1. 海南师范大学化学与化工学院,海南,海口,571158
2.
纸质出版日期:2011,
网络出版日期:2011-5-25,
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华英杰, 王崇太, 李天略, 等. Keggin型铬取代杂多离子PW11O39Cr(Ⅲ)(H2O)4-的电化学性质[J]. 中山大学学报(自然科学版)(中英文), 2011,50(3):68-73.
The Electrochemical Properties of the Keggintype Cr〖DK〗(Ⅲ〖DK〗)Substituted Heteropolyanion PW11O39Cr(Ⅲ)(H2O)4-[J]. Acta Scientiarum Naturalium Universitatis SunYatseni, 2011,50(3):68-73.
用循环伏安、交流伏安和交流阻抗法详细研究了Keggin型铬取代杂多离子PW
11
Cr(Ⅲ)O
4-
39
(PW
11
Cr) 的电化学性质。循环伏安扫描表明,1.0 mmol·L
-1
PW
11
Cr的H
3
PO
4
-HAc-H
3
BO
3
缓冲溶液(pH2.16)在玻碳电极上有三对氧化-还原波,发生在1.30/0.631 V处的准可逆波属于Cr(Ⅲ)/Cr(Ⅴ)电对的双电子氧化-还原响应,而位于-0.553/-0.505 V和-0.782/-0.725 V处的两对可逆波则对应于W-O骨架的双电子还原-氧化响应。PW
11
Cr三对氧化-还原波的峰电位皆与溶液的pH有关,随着溶液pH的增大,峰电位负移,峰电流降低,阴极和阳极的峰电位差增大,电极过程的可逆性降低。由第一个WO骨架还原波的峰电流与电位扫描速率平方根的关系得到PW
11
Cr在H
3
PO
4
-HAc-H
3
BO
3
溶液(pH 2.16)中的扩散系数为4.4×10
-6
cm
2
·s
-1
。交流阻抗谱表明,Cr(Ⅲ)/Cr(Ⅴ)电对的电极过程受异相电荷传递动力学控制,由相角与频率的关系得到其动力学参数
k
o
为0.67 cm·s
-1
;而W-O骨架的两个电极过程则受扩散控制。PW
11
Cr的电极过程存在吸附步骤。
Electrochemical properties of the PW
11
Cr(Ⅲ)O
4-
39
(PW
11
Cr) in H
3
PO
4
-HAc-H
3
BO
3
(pH 2.16) buffer were investigated in detail by cyclic voltammetry
AC voltammograms and alternating current impedance analyses. The result of cyclic voltammogram showed that three pairs of redox waves were observed on the glassy carbon (GC) electrode in H
3
PO
4
-HAc-H
3
BO
3
(pH 2.16) buffer solution containing 1.0 mmol12539;L
-1
PW
11
Cr. The pair of quasireversible wave at 1.30/0.631 V belonged to Cr(Ⅴ)/Cr(Ⅲ) two-electron redox
while the two pairs of reversible waved at -0.553/-0.505 V and -0.782/-0.725 V belonged to W-O skeleton twoelectron redox. When the pH value increased
the peak potential of the three pairs of twoelectron waves shifted negatively and the peak current decreased
which showed that H
+
was involved in the electrode process. In addition
the difference of peak potential between anode and cathode for each pair of waves increased
which showed reversibility of electrode process decreased. The diffusion coefficient
D
O
of PW
11
Cr calculated from linear relationship of peak current of the first skeleton reduction wave versus square root of potential scan rate was 4.4×10
-6
cm
2
·s
-1
in H
3
PO
4
-HAc-H
3
BO
3
(pH 2.16)buffer. AC impedance of Cr (Ⅲ) was a semicircle without Wahlberg line occurred at high frequency
which showed the anode oxidation process was controlled by heterogeneous charge transfer dynamics. The dynamic parameter
k
o
of electrode process was calculated from the relationship between phase angle and frequency. AC impedance of PW
11
Cr keleton reduction revealed the electrode process was controlled by diffusion.
Keggin型铬取代杂多离子循环伏安交流伏安交流阻抗
Keggin-type Cr-substituted heteropolytungstatecyclic voltammetryAC voltammetryAC impedance
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