL-53(Al). Based on the volumetric gas adsorption measurements, CO2, CH4, and N2 adsorption capacities decreased from 112.0, 46.4, and 19.6 cc (STP) gMIL-53(Al) -1 to 42.2, 13.0, and 4.3 cc (STP) gMIL-53(Al) -1 at 5 bar, respectively, upon IL incorporation. Data show that this postsynthesis modification leads to more than two and threefold increase in the ideal selectivity for CO2 over CH4 and N2 separations, respectively, as compared with pristine MIL-53(Al). The isosteric heat of adsorption (Qst) values show that IL incorporation increases CO2 affinity and decreases CH4 and N2 affinities. Cycling adsorption-desorption measurements show that the composite could be regenerated with almost no decrease in the CO2 adsorption capacity for six cycles and confirm the lack of any significant IL leaching. The results offer MIL-53(Al) as an excellent platform for the development of a new class of IL/MOF composites with exceptional performance for CO2 separation.