The activity of three [Cp*IrL(n)] (Cp* = pentamethylcyclopentadienyl) archetypal catalysts ([Cp*Ir (bpy)Cl]Cl (1, bpy = 2,2'-bipyridine), [Cp*Ir(bzpy)(NO(3))] (2, bzpy = 2-benzoylpyridine) and [Cp*Ir(H(2)O)(3)](NO(3))(2) (3)) for water oxidation to molecular oxygen was compared using cerium(IV) ammonium nitrate as a sacrificial oxidant. Kinetic studies were carried out by: i) measuring the depletion of Ce(4+) through UV-Vis spectroscopy, ii) directly detecting the evolved oxygen through the Clark electrode and iii) measuring the volume of the evolved oxygen. The kinetics of Ce(4+) consumption were zero-order in Ce(4+) for catalysts 2 and 3, while they were first-order for 1. The order with respect to catalyst was 1 for 1 and 2 while it was 1.5 for 3. As a consequence, 2 (TOF(max) = 14.4 min(-1)) and 3 (TOF(max) = 50.4 min(-1)) were found to be the most active catalysts at low and high catalyst concentration, respectively, while the performance of 1 (TOF(max) = 8.6 min(-1)) increased with increasing the concentration of Ce4(+.) 1 and 3 were found to be the most robust catalysts at low (3.1 mu M, TON = 1240) and high (7.0 mu M, TON = 4042) catalyst concentration, respectively. In situ NMR studies were performed under exactly the same conditions of the catalytic experiments. It was observed that Cp* underwent an oxidative degradation, ultimately leading to acetic, formic and glycolic acids. Several Ir-containing intermediates of the degradation process were intercepted and fully characterized in solution through 1D- and 2D-NMR experiments. DFT and NMR studies indicated that the degradation proceeds via an initial double oxidative functionalization of both the quanternary carbon and proton of a Cp* C-CH(3) moiety.

Activity and degradation pathways of pentamethyl-cyclopentadienyl-iridium catalysts for water oxidation

ZUCCACCIA, Daniele;
2011

Abstract

The activity of three [Cp*IrL(n)] (Cp* = pentamethylcyclopentadienyl) archetypal catalysts ([Cp*Ir (bpy)Cl]Cl (1, bpy = 2,2'-bipyridine), [Cp*Ir(bzpy)(NO(3))] (2, bzpy = 2-benzoylpyridine) and [Cp*Ir(H(2)O)(3)](NO(3))(2) (3)) for water oxidation to molecular oxygen was compared using cerium(IV) ammonium nitrate as a sacrificial oxidant. Kinetic studies were carried out by: i) measuring the depletion of Ce(4+) through UV-Vis spectroscopy, ii) directly detecting the evolved oxygen through the Clark electrode and iii) measuring the volume of the evolved oxygen. The kinetics of Ce(4+) consumption were zero-order in Ce(4+) for catalysts 2 and 3, while they were first-order for 1. The order with respect to catalyst was 1 for 1 and 2 while it was 1.5 for 3. As a consequence, 2 (TOF(max) = 14.4 min(-1)) and 3 (TOF(max) = 50.4 min(-1)) were found to be the most active catalysts at low and high catalyst concentration, respectively, while the performance of 1 (TOF(max) = 8.6 min(-1)) increased with increasing the concentration of Ce4(+.) 1 and 3 were found to be the most robust catalysts at low (3.1 mu M, TON = 1240) and high (7.0 mu M, TON = 4042) catalyst concentration, respectively. In situ NMR studies were performed under exactly the same conditions of the catalytic experiments. It was observed that Cp* underwent an oxidative degradation, ultimately leading to acetic, formic and glycolic acids. Several Ir-containing intermediates of the degradation process were intercepted and fully characterized in solution through 1D- and 2D-NMR experiments. DFT and NMR studies indicated that the degradation proceeds via an initial double oxidative functionalization of both the quanternary carbon and proton of a Cp* C-CH(3) moiety.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11390/949757
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