Influence of ultraviolet wavelengths on kinetics and selectivity for N-gases during TiO₂ photocatalytic reduction of nitrate

For drinking water applications, photocatalytic reduction processes beneficially transform aqueous nitrate to innocuous nitrogen gases (N-gases) but can produce nitrite and ammonia as undesirable aqueous by-products. We hypothesize that by-product selectivity is a function of light source and photon fluence dose, such that discrete wavelengths can increase yield of desirable N-gases. Experiments performed under different wavelength irradiation (ultraviolet- [UV] A, B, C) reduced nitrate in water to differing extents based on pH over the range of 1–8 or the presence of soluble organic electron donors. At an equivalent photon fluence dose, the most rapid nitrate loss in acidic solutions occurred using a combination of three UV-light emitting diodes (285 nm, 300 nm, 365 nm) closely followed by a polychromatic medium pressure UV lamp. A polychromatic xenon light source was least effective in reducing nitrate. Nitrite is an important intermediate during photocatalytic reduction of nitrate. Nitrite absorbs 330–380 nm light with high quantum efficiency. Thus, polychromatic or monochromatic light sources with strong UV-A emission more rapidly convert nitrite to by-products than UV-C monochromatic light sources. Nitrous acid (HONO) has a higher molar absorptivity (ε) and quantum efficiency than nitrite ion (pK_a = 3.39) around 350–370 nm. Selectivity towards N-gases is bifurcated at the nitrite intermediate and is strongly influenced by direct photolysis instead of photocatalytic reduction. Thus, the selectivity of by-products can be controlled by delivering light in the 350–370 nm wavelength range, where it enables photocatalytic processes to rapidly initiate NO₃⁻ reduction and delivers photons for direct photolysis of HONO.