Catalytic water reduction to hydrogen takes place when metal nanoparticles (M0‐NPs) of gold or palladium are charged with an excess of electrons by an electron‐transfer process from strong reducing α‐alcohol radicals such as ·C(CH3)2OH. The results reported in this study indicate that the M0‐NPs also catalyze the reduction of perchlorate by ·C(CH3)2OH radicals and by BH4–. The results point out that the M0‐NPs behave as nanoelectrodes. The catalytic reduction of perchlorate competes well with the catalytic reduction of water; that is, although the concentration of perchlorate is orders of magnitude smaller than that of water, the radicals reduce the perchlorate preferentially. Thus, we have identified a new way to deal with the residual perchlorate in water, using any reducing agent forming adsorbed hydrogen. The nature of the reactive reducing agent (M0‐NPs)n–/{(M0‐NPs) – Hm}(n–m)– [n = number of excess electrons and m = number of electrons given off after the same number of H atoms have been adsorbed] and the energetic processes, which might be different for the two M0‐NPs, are discussed. The results demonstrate that M0‐NPs can be developed as simple and effective catalysts for the removal of perchlorate from polluted aqueous solutions.
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