Anion adsorption behavior on Au colloid surface was investigated in virture of depositing monolayers of Au colloid on the self-assembled monolayers of cysteamine on a gold electrode. Po- tential-dependent anion adsorption-desorption waves via the nonfaradaic current were obtained by means of cyclic voltammetry at Au coltoid-modified gold electrodes in the potential range of -2 00-600 mV. The adsorption sequence in the order of adsorption peak potentials (Epa) is OH- >citrate3 ->H2PO4- >Cl->SO42->ClO4->NO3-. Among them, citrate3- exhibited an en- tirely irreversible adsorption. A rise in temperature can increase the rates of adsorption-desorp- tion and improve the reversibility of the adsorption-desorption of Cl-, SO42-, ClO4-, NO3- and H2PO-4. The adsorption peak potentials shifted more negatively for Ca. 63 mV as the anion con- centrations were increased by a decade factor. The change of pH from 7 to 1 slightly affected the adsorption peak potentials of Cl- and NO3-. Au colloids with a smaller size (16 nm) gave rise to a better reversibility of the adsorption-desorption process and lower adsorption currents. The ex- perimental results of citrate ions adsorption on Au colloid surface show that Au colloids with a smaller size prepared by sodium citrate method exhibited a higher stability in the solution in com- parison to those with larger sizes because of its higher ratio of charge/mass. In other words, the smaller gold nanoparticles are covered with citrate ions monolayer that can also be formed at larg- er gold nanoparticles by means of electrochemical scan.
HU Xiao-ya, XIAO Yi and CHEN Hong-yuan (Department of Chemistry, The State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, P. R. China)
The electrochemical behavior of the film of single wall carbon nanotube(SWNT) functionalized with carboxylic acid group was studied extensively at the glassy carbon(GC) electrode. One stable couple of waves corresponding to the redox of the carboxylic acid group, which was supported by the IR experiments, was observed. The electrode process involved four electrons, while the rate determining step was a one-electron reduction. The SWNT film modified electrode showed nice electrocatalytic behaviors toward the oxidations of some biomolecules such as dopamine, epinephrine and ascorbic acid.
The samples of 25 nL of chloride and cyanide were determined with a kind of glass capillary indicating electrodes by potentiometry. Silver was deposited by the silvermirror reaction on the inner surface of the glass capillary with a volume of 25 nL. The AgCl film and the AgI film were formed by the treatment of the capillary with a FeCl 3 solution and further with a KI solution. The samples were collected automatically into the capillary by the capillary ascension. The procedure in the measurement was merely to place a reference electrode and a capillary indicating electrode vertically on a strip filter paper containing a 01 mol/L NaNO 3 solution. The various i.d. of the capillary electrodes were used to determine samples ranging from 25 nL to dozens of microliters. The ranges of the linear response to chloride and cyanide were 32×10 -4 —22×10 -1 mol/L and 10×10 -5 —10×10 -1 mol/L with an average slope of 552 and 52—62 mV/decade , respectively. The samples with various concentrations of chloride and cyanide were determined, and the relative standard deviations were less than 7%.