A mechanistic evaluation for total removal of toxic hexavalent and trivalent chromium from water by oxygen vacancy-engineered nanocomposite

Oxygen vacancy-engineered nanocomposites are emerging materials in adsorption and photocatalysis research. This study evaluated total toxic Chromium removal by a nanocomposite of core-shell zeolite A@oxygen-vacant ZnO1_ X (ZA@ZnO1_X) from water using its coexisting dual characteristics. ZA@ZnO1_X has removed 98.3% of total Cr, achieving a discharge limit of 0.05 ppm of Cr(VI) after the photoreduction and adsorption simultaneously. The detailed structural and physicochemical properties of synthesized ZA@ZnO1_X nanocomposite show higher BET surface area, oxygen-vacant percentage, and visible light photoactivity than the sole ZnO1_X nanosheet. The photocatalytic reduction efficiency (PRE) effect is systematically studied on varying operational variables like pH, citric acid (CA), Cr(VI) concentration, catalyst load, presence of anions, and radical scavengers. ZA@ZnO1_X removed Cr(VI) and Cr(III) simultaneously by 98.5% PRE with a catalyst load of 4 g/l, CA= 5 mM, pH= 5.06 under halogen light irradiation (300 W, 240 V) for 50 mins. This experimental study evaluates the prominent role of oxygen vacancy of ZA@ZnO1_X for photocatalytic reduction of Cr(VI) and enhanced adsorption of Cr(III). The kinetic study reveals adsorption of both Cr(VI) and Cr(III) follows pseudo-second-order kinetics, whereas photoreduction of Cr(VI) follows pseudo-first-order kinetics. A possible mechanism of total Cr removal is sketched, supporting enhanced adsorption due to unsaturated Zn atoms and unpaired e- at the oxygen defect site, followed by photoreduction by photogenerated e- and COz center dot radical. The ZA@ZnO1_X performance is reduced by only 2.5% after five consecutive runs without deformation. The easy regeneration process makes it suitable for toxic total Cr removal, avoiding any secondary pollution.