Proton pump for O2 reduction catalyzed by 5,10,15,20-tetraphenylporphyrinatocobalt(II).
نویسندگان
چکیده
The role of 5,10,15,20-tetraphenylporphyrinatocobalt(II) ([Co(tpp)]) as a catalyst on molecular oxygen (O(2)) reduction by ferrocene (Fc) and its two derivatives, 1,1'-dimethylferrocene (DFc) and decamethylferrocene (DMFc) at a polarized water|1,2-dichloroethane (DCE) interface has been studied. The water|DCE interface essentially acts as a proton pump controlled by the Galvani potential difference across the interface, driving the proton transfer from water to DCE. [Co(tpp)] catalyzed O(2) reduction by Fc, DFc and DMFc is then followed to produce hydrogen peroxide (H(2)O(2)). The catalytic mechanism is similar to that proposed by Fukuzumi et al. for bulk reactions. This interfacial system provides a platform for a very efficient collection of H(2)O(2), by extraction immediately after its formation in DCE to the adjacent water phase, thus decreasing the possibility of degradation and further reaction with ferrocene derivatives.
منابع مشابه
Efficient water oxidation catalyzed by homogeneous cationic cobalt porphyrins with critical roles for the buffer base.
A series of cationic cobalt porphyrins was found to catalyze electrochemical water oxidation to O2 efficiently at room temperature in neutral aqueous solution. Co-5,10,15,20-tetrakis-(1,3-dimethylimidazolium-2-yl)porphyrin, with a highly electron-deficient meso-dimethylimidazolium porphyrin, was the most effective catalyst. The O2 formation rate was 170 nmol · cm(-2) · min(-1) (k(obs) = 1.4 × 1...
متن کاملRedox-driven membrane-bound proton pumps.
In recent years, remarkable progress has been made in our understanding of the structure and function of membrane-bound proton transporters at the molecular level. Perhaps the most challenging and complex of these molecular machines are the haem–copper oxidases. These enzymes are designed to activate the kinetically stable O2 molecule, to prevent the release of potentially toxic oxygen intermed...
متن کاملEnabling rechargeable non-aqueous Mg-O2 battery operations with dual redox mediators.
Dual redox mediators (RMs) were introduced for Mg-O2 batteries. 1,4-Benzoquinone (BQ) facilitates the discharge with an overpotential reduction of 0.3 V. 5,10,15,20-Tetraphenyl-21H,23H-porphine cobalt(ii) (Co(ii)TPP) facilitates the recharge with an overpotential decrease of up to 0.3 V. Importantly, the two redox mediators are compatible in the same DMSO-based electrolyte.
متن کاملX-ray structure and reaction mechanism of bovine heart cytochrome c oxidase.
X-ray structure of bovine heart cytochrome c oxidase in the fully oxidized state shows a peroxide bridging between Fe2+ and Cu2+ in the O2 reduction site. The bond distances for Fe-O and Cu-O are 2.52 and 2.16 A, respectively. The structure is consistent with antiferromagnetic coupling between the two metals, which has long been known and to recent redox titration results [J. Biol. Chem. 274 (1...
متن کاملMutation of a single residue in the ba3 oxidase specifically impairs protonation of the pump site.
The ba3-type cytochrome c oxidase from Thermus thermophilus is a membrane-bound protein complex that couples electron transfer to O2 to proton translocation across the membrane. To elucidate the mechanism of the redox-driven proton pumping, we investigated the kinetics of electron and proton transfer in a structural variant of the ba3 oxidase where a putative "pump site" was modified by replace...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Chemistry
دوره 15 10 شماره
صفحات -
تاریخ انتشار 2009