Inhibiting Effect of Chloride Ion for the Electro-oxidation Reaction of Four Organic Alcohols on a Chemically Modified Platinum Anode†

doi:10.7503/cjcu20141148

Abstract

Abstract:

On a bare platinum electrode and the chemically modified platinum electrode coated with poly-valine/3d-4f hybrid-metal cyano-bridged mixing coordination polymer(poly-valine/Nd-Fe-Mo CyMCP/Pt), the effect of chloride ion in supporting electrolyte on the voltammetric behavior of electro-oxidation reaction of methanol, ethanol, n-propanol and iso-propanol was quantitatively studied by cyclic voltammetry and chronoamperometry. The results showed that whether on a bare platinum anode or the modified platinum anode, there existed the inhibiting effect of the chloride ion on the four alcohols’ anodic oxidation reaction in the weak acidic medium. The inhibiting effect of chloride ion would become remarkable once the concentration of chloride ion exceeded the critical value between 10^-5—10^-6 mol/L region, the experiment results proved that the abundant adsorption of chloride ion at a platinum anode was the main reason leading to produce inhibition effect for four organic alcohols. In addition, by discussing the influences of chloride ion concentration on the value of some oxidative peaks’ current ratio in positive-going scan to negative-going scan and the variety of chronoamperometry curves for the anodic oxidation process of four alcohols, it was preliminarily deduced that the inhibiting degree of chloride ion had been significantly different when being acted on the electro-oxidation steps involved CO and CO₂ product formation or the electro-oxidation steps involved other product formation in the entire electrooxidation process of four alcohols.

Key words: Chloride ion, Electro-catalytic oxidation, Organic alcohol, Chemically modified electrode

CLC Number:

O657
O646

TrendMD:

MA Yongjun, DING Jing, JIN Zhimei, TIE Zhenzhen, ZHOU Min. Inhibiting Effect of Chloride Ion for the Electro-oxidation Reaction of Four Organic Alcohols on a Chemically Modified Platinum Anode^†[J]. Chem. J. Chinese Universities, 2015, 36(5): 864.

Figures/Tables 5

Fig.1 SEM images of poly-valine/Nd-Fe-Mo CyMCP/Pt modified electrode with low(A) and high(B) magnifications

Fig.2 Influence of chloride ion on the oxidative peak currents of methanol(A), ethanol(B), n-propanol(C) on the modified platinum anode(a) and a bare platinum anode(b) and the CV curves of ethanol on the modified platinum anode with different concentrations of chloride ion(D)(D) c(Cl-)/(mol·L-1): a—d: 0.1, 0.01, 0.001, 0.0001.

Fig.3 Influence of chloride ion on the oxidative peak current ratio(Ipf/Ipb) of methanol(A), ethanol(B), n-propanol(C) on the modified platinum anode(a) and a bare platinum anode(b) and the CV curves of methanol on the modified platinum anode with different concentrations of chloride ion(D)(D) c(Cl-)/(mol·L-1): a—d: 0.1, 0.01, 0.001, 0.0001.

Fig.4 Influence of chloride ion on the cyclic voltammograms of iso-propanol on modified electrodes at 25 ℃(A) and 60 ℃(B)-˖-˖ [Cl-]=0; —[Cl-]=0.001 mol/L. Inset of (A) show the relationship between chloride ion concentration and the current density of oxidative peak 2 of iso-propanol on the modified platinum anode(a) and bare platinum anode(b).

Fig.5 Influence of chloride ion on the chronoamperometric curves of methanol(A), ethanol(B), n-propanol(C) and iso-propanol(D) on the modified electrodeEapp/V: (A) 0.1; (B—D) 0.3. The insets show the relationship between chloride ion concentration and the chronoamperometric current density of four alcohols at 200 s on the modified platinum anode(a) and bare platinum anode(b), respectively.

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