Reduction-orientated selective removal of selenate by thiourea-functionalized polystyrene material

Abstract

Efficient removal of trace selenate [Se(VI)] from contaminated water is still challenging because of the inevitable interference from the coexisting anions toward the adsorption or ion-exchange process. Herein, a bifunctional material (NCS@CMPS) was proposed for selective removal of Se(VI) from a complex matrix. NCS@CMPS was subtly prepared by grafting a chloromethylated polystyrene substrate (CMPS) with thiourea, resulting in reductive groups (C-SH and C=S) and adsorptive sites (–NH-, –NH2, and C=NH2+) anchored on the skeleton of CMPS. Batch studies demonstrated an excellent removal efficiency and anti-interference capabilities of NCS@CMPS toward Se(VI), even with very high levels of competing anions (chloride, sulfate, phosphate, nitrate, and bicarbonate) over a wide pH range (3 ∼11). The in-situ reductive removal and the unique pH-buffering effect of NCS@CMPS were responsible for the high selectivity and the wide applicability. The XPS analyses identified the removal mechanisms of concentrating, reducing, and sequestrating of Se species inside NCS@CMPS, where the majority of Se species was reduced to Se(IV) (80.9%). In column mode, NCS@CMPS can treat over 10,000 bed volumes (BV) of a simulated Se(VI) wastewater ([Se]ini = 200 μg/L) to below 10 μg/L, whereas the capacity of its substrate (i.e., CMPS) was only 28 BV. Additionally, the exhausted NCS@CMPS can be regenerated by NaBH4-NaOH-HCl treatment for repeated use. Moreover, the effectiveness of NCS@CMPS in treating actual industrial Se(VI) wastewater was also validated.