Dual Role of Silicon-based Matrices in Electron Exchange Matrices for Waste Treatment.

Para chloro aniline (PCA) is a common toxic pollutant found in pharmaceutical wastewater. Our study suggests a novel PCA treatment method based on a heterogeneous advanced oxidation process (AOP) that proceeds in an electron exchange matrix (EEM) prepared by the incorporation of redox-active specie in silica matrices using the sol-gel synthesis route. The results, which are supported by DFT calculations, show that the silicon skeleton of the EEM has two important roles, both as a porous matrix that hosts the redox species and as an oxidant species involved in the AOP. The calculations indicate that the formation of a radical on the nitrogen is favored. The suggested mechanism could shed light on the AOP, which proceeds in a heterogenous system, and on its application inside the understudied EEMs that, until now, have been a virtual black box. A better understanding of the mechanism could lead to improved control over the heterogeneous processes that can play a critical role in industries with the need to treat small amounts of toxic compounds at low concentrations, such as in the pharmaceutical industry.

Heterogeneous Electrocatalytic Oxygen Evolution Reaction by a Sol-Gel Electrode with Entrapped Na3 [Ru2 (µ-CO3 )4 ]: The Effect of NaHCO3.

The Na3 [Ru2 (µ-CO3 )4 ] complex is acting as a water oxidation catalyst in a homogeneous system. Due to the significance of heterogeneous systems and the effect of bicarbonate on the kinetic, we studied the bicarbonate effect on the heterogeneous electrocatalyst by entrapping the Na3 [Ru2 (µ-CO3 )4 ] complex in a sol-gel matrix. We have developed two types of sol-gel electrodes, which differ by the precursor, and are demonstrating their stability over a minimum of 200 electrochemical cycles. The pH increases affected the currents and kcat for both types of electrodes, and their hydrophobicity, which was obtained from the precursor type, influenced the electrocatalytic process rate. The results indicate that NaHCO3 has an important role in the catalytic activity of the presented heterogeneous systems; without NaHCO3 , the diffusing species is probably OH- , which undergoes diffusion via the Grotthuss mechanism. To the best of our knowledge, this is the first study to present a simple and fast one-step entrapment process for the Na3 [Ru2 (µ-CO3 )4 ] complex by the sol-gel method under standard laboratory conditions. The results contribute to optimizing the WSP, ultimately helping expand the usage of hydrogen as a green and more readily available energy source.

Antibacterial Activity of Rose Bengal Entrapped in Organically Modified Silica Matrices.

Photosensitizers (PSs) are known as powerful antibacterial agents that are activated by direct exposure to visible light. PSs can be noncovalently entrapped into the silica gel network for their controlled release into a contaminated area. The immobilization of PS-containing gel matrices on a polymer support expands their possible applications, such as antibacterial surfaces and coatings, which can be used for the disinfection of liquids. In the current study, we report the use of Rose Bengal (RB) incorporated into organically modified silica matrices (RB@ORMOSIL matrices) by the sol-gel technique. The RB matrices exhibit high activity against Gram-positive and Gram-negative bacteria under illumination by white light. The amount and timing of solidifier addition to the matrix affected the interaction of the latter with the RB, which in turn could affect the antibacterial activity of RB. The most active specimen against both Gram-positive and Gram-negative bacterial cells was the RB6@ORMOSIL matrix immobilized on a linear low-density polyethylene surface, which was prepared by an easy, cost-effective, and simple thermal adhesion method. This specimen, RB6@OR@LLDPE, showed the low release of RB in an aqueous environment, and exhibited high long-term antibacterial activity in at least 14 rounds of recycled use against S. aureus and in 11 rounds against E. coli.

Sol-Gel Entrapped Lewis Acids as Catalysts for Biodiesel Production.

Replacing fossil fuels with biodiesel enables the emission of greenhouse gases to be decreased and reduces dependence on fossil fuels in countries with poor natural resources. Biodiesel can be produced by an esterification reaction between free fatty acids (FFAs) and methanol or by transesterification of triglycerides from oils. Both reactions require homogeneous or heterogeneous catalysis. Production of biodiesel catalyzed by heterogeneous catalysts seems to be the preferred route, enabling easy product separation. As we have previously shown, the Lewis acids AlCl3 and BF3 can serve as highly efficient catalysts under ultrasonic activation. The present study focused on the development of oleic acid (OA) esterification with methanol by the same catalysts immobilized in silica matrices using the sol-gel synthesis route. During the course of immobilization, AlCl3 converts to AlCl3 × 6H2O (aluminite) and BF3 is hydrolyzed with the production of B2O3. The immobilized catalysts can be reused or involved in a continuous process. The possibility of biodiesel production using immobilized catalysts under ultrasonic activation is shown for the conversion of FFAs into biodiesel in batch and continuous mode.

