Simple and Rapid Determination of Mercury Ions Based on 1,4-Dithiothreitol Assembled Gold Plate Electrode†

doi:10.7503/cjcu20140288

Abstract

Abstract:

A simply gold plate electrode(GPE) based on 1,4-dithiothreitol(DTT), which was self-assembled on a surface of flat gold film with a thickness of 100 nm, was developed to construct a novel selective electrode method for rapid detection of mercury ion. Through electrochemical impedance analysis and cyclic voltamme-tric method, the response mechanism of the electrode for selective recognition of Hg²⁺ was investigated, that the other terminal sulfhydryl group of DTT binding to Au surface can coordinate with Hg²⁺ due to their strong complexing interaction, resulting in change of membrane potential of the electrode surface. The proposed electrode possesses good potential performance responding to Hg²⁺ with a linear range of 1.0×10^-8—1.0×10^-3mol/L, a Nernst slope of (29.62±0.2) mV/-pc(25 ℃), and a detection limit of 5.1×10^-9mol/L in Tris-HCl buffer solution(pH=6.0). The electrode has short response time(20 s), good reproducibility and stability. No interference can be observed from most common ions like Cu²⁺, Fe²⁺, Na⁺, K⁺, Mg²⁺, Ba²⁺, Ca²⁺, Zn²⁺, Sn²⁺, Pb²⁺, Ag⁺, Al³⁺, Fe³⁺, Ni²⁺, N $O 2 -$ , I $O 3 -$ , Br $O 3 -$ and Cl $O 3 -$ . Compared with spectrophotometric method with dithizone, the proposed electrode can be well utilized to the determination of trace amount of Hg²⁺ in real water samples with a recovery rate of 98.20%—101.75%, showing promising application in environmental and other fields.

Key words: Gold plate electrode, 1, 4-Dithiothreitol, Self-assembled monolayer, Mercury ion, Selective recognition

CLC Number:

TrendMD:

CAO Tingting, CAO Zhong, HE Jinglin, LIANG Haiqin, XIAO Zhongliang. Simple and Rapid Determination of Mercury Ions Based on 1,4-Dithiothreitol Assembled Gold Plate Electrode^†[J]. Chem. J. Chinese Universities, 2014, 35(7): 1388.

Figures/Tables 12

Fig.1 Structure of DTT

Fig.2 Design of gold plate electrode(A) and SEM image of its section structure(B) (A) 1. Base plate; 2. gold film; 3. gold-film pin; 4. plastics film; 5. copper wire; 6. soldering tin; 7. silicone sealant.

Fig.3 SEM images of electrode surfaces for bare GPE(A), GPE/DTT(B) and GPE/DTT/Hg2+(C)

Fig.4 Schematic illustration of the response process of the electrode

Fig.5 Impedance(A) and cyclic voltammetry(B) plots of the electrodes for bare GPE(a), GPE/DTT(b) and GPE/DTT/Hg2+(c) in the media solution containing 2.0 mmol/L K3Fe(CN)6 and 0.2 mol/L Na2SO4

Fig.6 XPS spectra of the electrode surfaces for bare GPE(a), GPE/DTT(b) and GPE/DTT/Hg2+(c)

Fig.7 Effect of pH on sensitivity of GPE/DTT electrode

Fig.8 Potential response curve(A) and its linear relation plot(B) of GPE/DTT electrode to Hg2+ in Tris-HCl buffer(pH=6.0)

Fig.9 Dynamic response of the electrode to various concentrations of Hg2+ in Tris-HCl buffer(pH=6.0) c(Hg2+)/(mol·L-1): A. 0; B. 1.0×10-8; C. 1.0×10-7; D. 1.0×10-6; E. 1.0×10-5; F. 1.0×10-4.

Table 1 Reproducibility of GPE/DTT electrode

No.	Potential/mV
No.	1.0×10^-6mol/L Hg²⁺	1.0×10^-4mol/L Hg²⁺
1	131	189
2	130	188
3	131	189
4	131	189
5	129	188
6	130	187
7	130	188
8	131	188
9	130	189
10	131	190
AV	130.4	188.5
SD	±0.70	±0.85

Table 2 Selectivity coefficient of GPE/DTT electrode to Hg2+

Interfering ion	$K H g 2 +, M n + pot$	Interfering ion	$K H g 2 +, M n + pot$	Interfering ion	$K H g 2 +, M n + pot$
Na⁺	-4.95	Cu²⁺	-2.85	Sn²⁺	-3.25
K⁺	-3.20	Zn²⁺	-3.15	Ni²⁺	-3.48
Mg²⁺	-4.32	Pb²⁺	-3.65	N $O 2 -$	-4.69
Ba²⁺	-4.29	Ag⁺	-3.83	I $O 3 -$	-4.32
Ca²⁺	-3.58	Al³⁺	-3.63	Br $O 3 -$	-3.47
Fe²⁺	-3.15	Fe³⁺	-2.85	Cl $O 3 -$	-3.06

Table 2 Selectivity coefficient of GPE/DTT electrode to Hg2+

Interfering ion	$K H g 2 +, M n + pot$	Interfering ion	$K H g 2 +, M n + pot$	Interfering ion	$K H g 2 +, M n + pot$
Na⁺	-4.95	Cu²⁺	-2.85	Sn²⁺	-3.25
K⁺	-3.20	Zn²⁺	-3.15	Ni²⁺	-3.48
Mg²⁺	-4.32	Pb²⁺	-3.65	N $O 2 -$	-4.69
Ba²⁺	-4.29	Ag⁺	-3.83	I $O 3 -$	-4.32
Ca²⁺	-3.58	Al³⁺	-3.63	Br $O 3 -$	-3.47
Fe²⁺	-3.15	Fe³⁺	-2.85	Cl $O 3 -$	-3.06

Table 3 Recovery of the proposed GPE/DTT electrode for the determination of Hg2+ in real water samples compared with spectrophotometric method with dithizone

Sample	Concentration added/(μmol·L^-1)	Spectrophotometric method with dithizone		GPE/DTT electrode		Recovery(%)
Sample	Concentration added/(μmol·L^-1)	Mean/(μmol·L^-1)	SD		Mean/(μmol·L^-1)	SD
A	0.400	0.402	±0.016	0.407	±0.015	101.75
B	0.500	0.510	±0.013	0.491	±0.019	98.20
C	0.600	0.594	±0.014	0.604	±0.014	100.67
D	0.800	0.794	±0.013	0.797	±0.022	99.63
E	1.200	1.210	±0.015	1.206	±0.014	100.50
F	1.800	1.798	±0.011	1.796	±0.016	99.89

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