电解磁铁矿制备高铁酸盐工艺及其电化学性质研究
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摘要
本论文提出用隔膜式电解槽，在浓苛性碱溶液中，直流电解阳极氧化
Fe_3O_4制备高铁酸盐的新工艺。并就Fe_3O_4电极的组成、电解质种类及浓度、
电解液温度、表观阳极电流密度、电解时间等工艺因素，对生成高铁酸盐
电流效率的影响，进行了较为系统的研究。研究了Fe、Fe_3O_4、Pt、GC电
极在纯NaOH溶液中、及在含有FeO_4~(2-)或FeO_2~-的NaOH溶液中的循环伏
安特性；首次以GC电极发现了FeO_4~(2-)的阳极生成峰并提出将氧气析出反
应的阳极电流与生成FeO_4~(2-)的阳极电流分离开来的条件。
不论是Fe电极或是Fe_3O_4电极在NaOH电解液中，生成FeO_4~(2-)的电流
效率均比在KOH电解液中高出3-6倍。不同的温度下，NaOH电解液的浓
度从32.0wt.％变化到49.0wt.％，电流效率先增大后减小，在42wt.％时，
电流效率达到最高。在电解液中加入0.5wt.％的NaCl可以提高电流效率。
反应温度为303K、313K、328K时，FeO_4~(2-)的生成电流效率随着温度
的升高而逐渐降低。在电流密度等于10mA.cm~(-2)，电解液浓度为42wt.％时，
三个温度下的最高电流效率分别为44.1％，38.2％和31.6％。
电流密度是影响电流效率的重要因素，当电流密度太小时，生成FeO_4~(2-)
的速率低，电流效率较低；电流密度太大，析氧反应占阳极过程的主导地
位，生成FeO_4~(2-)的电流效率也较低；只在适宜的电流密度下才能获得较高
的电流效率。在温度为303、313、328K，电流密度为11.2，13.6，15mA.cm~(-2)
时所得最大电流效率分别为：47.8、45.8、41.1％。
随着电解时间的持续，由于较浓高铁酸盐分解速度的加剧和阳极再钝
化的逐渐形成，生成高铁酸盐的电流效率逐渐降低，溶液中的总铁含量与
高铁酸根含量之比逐渐增大。
Fe和Fe_3O_4电极的循环伏安曲线上，在0.65-0.70V的区域出现了一折
点，此折点为FeO_4~(2-)的生成峰；FeO_4~(2-)的阴极还原峰的峰电势在-0.15V附近。
以玻碳电极所测FeO_4~(2-)的阳极生成峰的峰电势介于760-960mV，且该
峰的峰电流密度随扫描速度、FeO_4~(2-)和FeO_2~-的浓度增大而增大；温度升高，
峰电位负移；峰电流密度与扫描次数、扫描方向、电解液通N_2除氧与否等
因素都有密切的联系。在FeO_4~(2-)的浓度为0.001-0.1mol/1时，以GC电极所
测FeO_4~(2-)还原峰的峰电流密度与FeG_4~(2-)浓度成线性关系（相关系数
R=0.998），这为定量分析FeO_4~(2-)的浓度提供了一种较为可靠的方法。
In this thesis, the technique for preparing sodium ferrate(VI) by electrolyzing
magnetite anode directly in concentrated NaOH solution was proposed for the first
time. A diaphragm cell was used, and the effect of preparing conditions was studied.
The results suggested that the composition of magnetite anode, the concentration of
NaOH, the temperature, the current density and the duration time of electrolysis were
the inlportant parameters, since the current efficiency greatly depended on them.
KOI-I and NaOH solutions were used as electrolyte. On the same conditions, the
current efficiency for producing ferrate(VI) was higher in NaOH than in KOH with
the ratio from 3 to 6. AS the concentration of electrolyte varied in the range of
32.Owt% to 49.Owt.%, the current efficiency for producing ferrate (VI) firstly
increased, then decreased, and it could be seen that the maximum current efficiency,
for all temperatures used, was at 42wt.% NaOH.
