Electrocatalytic O2 Reduction by an Organometallic Pd(III) Complex via a Binuclear Pd(III) Intermediate

Abstract

The development of electrocatalysts for the selective O2-to-H2O conversion, the O2 reduction reaction (ORR), is of great interest for improving the performance of fuel cells. In this context, molecular catalysts that are known to mediate the 4H+/4e– reduction of O2 to H2O tend to be marred by limited stability and selectivity in controlling the multiproton and multielectron transfer steps. Thus, evaluation of transition metal complexes, including organometallic species, for ORR reactivity could uncover molecular catalysts with improved properties. We have previously reported the synthesis and characterization of various organometallic PdIII complexes stabilized by the tetradentate ligand N,N′-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane (tBuN4). These complexes were shown to react with O2 and undergo oxidatively induced C–C and C–heteroatom bond formation reactions in the presence of O2. These O2-induced oxidative transformations prompted us to evaluate the ORR reactivity of such organometallic Pd complexes, which to the best of our knowledge has never been studied before for any molecular Pd catalyst. Herein, we report the ORR reactivity of the [(tBuN4)PdIIIMeCl]+ complex under both homogeneous and heterogeneous conditions in a nonaqueous and acidic aqueous electrolyte, respectively. Cyclic voltammetry and hydrodynamic electrochemical studies for [(tBuN4)PdIIIMeCl]+ revealed that the electrocatalytic reduction of O2 to H2O proceeds with Faradaic efficiencies (FEs) of 50–70% in the presence of acetic acid (AcOH) in MeCN. The selectivity toward H2O production further improved the FE to 80–90% in an acidic aqueous medium (pH 0), upon immobilization of the molecular catalyst onto edge plane graphite (EPG) electrodes. Analysis of electrochemical data suggests the formation of a binuclear PdIII intermediate in solution, likely a PdIII-peroxo-PdIII species, which dictates the thermochemistry of the ORR process for [(tBuN4)PdIIIMeCl]+ in MeCN, thus being a rare example of a bimolecular ORR process. The maximum second-order turnover frequency TOFmax2 = 2.76 × 108 M–1 s–1 was determined for 0.32 mM of [(tBuN4)PdIIIMeCl]+ in the presence of 1 M AcOH in O2-saturated MeCN with an overpotential of 0.32 V. By comparison, a comparatively lower TOFmax2 = 1.25 × 105 M–1 s–1 at a higher overpotential of 0.8 V was observed for [(tBuN4)PdIIIMeCl]PF6 adsorbed onto EPG electrodes in O2-saturated 1 M H2SO4 aqueous solution. Overall, reported herein is a detailed ORR reactivity study using a PdIII organometallic complex to benchmark its selectivity and energetics toward O2 reduction in MeCN and acidic aqueous solutions.