Philipp Kurz

Synthetic manganese–calcium oxides mimic the water-oxidizing complex of photosynthesis functionally and structurally

In the worldwide search for sustainable energy technologies, water oxidation by abundant low-cost materials is of key importance. In nature, this process is efficiently catalyzed by an intricate manganese–calcium (Mn4Ca) complex bound to the proteins of photosystem II (PSII). Recently synthetic manganese–calcium oxides were found to be active catalysts of water oxidation but at the atomic level their structure has remained elusive. To investigate these amorphous catalysts, extended-range X-ray absorption spectroscopy (XAS) at the K-edges of both manganese and calcium was performed. The XAS results reveal striking similarities between the synthetic material and the natural Mn4Ca complex. The oxidation state of manganese in the active oxides was found to be close to +4, but MnIII ions are present as well at a level of about 20%. Neighboring Mn ions are extensively interconnected by two bridging oxygens, a characteristic feature of layered manganese oxides. However, the oxides do not exhibit long-range order, as opposed to canonical, but catalytically inactive MnIII- or MnIV-oxides. Two different Ca-containing motifs were identified. One of them results in the formation of Mn3CaO4 cubes, as also proposed for the natural paragon in PSII. Other calcium ions likely interconnect oxide-layer fragments. We conclude that these readily synthesized manganese–calcium oxides are the closest structural and functional analogs to the native PSII catalyst found so far. Evolutionary implications are considered. From the differences to inactive manganese oxides, we infer structural features facilitating the catalysis of water oxidation in both the protein-bound Mn4Ca complex of PSII and in the synthetic oxides.

Layered manganese oxides for water-oxidation: alkaline earth cations influence catalytic activity in a photosystem II-like fashion

In reaction sequences for light driven water-splitting into H2 and O2, water-oxidation is a crucial reaction step. In vivo, the process is catalysed within a photoenzyme called photosystem II (PSII) by a μ-oxido CaMn4 cluster, the oxygen-evolving complex (OEC). The OEC is known to be virtually inactive if Ca2+ is removed from its structure. Activity can be restored not only by the addition of Ca2+ but also Sr2+ 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-, Sr- and 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 structure-reactivity 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, Sr2+ is the “second best choice” for the secondary cation. The results thus support mechanistic proposals which involve an important catalytic role for Ca2+ in biological water-oxidation. Additionally, they offer valuable hints for the development of synthetic, manganese-based water-oxidation catalysts for artificial photosynthesis.

Calcium Manganese Oxides as Oxygen Evolution Catalysts: O2 Formation Pathways Indicated by 18O‐Labelling Studies

Oxygen evolution catalysed by calcium manganese and manganese-only oxides was studied in (18)O-enriched water. Using membrane-inlet mass spectrometry, we monitored the formation of the different O(2) isotopologues (16)O(2), (16)O(18)O and (18)O(2) in such reactions simultaneously with good time resolution. From the analysis of the data, we conclude that entirely different pathways of dioxygen formation catalysis exist for reactions involving hydrogen peroxide (H(2)O(2)), hydrogen persulfate (HSO(5)(-)) or single-electron oxidants such as Ce(IV) and [Ru(III) (bipy)(3)](3+) . Like the studied oxide catalysts, the active sites of manganese catalase and the oxygen-evolving complex (OEC) of photosystem II (PSII) consist of μ-oxido manganese or μ-oxido calcium manganese sites. The studied processes show very similar (18)O-labelling behaviour to the natural enzymes and are therefore interesting model systems for in vivo oxygen formation by manganese metalloenzymes such as PSII.

The Role of Autotrophic Picocyanobacteria in Calcite Precipitation in an Oligotrophic Lake

A 1-year field study monitoring depth profiles of picoplankton and physicochemical data in the oligotrophic Lake Lucerne (Switzerland) showed that picocyanobacteria play an important role in the CaCO3 precipitation process. Laboratory experiments with Mychonastes and Chlorella, isolated from Lake Lucerne and Synechococcus using ion selective electrodes, scanning electron microscopy and X-ray powder diffraction clearly demonstrated the potential of picoplankton for fast and effective CaCO3 precipitation. The combination of a field study with laboratory experiments confirmed the previous reports of picocyanobacteria triggering the CaCO3 precipitation in hardwater oligotrophic lakes. Electron micrographs of particles from the water column often reveal the size and shape of picoplankton cells covered by calcite. In addition the results from the laboratory approach indicated that algae and bacteria induced different precipitation mechanisms. Experiments with Mychonastes and Chlorella produced crystalline calcite completely covering the cells. Experiments with the cyanobacteria Synechococcus, however, yielded amorphous, micritic CaCO3, indicating a different precipitation process.

