Flexibility in metal–organic frameworks : a basic understanding

Much has been written about the fundamental aspects of the metal-organic frameworks (MOFs). Still, details concerning the MOFs with structural flexibility are not comprehensively understood. However, a dramatic increase in research activities concerning rigid MOFs over the years has brought deeper levels of understanding for their properties and applications. Nonetheless, robustness and flexibility of such smart frameworks are intriguing for different research areas such as catalysis, adsorption, etc. This manuscript overviews the different aspects of framework flexibility. The review has touched lightly on several ideas and proposals, which have been demonstrated within the selected examples to provide a logical basis to obtain a fundamental understanding of their synthesis and behavior to external stimuli

The Photocatalytic and antibacterial performance of Nitrogen-Doped TiO2: Surface-structure dependence and Silver-deposition effect

Catalysts for visible-light-driven oxidative cleaning processes and antibacterial applications (also in the dark) were developed. In order to extend the photoactivity of titanium dioxide into the visible region, nitrogen-doped TiO2 catalysts with hollow and non-hollow structures were synthesized by co-precipitation (NT-A) and sol–gel (NT-U) methods, respectively. To increase their photocatalytic and antibacterial efficiencies, various amounts of silver were successfully loaded on the surfaces of these catalysts by using a facile photo-deposition technique. Their physical and chemical properties were evaluated by using scanning electron microscopy (SEM), transmission electron microscopy–energy dispersive X-ray spectroscopy (TEM–EDS), Brunauer–Emmett–Teller (BET) surface area, X-ray diffraction (XRD), and diffuse reflectance spectra (DRS). The photocatalytic performances of the synthesized catalysts were examined in coumarin and 1,4-hydroquinone solutions. The results showed that the hollow structure of NT-A played an important role in obtaining high specific surface area and appreciable photoactivity. In addition, Ag-loading on the surface of non-hollow structured NT-U could double the photocatalytic performance with an optimum Ag concentration of 10−6 mol g−1, while a slight but monotonous decrease was caused in this respect for the hollow surface of NTA upon increasing Ag concentration. Comparing the catalysts with different structures regarding the photocatalytic performance, silverized non-hollow NT-U proved competitive with the hollow NT-A catalyst without Ag-loading for efficient visible-light-driven photocatalytic oxidative degradations. The former one, due to the silver nanoparticles on the catalyst surface, displayed an appreciable antibacterial activity, which was comparable to that of a reference material practically applied for disinfection in polymer coatings

Case Studies for Clean Technology Development in the Chemical Industry Using Zeolite Based Catalysts

This paper deals with the practical implementation of cleaner technologies in the chemical industry, using two case studies as an illustration. The first case study deals with the removal of NOx and N2O gases over an iron-doped ZSM-5 catalyst developed for tail gas treatment in nitric acid manufacturing. The aim for this case study was to investigate the efficiency of the zeolitic catalyst in the DeNOx process and to compare its catalytic activity with the conventional vanadia-titania. By the experiments carried out, it can be concluded that the new technological developments could significantly contribute to a decrease in environmental pollution. The second case study focuses on zeolite-based catalysts prepared from zeolitic tuff by the impregnation method, for biodiesel production from waste sunflower vegetable oil. The effects of operating and processing variables such as reaction temperature and time were investigated. The results showed that the highest biodiesel yield was 96.7% at an 11.5 MeOH/oil molar ratio, in the presence of 6.4 wt % catalyst at a 50 °C reaction temperature and reaction time of 2 h. The properties of the biodiesel that was produced, such as the viscosity, meet the required specifications of standard JUS EN14214. The common feature of the two different case studies is that both technologies use zeolite catalysts, namely naturally-occurring zeolitic tuff and synthetic ZSM type zeolite catalyst. The examples shown emphasize the importance of the zeolites in clean chemical technologies, which contribute to the protection of the environment

New Approaches in Modeling and Simulation of CO₂Absorption Reactor by Activated Potassium Carbonate Solution

The increase of CO2 concentration in the atmosphere is in strong relation with the human-induced warming up due to industrial processes, transportation, etc. In order to reduce the CO2 content, end of pipe post-combustion methods can be used in addition to other methods and techniques. The CO2 capture by absorption in potassium carbonate⁻bicarbonate activated solutions remains a viable method. In this study, a mathematical model for a packed bed reactor has been developed and tested. The mathematical model is tested for an industrial reactor based on CO2 absorption in Carsol solutions. The proposed model was validated by resolving for CO2 and water content, carbonate⁻bicarbonate, concentrations etc. For each operational parameter the error was calculated. The error for CO2 concentration is up to 4%. The height of the packed reactor is calculated as function of CO2 concentration in the final gas phase. The validated model can also be used for absorbing other CO2 streams taking into account the fact that its efficiency was proved in industrial scale. Future reactors used for CO2 absorption should consist of two parts in order to use partially regenerated solutions in the first part, with significant energy savings in the operational costs

Flexibility in metal-organic frameworks : a fundamental understanding

Metal-organic frameworks (MOFs) had until recently the reputation of being one of the most critical porous materials. Their flexibility, however, has gained a lot of attention due to the wide selection of possible combinations between metal nods and/or ligands. Nonetheless, it is not always easy to identify the source of flexibility. This chapter focuses on the origin of flexibility, and the substantial geometrical changes that can occur due to external stimuli, such as temperature, pressure, light, gas or solvent adsorption. Flexibility control methods have also been discussed along with possible characterization techniques to help to identify the source of flexibility. Practical applications of flexible MOFs in gas separation and other processes are also discussed. In this respect, several prized examples covered by the literature are present to help in a comprehensive understanding in terms of design and structure tunability of flexible MOFs

