Fast and efficient removal of Cr(VI) to ppb level together with Cr(III) sequestration in water using layered double hydroxide interclated with diethyldithiocarbamate.

It is still a great challenge to find an eco-friendly, easy-to-synthesize, and cheap adsorbent to rapidly remove Cr(VI) to ppb level in the Cr(VI)-polluted water. Herein, a new layered double hydroxide nanocage intercalated with diethyldithiocarbamate (DDTC-LDH) was fabricated via a facile calcination-rehydration method. The DDTC-LDH rapidly decreased Cr(VI) concentration from 5 to <0.05 mg/L within 35 min, and only a few seconds were required to completely remove it at an initial concentration of 0.5-1 mg/L, primarily attributed to the effective adsorption-reduction of Cr(VI) to Cr(III) by sulfur atoms in CS and CS groups. Attractively, the generated Cr(III) was also quickly removed to below 0.1 mg/L via an opportune Lewis hard-hard interaction with C-SOx groups produced through CS oxidation. Additionally, Cr(VI) could be removed by DDTC-LDH at a wide pH application range (3.17-10.78) and with weak effects by coexisting anions (Cl-, NO3-, CO32-, SO42-, and PO43-). We systematically analyzed and proposed the mechanisms for Cr(VI) removal by the DDTC-LDH, orderly containing electrostatic attraction, Cr(VI) complexation by sulfur atoms in CS and CS groups, reduction of the Cr(VI) to Cr(III) by the CS and CS groups, and Cr(III) complexation by sulfur atoms in C-SOx groups. Our results provide new insights into the Cr(VI) removal using organosulfur compounds, that is to say, the organosulfur group Lewis hardness increased (from C-S to C-SOx) as the Cr species Lewis hardness increased (from Cr(VI) to Cr(III)), so as to opportunely ensure fast and efficient capture of both Cr(VI) and Cr(III) via Lewis acid-base interactions.