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| - Electrochemical Deposition of Biferrocene Derivative-Attached Gold Nanoparticles and theMorphology of the Formed Film
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| - The electrodeposition phenomenon of octyl thiolate-stabilized gold nanoparticles with a 2.3 ± 0.5 nm corediameter modified with biferrocene-terminated alkanethiolates on their surface (Aun−BFc) has been investigatedusing cyclic voltammetry, STM and AFM morphological observation, and electrochemical quartz crystalmicrobalance (EQCM) of the deposited Aun−BFc film. Consecutive potential scans causing two-step one-electron oxidation of the biferrocene units of Aun−BFc in CH2Cl2 electrolyte solution produce the adhesiveAun−BFc film on electrode surface. The deposition rate is lower for the biferrocene derivative on one particleθBFc with a smaller modification number and a kind of electrolyte anion: ClO4- ∼ BF4- ≫ PF6-. The STMand AFM images have revealed that the thickness of the Aun−BFc film grows gradually by increasing thenumber of cyclic scans, forming many monolayer-level domains with ca. 80 nm diameter of the assembledAun−BFcs. The average interparticle spacing of neighboring Aun−BFcs in the film is 7.5 nm, which is longerthan the estimated diameter of whole Aun−BFc species (5.9 nm). Analysis of boron in the film electrodepositedin Bu4NBF4−CH2Cl2 by the prompt γ-ray neutron activation (PGA) method shows that the BF4- ion isincorporated in the film. EQCM measurement suggests that not only ions but also the included CH2Cl2 solventmolecules in the film are moved in and out reversibly in a potential range of E0‘2 of Aun−BFc. These resultsindicate that the formation of ionic lattice including Aun−BFc2+ and counterion is accompanied by the exclusionof CH2Cl2 solvent molecules among the particles in the initial deposition process.
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