Artificial Photosynthesis for Solar Fuels – an Evolving Research Field within AMPEA, a Joint Programme of the European Energy Research Alliance

Abstract On the path to an energy transition away from fossil fuels to sustainable sources, the European Union is for the moment keeping pace with the objectives of the Strategic Energy Technology-Plan. For this trend to continue after 2020, scientific breakthroughs must be achieved. One main objective is to produce solar fuels from solar energy and water in direct processes to accomplish the efficient storage of solar energy in a chemical form. This is a grand scientific challenge. One important approach to achieve this goal is Artificial Photosynthesis. The European Energy Research Alliance has launched the Joint Programme “Advanced Materials & Processes for Energy Applications” (AMPEA) to foster the role of basic science in Future Emerging Technologies. European researchers in artificial photosynthesis recently met at an AMPEA organized workshop to define common research strategies and milestones for the future. Through this work artificial photosynthesis became the first energy research sub-field to be organised into what is designated “an Application” within AMPEA. The ambition is to drive and accelerate solar fuels research into a powerful European field – in a shorter time and with a broader scope than possible for individual or national initiatives. Within AMPEA the Application Artificial Photosynthesis is inclusive and intended to bring together all European scientists in relevant fields. The goal is to set up a thorough and systematic programme of directed research, which by 2020 will have advanced to a point where commercially viable artificial photosynthetic devices will be under development in partnership with industry.

Oxygen evolving reactions catalysed by manganese–oxo-complexes adsorbed on clays

A series of dinuclear manganese-oxo-complexes was prepared and adsorbed on kaolinite and montmorillonite clays. As indicated by UV-Vis spectroscopy, immobilization of the manganese compounds greatly altered the electronic properties due to strong interactions with the clay surfaces. When studied for their ability to catalyze oxygen formation upon reactions with the strong oxygen-transferring oxidants H(2)O(2) and oxone, it was found that surface adsorption yielded catalysts of improved performance for oxygen formation in aqueous media. Both the rates of oxygen evolution and catalyst stabilities were significantly increased for the clay hybrids of most complexes in comparison to homogeneous solutions of the compounds. Additionally, four heterogeneous systems were also found to catalyze the evolution of O(2) in reactions with the non-oxygen transferring, single- electron oxidation agent Ce(IV)--a reaction not observed for any dinuclear manganese complex in homogeneous reaction. Implications of these observations concerning the mechanism of oxygen formation and the development of manganese-based water oxidation catalysts are discussed.

Two tetranuclear Mn-complexes as biomimetic models of the oxygen evolving complex in Photosystem II. A synthesis, characterisation and reactivity study

In this work we report the preparation of two metallamacrocyclic tetranuclear manganese(II) complexes, [L1(4)Mn4](ClO4)4 and [L2(4)Mn4](ClO4)4 where L1 and L2 are the anions of the heptadentate ligands 2-((2-(bis(pyridin-2-ylmethyl)amino)ethyl)(methyl)amino)acetic acid and 2-(benzyl(2-(bis(pyridin-2-ylmethyl)amino)ethyl)amino)acetic acid), respectively. The complexes have been fully characterized by ESI-MS, elemental analysis, single-crystal X-ray diffraction, magnetic susceptibility, and EPR spectroscopy. Electrochemical reactions as well as reactions with different chemical redox reagents have been performed and a reversible two electron oxidation per manganese ion has been identified. The reaction of [L1(4)Mn4](ClO4)4 with oxone or cerium(IV) results in the evolution of oxygen which makes this system interesting for future studies in the search for a functional mimic of the oxygen evolving complex in Photosystem II.

Water oxidation catalysis by birnessite@iron oxide core-shell nanocomposites.

In this work, magnetic nanocomposite particles were prepared for water oxidation reactions. The studied catalysts consist of maghemite (γ-Fe2O3), magnetite (Fe3O4), and manganese ferrite (MnFe2O4) nanoparticles as cores coated in situ with birnessite-type manganese oxide shells and were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermal, chemical, and surface analyses, and magnetic measurements. The particles were found to be of nearly spherical core-shell architectures with average diameter of 150 nm. Water oxidation catalysis was examined using Ce(4+) as the sacrificial oxidant. All core-shell particles were found to be active water oxidation catalysts. However, the activity was found to depend on a variety of factors like the type of iron oxide core, the structure and composition of the shell, the coating characteristics, and the surface properties. Catalysts containing magnetite and manganese ferrite as core materials displayed higher catalytic activities per manganese ion (2650 or 3150 mmolO2 molMn(-1) h(-1)) or per mass than nanoiron oxides (no activity) or birnessite alone (1850 mmolO2 molMn(-1) h(-1)). This indicates synergistic effects between the MnOx shell and the FeOx core of the composites and proves the potential of the presented core-shell approach for further catalyst optimization. Additionally, the FeOx cores of the particles allow magnetic recovery of the catalyst and might also be beneficial for applications in water-oxidizing anodes because the incorporation of iron might enhance the overall conductivity of the material.

Water Oxidation Catalysis by Synthetic Manganese Oxides with Different Structural Motifs: A Comparative Study

Manganese oxides are considered to be very promising materials for water oxidation catalysis (WOC), but the structural parameters influencing their catalytic activity have so far not been clearly identified. For this study, a dozen manganese oxides (MnOx ) with various solid-state structures were synthesised and carefully characterised by various physical and chemical methods. WOC by the different MnOx was then investigated with Ce(4+) as chemical oxidant. Oxides with layered structures (birnessites) and those containing large tunnels (todorokites) clearly gave the best results with reaction rates exceeding 1250

A manganese oxido complex bearing facially coordinating trispyridyl ligands – is coordination geometry crucial for water oxidation catalysis?

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