Mixed-Metal MOF-74 Templated Catalysts for Efficient Carbon Dioxide Capture and Methanation

The vast chemical and structural tunability of metal–organic frameworks (MOFs) are beginning to be harnessed as functional supports for catalytic nanoparticles spanning a range of applications. However, a lack of straightforward methods for producing nanoparticle-encapsulated MOFs as efficient heterogeneous catalysts limits their usage. Herein, a mixed-metal MOF, NiMg-MOF-74, is utilized as a template to disperse small Ni nanoclusters throughout the parent MOF. By exploiting the difference in Ni O and Mg O coordination bond strength, Ni²⁺ is selectively reduced to form highly dispersed Ni nanoclusters constrained by the parent MOF pore diameter, while Mg²⁺ remains coordinated in the framework. By varying the ratio of Ni to Mg in the parent MOF, accessible surface area and crystallinity can be tuned upon thermal treatment, influencing CO₂ adsorption capacity and hydrogenation selectivity. The resulting Ni nanoclusters prove to be an active catalyst for CO₂ methanation and are examined using extended X-ray absorption fine structure and X-ray photoelectron spectroscopy. By preserving a segment of the Mg²⁺-containing MOF framework, the composite system retains a portion of its CO₂ adsorption capacity while continuing to deliver catalytic activity. The approach is thus critical for designing materials that can bridge the gap between carbon capture and CO₂ utilization.     

On the flash sintering behavior of Li:ZnO—Evidence of electrode asymmetry driven by electrochemical reactions

The synthesis, subsequent flash sintering (FS) characteristics and microstructures of pure and Li-incorporated ZnO powders are reported. At low concentrations, Li is a substitutional occupant in ZnO but becomes an amphoteric dopant (substitutional and interstitial occupant) at higher concentrations inferred from a contraction reversal of the unit cell volume. Increasing Li reduces the average flash temperature of ZnO modestly by 15°C, and a doubling of the linear shrinkage. A discernible color smear (yellow–white–dark) stretching from the anode to cathode imputable to strong electromigration is also observed. Microanalyses of the electrode regions establish clear evidence of electrochemical (EC) lithiation into ZnO and the formation of Li–Zn compounds not observed in conventional sintering (CS). Interestingly, in contrast to CS, the addition of Li enhances coarsening during FS, suggestive of a dissolution–reprecipitation process concurrent with the EC lithiation process. Evidence for considerable (local) yet tangible temperature, chemical and microstructural asymmetry among electrodes driven by EC reactions is presented. Probable mechanisms, leading to these observations, are discussed.     

Dorzolamide nanoliposome as a long action ophthalmic delivery system in open angle glaucoma and ocular hypertension patients

Importance: To reduce the frequency of dorzolamide eye drop administration and increasing the duration of action.

Background: This study aims to compare the effect of dorzolamide loaded-nanoliposome with marketed dorzolamide HCl eye drop on intraocular pressure in primary open angle glaucoma and ocular hypertension patients.

Design: A randomized study was conducted in a hospital.

Participants: Twenty patients with primary open angle glaucoma or ocular hypertension (in both eyes) diagnosis were recruited as participants.

Methods: Dorzolamide loaded-nanoliposome was prepared by thin layer hydration method and characterized. Intra ocular pressure were compared between the two groups who received marketed dorzolamide solution or dorzolamide-loaded nanoliposome.

Main outcome measures: The main outcome measures include intraocular pressure initially (day 0) and on days 14 and 28 and adverse effect of dorzolamide-loaded nanoliposome eye drop.

Results: Based on the results of repeated measure, intra ocular pressure was seen to decrease in both the groups. But these reductions in the intervention group (dorzolamide-loaded eye drop) were significantly higher than those in control group (p?Conclusion: This study confirmed safety and long-lasting efficacy of dorzolamide loaded-nanoliposome eye drop. The highly enhanced permeation through the cornea can be attributed to similarity of phospholipid bilayer of liposomes to the biological membrane and their small particle size and positive zeta potential.     