Scandium Recovery Methods from Mining, Metallurgical Extractive Industries, and Industrial Wastes

The recovery of scandium (Sc) from wastes and various resources using solvent extraction (SX) was discussed in detail. Moreover, the metallurgical extractive procedures for Sc recovery were presented. Acidic and neutral organophosphorus (OPCs) extractants are the most extensively used in industrial activities, considering that they provide the highest extraction efficiency of any of the valuable components. Due to the chemical and physical similarities of the rare earth metals, the separation and purification processes of Sc are difficult tasks. Sc has also been extracted from acidic solutions using carboxylic acids, amines, and acidic β-diketone, among other solvents and chemicals. For improving the extraction efficiencies, the development of mixed extractants or synergistic systems for the SX of Sc has been carried out in recent years. Different operational parameters play an important role in the extraction process, such as the type of the aqueous phase and its acidity, the aqueous (A) to organic (O) and solid (S) to liquid (L) phase ratios, as well as the type of the diluents. Sc recovery is now implemented in industrial production using a combination of hydrometallurgical and pyrometallurgical techniques, such as ore pre-treatment, leaching, SX, precipitation, and calcination. The hydrometallurgical methods (acid leaching and SX) were effective for Sc recovery. Furthermore, the OPCs bis(2-ethylhexyl) phosphoric acid (D2EHPA/P204) and tributyl phosphate (TBP) showed interesting potential taking into consideration some co-extracted metals such as Fe(III) and Ti(IV)

Polystyrene-Fe3O4-MWCNTs Nanocomposites for Toluene Removal from Water

In this research, multi-walled carbon nanotubes (MWCNTs) were functionalized by oxidation with strong acids HNO3, H2SO4, and H2O2. Then, magnetite/MWCNTs nanocomposites were prepared and polystyrene was added to prepare polystyrene/MWCNTs/magnetite (PS:MWCNTs:Fe) nanocomposites. The magnetic property of the prepared nano-adsorbent PS:MWCNTs:Fe was successfully checked. For characterization, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and BET surface area were used to determine the structure, morphology, chemical nature, functional groups, and surface area with pore volume of the prepared nano-adsorbents. The adsorption procedures were carried out for fresh MWCNTs, oxidized MWCNTs, MWCNTs-Fe, and PS:MWCNTs:Fe nanocomposites in batch experiments. Toluene standard was used to develop the calibration curve. The results of toluene adsorption experiments exhibited that the PS:MWCNTs:Fe nonabsorbent achieved the highest removal efficiency and adsorption capacity of toluene removal. The optimum parameters for toluene removal from water were found to be 60 min, 2 mg nano-sorbent dose, pH of 5, solution temperature of 35 °C at 50 mL volume, toluene concentration of 50 mg/L, and shaking speed of 240 rpm. The adsorption kinetic study of toluene followed the pseudo-second-order kinetics, with the best correlation (R2) value of 0.998, while the equilibrium adsorption study showed that the Langmuir isotherm was obeyed, which suggested that the adsorption is a monolayer and homogenous

Degradation of diisopropyl methylphosphonate in aqueous solutions by ultrasonic irradiation combined with oxidation process

The degradation of diisopropyl methylphosphonate (DIMP) in aqueous solutions was studied using ultrasound irradiation with a fixed frequency of 26.2 kHz, following the first-order kinetic model. The study's primary goal was to determine the influence of the following experimental parameters: the pH (at different values of 2, 7 and 10), the initial concentration of DIMP (at different concentrations: 7, 14, 30, 50, 80 mg/L), the processing time (at different periods: 15, 30, 45, 60, 80, 90 min), and the concentration of the additive CCl4 (at different concentrations: 0.002, 0.004, 0.006, 0.008 mg/L). A DIMP removal efficiency of 98% from aqueous solution was obtained at pH 10 and 0.008 mg/L CCl4, after an ultrasound irradiation time of 45 min, pointing out the influence of the above-mentioned experimental parameters on the DIMP degradation process

Characterization of Various Titanium-Dioxide-Based Catalysts Regarding Photocatalytic Mineralization of Carbamazepine also Combined with Ozonation

Titanium-dioxide-based semiconductors proved to be appropriate for photocatalytic application to efficiently degrade emerging organic pollutants such as various herbicides, pesticides, and pharmaceuticals in waters of environmental importance. The characterization of various TiO2 catalysts, both bare and modified (Ag- and/or N-doped), by mechanochemical treatment was carried out in this work, regarding their structure, morphology, and photocatalytic activity. For the latter investigations, carbamazepine, an antidepressant, proved to be applicable and versatile. The photocatalytic behavior of the catalysts was studied under both UV and visible light. Besides the decomposition efficiency, monitoring the intermediates provided information on the degradation mechanisms. Mechanochemical treatment significantly increased the particle size (from 30 nm to 10 μm), causing a considerable (0.14 eV) decrease in the band gap. Depending on the irradiation wavelength and the catalyst, the activity orders differed, indicating that, in the mineralization processes of carbamazepine, the importance of the different oxidizing radicals considerably deviated, e.g., Ag-TiO2 < DP25-TiO2 < ground-DP25-TiO2 < N-TiO2 ≈ N-Ag-TiO2 for O2•− and N-TiO2 ≈ Ag-TiO2 < N-Ag-TiO2 < ground-DP25-TiO2 ≈ DP25-TiO2 for HO• generation under UV irradiation. Toxicity studies have shown that the resulting intermediates are more toxic than the starting drug molecule, so full mineralization is required. This could be realized by a synergistic combination of heterogeneous photocatalysis and ozonation