The fundamental understanding of liquid-phase catalytic reactions is unavoidably complicated when the catalyst is prone to leaching since questions inevitably arise as to the true nature of the catalyst. While the catalytic reduction of 4-nitrophenol by borohydride is widely accepted as a trusted model reaction, it has faced little scrutiny concerning the potential impact of leached species or the appropriateness of assigning catalytic activity to the inserted nanostructures without rigorous experimental verification. Here, we present results from a spectroscopically monitored split test in which supported silver catalysts are physically separated from the reactants midway through the reaction. It is unambiguously demonstrated that the influence of leaching is far from benign, instead acting to extinguish the catalytic activity of the inserted nanostructures while giving rise to an unsupported heterogeneous catalyst that is the true catalytic entity. With only submonolayer quantities of silver leached from the supported structures, the unsupported species must be exceedingly catalytic. Moreover, it is shown that leaching is inherent to aqueous media containing dissolved oxygen, without which the supported nanostructures remain catalytically active. With the same nanomaterial being able to act either as a heterogeneous catalyst or as a reservoir from which leached metal is derived, such influences have undoubtedly compromised prior studies. We, nevertheless, capitalize on the sensitivity of 4-nitrophenol reduction to leached species by using it as a reaction-based indicator able to quantitatively determine the time dependence of the leaching process and enhancements to oxidative etching when silver, copper, palladium, platinum, and gold are exposed to chloride ions
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