Effect of NaBH sub(4) on properties of nanoscale zero-valent iron and its catalytic activity for reduction of p-nitrophenol

The reduction of p-nitrophenol (p-NP) to p-aminophenol (p-AP) by nanoscale zero-valent iron (NZVI)/NaBH sub(4) system in an oxygen environment was studied by means of liquid chromatography, spectroscopy (vibration and X-ray photoelectron), solid analyses (transmission electron microscopy and X-ray diffraction) and density functional theory (DFT) calculations. Addition of NaBH sub(4) into NZVI suspension showed the disintegration of NZVI (60-100 nm), resulting in the formation of much smaller particles (15-40nm) due to the chemical etching of outermost surfaces (i.e., magnetite). Interestingly, complete reduction of p-NP and high conversion efficiency of p-AP (>98%) were observed in NZVI/NaBH sub(4) system even after four recycling which is quite comparable with widely used noble metallic catalysts. Surface analysis confirmed that NaBH sub(4) can prevent the oxidation of NZVI surface, leading to the continuous reduction of p-NP in oxygen environments. Experimental results and DFT calculations suggested that not only the formation of smaller NZVI but also thermodynamic preferences for reduction of p-NP on outermost surfaces of NZVI (i.e., magnetite) may significantly affect the reduction process of p-NP in NZVI/NaBH sub(4) system. These novel findings can promote the development of new NZVI technologies which can be used for wastewater reductive treatment in oxygen environments.