The Competition between 4-Nitrophenol Reduction and BH4- Hydrolysis on Metal Nanoparticle Catalysts.

Abstract

Assessing competitive environmental catalytic reduction processes via NaBH4 is essential, as BH4- is both an energy carrier (as H2) and a reducing agent. A comprehensive catalytic study of the competition between the borohydride hydrolysis reaction (BHR, releasing H2) and 4-nitrophenol reduction via BH4- on M0- and M/M' (alloy)-nanoparticle catalysts is reported. The results reveal an inverse correlation between the catalytic efficiency for BH4- hydrolysis and 4-nitrophenol reduction, indicating that catalysts performing well in one process exhibit lower activity in the other. Plausible catalytic mechanisms are discussed, focusing on the impact of reaction products such as 4-aminophenol and borate on the rate and yield of BH4- hydrolysis. The investigated catalysts were Ag0, Au0, Pt0, and Ag/Pt-alloy nanoparticles synthesized without any added stabilizer. Notably, the observed rate constants for the 4-nitrophenol reduction on Ag0, Ag-Pt (9:1), and Au0 are significantly higher than the corresponding rate constants for BH4- hydrolysis, suggesting that most reductions do not proceed through surface-adsorbed hydrogen atoms, as observed for Pt0 nanoparticles. This research emphasizes the conflicting nature of BH4- hydrolysis and reduction processes, provides insights for designing improved catalysts for competitive reactions, and sheds light on the catalyst properties required for each specific process.