Energetics and Kinetics of S-State Transitions Monitored by Delayed Chlorophyll Fluorescence

Understanding energetic and kinetic parameters of intermediates formed in the course of the reaction cycle (S-state cycle) of photosynthetic water oxidation is of high interest and could support the rationale designs of artificial systems for solar fuels. We use time-resolved measurements of the delayed chlorophyll fluorescence to estimate rate constants, activation energies, free energy differences, and to discriminate between the enthalpic and the entropic contributions to the decrease of the Gibbs free energy of the individual transitions. Using a joint-fit simulation approach, kinetic parameters are determined for the reaction intermediates in the S-state transitions in buffers with different pH in H2O and in D2O

Electrochemical water splitting by layered and 3D cross-linked manganese oxides: correlating structural motifs and catalytic activity

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.Manganese based precious metal-free electrocatalysts for the oxygen evolution reaction (OER) are promising materials for energy storage systems based on dark or photo-coupled water electrolysis, because they are active, inexpensive and of low toxicity. In this work, atomic scale structure–activity relationships of two different nano-structured manganese oxides, MnOx, are established using a combination of X-ray absorption, diffraction and electrochemistry. Prepared by chemical symproportionation (s-MnOx) and impregnation (i-MnOx), the s-MnOx catalyst consisted of a layered structure similar to δ-MnO2 while the i-MnOx catalyst displayed a mixture of tunnelled, 3D cross-linked β- and defective γ-MnO2 structures. During electrocatalytic oxygen evolution the structural motifs of both MnOx remain largely unchanged, but the oxidation state of Mn increases from 3.5 to 3.9–4. Kinetic parameters of the electrocatalytic oxygen evolution reaction were extracted using Tafel slope analysis and pH titration experiment, and the role of the protons abstracted was analyzed. The study reveals fundamental differences of general importance in the catalytic activity between layered and cross-linked structures. The exclusive presence of di-μ-oxo-bridged Mn ions in the layered structure is coupled to a pronounced redox and charge capacity behaviour. This ensured efficient use of surface and bulk active sites, and resulted in a relatively large Tafel slope. Consequently, the intrinsic OER activity is especially high in s-MnOx. In contrast, 3D cross-linked structures with both mono- and di-μ-oxo-bridged Mn ions resulted in lower intrinsic activity but smaller Tafel slope, and thus favourable activity at technological water-splitting rates. The insights from this comparative study will provide guidance in the structural design and optimization of other non precious metal oxide OER catalysts.DFG, EXC 314, Unifying Concepts in Catalysi

correlating structural motifs and catalytic activity

Manganese based precious metal-free electrocatalysts for the oxygen evolution reaction (OER) are promising materials for energy storage systems based on dark or photo-coupled water electrolysis, because they are active, inexpensive and of low toxicity. In this work, atomic scale structure–activity relationships of two different nano-structured manganese oxides, MnOx, are established using a combination of X-ray absorption, diffraction and electrochemistry. Prepared by chemical symproportionation (s-MnOx) and impregnation (i-MnOx), the s-MnOx catalyst consisted of a layered structure similar to δ-MnO2 while the i-MnOx catalyst displayed a mixture of tunnelled, 3D cross-linked β- and defective γ-MnO2 structures. During electrocatalytic oxygen evolution the structural motifs of both MnOx remain largely unchanged, but the oxidation state of Mn increases from 3.5 to 3.9–4. Kinetic parameters of the electrocatalytic oxygen evolution reaction were extracted using Tafel slope analysis and pH titration experiment, and the role of the protons abstracted was analyzed. The study reveals fundamental differences of general importance in the catalytic activity between layered and cross-linked structures. The exclusive presence of di-μ-oxo-bridged Mn ions in the layered structure is coupled to a pronounced redox and charge capacity behaviour. This ensured efficient use of surface and bulk active sites, and resulted in a relatively large Tafel slope. Consequently, the intrinsic OER activity is especially high in s-MnOx. In contrast, 3D cross-linked structures with both mono- and di-μ-oxo-bridged Mn ions resulted in lower intrinsic activity but smaller Tafel slope, and thus favourable activity at technological water- splitting rates. The insights from this comparative study will provide guidance in the structural design and optimization of other non precious metal oxide OER catalysts

