Hydrogen peroxide reaction with platinum

The first reported porphyrin complexes of platinum(IV) date from 1980 and were obtained by hydrogen peroxide oxidation of platinum(II) porphyrin complexes in an acidic medium (HC1).479 Since then oxidation of platinum(II) complexes of other porphyrins has been achieved by the same method,480 and by chlorine,481 or bromine482 oxidation. Reaction with iodine did not lead to oxidation and treatment of platinum(IV) porphyrin complexes with iodide resulted in reduction to platinum(II). 

Our approach utilized the metals gold, platinum, then later gold, platinum, and nickel electroplated in succession because the catalytic decomposition of hydrogen peroxide reaction we tested was most efficiently catalyzed with platinum.After fabrication of the nanowires they were freed by removing the conductive silver backing with nitric acid and the sacrificial template with a strong base, sodium hydroxide. Then nanorods were washed with deionized water and ultracentrifuged to achieve a neutral pH. 

The reduction of hydrogen peroxide (reaction 14 or 15) may start with either an electrochemical step [10,55,56] or a chemical step [23, 24,57—59]. Molecular oxygen should be formed if the Haber-Grinberg mechanism [60] of the catalytic decomposition of H2O2 on platinum... 

The electrolytic processes for commercial production of hydrogen peroxide are based on (/) the oxidation of sulfuric acid or sulfates to peroxydisulfuric acid [13445-49-3] (peroxydisulfates) with the formation of hydrogen and (2) the double hydrolysis of the peroxydisulfuric acid (peroxydisulfates) to Caro s acid and then hydrogen peroxide. To avoid electrolysis of water, smooth platinum electrodes are used because of the high oxygen overvoltage. The overall reaction is... 

When the electrode is placed in an aqueous solution of glucose which has been suitably diluted with a phosphate buffer solution (pH 7.3), solution passes through the outer membrane into the enzyme where hydroxen peroxide is produced. Hydrogen peroxide can diffuse through the inner membrane which, however, is impermeable to other components of the solution. The electrode vessel contains phosphate buffer, a platinum wire and a silver wire which act as electrodes. A potential of 0.7 volts is applied to the electrodes (the apparatus shown in Fig. 16.17 is suitable) with the platinum wire as anode. At this electrode the reaction H202->02 + 2H+ +2e takes place, and the oxygen produced is reduced at the silver cathode ... 

Attempted reaction of 1,3-pentadiene with the optically active diboron derived from dialkyl tartrate in the presence of a phosphine-free platinum catalyst gave poor diastereoselectivity (20% de).63 Better selectivity has been attained with a modified platinum catalyst bearing a PCy3 ligand (Scheme 6).64 The reaction of allylborane thus obtained with an aldehyde followed by oxidation with basic hydrogen peroxide affords the corresponding diol derivative with moderate ee. 

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