title: Role of palladium in the redox electrochemistry of ferrocene monocarboxylic acid encapsulated within ORMOSIL networks.
abstract: We report herein the effect of palladium on the redox electrochemistry of ferrocene monocarboxylic acid encapsulated within an organically modified sol-gel glass network (ORMOSIL). It has been found that amount of palladium and its geometrical distribution significantly alter the redox electrochemistry of FcMCA. The geometrical distribution of palladium has been controlled by two methods: (i) palladium is allowed to link within nanostructured network of the ORMOSIL which was subsequently availed from the reactivity of palladium chloride and trimethoxysilane; (ii) palladium powder is encapsulated together FcMCA thus allowing the presence of palladium within the nanoporous domain. The content of palladium is varied by controlling the reaction dynamics of palladium chloride and trimethoxysilane interaction. For this we initially allowed to trigger hydrolysis, condensation and poly-condensation of trimethoxysilane and dimethyldiethoxysilane in acidic medium and subsequently partially dried ORMOSIL film was allowed to interact with palladium chloride. Even with partially dried ORMOSIL derived from trimethoxysilane and dimethyldiethoxysilane undergoes rapid interaction with palladium chloride and the transparent color of ORMOSIL changed to a black colour due to the formation of palladium silicon linkage. The palladium-silicon linkage has been identified by NMR, UV-VIS and transmission electron spectroscopy. The electrochemistry of FcMCA encapsulated within such an ORMOSIL matrix has been studied. Excellent redox electrochemistry of ferrocene monocarboxylic acid having peak potential separation tending to 0 for a multilayered electrode was investigated. The palladium content has been found to affect the redox electrochemistry of ferrocene as well as electrocatalytic efficiency of new ORMOSIL material. The electroanalysis of NADH is reported. The modified electrode is very sensitive to NADH with lowest detection limit of < 1 microM.
authors.affiliation: Department of Applied Chemistry, Institute of Technology, Banaras Hindu University, Varanasi-221, India. pcpandey@bhu.ac.in
authors.forename: P C
authors.initials: PC
authors.lastname: Pandey
authors.forename: B C
authors.initials: BC
authors.lastname: Upadhyay
mesh_terms: D002264:Carboxylic Acids; D004563:Electrochemistry / Q000379:methods*; D004566:Electrodes; D005296:Ferrous Compounds / Q000737:chemistry*; D000075163:Metallocenes; D009243:NAD; D010084:Oxidation-Reduction; D010165:Palladium / Q000737:chemistry*; D012833:Siloxanes / Q000737:chemistry*
chemical_list: D002264:Carboxylic Acids; D005296:Ferrous Compounds; D000075163:Metallocenes; D012833:Siloxanes; C510784:ormosil; D009243:NAD; D010165:Palladium; C004998:ferrocene