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

Sustainable photocatalysis can effectively reduce the radioactive ⁹⁹TcO₄^- to less soluble TcO₂·<i>n</i>H₂O(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 NO_<i>x</i>, resulting in the decrease in the Re(VII) reduction ratio. Under the conditions of 4% (volume ratio) HCOOH and pH = 3, the yield of NO_<i>x</i> 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·<i>n</i>H₂O(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.