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

Edge atoms effects on the perpendicular anisotropy of ultrathin magnetic layers

The present work reports experimental and theoretical results for electrodeposited Co/Au(111) ultrathin layers with very specific magnetic behavior. We show that the observed two peaks in the out-of-plane magnetization versus deposition time variation could be explained by the remarkably high perpendicular anisotropy of the perimeter atoms of low- dimensional islands formed during the layer-by-layer growth, as compared to that of the surface atoms. Our results indicate that it is possible to sustain high anisotropy in very small grains without coming across the superparamagnetic limit, opening excellent opportunities for materials engineering

Operando Raman spectroscopy tracks oxidation-state changes in an amorphous Co oxide material for electrocatalysis of the oxygen evolution reaction

Transition metal oxides are of high interest in both energy storage (batteries) and production of non-fossil fuels by (photo)electrocatalysis. Their functionally crucial charge (oxidation state) changes and electrocatalytic properties are best investigated under electrochemical operation conditions. We established operando Raman spectroscopy for investigation of the atomic structure and oxidation state of a non-crystalline, hydrated, and phosphate-containing Co oxide material (CoCat), which is an electrocatalyst for the oxygen evolution reaction (OER) at neutral pH and is structurally similar to LiCoO2 of batteries. Raman spectra were collected at various sub-catalytic and catalytic electric potentials. 2H labeling suggests Co oxidation coupled to Co—OH deprotonation at catalytic potentials. 18O labeling supports O—O bond formation starting from terminally coordinated oxygen species. Two broad bands around 877 cm−1 and 1077 cm−1 are assigned to CoCat-internal H2PO4-. Raman peaks corresponding to terminal oxide (Co=O) or reactive oxygen species were not detectable; 1000–1200 cm−1 bands were instead assigned to two-phonon Raman scattering. At an increasingly positive potential, the intensity of the Raman bands decreased, which is unexpected and explained by self-absorption relating to CoCat electrochromism. A red-shift of the Co—O Raman bands with increasing potentials was described by four Gaussian bands of potential-dependent amplitudes. By linear combination of Raman band amplitudes, we can follow individually the Co(2+/3+) and Co(3+/4+) redox transitions, whereas previously published x-ray absorption spectroscopy analysis could determine only the averaged Co oxidation state. Our results show how electrochemical operando Raman spectroscopy can be employed as a potent analytical tool in mechanistic investigations on OER catalysis

Edge atoms effects on the perpendicular anisotropy of ultrathin magnetic layers

The present work reports experimental and theoretical results for electrodeposited Co/Au(111) ultrathin layers with very specific magnetic behavior. We show that the observed two peaks in the out-of-plane magnetization versus deposition time variation could be explained by the remarkably high perpendicular anisotropy of the perimeter atoms of low-dimensional islands formed during the layer-by-layer growth, as compared to that of the surface atoms. Our results indicate that it is possible to sustain high anisotropy in very small grains without coming across the superparamagnetic limit, opening excellent opportunities for materials engineering

Cyanamide route to calcium-manganese oxide foams for water oxidation

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.In nature, photosynthetic water oxidation is efficiently catalysed at a protein-bound μ-oxido Mn4Ca cluster. This cluster consists of earth abundant, non-toxic elements and serves as a paragon for development of synthetic catalysts. In this study we developed porous calcium–manganese oxides with a unique foam-like nanostructure prepared via a facile and robust synthetic route using cyanamide as a porogen. A series of such oxide foams annealed at different temperatures was characterized by TEM, SEM, XRD, N2 physisorption, and X-ray absorption spectroscopy (XAS) in order to correlate crystallinity, atomic structure, surface area and oxidation state of the materials with catalytic activity. Some of the resulting Ca–Mn oxides show high activity as catalysts for water oxidation in the presence of cerium(IV) ammonium nitrate as a non-oxo transfer oxidant. An amorphous calcium–manganese-oxide foam with 130 m2 g−1 surface area and Mn oxidation state of +3.6 was identified to be most active; its activity is superior to previously reported Ca–Mn oxides. At the atomic level, this material shares structural motifs with the biological paragon as revealed by dual-edge XAS at the Mn and Ca K-edge. Rather than nanostructure and surface area, the atomic structure of the Ca–Mn oxide and the extent of structural order appear to be crucial determinants of catalytic activity. Fully disordered low-valent Mn materials as well as high-valent but crystalline Mn–Ca oxides are unreactive. Highly disordered variants of layered manganese oxide with Ca and water molecules interfacing layer fragments are most reactive.DFG, EXC 314, Unifying Concepts in Catalysi

