Making Oxygen with Ruthenium Complexes
ABSTRACT Mastering the production of solar fuels by artificial photosynthesis would be a considerable feat, either by water splitting into hydrogen and oxygen or reduction of CO(2) to methanol or hydrocarbons: 2H(2)O + 4hnu --> O(2) + 2H(2); 2H(2)O + CO(2) + 8hnu --> 2O(2) + CH(4). It is notable that water oxidation to dioxygen is a key half-reaction in both. In principle, these solar fuel reactions can be coupled to light absorption in molecular assemblies, nanostructured arrays, or photoelectrochemical cells (PECs) by a modular approach. The modular approach uses light absorption, electron transfer in excited states, directed long range electron transfer and proton transfer, both driven by free energy gradients, combined with proton coupled electron transfer (PCET) and single electron activation of multielectron catalysis. Until recently, a lack of molecular catalysts, especially for water oxidation, has limited progress in this area. Analysis of water oxidation mechanism for the "blue" Ru dimer cis,cis-[(bpy)(2)(H(2)O)Ru(III)ORu(III)(OH(2))(bpy)(2)](4+) (bpy is 2,2'-bipyridine) has opened a new, general approach to single site catalysts both in solution and on electrode surfaces. As a catalyst, the blue dimer is limited by competitive side reactions involving anation, but we have shown that its rate of water oxidation can be greatly enhanced by electron transfer mediators such as Ru(bpy)(2)(bpz)(2+) (bpz is 2,2'-bipyrazine) in solution or Ru(4,4'-((HO)(2)P(O)CH(2))(2)bpy)(2)(bpy)(2+) on ITO (ITO/Sn) or FTO (SnO(2)/F) electrodes. In this Account, we describe a general reactivity toward water oxidation in a class of molecules whose properties can be "tuned" systematically by synthetic variations based on mechanistic insight. These molecules catalyze water oxidation driven either electrochemically or by Ce(IV). The first two were in the series Ru(tpy)(bpm)(OH(2))(2+) and Ru(tpy)(bpz)(OH(2))(2+) (bpm is 2,2'- bipyrimidine; tpy is 2,2':6',2''-terpyridine), which undergo hundreds of turnovers without decomposition with Ce(IV) as oxidant. Detailed mechanistic studies and DFT calculations have revealed a stepwise mechanism: initial 2e(-)/2H(+) oxidation, to Ru(IV)=O(2+), 1e(-) oxidation to Ru(V)=(3+), nucleophilic H(2)O attack to give Ru(III)-OOH(2+), further oxidation to Ru(IV)(O(2))(2+), and, finally, oxygen loss, which is in competition with further oxidation of Ru(IV)(O(2))(2+) to Ru(V)(O(2))(3+), which loses O(2) rapidly. An extended family of 10-15 catalysts based on Mebimpy (Mebimpy is 2,6-bis(1-methylbenzimidazol-2-yl)pyridine), tpy, and heterocyclic carbene ligands all appear to share a common mechanism. The osmium complex Os(tpy)(bpy)(OH(2))(2+) also functions as a water oxidation catalyst. Mechanistic experiments have revealed additional pathways for water oxidation one involving Cl(-) catalysis and another, rate enhancement of O-O bond formation by concerted atom-proton transfer (APT). Surface-bound [(4,4'-((HO)(2)P(O)CH(2))(2)bpy)(2)Ru(II)(bpm)Ru(II)(Mebimpy)(OH(2))](4+) and its tpy analog are impressive electrocatalysts for water oxidation, undergoing thousands of turnovers without loss of catalytic activity. These catalysts were designed for use in dye-sensitized solar cell configurations on TiO(2) to provide oxidative equivalents by molecular excitation and excited-state electron injection. Transient absorption measurements on TiO(2)-[(4,4'((HO)(2)P(O)CH(2))(2)bpy)(2)Ru(II)(bpm)Ru(II)(Mebimpy)(OH(2))](4+), (TiO(2)-Ru(II)-Ru(II)OH(2)) and its tpy analog have provided direct insight into the interfacial and intramolecular electron transfer events that occur following excitation. With added hydroquinone in a PEC configuration, APCE (absorbed-photon-to-current-efficiency) values of 4-5% are obtained for dehydrogenation of hydroquinone, H(2)Q + 2hnu --> Q + H(2). In more recent experiments, we are using the same PEC configuration to investigate water splitting.
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ABSTRACT: Luminescence and imaging studies of 500 nm diameter colloidal silica stained with the transition metal complex [Ru(bpy)3Cl2], [Ru(bpy)3⊂SiNP], have been detailed and suggest that such particles are ideal for particle tracking velocimetry (PTV) or particle imaging velocimetry (PIV) for analysis of fluid flow in microchannels. Silica particles were synthesized using a modification to the St¨ober synthesis to cage the transition metal complex within the core of the nanoscale particles. The particles [Ru(bpy)3⊂SiNP] exhibit luminescence at 620 nm, characteristic of the caged [Ru(bpy)3]2+ species with a lifetime of 790 ns upon excitation at 450 nm. A collection of the luminescence spectra from the images of the particles in a microchannel have the same profile as the spectra collected from solutions of [Ru(bpy)3⊂SiNP], confirming that the luminescence images are attributed to [Ru(bpy)3]2+ luminescence. PIV and PTV measurements from image sequences give flow velocities that match well with the theoretical velocity profile for a rectangular-sided microchannel of 100 μm depth.Measurement Science and Technology 06/2012; 23(8):084004. DOI:10.1088/0957-0233/23/8/084004 · 1.35 Impact Factor
- Manganese: Chemical Properties, Medicinal Uses and Environmental Effects, Edited by Shu Tian Gan and Hui Rong Kong, 01/2012: chapter 2: pages 27-50; Nova Science Publishers.
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ABSTRACT: Deltahedral Zintl ions Ge94- are disubstituted with organic fragments that have various functional groups. Some of the latter are appropriate for coordination to transition-metals to eventually form coordination compounds where the organo-Zintl species act as ligands. Examples of [Ge9R2]2- include R = –CHCH-Im(Me), –CHCH–C6H4–OMe, –CHCH-Fc, –CHCH–(CH2)4–CCH, –CHCH–C6H4–CCH, CHCH–C6H4–NH2, CHCH-Py, –CHCH–(CH2)3–CN, –CHCHCH(OEt)2, –C(CH3)2CCH. Furthermore, the reported coexistence of [Fe(en)3]2+ and [Ge9-(CHCH-Fc)2]2- in the structure of [Fe(en)3][Ge9-(CHCH-Fc)2]•3.5en shows that some transition metals in 2 + oxidation state may not oxidize the disubstituted clusters and could potentially coordinate to them.Journal of Organometallic Chemistry 12/2012; s 721–722:85–91. DOI:10.1016/j.jorganchem.2012.05.006 · 2.30 Impact Factor