Development of efficient and economic water oxidation catalysts (WOCs) remains a crucial bottleneck on the way to artificial photosynthesis applications. Over the past few decades, WOC research has turned into a fascinating interdisciplinary field that ranges from bio-inspired molecular design over nanomaterials and thin films to solid materials tuning. Under the umbrella of WOC optimization, advanced in situ/operando analytical techniques are being developed as increasingly powerful tools to elucidate the controversial discussions about the molecular or nanoscale nature of many WOCs. More and more of these approaches also enable the monitoring of possible key intermediates as an essential prerequisite for proposing catalytic mechanisms. This review is organized in three main parts: first, recent highlights outline frontiers in WOC development, such as the benefits of connecting molecular WOCs with solids along with the introduction of molecular concepts into heterogeneous WOC research. Next, a brief overview of emerging in situ/operando approaches demonstrates new options for monitoring WOC transformations. Finally, selected monitoring studies over the entire WOC dimensionality spectrum illustrate interesting cases of catalytic border crossings as new input for WOC construction.
We introduce the novel Co 4 O 4 complex [Co II 4 (hmp) 4 (μ-OAc) 2 (μ 2 -OAc) 2 (H 2 O) 2 ] (1) (hmp = 2-(hydroxymethyl)pyridine) as the first Co(II)-based cubane water oxidation catalyst. Monodentate acetate and aqua ligands lend the flexible environment of 1 closest resemblance to photosystem II among its tetranuclear mimics to date. Visible-light-driven catalytic activity of 1 increases with pH value through aqua ligand deprotonation. The Co(II) core combines robustness and stability with flexibility through a new type of water-oxidation mechanism via mobile ligands.
Open-core polyoxometalates are powerful precursors with pre-organized metal centers for the tunable synthesis of cobalt tungstate-based water oxidation electrocatalysts.
Comprehensive computational modelling with advanced analytical investigations provides insight into mechanisms and active species of noble metal-free polyoxometalate oxidation catalysts.
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