Novel Hydrophobic Functionalized UiO-66 Series: Synthesis, Characterization, and Evaluation of Their Structural and Physical-Chemical Properties.

A novel set of four functionalized hydrophobic UiO-66-NHR series were synthesized through postsynthetic procedures, utilizing various benzoyl chlorides and UiO-66-NH2 as starting materials. This synthesis method was carried out by employing p- (1) and o-toluoyl (2), as well as 2- (3) and 4-fluorobenzoyl (4) substituents. The analysis of the resulting compounds was performed using conventional spectroscopic methods such as FT-IR and 1H NMR to quantify the conversion rate into amide. Furthermore, SEM and XPS techniques were employed for morphological and surface analysis. Finally, the evaluation of the chemical stability and contact angle using the sessile drop method was performed to evaluate the technological potential of these compounds for application in aqueous and acidic media (such as selective separation of different metals and wastewater recovery).

A State-of-the-Art of Metal-Organic Frameworks for Chromium Photoreduction vs. Photocatalytic Water Remediation.

Hexavalent chromium (Cr(VI)) is a highly mobile cancerogenic and teratogenic heavy metal ion. Among the varied technologies applied today to address chromium water pollution, photocatalysis offers a rapid reduction of Cr(VI) to the less toxic Cr(III). In contrast to classic photocatalysts, Metal-Organic frameworks (MOFs) are porous semiconductors that can couple the Cr(VI) to Cr(III) photoreduction to the chromium species immobilization. In this minireview, we wish to discuss and analyze the state-of-the-art of MOFs for Cr(VI) detoxification and contextualizing it to the most recent advances and strategies of MOFs for photocatalysis purposes. The minireview has been structured in three sections: (i) a detailed discussion of the specific experimental techniques employed to characterize MOF photocatalysts, (ii) a description and identification of the key characteristics of MOFs for Cr(VI) photoreduction, and (iii) an outlook and perspective section in order to identify future trends.

Copper-Modified Polymeric Membranes for Water Treatment: A Comprehensive Review.

In the last decades, the incorporation of copper in polymeric membranes for water treatment has received greater attention, as an innovative potential solution against biofouling formation on membranes, as well as, by its ability to improve other relevant membrane properties. Copper has attractive characteristics: excellent antimicrobial activity, high natural abundance, low cost and the existence of multiple cost-effective synthesis routes for obtaining copper-based materials with tunable characteristics, which favor their incorporation into polymeric membranes. This study presents a comprehensive analysis of the progress made in the area regarding modified membranes for water treatment when incorporating copper. The notable use of copper materials (metallic and oxide nanoparticles, salts, composites, metal-polymer complexes, coordination polymers) for modifying microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), forward osmosis (FO) and reverse osmosis (RO) membranes have been identified. Antibacterial and anti-fouling effect, hydrophilicity increase, improvements of the water flux, the rejection of compounds capacity and structural membrane parameters and the reduction of concentration polarization phenomena are some outstanding properties that improved. Moreover, the study acknowledges different membrane modification approaches to incorporate copper, such as, the incorporation during the membrane synthesis process (immobilization in polymer and phase inversion) or its surface modification using physical (coating, layer by layer assembly and electrospinning) and chemical (grafting, one-pot chelating, co-deposition and mussel-inspired PDA) surface modification techniques. Thus, the advantages and limitations of these modifications and their methods with insights towards a possible industrial applicability are presented. Furthermore, when copper was incorporated into membrane matrices, the study identified relevant detrimental consequences with potential to be solved, such as formation of defects, pore block, and nanoparticles agglomeration during their fabrication. Among others, the low modification stability, the uncontrolled copper ion releasing or leaching of incorporated copper material are also identified concerns. Thus, this article offers modification strategies that allow an effective copper incorporation on these polymeric membranes and solve these hinders. The article finishes with some claims about scaling up the implementation process, including long-term performance under real conditions, feasibility of production at large scale, and assessment of environmental impact.

Understanding the Phenomenon of Copper Ions Release from Copper-Modified TFC Membranes: A Mathematical and Experimental Methodology Using Shrinking Core Model.

Type of metal and metal-oxide NPs added to modify Thin-Film Composites Reverse Osmosis Membranes (TFC-RO) can alter their anti-biofouling properties by changing the dissolution process. The development of a mathematical model can facilitate the selection of these NPs. This work consists of a mathematical and experimental methodology to understand copper-based NPs dissolution of three copper species incorporated into TFC-RO membranes: Cu-NPs, CuO-NPs and Cu-Oligomer complexes formed in situ during the polymerization process. Biocidal capacity of copper species into the membrane was evaluated using colony forming unit method (CFU) over E. coli. In addition, copper ion release kinetics for both NPs and modified membranes were determined. A model based on the shrinking core model (SCM) was validated and applied to determine the limiting rate step in the dissolution process and simulate the ion release kinetics. Fitted curves reached a good adjustment with the experimental data, demonstrating the SCM can be applied to predict ion release process for copper-based NPs in suspension and the modified membranes. All membranes reached similar inhibition rate >50%, however, differences in the dissolution level of copper-based NPs in membrane were noted, suggesting a dual-type effect that defined the copper toxicity into the membrane, associated to the dissolution capacity and ROS production.

Chromium Speciation in Zirconium-Based Metal-Organic Frameworks for Environmental Remediation.

Acute CrVI water pollution due to anthropogenic activities is an increasing worldwide concern. The high toxicity and mobility of CrVI makes it necessary to develop dual adsorbent/ion-reductive materials that are able to capture CrVI and transform it efficiently into the less hazardous CrIII . An accurate description of chromium speciation at the adsorbent/ion-reductive matrix is key to assessing whether CrVI is completely reduced to CrIII , or if its incomplete transformation has led to the stabilization of highly reactive, transient CrV species within the material. With this goal in mind, a dual ultraviolet-visible and electron paramagnetic spectroscopy approach has been applied to determine the chromium speciation within zirconium-based metal-organic frameworks (MOFs). Our findings point out that the generation of defects at Zr-MOFs boosts CrVI adsorption, whilst the presence of reductive groups on the organic linkers play a key role in stabilizing it as isolated and/or clustered CrIII ions.