Antagonistic Effect of Nitrate Conversion on Photocatalytic Reduction of Aqueous Pertechnetate and Perrhenate.

Abstract

Sustainable photocatalysis can effectively reduce the radioactive 99TcO4- to less soluble TcO2·nH2O(s), but the reduction efficiency is highly susceptible to coexisting nitrate (NO3-). Here, we quantitatively investigate photocatalytic remediation conditions for Tc-contaminated water stimulated by the analogue perrhenate (ReO4-) in the presence of NO3-, and we elucidate the influence mechanism of NO3- by in situ characterizations. The interfering NO3- can compete with Re(VII) for the carbonyl radical (·CO2-) produced by formic acid (HCOOH) oxidation to generate nitrogen-containing products such as NH4+, NO2-, and NOx, resulting in the decrease in the Re(VII) reduction ratio. Under the conditions of 4% (volume ratio) HCOOH and pH = 3, the yield of NOx is the lowest, and the selectivity of N2 reaches 93%, which makes the overall reaction more in line with the pollution-free concept. The X-ray absorption fine structure reveals that the redox product Re(IV) mainly exists in the form of ReO2·nH2O(s) and is accompanied by a decrease with the increase in NO3- concentration. Re(VII)/Tc(VII) reduction suffers from a serious interferential effect of NO3-, whereas the higher the concentration of NO3-, the more conducive to slowing down the reoxidation of the reduction products, which is advantageous for the subsequent sequestration or separation.