Photocatalytic mineralisation of organic compounds: a comparison of flame-made TiO2 catalysts

A comparative photocatalytic analysis was carried out on TiO₂ made in a Flame Spray Pyrolysis (FSP) process and flame-made Degussa P25. Both have similar crystallinity, phase composition, phase segregation and a non-porous surface. Hence comparison was made based on their difference in specific surface area, organic adsorption and the amount of OH• generated upon illumination. The photocatalytic activity tests were carried out using the following series of organic compounds: sucrose, glucose, fructose, maleic acid, glyoxylic acid, oxalic acid, isobutyric acid, phenol and methanol. FSP-made TiO₂ outperformed P25 for saccharides mineralisation, while for phenol and methanol mineralisation P25 was better than FSP-made TiO₂. Similar mineralisation rates were observed for both FSP-made and P25 TiO₂ for the mineralisation of carboxylic acids. This shows that the relative performance of the photocatalysts depends on the type of organic compounds to be degraded. The high surface area and possibly a more efficient interfacial charge transfer of FSP-made TiO₂ provided an efficient pathway for saccharides mineralisation. As for phenol and methanol, the mineralisation rates were higher when using P25 due to the greater amount of OH• radicals generated by this photocatalyst. The fast mineralisation rates of carboxylic acids made degradation of these organic compounds to be less affected by the TiO₂ photocatalyst properties and conditions tested in this work.     

Rheological,Thermodynamic, and Gas Solubility Properties of Phenylacetic Acid‐Based Deep Eutectic Solvents

Choline chloride + phenylacetic acid‐based deep eutectic solvents are studied. Their most relevant experimental physicochemical properties at different mixing ratios together with the CO₂ solubility data obtained in wide pressure and temperature ranges are reported. The presented materials exhibit a significant CO₂ capture performance with low corrosion effect when compared with the most common amine‐based CO₂ capture agents. Detailed rheological measurements are carried out and various models are applied to describe the dynamic flow behavior of the solvents. The CO₂ absorption mechanism is evaluated by studying the behavior of the liquid gas and interface. Due to the advantages of low cost, nontoxicity, and favorable physical properties, these solvents are an environmentally promising alternative for effective CO₂ capture technological applications.     

Estimation of the Stress-Strength Reliability for Exponentiated Pareto Distribution Using Median and Ranked Set Sampling Methods

In reliability analysis, the stress-strength model is often used to describe the life of a component which has a random strength (X) and is subjected to a random stress (Y). In this paper, we considered the problem of estimating the reliability R=P [Y<X] when the distributions of both stress and strength are independent and follow exponentiated Pareto distribution. The maximum likelihood estimator of the stress strength reliability is calculatedunder simple random sample, ranked set sampling and median ranked set sampling methods. Four different reliability estimators under median ranked set sampling are derived. Two estimators are obtained when both strength and stress have an odd or an even set size. The two other estimators are obtained when the strength has an odd size and the stress has an even set size and vice versa. The performances of the suggested estimators are compared with their competitors under simple random sample via a simulation study. The simulation study revealed that the stress strength reliability estimates based on ranked set sampling and median ranked set sampling are more efficient than their competitors via simple random sample. In general, the stress strength reliability estimates based on median ranked set sampling are smaller than the corresponding estimates under ranked set sampling and simple random sample methods.     

Carbon‐Based Metal‐Free Catalysts for Electrocatalytic Reduction of Nitrogen for Synthesis of Ammonia at Ambient Conditions

