TY - JOUR
T1 - Electrochemically Driven Water Oxidation by a Highly Active Ruthenium-Based Catalyst
AU - Shatskiy, Andrey
AU - Bardin, Andrey A.
AU - Oschmann, Michael
AU - Matheu, Roc
AU - Benet-Buchholz, Jordi
AU - Eriksson, Lars
AU - Kärkäs, Markus D.
AU - Johnston, Eric V.
AU - Gimbert-Suriñach, Carolina
AU - Llobet, Antoni
AU - Åkermark, Björn
PY - 2019/5/21
Y1 - 2019/5/21
N2 - © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The highly active ruthenium-based water oxidation catalyst [Ru X (mcbp)(OH n )(py) 2 ] [mcbp 2− =2,6-bis(1-methyl-4-(carboxylate)benzimidazol-2-yl)pyridine; n=2, 1, and 0 for X=II, III, and IV, respectively], can be generated in a mixture of Ru III and Ru IV states from either [Ru II (mcbp)(py) 2 ] or [Ru III (Hmcbp)(py) 2 ] 2+ precursors. The precursor complexes are isolated and characterized by single-crystal X-ray analysis, NMR, UV/Vis, EPR, and FTIR spectroscopy, ESI-HRMS, and elemental analysis, and their redox properties are studied in detail by electrochemical and spectroscopic methods. Unlike the parent catalyst [Ru(tda) (py) 2 ] (tda 2− =[2,2′:6′,2′′-terpyridine]-6,6′′-dicarboxylate), for which full transformation into the catalytically active species [Ru IV (tda)(O)(py) 2 ] could not be carried out, stoichiometric generation of the catalytically active Ru–aqua complex [Ru X (mcbp)(OH n )(py) 2 ] from the Ru II precursor was achieved under mild conditions (pH 7.0) and short reaction times. The redox properties of the catalyst were studied and its activity for electrocatalytic water oxidation was evaluated, reaching a maximum turnover frequency (TOF max ) of around 40 000 s −1 at pH 9.0 (from foot-of-the-wave analysis), which is comparable to the activity of the state-of-the-art catalyst [Ru IV (tda)(O)(py) 2 ].
AB - © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim The highly active ruthenium-based water oxidation catalyst [Ru X (mcbp)(OH n )(py) 2 ] [mcbp 2− =2,6-bis(1-methyl-4-(carboxylate)benzimidazol-2-yl)pyridine; n=2, 1, and 0 for X=II, III, and IV, respectively], can be generated in a mixture of Ru III and Ru IV states from either [Ru II (mcbp)(py) 2 ] or [Ru III (Hmcbp)(py) 2 ] 2+ precursors. The precursor complexes are isolated and characterized by single-crystal X-ray analysis, NMR, UV/Vis, EPR, and FTIR spectroscopy, ESI-HRMS, and elemental analysis, and their redox properties are studied in detail by electrochemical and spectroscopic methods. Unlike the parent catalyst [Ru(tda) (py) 2 ] (tda 2− =[2,2′:6′,2′′-terpyridine]-6,6′′-dicarboxylate), for which full transformation into the catalytically active species [Ru IV (tda)(O)(py) 2 ] could not be carried out, stoichiometric generation of the catalytically active Ru–aqua complex [Ru X (mcbp)(OH n )(py) 2 ] from the Ru II precursor was achieved under mild conditions (pH 7.0) and short reaction times. The redox properties of the catalyst were studied and its activity for electrocatalytic water oxidation was evaluated, reaching a maximum turnover frequency (TOF max ) of around 40 000 s −1 at pH 9.0 (from foot-of-the-wave analysis), which is comparable to the activity of the state-of-the-art catalyst [Ru IV (tda)(O)(py) 2 ].
KW - artificial photosynthesis
KW - electrocatalysis
KW - homogeneous catalysis
KW - ruthenium
KW - water oxidation
UR - http://www.mendeley.com/research/electrochemically-driven-water-oxidation-highly-active-rutheniumbased-catalyst
U2 - 10.1002/cssc.201900097
DO - 10.1002/cssc.201900097
M3 - Article
C2 - 30759324
SN - 1864-5631
VL - 12
SP - 2251
EP - 2262
JO - ChemSusChem
JF - ChemSusChem
ER -