Reduction of nitrobenzene with NaBH4 using zero-valent iron nanoparticles (ZVI-NPs) and NiCl2∙6H2O incorporated in organically modified hybrid silica matrices as ZVI@ORMOSIL and Ni(II)@ORMOSIL catalysts is proposed as a remediation strategy. Ni(II)@ORMOSIL is prepared by ion-exchanging H+ of the ORMOSIL matrix with NiII. Ni(II)@ORMOSIL is a pre-catalyst that undergoes reduction by NaBH4 by an in-situ reaction and promotes nitrobenzene reduction by the unconsumed NaBH4, leading to sparing use of the catalyst. Ni(II)@ORMOSIL undergoes color change from green to black in this process, returning to a green hue after washing and drying. Nitrobenzene reductions were examined in aqueous acetonitrile solvent mixtures, and the reduction cascade produced the reaction end-products with catalytic implications. Plausible mechanisms of ZVI@ORMOSIL and Ni(II)@ORMOSIL catalyzed reductions of nitrobenzene are discussed. This work is the first to report M(II)@ORMOSIL pre-catalysts for in-situ reduction of nitrobenzene, and expands the scope of the ORMOSIL series of catalysts for the reduction of polluting compounds. This approach enables the development of catalysts that use very low concentrations of transition metal cations.
The efficient reductive dechlorination, as remediation of dichloroacetamide and monochloroacetamide, toxic and abundant pollutants, using sodium borohydride catalyzed by zero valent iron nanoparticles (ZVI-NPs), entrapped in organically modified hybrid silica matrices prepared via the sol-gel route, ZVI@ORMOSIL, is demonstrated. The results indicate that the extent of the dechlorination reaction depends on the nature of the substrate and on the reaction medium. By varying the amount of catalyst or reductant in the reaction it was possible to obtain conditions for full dechlorination of these pollutants to nontoxic acetamide and acetic acid. A plausible mechanism of the catalytic process is discussed. The present work expands the scope of ZVI-NP catalyzed reduction of polluting compounds, first reports the catalytic parameters of chloroacetamide reduction, and offers additional insight into the heterogeneous catalyst structure of M0@ORMOSIL sol-gel. The ZVI@ORMOSIL catalyst is ferromagnetic and hence can be recycled easily.
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.
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.