Antibacterial Composites of Cuprous Oxide Nanoparticles and Polyethylene.

Cuprous oxide nanoparticles (Cu2ONPs) were used for preparing composites with linear low-density polyethylene (LLDPE) by co-extrusion, thermal adhesion, and attachment using ethyl cyanoacrylate, trimethoxyvinylsilane, and epoxy resin. The composites were examined by Scanning electron microscope and tested for their antibacterial activity against Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli. All of these composites-except for the one obtained by extrusion-eradicated cells of both bacteria within half an hour. The composite prepared by thermal adhesion of Cu2ONPs on LLDPE had the highest external exposure of nanoparticles and exhibited the highest activity against the bacteria. This composite and the one obtained using ethyl cyanoacrylate showed no leaching of copper ions into the aqueous phase. Copper ion leaching from composites prepared with trimethoxyvinylsilane and epoxy resin was very low. The antibacterial activity of the composites can be rated as follows: obtained by thermal adhesion > obtained using ethyl cyanoacrylate > obtained using trimethoxyvinylsilane > obtained using epoxy resin > obtained by extrusion. The composites with the highest activity are potential materials for tap water and wastewater disinfection.

Effect of Sol-Gel Silica Matrices on the Chemical Properties of Adsorbed/Entrapped Compounds.

The sol-gel process enables the preparation of silica-based matrices with tailored composition and properties that can be used in a variety of applications, including catalysis, controlled release, sensors, separation, etc. Commonly, it is assumed that silica matrices prepared via the sol-gel synthesis route are "inert" and, therefore, do not affect the properties of the substrate or the catalyst. This short review points out that porous silica affects the properties of adsorbed/entrapped species and, in some cases, takes an active part in the reactions. The charged matrix affects the diffusion of ions, thus affecting catalytic and adsorption processes. Furthermore, recent results point out that ≡Si-O. radicals are long-lived and participate in redox processes. Thus, clearly, porous silica is not an inert matrix as commonly considered.

Elucidation of a mechanism for the heterogeneous electro-fenton process and its application in the green treatment of azo dyes.

Vast efforts are directed today toward the development of efficient, green methods for the degradation of toxic compounds, especially those that are water-soluble. Though Fenton reactions are commonly used in wastewater treatment, their mechanisms and the active species involved remain obscure due to their mechanistic complexity. In this work, the mechanism of an electro-Fenton reaction, in which a FeLaO3 catalyst was entrapped in a sol-gel matrix, was studied in the presence of azo dyes as the model for toxic compounds. Increased knowledge about this important mechanism will confer greater control over related processes and enable a more efficient and green degradation method. DFT calculations showed that in the presence of Fe(IV), OH are formed under acidic conditions and that both the iron and hydroxyl species function as oxidation reagents in the degradation process. The structure of the formed Fe(IV) embedded in the solid matrix was not the typical tetravalent structure. Entrapment in the sol-gel matrix stabilized the catalyst, enhanced its efficiency and enabled it to be recycled. Sol-gel matrices constitute a simple method for the degradation of stable and toxic compounds under extreme pH conditions. The findings of this study are highly significant for the treatment of typically acidic wastewaters.

Advanced sol-gel process for efficient heterogeneous ring-closing metathesis.

Olefin metathesis, a powerful synthetic method with numerous practical applications, can be improved by developing heterogeneous catalysts that can be recycled. In this study, a single-stage process for the entrapment of ruthenium-based catalysts was developed by the sol-gel process. System effectiveness was quantified by measuring the conversion of the ring-closing metathesis reaction of the substrate diethyl diallylmalonate and the leakage of the catalysts from the matrix. The results indicate that the nature of the precursor affects pore size and catalyst activity. Moreover, matrices prepared with tetraethoxysilane at an alkaline pH exhibit a better reaction rate than in the homogenous system under certain reaction conditions. To the best of our knowledge, this is the first study to present a one-step process that is simpler and faster than the methods reported in the literature for catalyst entrapment by the sol-gel process under standard conditions.