The current efficiency for producing ferrate (VI) decreased with temperature
increasing. The highest current efficiency for the temperature range 303 to 328K was
obtained after 60mm of electrolysis at an anodic current density of 1 OmA.cm2, they
were 44.1%, 32.8% and 3 1.6% at 303,313 and 328K, respectively.
The current efficiency for producing ferrate (VI) greatly relied on the current
density. If the current density was too small, the formation rate of ferrate (VI) was
slow, so the current efficiency was not large enough. While the current density was
too high, decrease in the ferrate (VI) yields by enhancement of the polarization and
the parasitic oxygen evolution reaction. Therefore, there was one optimum current
density at every temperature. The maximum current efficiency was 47.8%, 45.8% and
41.1% for the case of at 303K and at 1l.2mA.cm , at 313K and at 13.6 mA.cm , at
328K and at 15.0 niA.cm respectively.
With increasing the electrolysis duration, the current efficiency decreased.
Comparably the ratio of total iron to Fe6~ content in the anolyte increased.
For the feature of the Cyclic Voltammetric curves for the stationary magnetlte
3
electrode, an inflection pint was observed in the potential range 650-700mv. And we
also found a well-defined cathodic current peak at about ?0.1 5V vs. Hg/HgO in
l6mol/l NaOH, corresponding to the reduction of ferrate(VI).
Cyclic voltammetric curves were measured using stationary glass carbon (GC)
electrode in I 6M NaOH solution containing Fe(TII) or Fe042 in the concentration
range of 0.01?.02M and 0.00l--0.1M respectively. A previously no described anodic
current peak clearly separated from that of oxygen evolution, with peak potential in
the region of 740?60 mV vs. Hg/HgO(1 6M NaOH). was reported, which was
identified as the oxidation of FeOj to Fe042. The current density (CD) and the peak
potential of the anodic peak were dependent strongly on the electrolyte temperature,
the scan rate and the cyclic number. A linear relationship with correlation coefficient
R=O.998 was obtained between the cathodic peak CD and the concentration of Fe02
over the range 0.O0l?.1 mol.1?in the 16 NaOH solution. This provided a base for
quantitative analysis the concentration of Fe042 in alkaline solution
Fe_3O_4制备高铁酸盐的新工艺。并就Fe_3O_4电极的组成、电解质种类及浓度、
电解液温度、表观阳极电流密度、电解时间等工艺因素，对生成高铁酸盐
电流效率的影响，进行了较为系统的研究。研究了Fe、Fe_3O_4、Pt、GC电
极在纯NaOH溶液中、及在含有FeO_4~(2-)或FeO_2~-的NaOH溶液中的循环伏
安特性；首次以GC电极发现了FeO_4~(2-)的阳极生成峰并提出将氧气析出反
应的阳极电流与生成FeO_4~(2-)的阳极电流分离开来的条件。
不论是Fe电极或是Fe_3O_4电极在NaOH电解液中，生成FeO_4~(2-)的电流
效率均比在KOH电解液中高出3-6倍。不同的温度下，NaOH电解液的浓
度从32.0wt.％变化到49.0wt.％，电流效率先增大后减小，在42wt.％时，
电流效率达到最高。在电解液中加入0.5wt.％的NaCl可以提高电流效率。
反应温度为303K、313K、328K时，FeO_4~(2-)的生成电流效率随着温度
的升高而逐渐降低。在电流密度等于10mA.cm~(-2)，电解液浓度为42wt.％时，
三个温度下的最高电流效率分别为44.1％，38.2％和31.6％。
电流密度是影响电流效率的重要因素，当电流密度太小时，生成FeO_4~(2-)
的速率低，电流效率较低；电流密度太大，析氧反应占阳极过程的主导地
位，生成FeO_4~(2-)的电流效率也较低；只在适宜的电流密度下才能获得较高
的电流效率。在温度为303、313、328K，电流密度为11.2，13.6，15mA.cm~(-2)
时所得最大电流效率分别为：47.8、45.8、41.1％。
随着电解时间的持续，由于较浓高铁酸盐分解速度的加剧和阳极再钝
化的逐渐形成，生成高铁酸盐的电流效率逐渐降低，溶液中的总铁含量与
高铁酸根含量之比逐渐增大。
Fe和Fe_3O_4电极的循环伏安曲线上，在0.65-0.70V的区域出现了一折
点，此折点为FeO_4~(2-)的生成峰；FeO_4~(2-)的阴极还原峰的峰电势在-0.15V附近。
以玻碳电极所测FeO_4~(2-)的阳极生成峰的峰电势介于760-960mV，且该
峰的峰电流密度随扫描速度、FeO_4~(2-)和FeO_2~-的浓度增大而增大；温度升高，
峰电位负移；峰电流密度与扫描次数、扫描方向、电解液通N_2除氧与否等
因素都有密切的联系。在FeO_4~(2-)的浓度为0.001-0.1mol/1时，以GC电极所
