In the sustainable production of non-fossil fuels, water oxidation is pivotal. Development of efficient catalysts based on manganese is desirable because this element is earth-abundant, inexpensive, and largely non-toxic. We report an electrodeposited Mn oxide (MnCat) that catalyzes electrochemical water oxidation at neutral pH at rates that approach the level needed for direct coupling to photoactive materials. By choice of the voltage protocol we could switch between electrodeposition of inactive Mn oxides (deposition at constant anodic potentials) and synthesis of the active MnCat (deposition by voltage-cycling protocols). Electron microscopy reveals that the MnCat consists of nanoparticles (100 nm) with complex fine-structure. X-ray spectroscopy reveals that the amorphous MnCat resembles the biological paragon, the water-splitting Mn 4 Ca complex of photosynthesis, with respect to mean Mn oxidation state (ca. +3.8 in the MnCat) and central structural motifs. Yet the MnCat functions without calcium or other bivalent ions. Comparing the MnCat with electrodeposited Mn oxides inactive in water oxidation, we identify characteristics that likely are crucial for catalytic activity. In both inactive Mn oxides and active ones (MnCat), extensive di-m-oxo bridging between Mn ions is observed. However in the MnCat, the voltage-cycling protocol resulted in formation of Mn III sites and prevented formation of well-ordered and unreactive Mn IV O 2 . Structure-function relations in Mn-based wateroxidation catalysts and strategies to design catalytically active Mn-based materials are discussed. Knowledge-guided performance optimization of the MnCat could pave the road for its technological use. Broader contextThreatening global climate changes and unsecured supply of fossil fuels call for a global transition toward sustainable energyconversion systems. The storage of wind or solar energy by formation of energy-rich fuel molecules could play a central role in both transient storage of the intermittently provided energy and replacement of fossil fuels in the transportation sector. Whether hydrogen or a carbon-based fuel is the target, in any event the extraction of reducing equivalents and protons from water (that is, water oxidation) is pivotal. In search of water-oxidation catalysts that ultimately could play a role at a global scale, we and others are aiming at development of simple routes towards formation of Mn-based catalysts. Manganese excels by high availability and low toxicity; and in oxygenic photosynthesis, nature has demonstrated that a Mn-based catalyst can oxidize water efficiently. When aiming at an 'artificial leaf' with a Mn-based catalyst directly coupled to a solar-energy-converting material, the activity of the catalyst (per area) needs to cope with the incoming photon flux. Moreover the device design typically requires the use of benign synthesis and operation conditions, that is, temperatures close to room temperature and pH close to neutral. As an important first step, we report a simple protocol for e...

