Optimization and verification of selective removal of organophosphate esters from wastewater by molecularly imprinted adsorbent

Abstract

Tributyl phosphate (TNBP), a new type of flame retardant, is an emerging pollutant and has been frequently detected in various matrices such as wastewater. Efficient removal of TNBP is critical for wastewater treatment. In this study, molecularly imprinted polymer (MIP) was prepared using precipitation polymerization for selective adsorption of TNBP. The results showed that MIP had a porous structure and formed effective imprinting cavities, which was primarily responsible for its superior adsorption ability. The adsorption of TNBP by MIP was carried out following both the pseudo-secondary kinetic model and the Langmuir isothermal adsorption model. MIP adsorbed TNBP rapidly and reached adsorption equilibrium within 30 min with 923 μmol g−1 at 298 K. The adsorption capacity and adsorption rate of MIP were respectively 2 and 5.49 times those of non-molecularly imprinted polymers. In addition, MIP could effectively counter disturbances from external parameters like temperature and pH, exhibiting strong environmental flexibility. MIP can specifically adsorb organophosphate esters, and can selectively adsorb TNBP under the interference of coexisting contaminants such as1,3-diphenylguanidine and isazofos. In actual bodies of water, MIP's highly selective adsorption of TNBP retains its advantage. The selective adsorption of MIP was mainly due to the common phosphate skeleton, and the specific substituent of organophosphate esters played an important role in the imprinting process. Hydrogen bonding might be involved in the polymerization process of TNBP with acrylamide and the adsorption process of TNBP by MIP.MIP exhibited good reuse efficiency, the total adsorption capacity decreased by no more than 25% after 7 reuse cycles. This study provides a simple and efficient method for selective removal of organophosphate from wastewater.