Molecular Insights into Ternary Surface Complexation of Arsenite and Cadmium on TiO2.
Insights from molecular-level mechanisms of arsenite [As(III)] and cadmium (Cd) co-adsorption on TiO2 can further our understanding of their synergistic removal in industrial wastewaters. The motivation for our study is to explore the interfacial interactions of neutrally charged As(III) and cationic Cd(2+) on nanocrystalline TiO2 using multiple complementary techniques. The results of adsorption edge, ζ potential, and surface complexation modeling suggest that coexistence of As(III) and Cd(2+) enhanced their synergistic adsorption on TiO2 and, consequently, resulted in the formation of a ternary surface complex. This ternary surface complex, in turn, inhibited the metal release into the aqueous phase and, therefore, facilitated the immobilization of the heavy metals. Our in situ flow-cell attentuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and extended X-ray absorption fine structure (EXAFS) spectroscopy evidence showed that, regardless of the order of contact, As(III) was preferentially adsorbed on TiO2 rather than Cd. In agreement with our spectroscopic analysis, quantum chemistry calculations also illustrated that the Cd-As(III)-TiO2 ternary surface complex should be formed with the adsorbed As(III) as the bridging molecule. At high As(III) concentrations, the formation of the Cd-As(III)-TiO2 complex is responsible for the Cd removal. The simultaneous removal mechanisms will further our understanding of the removal of multiple pollutants in industrial wastewaters.
†State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, People's Republic of China.
Shan
S
Hu
†State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, People's Republic of China.
Li
L
Yan
‡National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan.
Tingshan
T
Chan
†State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, People's Republic of China.
Chuanyong
C
Jing
D000327:Adsorption; D018053:Arsenites / Q000737:chemistry*; D002104:Cadmium / Q000737:chemistry*; D005591:Chemical Fractionation; D003198:Computer Simulation; D006863:Hydrogen-Ion Concentration; D017550:Spectroscopy, Fourier Transform Infrared; D055672:Static Electricity; D013499:Surface Properties; D014025:Titanium / Q000737:chemistry*; D056928:X-Ray Absorption Spectroscopy
D018053:Arsenites; D002104:Cadmium; C009495:titanium dioxide; D014025:Titanium; C015001:arsenite