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Chemical Structure| 7782-85-6 Chemical Structure| 7782-85-6
Chemical Structure| 7782-85-6

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Kessinger, Matthew ; Whittemore, Thomas ; Grandi, Silvia ; Danilov, Evgeny O ; Caramori, Stefano ; Castellano, Felix N , et al.

Abstract: The oxidation of metal-aquo and -hydroxo complexes to generate the high-valent metal-oxo species used in oxidative catalysis is often kinetically slow due to sluggish proton transfer between ligated −H2O/−OH in the proton-coupled electron transfer (PCET) chemistry. In this research, a ruthenium water oxidation catalyst anchored to a conductive tin-doped indium oxide (ITO) thin film, abbreviated ITO|RuII−OH2, was characterized by spectroscopic and electrochemical methods in acetate or phosphate buffers. The deprotonated intermediate, RuII−OH, was observed spectroscopically in the PCET half-reaction ITO(e-)|RuIII−OH + H+ → ITO| RuII−OH2 indicating an underlying stepwise ET-PT mechanism. In contrast, at elevated buffer concentrations, this intermediate was absent, and a 2−4 order of magnitude increase in the proton transfer rate constant was observed. Kinetic data for this PCET reaction measured as a function of the driving force provided the reorganization energy λ = 1.05 eV and was assigned to a concerted electron−proton transfer (EPT) mechanism. In addition, the standard heterogeneous rate constants for two PCET equilibria, RuIII−OH + H+ + e- ⇌ RuII−OH2 and RuIV = O + H+ + e- ⇌ RuIII−OH were enhanced by these same buffers. Collectively, the data show that the added buffers can enhance the kinetics and thermodynamics for PCET reactions relevant to oxidative catalysis.

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Product Details of Sodium phosphate dibasic heptahydrate

CAS No. :7782-85-6
Formula : H15Na2O11P
M.W : 268.07
SMILES Code : O=P([O-])([O-])O.[H]O[H].[H]O[H].[H]O[H].[H]O[H].[H]O[H].[H]O[H].[H]O[H].[Na+].[Na+]
English Name :Sodium phosphate dibasic heptahydrate
MDL No. :MFCD00149180
InChI Key :PYLIXCKOHOHGKQ-UHFFFAOYSA-L
Pubchem ID :6096963

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