Structurally Precise Two-Transition-Metal Water Oxidation Catalysts: Quantifying Adjacent 3d Metals by Synchrotron X-Radiation Anomalous Dispersion Scattering.

Mixed 3d metal oxides are some of the most promising water oxidation catalysts (WOCs), but it is very difficult to know the locations and percent occupancies of different 3d metals in these heterogeneous catalysts. Without such information, it is hard to quantify catalysis, stability, and other properties of the WOC as a function of the catalyst active site structure. This study combines the site selective synthesis of a homogeneous WOC with two adjacent 3d metals, [Co 2 Ni 2 (PW 9 O 34 ) 2 ] 10- ( Co 2 Ni 2 P 2 ) as a tractable molecular model for CoNi oxide, with the use of multiwavelength synchrotron X-radiation anomalous dispersion scattering (synchrotron XRAS) that quantifies both the location and percent occupancy of Co (∼97% outer-central-belt positions only) and Ni (∼97% inner-central-belt positions only) in Co 2 Ni 2 P 2 . This mixed-3d-metal complex catalyzes water oxidation an order of magnitude faster than its isostructural analogue, [Co 4 (PW 9 O 34 ) 2 ] 10- ( Co 4 P 2 ). Four independent and complementary lines of evidence confirm that Co 2 Ni 2 P 2 and Co 4 P 2 are the principal WOCs and that Co 2+ (aq) is not. Density functional theory (DFT) studies revealed that Co 4 P 2 and Co 2 Ni 2 P 2 have similar frontier orbitals, while stopped-flow kinetic studies and DFT calculations indicate that water oxidation by both complexes follows analogous multistep mechanisms, including likely Co-OOH formation, with the energetics of most steps being lower for Co 2 Ni 2 P 2 than for Co 4 P 2 . Synchrotron XRAS should be generally applicable to active-site-structure-reactivity studies of multi-metal heterogeneous and homogeneous catalysts.