测FeO_4~(2-)还原峰的峰电流密度与FeG_4~(2-)浓度成线性关系（相关系数
R=0.998），这为定量分析FeO_4~(2-)的浓度提供了一种较为可靠的方法。
In this thesis, the technique for preparing sodium ferrate(VI) by electrolyzing
magnetite anode directly in concentrated NaOH solution was proposed for the first
time. A diaphragm cell was used, and the effect of preparing conditions was studied.
The results suggested that the composition of magnetite anode, the concentration of
NaOH, the temperature, the current density and the duration time of electrolysis were
the inlportant parameters, since the current efficiency greatly depended on them.
KOI-I and NaOH solutions were used as electrolyte. On the same conditions, the
current efficiency for producing ferrate(VI) was higher in NaOH than in KOH with
the ratio from 3 to 6. AS the concentration of electrolyte varied in the range of
32.Owt% to 49.Owt.%, the current efficiency for producing ferrate (VI) firstly
increased, then decreased, and it could be seen that the maximum current efficiency,
for all temperatures used, was at 42wt.% NaOH.
The current efficiency for producing ferrate (VI) decreased with temperature
increasing. The highest current efficiency for the temperature range 303 to 328K was
obtained after 60mm of electrolysis at an anodic current density of 1 OmA.cm2, they
were 44.1%, 32.8% and 3 1.6% at 303,313 and 328K, respectively.
The current efficiency for producing ferrate (VI) greatly relied on the current
density. If the current density was too small, the formation rate of ferrate (VI) was
slow, so the current efficiency was not large enough. While the current density was
too high, decrease in the ferrate (VI) yields by enhancement of the polarization and
the parasitic oxygen evolution reaction. Therefore, there was one optimum current
density at every temperature. The maximum current efficiency was 47.8%, 45.8% and
41.1% for the case of at 303K and at 1l.2mA.cm , at 313K and at 13.6 mA.cm , at
328K and at 15.0 niA.cm respectively.
With increasing the electrolysis duration, the current efficiency decreased.
Comparably the ratio of total iron to Fe6~ content in the anolyte increased.
For the feature of the Cyclic Voltammetric curves for the stationary magnetlte
3
electrode, an inflection pint was observed in the potential range 650-700mv. And we
also found a well-defined cathodic current peak at about ?0.1 5V vs. Hg/HgO in
l6mol/l NaOH, corresponding to the reduction of ferrate(VI).
Cyclic voltammetric curves were measured using stationary glass carbon (GC)
electrode in I 6M NaOH solution containing Fe(TII) or Fe042 in the concentration
range of 0.01?.02M and 0.00l--0.1M respectively. A previously no described anodic
current peak clearly separated from that of oxygen evolution, with peak potential in
the region of 740?60 mV vs. Hg/HgO(1 6M NaOH). was reported, which was
identified as the oxidation of FeOj to Fe042. The current density (CD) and the peak
potential of the anodic peak were dependent strongly on the electrolyte temperature,
the scan rate and the cyclic number. A linear relationship with correlation coefficient
R=O.998 was obtained between the cathodic peak CD and the concentration of Fe02
over the range 0.O0l?.1 mol.1?in the 16 NaOH solution. This provided a base for
quantitative analysis the concentration of Fe042 in alkaline solution
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