LLDPE Composites with Nanosized Copper and Copper Oxides for Water Disinfection.

Consumption of contaminated water may lead to dangerous and even fatal water-borne diseases. Disinfection of drinking water is the most effective solution for this problem. The most common water treatment methods are based on the use of toxic disinfectants. Composites of polymers with nanosized metals and their oxides may become a good alternative to the existing methods. Expanding the scope of our previous publication, copper, cuprous, and copper oxide nanoparticles were immobilized onto linear low-density polyethylene by a simple thermal adhesion method. The antibacterial efficiency of the immobilized nanoparticles was tested against Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus in batch experiments and for the first time the efficiency of these composites is reported for continuous flow regime. Immobilized copper and cuprous oxide nanoparticles demonstrated a high ability to eradicate bacteria after 30 min. These composites showed no or very limited leaching of copper ions into the aqueous phase both in the presence and in the absence of a bacterial suspension. Immobilized copper and cuprous oxide nanoparticles can be used for batch or continuous disinfection of water.

SilverSil: A New Class of Antibacterial Materials of Broad Scope.

Consisting of organically modified silica (ORMOSIL) physically doped with Ag nanoparticles, the SilverSil new class of antibacterial materials of broad scope reported herein shows remarkably high and stable activity against representative Gram-positive and Gram-negative bacteria. The low cost, ease of application and excellent health and environmental profile of SilverSil hybrid glassy coatings open the route to their widespread utilization across domestic, hospital, school, industrial and commercial environments and in consumer products.

New Antivirals and Antibacterials Based on Silver Nanoparticles.

The rediscovery of the medical uses of silver provides another noticeable example, this time at the interface of chemistry and medicine, of the real (and nonlinear) progress of scientific research. Several new silver-based antimicrobial products have thus been commercialized in the last two decades. Next-generation antibacterials and antivirals of broad scope, low toxicity and affordable cost, we argue in this study, will be based on microencapsulated Ag nanoparticles.

Effective and Green Removal of Trichloroacetic Acid from Disinfected Water.

An innovative catalyst is reported for removing suspect carcinogen trichloroacetic acid (TCA) found in water after chlorination. SilverSil, a methyl-modified silica xerogel doped with Ag nanoparticles, shows remarkably high and stable activity as heterogeneous catalyst for the reductive dehalogenation of TCA with NaBH4 as reducing agent. Chloroacetic acid and acetic acid are the main products of the highly reproducible reductive dehalogenation. The low cost, high stability and ease of application of the SilverSil sol-gel catalyst to continuous processes open the route to the industrial uptake of SilverSil to free chlorinated waters from a probable human carcinogenic agent exerting significant genotoxic and cytotoxic effects.

Off the Radar: Comparative Evaluation of Radial Visualization Solutions for Composite Indicators.

A composite indicator (CI) is a measuring and benchmark tool used to capture multi-dimensional concepts, such as Information and Communication Technology (ICT) usage. Individual indicators are selected and combined to reflect a phenomena being measured. Visualization of a composite indicator is recommended as a tool to enable interested stakeholders, as well as the public audience, to better understand the indicator components and evolution over time. However, existing CI visualizations introduce a variety of solutions and there is a lack in CI's visualization guidelines. Radial visualizations are popular among these solutions because of CI's inherent multi-dimensionality. Although in dispute, Radar-charts are often used for CI presentation. However, no empirical evidence on Radar's effectiveness and efficiency for common CI tasks is available. In this paper, we aim to fill this gap by reporting on a controlled experiment that compares the Radar chart technique with two other radial visualization methods: Flower-charts as used in the well-known OECD Betterlife index, and Circle-charts which could be adopted for this purpose. Examples of these charts in the current context are shown in Figure 1. We evaluated these charts, showing the same data with each of the mentioned techniques applying small multiple views for different dimensions of the data. We compared users' performance and preference empirically under a formal task-taxonomy. Results indicate that the Radar chart was the least effective and least liked, while performance of the two other options were mixed and dependent on the task. Results also showed strong preference of participants toward the Flower chart. Summarizing our results, we provide specific design guidelines for composite indicator visualization. Fig. 1: Three radial solutions for composite indicator visualizations compared empirically for users' performance and preferences.