RESUMO
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.
RESUMO
Despite rapid technological progress, heavy metal water pollution, and particularly arsenic contamination, remains a significant global challenge. In addition, the stabilization of trivalent arsenic as neutral arsenite (AsIII) species hinders its removal by conventional sorbents. While adsorption of anionic arsenate (AsV) species is in principle more feasible, there are only few adsorbents capable of adsorbing both forms of arsenic. In this work, we explore the potential of two well-known families of Metal-Organic Frameworks (MOFs), UiO-66 and MIL-125, to simultaneously adsorb and photo-oxidize arsenic species from water. Our results demonstrate that the formation of AsV ions upon light irradiation promotes the subsequent adsorption of AsIII species. Thus, we propose the combined utilization of photocatalysis and adsorption with Metal-Organic Framework photocatalysts for water remediation purposes.