The Interaction of Water with Free Mn4O4+ Clusters: Deprotonation and Adsorption‐Induced Structural Transformations |
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| Authors: | Dr Sandra M Lang Prof?Dr Thorsten M Bernhardt Denis M Kiawi Dr Joost M Bakker Dr Robert N Barnett Prof?Dr Uzi Landman |
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| Institution: | 1. Institute of Surface Chemistry and Catalysis, University of Ulm, Albert‐Einstein‐Allee 47, 89069 Ulm (Germany);2. Radboud University, Institute for Molecules and Materials, FELIX Laboratory, Toernooiveld 7, 6525 ED Nijmegen (The Netherlands);3. Anton Pannekoek Institute, University of Amsterdam, Science Park 904, 1098 XH Amsterdam (The Netherlands);4. School of Physics, Georgia Institute of Technology, Atlanta, Georgia 30332‐0430 (United States) |
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| Abstract: | As the biological activation and oxidation of water takes place at an inorganic cluster of the stoichiometry CaMn4O5, manganese oxide is one of the materials of choice in the quest for versatile, earth‐abundant water splitting catalysts. To probe basic concepts and aid the design of artificial water‐splitting molecular catalysts, a hierarchical modeling strategy was employed that explores clusters of increasing complexity, starting from the tetramanganese oxide cluster Mn4O4+ as a molecular model system for catalyzed water activation. First‐principles calculations in conjunction with IR spectroscopy provide fundamental insight into the interaction of water with Mn4O4+, one water molecule at a time. All of the investigated complexes Mn4O4(H2O)n+ (n=1–7) contain deprotonated water with a maximum of four dissociatively bound water molecules, and they exhibit structural fluxionality upon water adsorption, inducing dimensional and structural transformations of the cluster core. |
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| Keywords: | ab initio calculations manganese oxide oxygen evolving complex vibrational spectroscopy water splitting |
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