TY - JOUR
T1 - An exceptionally fast homogeneous carbon-free cobalt-based water oxidation catalyst
AU - Lv, Hongjin
AU - Song, Jie
AU - Geletii, Yurii V.
AU - Vickers, James W.
AU - Sumliner, Jordan M.
AU - Musaev, Djamaladdin G.
AU - Kögerler, Paul
AU - Zhuk, Petro F.
AU - Bacsa, John
AU - Zhu, Guibo
AU - Hill, Craig L.
PY - 2014/7/2
Y1 - 2014/7/2
N2 - An all-inorganic, oxidatively and thermally stable, homogeneous water oxidation catalyst based on redox-active (vanadate(V)-centered) polyoxometalate ligands, Na10[Co4(H2O)2(VW 9O34)2]·35H2O (Na 101-V2, sodium salt of the polyanion 1-V2), was synthesized, thoroughly characterized and shown to catalyze water oxidation in dark and visible-light-driven conditions. This synthetic catalyst is exceptionally fast under mild conditions (TOF > 1 × 103 s-1). Under light-driven conditions using [Ru(bpy)3]2+ as a photosensitizer and persulfate as a sacrificial electron acceptor, 1-V2 exhibits higher selectivity for water oxidation versus bpy ligand oxidation, the final O2 yield by 1-V2 is twice as high as that of using [Co 4(H2O)2(PW9O34) 2]10- (1-P2), and the quantum efficiency of O2 formation at 6.0 μM 1-V2 reaches ∼68%. Multiple experimental results (e.g., UV-vis absorption, FT-IR, 51V NMR, dynamic light scattering, tetra-n-heptylammonium nitrate-toluene extraction, effect of pH, buffer, and buffer concentration, etc.) confirm that the polyanion unit (1-V2) itself is the dominant active catalyst and not Co2+(aq) or cobalt oxide.
AB - An all-inorganic, oxidatively and thermally stable, homogeneous water oxidation catalyst based on redox-active (vanadate(V)-centered) polyoxometalate ligands, Na10[Co4(H2O)2(VW 9O34)2]·35H2O (Na 101-V2, sodium salt of the polyanion 1-V2), was synthesized, thoroughly characterized and shown to catalyze water oxidation in dark and visible-light-driven conditions. This synthetic catalyst is exceptionally fast under mild conditions (TOF > 1 × 103 s-1). Under light-driven conditions using [Ru(bpy)3]2+ as a photosensitizer and persulfate as a sacrificial electron acceptor, 1-V2 exhibits higher selectivity for water oxidation versus bpy ligand oxidation, the final O2 yield by 1-V2 is twice as high as that of using [Co 4(H2O)2(PW9O34) 2]10- (1-P2), and the quantum efficiency of O2 formation at 6.0 μM 1-V2 reaches ∼68%. Multiple experimental results (e.g., UV-vis absorption, FT-IR, 51V NMR, dynamic light scattering, tetra-n-heptylammonium nitrate-toluene extraction, effect of pH, buffer, and buffer concentration, etc.) confirm that the polyanion unit (1-V2) itself is the dominant active catalyst and not Co2+(aq) or cobalt oxide.
UR - http://www.scopus.com/inward/record.url?scp=84903702805&partnerID=8YFLogxK
U2 - 10.1021/ja5045488
DO - 10.1021/ja5045488
M3 - Article
AN - SCOPUS:84903702805
SN - 0002-7863
VL - 136
SP - 9268
EP - 9271
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 26
ER -