Preparative History vs Driving Force in Water Oxidation Catalysis: Parameter Space Studies of Cobalt Spinels

The development of efficient, stable, and economic water oxidation catalysts (WOCs) is a forefront topic of sustainable energy research. We newly present a comprehensive three-step approach to systematically investigate challenging relationships among preparative history, properties, and performance in heterogeneous WOCs. To this end, we studied (1) the influence of the preparative method on the material properties and (2) their correlation with the performance as (3) a function of the catalytic test method. Spinel-type Co₃O₄ was selected as a clear-cut model WOC and synthesized via nine different preparative routes. In search of the key material properties for high catalytic performance, these cobalt oxide samples were characterized with a wide range of analytical methods, including X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, powder X-ray diffraction, Raman spectroscopy, BET surface area analysis, and transmission electron microscopy. Next, the corresponding catalytic water oxidation activities were assessed with the three most widely applied protocols to date, namely, photocatalytic, electrocatalytic, and chemical oxidation. The activity of the Co₃O₄ samples was found to clearly depend on the applied test method. Increasing surface area and disorder as well as a decrease in oxidation states arising from low synthesis temperatures were identified as key parameters for high chemical oxidation activity. Surprisingly, no obvious property-performance correlations were found for photocatalytic water oxidation. In sharp contrast, all samples showed similar activity in electrochemical water oxidation. The substantial performance differences between the applied protocols demonstrate that control and comprehensive understanding of the preparative history are crucial for establishing reliable structure-performance relationships in WOC design.