Collaborative adsorption and photocatalytic degradation of high concentration pharmaceutical pollutants in water using a novel dendritic fibrous nano-silica modified with chitosan and UiO-66.

This study presents a novel hybrid mesoporous material for degrading drug pollutants in water. The hybrid materials, derived from UiO-66 metal-organic framework and chitosan, coated on nano-silica, showed excellent drug adsorption through hydrogen-bonding interactions and efficient photodegradation of antibiotics. The hybrid material's enhanced conductivity and reduced band gap significantly improved pollution reduction by minimising electron-hole recombination. This allows for more efficient charge transport and better light absorption, boosting the material's ability to break down pollutants. Structural and morphological analyses were conducted using various techniques, including scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, Brunauer-Emmett-Teller analysis, X-ray photoelectron spectroscopy, and thermogravimetric analysis. Optimising the adsorption-photodegradation process involved investigating pH, catalyst dose, and radiation time. Non-linear optimisation revealed an efficiency exceeding 85 % for 400 mg/L tetracycline and doxycycline, the model antibiotics. The optimal parameters for maximal elimination were determined as pH = 4.3, hybrid mesosphere dose = 4.0 mg/mL, and radiation time = 10 min. Kinetic studies favored pseudo-second-order diffusion models over pseudo-first-order models. The hybrid mesosphere showed sustained efficiency after three cycles and performed well in real aqueous samples, removing over 80 % of each antibiotic. This study demonstrates the potential of the hybrid mesoporous material for removing pharmaceutical pollutants in water systems.

Minimum ignition energies and laminar burning velocities of ammonia, HFO-1234yf, HFC-32 and their mixtures with carbon dioxide, HFC-125 and HFC-134a.

Given the safety issues associated with flammability characteristics of alternative environmentally-friendly refrigerants, it is vital to establish measurement systems to accurately analyse the flammability of these mildly flammable refrigerants. In this study, we used a customised Hartmann bomb analogue to measure the minimum ignition energy (MIE) and laminar burning velocity (BV) for refrigerant/air mixtures of pure ammonia (R717), R32, R1234yf and mixtures of R32 and R1234yf with non-flammable refrigerants of R134a, R125 and carbon dioxide (R744). The MIEs of R717, R32, and R1234yf were measured at an ambient temperature of 24 °C to be (18.0 ± 1.4), (8.0 ± 1.5) and (510 ± 130) mJ at equivalence ratios of 0.9, 1.27 and 1.33, respectively. Adding the non-flammable refrigerants R134a, R125 and R744 along with R32 at volumetric concentrations of 5% each to R1234yf reduced the latter compound's flammability and increased its MIE by one order of magnitude. The laminar burning velocities of pure R717 and R32 were measured at an equivalence ratio of 1.1 using the flat flame method and found to be 8.4 and 7.4 cm/s, respectively. Adding 5% R1234yf to R32 decreased the laminar burning velocity by 11%, while a further 5% addition of R1234yf resulted in a decrease of over 30% in the laminar burning velocity.

Flexible Adsorbents at High Pressure: Observations and Correlation of ZIF-7 Stepped Sorption Isotherms for Nitrogen, Argon, and Other Gases.

Stepped adsorption isotherms with desorption hysteresis were measured for nitrogen, argon, ethane, carbon dioxide, and methane at pressures up to 17 MPa on zeolitic imidazolate framework-7 (ZIF-7) using a gravimetric sorption analyzer. Such stepped sorption isotherms have not been previously reported for nitrogen or argon on ZIF-7, and required the application of pressures as high as 15 MPa to trigger the ZIF-7 structural phase transition at temperatures around 360 K. The stepped hysteretic sorption isotherms measured for carbon dioxide, methane, and ethane were consistent with previous observations reported in the literature. To correlate these stepped hysteretic sorption isotherms, a semi-empirical model was developed by combining a three-parameter Langmuir equation to describe the Type I aspect of the isotherm, with a model designed to describe the temperature-dependent ZIF-7 structural phase transition. Excellent fits of the combined adsorption and desorption branches were achieved by adjusting nine parameters in the temperature-dependent model, with root-mean-square deviations within 2.5 % of the highest measured adsorption capacity. Each parameter of the new semi-empirical model has a physical basis, allowing them to be estimated or compared independently.

Influence of Mineral Composition of Chars Derived by Hydrothermal Carbonization on Sorption Behavior of CO2, CH4, and O2.

The doping of SiO2 and Fe2O3 into hydrochars that were produced by the hydrothermal carbonization of cellulose was studied with respect to its impact on the resulting surface characteristics and sorption behavior of CO2, CH4, and O2. During pyrolysis, the structural order of the Fe-doped char changed, as the fraction of highly ordered domains increased, which was not observed for the undoped and Si-doped chars. The Si doping had no apparent influence on the oxidation temperature of the hydrochar in contrast to the Fe-doped char where the oxidation temperature was reduced because of the catalytic effect of Fe. Both dopants reduced the micro-, meso- and macroporous surface areas of the chars, although the Fe-doped chars had larger meso- and macroporosity than the Si-doped char. However, the increased degree in the structural order of the carbon matrix of the Fe-doped char reduced its microporosity relative to the Si-doped char. The adsorption of CO2 and CH4 on the chars at temperatures between 273.15 and 423.15 K and at pressures up to 115 kPa was slightly inhibited by the Si doping but strongly suppressed by the Fe doping. For O2, however, the Si doping promoted the observed adsorption capacity, while Fe doping also showed an inhibiting effect.

Temperature dependence of adsorption hysteresis in flexible metal organic frameworks.

"Breathing" and "gating" are striking phenomena exhibited by flexible metal-organic frameworks (MOFs) in which their pore structures transform upon external stimuli. These effects are often associated with eminent steps and hysteresis in sorption isotherms. Despite significant mechanistic studies, the accurate description of stepped isotherms and hysteresis remains a barrier to the promised applications of flexible MOFs in molecular sieving, storage and sensing. Here, we investigate the temperature dependence of structural transformations in three flexible MOFs and present a new isotherm model to consistently analyse the transition pressures and step widths. The transition pressure reduces exponentially with decreasing temperature as does the degree of hysteresis (c.f. capillary condensation). The MOF structural transition enthalpies range from +6 to +31 kJ·mol-1 revealing that the adsorption-triggered transition is entropically driven. Pressure swing adsorption process simulations based on flexible MOFs that utilise the model reveal how isotherm hysteresis can affect separation performance.