Catalytic Reduction of 4-Nitrophenol: A Quantitative Assessment of the Role of Dissolved Oxygen in Determining the Induction Time.

The reduction of 4-nitrophenol to 4-aminophenol by borohydride is one of the foremost model catalytic reactions because it allows for a straightforward assessment of catalysts using the kinetic parameters extracted from the real-time spectroscopic monitoring of an aqueous solution. Crucial to its standing as a model reaction is a comprehensive mechanistic framework able to explain the entire time evolution of the reaction. While much of this framework is in place, there is still much debate over the cause of the induction period, an initial time interval where no reaction seemingly occurs. Here, we report on the simultaneous monitoring of the spectroscopic signal and the dissolved oxygen content within the aqueous solution. It reveals that the induction period is the time interval required for the level of dissolved oxygen to fall below a critical value that is dependent upon whether Au, Ag, or Pd nanoparticles are used as the catalyst. With this understanding, we are able to exert complete control over the induction period, being able to eliminate it, extend it indefinitely, or even induce multiple induction periods over the course of a single reaction. Moreover, we have determined that the reaction product, 4-aminophenol, in the presence of the same catalyst reacts with dissolved oxygen to form 4-nitrophenolate. The implication of these results is that the induction period relates, not to some activation of the catalyst, but to a time interval where the reaction product is being rapidly transformed back into a reactant by a side reaction.