The development of processes for removal of micropollutants (MPs) from waters is a major focus of TAML research. In TAML processes, the rate of MP oxidation is proportional to the low and decreasing [MP] while that of the competing catalyst inactivation is not. Consequently, design to slow inactivation can advance especially heterogeneous TAML catalysis where persistence is not environmentally threatening. A new kinetic tool has enabled scrutiny of TAML inactivation at neutral pH. A linear free energy relationship between the rate constants for the inactivation (ki) of 15 “Old-TAMLs” and the rate constants for the oxidations of a model substrate (kII) shows that when Old-TAMLs more rapidly oxidize substrates, inactivation is also more rapid ruling out oxidative decay and implicates nucleophilic attack as the lifetime governing chemistry. Measured dependences of ki on [H2O2] and [OH-] confirm nucleophilic decay and led us to design “New-TAMLs” that resist nucleophilic processes.

Design of longer-lived TAML catalysts

253rd National Meeting (2017)

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