Syntheses, Electrode Preparations, Electrolytes and Two Fundamental Questions

The efficient catalysis of the four-electron oxidation of water to molecular oxygen is a central challenge for the development of devices for the production of solar fuels. This is equally true for artificial leaf-type structures and electrolyzer systems. Inspired by the oxygen evolving complex of Photosystem II, the biological catalyst for this reaction, scientists around the globe have investigated the possibility to use manganese oxides (“MnOx”) for this task. This perspective article will look at selected examples from the last about 10 years of research in this field. At first, three aspects are addressed in detail which have emerged as crucial for the development of efficient electrocatalysts for the anodic oxygen evolution reaction (OER): (1) the structure and composition of the “MnOx” is of central importance for catalytic performance and it seems that amorphous, MnIII/IV oxides with layered or tunnelled structures are especially good choices; (2) the type of support material (e.g. conducting oxides or nanostructured carbon) as well as the methods used to immobilize the MnOx catalysts on them greatly influence OER overpotentials, current densities and long-term stabilities of the electrodes and (3) when operating MnOx-based water-oxidizing anodes in electrolyzers, it has often been observed that the electrocatalytic performance is also largely dependent on the electrolyte’s composition and pH and that a number of equilibria accompany the catalytic process, resulting in “adaptive changes” of the MnOx material over time. Overall, it thus has become clear over the last years that efficient and stable water-oxidation electrolysis by manganese oxides can only be achieved if at least four parameters are optimized in combination: the oxide catalyst itself, the immobilization method, the catalyst support and last but not least the composition of the electrolyte. Furthermore, these parameters are not only important for the electrode optimization process alone but must also be considered if different electrode types are to be compared with each other or with literature values from literature. Because, as without their consideration it is almost impossible to draw the right scientific conclusions. On the other hand, it currently seems unlikely that even carefully optimized MnOx anodes will ever reach the superb OER rates observed for iridium, ruthenium or nickel-iron oxide anodes in acidic or alkaline solutions, respectively. So at the end of the article, two fundamental questions will be addressed: (1) are there technical applications where MnOx materials could actually be the first choice as OER electrocatalysts? and (2) do the results from the last decade of intensive research in this field help to solve a puzzle already formulated in 2008: “Why did nature choose manganese to make oxygen?”

the influence of phosphate on structure and activity

Two types of manganese oxides have been prepared by hydrolysis of tetranuclear Mn(III) complexes in the presence or absence of phosphate ions. The oxides have been characterized structurally using X-ray absorption spectroscopy and functionally by O2 evolution measurements. The structures of the oxides prepared in the absence of phosphate are dominated by di-μ-oxo bridged manganese ions that form layers with limited long-range order, consisting of edge-sharing MnO6 octahedra. The average manganese oxidation state is +3.5. The structure of these oxides is closely related to other manganese oxides reported as water oxidation catalysts. They show high oxygen evolution activity in a light-driven system containing [Ru(bpy)3]2+ and S2O82− at pH 7. In contrast, the oxides formed by hydrolysis in the presence of phosphate ions contain almost no di-μ-oxo bridged manganese ions. Instead the phosphate groups are acting as bridges between the manganese ions. The average oxidation state of manganese ions is +3. This type of oxide has much lower water oxidation activity in the light-driven system. Correlations between different structural motifs and the function as a water oxidation catalyst are discussed and the lower activity in the phosphate containing oxide is linked to the absence of protonable di-μ-oxo bridges