Effect of precursor type on the reduction of concentrated nitrate using zero-valent copper and sodium borohydride.

In this study, we demonstrated that the choice of precursor has a strong effect on the reduction of nitrate (NO3-) using zero-valent copper (Cu0) synthesized by sodium borohydride (NaBH4). Different precursors: CuSO4, CuO, Cu2O, Cu powder, and Cu mesh were used to reduce NO3- at 677 mg-N/L under the reducing conditions of NaBH4. Compared with the prehydrolyzed samples, those prepared without prehydrolysis exhibited lower reduction rates, longer times and higher concentrations of nitrite (NO2-) intermediate. It was found that one-time addition of NaBH4 resulted in higher reduction rate and less NO2- intermediate than two-step addition. Results showed that Cu0 from CuSO4 possessed the smallest particle size (890.9 nm), highest surface area (26.0 m2/g), and highest reaction rate (0.166 min-1). Values of pseudo-first-order constant (kobs) were in the order: CuSO4 > CuO > Cu2O > Cu powder >Cu mesh. However, values of surface area-normalized reaction rate (kSA) were approximately equal. It was proposed that NO3- was reduced to NO2- on Cu0, and then converted to NH4+ and N2, respectively; H2 generated from both NaBH4 hydration and Cu (II) reduction contributed to NO3- reduction as well.

Reduction of concentrated nitrate by using in situ synthesized zero-valent copper.

Although zero-valent iron represents a promising approach for reduction of nitrate (NO(3)(-)) in water, its application in concentrated nitrate is limited by surface passivation. In this study, an alternative approach using in situ synthesized zero-valent copper (Cu(0)) produced by borohydride (NaBH(4)) was investigated. Complete reduction was observed within 55 min by reacting 677 mg-N/L of NO(3)(-) with CuO (0.312 g/L) and NaBH(4) (4.16 g/L) at 60 °C. The pseudo-first-order rate constant was 0.059 min(-1), and it increased threefold when the CuO dose was increased to 1.24 g/L. Increasing the NaBH(4) dose produced less nitrite (NO(2)(-)) throughout the experiments, indicating that it is the primary agent for reducing NO(2)(-). The initial pH exerted a significant effect on the reaction rate, and NO(3)(-) was rapidly reduced when the initial pH was less than 4. Based on the research findings, possible reaction pathways for NO(3)(-) reduction by Cu(0) are proposed in this work.