Synthesis of manganese citrates was carried out in the presence and absence of fluoride ions. The presence of HF or NaF led to the formation of new layered manganese citrates whose crystal structures were determined by single-crystal X-ray diffraction. The prepared single-phase citrates with and without fluoride ions were then used as precursors for the preparation of mesoporous MnxOy and hierarchically porous MnxOy@C phases, which could be of interest for catalytic, sorption, and electrochemical applications.
The fast adsorption kinetics of zeolitic imidazolate frameworks (ZIFs) enable a wide range of sorption applications. The most commonly used framework, ZIF-8, is relatively non-polar. Increasing the polarity of ZIF-8 through the encapsulation of different polar species shows promise for enhancing the sorption performance for pure CO2. Recently, the outlook has re-focused on gas mixtures, mostly in the context of post-combustion CO2 capture from wet flue gasses. While water is known to sometimes have a synergistic effect on CO2 sorption, we still face the potential problem of preferential water vapor adsorption. Herein, we report the preparation of three ZIF-8/organic dye (OD) composites using Congo red, Xylenol orange, and Bromothymol blue, and their impact on the sorption properties for CO2, water, and a model wet CO2 system at 50% RH. The results show that the preparation of OD composites can be a promising way to optimize adsorbents for single gasses, but further work is needed to find superior ZIF@OD for the selective sorption of CO2 from wet gas mixtures.
The present study focuses on clinoptilolite (CLI)-rich natural zeolitic tuffs and their photocatalytic activity in the degradation of cationic organic dyes. CLI from different regions was tested in the photocatalytic degradation of methylene blue (MB) as a model cationic dye. The photocatalytic tests were performed at room temperature and atmospheric pressure under visible light irradiation. For all the CLI samples, the highest activity was observed at pH = 6. Total MB degradation varied between 70 and 91% (C0 = 10 mg dm–3, 0.2 g dm–3 of photocatalyst, during 300 min). It is suggested that the presence of Fe species in the studied tuffs is responsible for the photocatalytic activity. The activity increases linearly with the Fe content in the tuffs. The MB photodegradation follows the Langmuir–Hinshelwood kinetic model. The recyclability tests showed good stability and efficiency of the photocatalyst. The degradation rate decreased from 91 to 69% during three reaction cycles, indicating a promising potential of natural zeolites in the treatment of textile industry wastewater.
Disposal of copper, manganese and iron is particularly problematic in wastewater of metallurgical and galvanization plants, the electronics industry and agriculture. On the other hand, volatile organic compounds (VOCs), emitted from industrial processes, transportation and consumer products are the main class of air pollutants. The study revealed the potential of waste metal-loaded zeolite, generated through wastewater treatment procedures, to be utilised as an effective VOC removal catalyst for air treatment. In the first step, we have evaluated the sorption performance of natural zeolite clinoptilolite (HEU type), and synthetic zeolite 4A (LTA type) for the simultaneous removal of Cu2+, Mn2+ and Fe3+ species from aqueous solution. By a detailed sorption study, we determined the optimum sorption conditions and maximum metal concentrations in wastewater that can be after treatment disposed of in rivers or municipal plants. The efficiency of both zeolites for metal immobilization was demonstrated for concentrations up to 5 mg metals/1 g zeolite. These waste Cu-, Mn- and Fe-loaded zeolites were thermally treated at 540 °C before the second step, where we evaluated their catalytic performance in removing VOC. The thermally treated waste Cu-, Mn- and Fe-loaded natural zeolite clinoptilolite showed good catalytic performance in total toluene oxidation as a model VOC (conversion rate up to 96% at 510°C) and cycling stability (less than 15% drop in conversion rate in 4 h). In contrast, this is not the case for thermally treated waste Cu-, Mn- and Fe-loaded synthetic zeolite 4A.
The increasing demand for heating/cooling is of grave concern due to the ever-increasing population. One method that addresses this issue and uses renewable energy is Thermochemical Energy Storage (TCES), which is based on the reversible chemical reactions and/or sorption processes of gases in solids or liquids. Zeolitic imidazolate frameworks (ZIFs), composed of transition metal ions (Zn, Co, etc.) and imidazolate linkers, have gained significant interest recently as porous adsorbents in low temperature sorption-based TES (sun/waste heat). In this study, we examined two different sodalite-type ZIF structures (ZIF-8 and ZIF-90) for their potential heat storage applications, based on the adsorption of water, methanol and ethanol as adsorbates. Both ZIF structures were analysed using PXRD, TGA, SEM and N2 physisorption while the % adsorbate uptake and desorption enthalpy was evaluated using TGA and DSC analysis, respectively. Among the studied adsorbent–adsorbate pairs, ZIF-90-water showed the highest desorption enthalpy, the fastest sorption kinetics and, therefore, the best potential for use in heat storage/reallocation applications. This was due to its significantly smaller particle size and higher specific surface area, and the presence of mesoporosity as well as polar groups in ZIF-90 when compared to ZIF-8.
We present here important new findings on the direct synthesis of bimetal Cu-Mn containing porous silica catalyst and the effects of structure-directing agent removal from the prepared nanomaterial on the evolution of surface catalytic sites. The extraction-calcination procedure of the structure-directing agent removal led to the formation of Cu and Mn oxo-clusters and Cu and Mn oxide nanoparticles smaller than 5 nm, while the solely calcination procedure led to the mentioned species and in addition to the appearance of CuO nanoparticles 20 nm in size. Catalysts were tested in the Fenton-like catalytic degradation of dyes with different molecular charge (cationic, anionic, and zwitterionic) as model organic pollutants in wastewater at neutral pH. Significantly faster degradation of cationic and anionic dyes in the first 60 min was observed with the catalyst containing larger CuO nanoparticles (>20 nm) due to the less hindered generation of •OH radicals and slower obstructing of the active sites on the catalysts surface by intermediates. However, this was not found beneficial for zwitterionic dye with no adsorption on the catalysts surface, where the catalyst with smaller Cu species performed better.