Electronic Supplementary Information ( ESI ) Ambient Rutile VO 2 ( R ) Hollow Hierarchitectures with Rich Grain Boundaries from New-State Nsutite-Type VO 2 , Displaying Enhanced Hydrogen Adsorption Behavior
S1. Shape evolution of the new-state VO 2 hollow spherical nanoarchitectures S2. Compositional characterization of the new-state nsutite-type VO 2 precursor S3. Summary XRD patterns of the nsutite-type VO 2 prepared by different chemical reactions S4. Structural determination of new-state VO 2 S5. Calculation details and phase conversion process from the new-state nsutite-type VO 2 to rutile VO 2 (R) S6. Characterization of the GBR-VO 2 (R) hollow hierarchitectures S7. Gas adsorption experiments of different vanadium oxides
Electronic Supplementary Information
Giuseppe Mattioli, 2, ∗ Marcel Risch, Aldo Amore Bonapasta, Holger Dau, and Leonardo Guidoni 2, † Istituto di Struttura della Materia (ISM) del Consiglio Nazionale delle Ricerche, Via Salaria Km 29.5, CP 10, 00016 Monterotondo Stazione, Italy Dept. of Physics, “Sapienza” Università di Roma, P.le A. Moro 2, 00185 Roma, Italy Dept. of Physics, Freie Universität Berlin, Arnimallee 14, 14195 Berlin, Germany Dipartimento di Chimica, Ingegneria Chimica e Materiali, Università de L’Aquila, Località Campo di Pile, 67100 L’Aquila, Italy
[Ni]
How do [NiFe] hydrogenases activate H(2)? Hydrogenases are key enzymes in the biological hydrogen and energy metabolism; the mechanism of H(2) activation, however, is unclarified. In particular, the oxidation states of the metals involved are discussed controversially. The title complex demonstrates that a distorted diamagnetic Ni(II) center and thiolate donors are sufficient (see picture) to catalyze the key reaction of hydrogenases, the H(2) heterolysis.