Water oxidation by amorphous oxides is of high interest in artificial photosynthesis and other routes towards non-fossil fuels, but the mode of catalysis in these materials is insufficiently understood. We tracked mechanistically relevant oxidation-state and structural changes of an amorphous Co-based catalyst film by in-situ experiments combining directly synchrotron-based X-ray absorption spectroscopy (XAS) with electrocatalysis. Unlike a classical solid-state material, the bulk material is found to undergo chemical changes. Two redox transitions at midpoints potentials of about 1.0 V (Co II 0.4Co III 0.6  all-Co III ) and 1.2 V (all-Co III  Co III 0.8Co IV 0.2) vs. NHE at pH 7 are coupled to structural changes. These redox transitions can be induced by variation of either electric potential or pH; they are broader than predicted by a simple Nernstian model, suggesting interacting bridged cobalt ions. Tracking reaction kinetics by UV-Vis-absorption and time-resolved mass spectroscopy reveal that accumulated oxidizing equivalents facilitate dioxygen formation. On these grounds, a new framework model of catalysis in the amorphous, hydrated and volume-active oxide is proposed: Within the oxide film, cobalt ions at the margins of Co-oxo fragments undergo Co II Co III Co IV oxidationstate changes coupled to structural modification and deprotonation of Co-oxo bridges. By encounter of two (or more) Co IV ions, an active site is formed at which the O-O bondformation step can take place. The Tafel slope is determined by both the interaction between cobalt ions (width of the redox transition) and their encounter probability. Our results represent a first step toward development of new concepts that address the solid-molecular Janus nature of the amorphous oxide. Insights and concepts described herein for the Co-based catalyst film may be of general relevance also for other amorphous oxides with water-oxidation activity. EXPERIMENTAL XAS measurements -in-situ experimentCoCat-coated electrodes were prepared by electrodeposition in a separate electrochemical setup before start of the in-situ XAS measurements from a solution of 0.5 mM Co 2+ ions in 0.1 M KPi at pH 7 (deposition of about 50 nmol cm -1 of Co ions, see ESI for further details). The in-situ XAS measurements were performed at the SuperXAS beamline of the Swiss Light Source (SLS) in Villigen, Switzerland. The excitation energy was selected by a double-crystal monochromator (Si-111, detuning to 50 % intensity, scan range of 7650-8400 eV) and used to irradiate the backside of the ITO/PET electrode at an angle of 45°. The spot size of the X-ray beam on the sample was 5 mm × 1 mm. Due to employment of a large spot size (defocussed beam) and a rapid-scanning mode, the influence of radiation-induced modifications was negligible, as verified in control experiments. The cobalt K-edge fluorescence was monitored perpendicular to the incident beam by a scintillation detector (19.6 cm 2 active area, 51BMI/2E1-YAP-Neg, Scionix), which was shielded by a 25 μm iron foil agai...

In reaction sequences for light driven water-splitting into H 2 and O 2 , water-oxidation is a crucial reaction step. In vivo, the process is catalysed within a photoenzyme called photosystem II (PSII) by a m-oxido CaMn 4 cluster, the oxygen-evolving complex (OEC). The OEC is known to be virtually inactive if Ca 2+ is removed from its structure. Activity can be restored not only by the addition of Ca 2+ but also Sr 2+ ions. We have recently introduced layered calcium manganese oxides of the birnessite mineral family as functional synthetic model compounds for the OEC. Here, we present the syntheses of layered manganese oxides where we varied the interlayer cations, preparing a series of K-, Ca-, Srand Mg-containing birnessites. Structural motifs within these materials were determined using X-ray absorption spectroscopy (XAS) showing that all materials have similar atomic structures despite their different elemental compositions. Water-oxidation experiments were carried out to elucidate structurereactivity relations. These experiments demonstrated that the oxides-like the OEC-require the presence of calcium in their structures to reach maximum catalytic activity. As another similarity to the OEC, Sr 2+ is the ''second best choice'' for the secondary cation. The results thus support mechanistic proposals which involve an important catalytic role for Ca 2+ in biological water-oxidation. Additionally, they offer valuable hints for the development of synthetic, manganese-based wateroxidation catalysts for artificial photosynthesis.

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In photosynthesis, water is oxidized at a protein-bound Mn(4)Ca complex. Artificial water-oxidation catalysts that are similarly efficient and based on inexpensive and abundant materials are of great interest. Recently, assembly of a catalyst as an amorphous layer on inert cathodes by electrodeposition starting from an aqueous solution of cobalt ions and potassium phosphate has been reported. X-ray absorption spectroscopy on the cobalt catalyst film (CoCF) suggests that its central structural unit is a cluster of interconnected complete or incomplete Co(III)-oxo cubanes. Potassium ligation to Co-bridging oxygens could result in Co(3)K(mu-O)(4) cubanes, in analogy to the Mn(3)Ca(mu-O)(4) cubane motif proposed for the photosynthetic Mn complex. The similarities in function and oxidative self-assembly of CoCF and the catalytic Mn complex in photosynthesis are striking. Our study establishes a close analogy also with respect to the metal-oxo core of the catalyst.