The electrocatalytic nitrogen reduction reaction (NRR) is a promising catalytic system for N₂ fixation in ambient conditions. Currently, metal‐based catalysts are the most widely studied catalysts for electrocatalytic NRR. Unfortunately, the low selectivity and poor resistance to acids and bases, and the low Faradaic efficiency, production rate, and stability of metal‐based catalysts for NRR make them uncompetitive for the synthesis of ammonia in comparison to the industrial Haber–Bosch process. Inspired by applications of carbon‐based metal‐free catalysts (CMFCs) for the oxygen reduction reaction (ORR) and CO₂ reduction reaction (CO₂RR), the studies of these CMFCs in electrocatalytic NRR have attracted great attention in the past year. However, due to the differences in electrocatalytic NRR, there are several critical issues that need to be addressed in order to achieve rational design of advanced carbon‐based metal‐free electrocatalysts to improve activity, selectivity, and stability for NRR. Herein, the recent developments in the field of carbon‐based metal‐free NRR catalysts are presented, along with critical issues, challenges, and perspectives concerning metal‐free catalysts for electrocatalytic reduction of nitrogen for synthesis of ammonia at ambient conditions.     

Generalized Marshall Olkin Inverse Lindley Distribution with Applications

In this article, a new generalization of the inverse Lindley distribution is introduced based on Marshall-Olkin family of distributions. We call the new distribution, the generalized Marshall-Olkin inverse Lindley distribution which offers more flexibility for modeling lifetime data. The new distribution includes the inverse Lindley and the Marshall-Olkin inverse Lindley as special distributions. Essential properties of the generalized Marshall-Olkin inverse Lindley distribution are discussed and investigated including, quantile function, ordinary moments, incomplete moments, moments of residual and stochastic ordering. Maximum likelihood method of estimation is considered under complete, Type-I censoring and Type-II censoring. Maximum likelihood estimators as well as approximate confidence intervals of the population parameters are discussed. A comprehensive simulation study is done to assess the performance of estimates based on their biases and mean square errors. The notability of the generalized Marshall-Olkin inverse Lindley model is clarified by means of two real data sets. The results showed the fact that the generalized Marshall-Olkin inverse Lindley model can produce better fits than power Lindley, extended Lindley, alpha power transmuted Lindley, alpha power extended exponential and Lindley distributions.     

Synthesis,characterization and surface modification of ZnCrFeO4 nanoparticles

The aim of this research was to investigate zinc chromium ferrite (ZnCrFeO₄) nanoparticles, synthesized using the sol gel technique with nanoparticle size controlled through a two-stage annealing process. Stage one was a low temperature firing which produced low quality nanocrystals with an average size of 15 nm. This was followed by a second firing stage at high temperature which enhanced the crystal quality. The nanoparticles were then coated with a bio-compatible shell to form a stable suspension in the ferrofluid carrier. The resulting nanoparticles were found by electron microscopy, atomic force microscopy and X-ray diffraction studies to have excellent crystal quality. The average size was 8.5 nm. Preliminary cell culture studies indicated the ZnCrFeO₄ nanoparticles were non-toxic. The relatively high measured value of the relaxivity r₂ showed that the nanoparticle coating was effective in substantially reducing aggregation and enhancing the properties of the nanoparticles associated with contrast enhancement in MRI.     

Multi-wavelength spectroscopic and chromatography study on the photocatalytic oxidation of natural organic matter

The effect of TiO₂ photocatalytic oxidation on the natural organic matter (NOM) properties of two Australian surface waters were quantified using UV-vis spectroscopy, high performance size exclusion chromatography (HPSEC) with a multi-wavelength UV detector, liquid chromatography with organic carbon detector (LC-OCD), and trihalomethane formation potential (THMFP) analyses. Both the UV absorbance at wavelengths greater than 250 nm and dissolved organic carbon (DOC) content decreased significantly with treatment, although complete mineralization of NOM could not be achieved. Multi-wavelength UV detection of HPSEC analysis was shown to be useful to display further changes to NOM composition and molecular weight profiles because the organic molecules was transformed into compounds that absorb weakly at the typical detection wavelength of 250-260 nm. The multi-wavelength HPSEC results also revealed that photocatalytic oxidation yields by-products with a low aromaticity and low molecular weight. The LC-OCD chromatograms indicated that low molecular acids and neutral compounds remained after photocatalytic oxidation. Those groups of compounds did not seem to contribute significantly to the formation of trihalomethanes.