三维电催化破络Ni-EDTA性能及机制

doi:10.16085/j.issn.1000-6613.2023-1908

摘要/Abstract

摘要：

三维电催化是处理金属络合物有机废水的高效技术，然而其破络机制尚不明晰。本研究以镀钌铱钛板为阳极，不锈钢板为阴极，引入颗粒电极，构建三维电催化体系，对含Ni-EDTA络合物的模拟废水进行破络处理。结果表明Ni-EDTA破络去除效果与电解质种类、电解质浓度、电流密度和初始pH有关，且均符合二级反应动力学。在电解质为NaCl，电解质浓度0.25g/L，电流密度1.0mA/cm²以及初始pH为3.0条件下Ni-EDTA和COD的去除率最高，分别达到85.05%和80.48%，其速率常数为0.0053min^-1，R²为0.9893。电化学测试表明颗粒电极的加入增加了催化活性位点、催化反应传质面积和电荷储存位点，增强了电子转移，提高了电催化性能。通过三维荧光光谱法、紫外光谱法、活性组分鉴定，分析EDTA降解过程，揭示了三维电催化对Ni-EDTA的高效破络机制，为金属络合有机废水处理提供理论基础和技术支撑。

关键词: 三维电极体系, Ni-EDTA废水, 破络机制, 破络效能, 动力学

Abstract:

Three-dimensional electrocatalysis is an efficient technology for treating organic wastewater containing metal complexes, but the decomplexation mechanism is still unclear. This study constructed a three-dimensional electrocatalytic system to decomplex simulated wastewater containing Ni-EDTA complex, with ruthenium and iridium coated titanium plate as the anode, and stainless steel plate as the cathode. The results indicated that the removal rate of Ni-EDTA is related to the type of electrolyte, electrolyte concentration, current density, and initial pH, and all complied with the second-order reaction kinetics. The highest removal rates of Ni-EDTA and COD were 85.05% and 80.48%, respectively with NaCl solution as the electrolyte and concentration of 0.25g/L, under 1.0mA/cm² current density, and an initial pH of 3.0. The rate constants were 0.0053min^-1 and R² was 0.9893. Electrochemical testing showed that the addition of particle electrodes increased the catalytic active sites, catalytic reaction mass transfer area, and charge storage sites, enhanced electron transfer, and improved the electrocatalytic performance. By using three-dimensional fluorescence spectroscopy, ultraviolet spectroscopy, and active component identification, the degradation process of EDTA was analyzed to reveal the efficient mechanism of three-dimensional electrocatalysis for Ni-EDTA decomplexing. This work provides a theoretical basis and technical support for the treatment of metal-complexed organic wastewater.

Key words: three-dimensional electrode system, Ni-EDTA wastewater, decomplexing mechanism, effect and energy consumption of decomplexation, kinetics

中图分类号:

TQ15

张硕, 冯岩, 卢玉玉, 贾新强, 邱立平. 三维电催化破络Ni-EDTA性能及机制[J]. 化工进展, 2024, 43(11): 6573-6582.

ZHANG Shuo, FENG Yan, LU Yuyu, JIA Xinqiang, QIU Liping. Performance and mechanism of Ni-EDTA decomplexing by three-dimensional electrocatalysis[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6573-6582.

图/表 12

图1 三维电催化装置

图2 电解质种类对破络效能影响

图3 不同NaCl浓度对破络效能的影响

图4 电流密度对破络效能的影响

图5 初始pH对破络效能影响

表1 反应动力学拟合结果

反应级数	动力学方程	速率常数	相关系数
零级	C_t =-0.0545t+6.5187	0.0545	0.7205
一级	ln(C₀/C_t )=0.0152t+0.3337	0.0152	0.8943
二级	1/C_t =0.0053t+0.1334	0.0053	0.9893

图6 二维及三维体系电化学性能

表2 电化学阻抗元件拟合参数

反应体系	R_e/Ω	R_ct/Ω	C_dl/F
二维体系	7.700	33.300	3.000×10^-8
三维体系	7.981	10.940	4.360×10^-8

图7 电催化体系羟基自由基荧光光谱

图8 叔丁醇存在时COD去除率变化

图9 Ni-EDTA破络过程中紫外光谱变化

图10 三维电催化体系破络Ni-EDTA机制及转化途径

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