铜铝双金属复合离子液体的电化学行为及电沉积铜机理

doi:10.11949/0438-1157.20220084

摘要/Abstract

摘要：

铜铝双金属复合离子液体是新型碳四烷基化技术所用的绿色催化剂，电化学处理是回收工业应用过程外排复合离子液体中金属铜的有效途径之一，为此需要深入研究其电化学行为和电沉积铜机理。循环伏安研究发现，铜铝双金属复合离子液体在Pt盘电极、W盘电极和玻碳电极上的还原过程均包括铜的欠电势沉积、Cu(Ⅰ)的还原和铜的超电势沉积，氧化过程均包括Cu→Cu(Ⅰ)、Cu(Ⅰ)→Cu(Ⅱ)。计时安培研究表明，铜的成核方式为三维瞬时成核。长周期实验结果显示Cu(Ⅰ)的浓度随着时间下降的趋势变缓，表明电沉积铜速率逐步下降。电沉积电势对沉积产物的形貌影响较大，-2.60 V下的产物形貌更平整致密。XRD结果表明在-1.20~-2.60 V电势下阴极电沉积只生成金属铜。

关键词: 复合离子液体, 电化学, 循环伏安, 还原, 氧化, 电沉积铜

Abstract:

Cu-Al bimetallic composite ionic liquid is a novel green catalyst for isobutane alkylation in oil refining industry, and small amount of catalyst is inevitably emitted during industrial application. Electrochemical treatment is one of the effective ways for the resource utilization of Cu-Al bimetallic composite ionic liquid, and the in-depth exploration of electrochemical behavior and electrodeposition mechanism provide theoretical guidance for the efficient utilization of metal resources. By cyclic voltammetry, it was found that there were three cathodic reduction regions for Cu-Al bimetallic composite ionic liquid in cyclic voltammograms on Pt electrode, W electrode and glassy carbon electrode, and the reactions were copper underpotential deposition, Cu(Ⅰ) reduction and copper overpotential deposition. The anodic oxidation peaks were Cu→Cu(Ⅰ), Cu(Ⅰ)→Cu(Ⅱ). For W electrode, the copper underpotential deposition process and the Cu(Ⅰ) reduction process were both irreversible electrochemical reaction processes controlled by diffusion. Chronoamperometry indicated that the nucleation and growth process of copper was three-dimensional instantaneous nucleation. Long-term electrodeposition of Cu-Al bimetallic composite ionic liquid showed that the decreasing trend of Cu(Ⅰ) concentration with time slowed down, indicating that the rate of copper electrodeposition decreased with time. The electrodeposition potential had a certain effect on the morphology of the deposited products. The morphology of the deposited product obtained at -2.60 V was smooth and dense, and presented regular granular shape. XRD patterns of the electrodeposits showed that there was only copper produced on cathode by the electrodeposition of the composite ionic liquid.

Key words: composite ionic liquid, electrochemistry, cyclic voltammetry, reduction, oxidation, copper electrodeposition

中图分类号:

TQ 153

欧阳萍, 张睿, 周剑, 刘海燕, 刘植昌, 徐春明, 孟祥海. 铜铝双金属复合离子液体的电化学行为及电沉积铜机理[J]. 化工学报, 2022, 73(7): 3212-3221.

Ping OUYANG, Rui ZHANG, Jian ZHOU, Haiyan LIU, Zhichang LIU, Chunming XU, Xianghai MENG. Electrochemical behavior and copper electrodeposition mechanism of Cu-Al bimetallic composite ionic liquid[J]. CIESC Journal, 2022, 73(7): 3212-3221.

图/表 13

图1 铜铝双金属复合离子液体在Pt盘电极(a)、W盘电极(b)、玻碳电极(c)的循环伏安曲线(扫描速率为100 mV?s-1)

Fig.1 Cyclic voltammograms of Cu-Al bimetallic composite ionic liquid on Pt electrode (a), W electrode (b) and glass carbon electrode (c) with the scanning rate of 100 mV?s-1

表1 铜铝双金属复合离子液体在不同工作电极上CV曲线峰电位

Table 1 Cyclic voltametric data of Cu-Al bimetallic composite ionic liquid on different working electrodes

Electrode	Cu UPD/V	Electrodeposition of Cu(Ⅰ)/V	Cu→ Cu(Ⅰ)/V	Cu(Ⅰ)→Cu(Ⅱ)/V
Pt	0.07，-0.43	-1.55	-0.30	0.29
W	-0.08	-1.32	-0.31	0.54
GC	0.04，-0.47	-2.21	-0.52	0.36

图2 铜铝双金属复合离子液体在W盘电极上不同扫描速率下的循环伏安曲线

Fig.2 Cyclic voltammograms of Cu-Al bimetallic composite ionic liquid on W electrode with different scanning rates

图3 阴极峰电流ip与v1/2的关系

Fig.3 Relationship between cathodic peak current ipand v1/2

表2 铜铝双金属复合离子液体在W盘工作电极上不同扫描速率下的CV曲线的氧化峰数据

Table 2 Data of oxidation peaks of CV curves of Cu-Al bimetallic composite ionic liquid on W electrode under different scanning rates

v/(mV?s^-1)	E $p a a 1$ /V	E $p / 2 a 1$ /V	I_a1/(mA?cm^-2)	E $p a a 2$ /V	E $p / 2 a 2$ /V	I_a2/(mA?cm^-2)	∣I_c2/I_a2∣
100	0.50	0.33	12.81	-0.31	-0.54	21.98	0.57
200	0.53	0.39	14.95	-0.23	-0.49	26.50	0.58
300	0.58	0.44	17.51	-0.12	-0.42	31.68	0.64
400	0.67	0.52	19.52	-0.09	-0.37	34.68	0.65
500	0.70	0.54	21.54	-0.02	-0.35	38.25	0.66
600	0.80	0.62	23.91	0.05	-0.32	41.72	0.69
average	—	—	—	—	—	—	0.63

表2 铜铝双金属复合离子液体在W盘工作电极上不同扫描速率下的CV曲线的氧化峰数据

Table 2 Data of oxidation peaks of CV curves of Cu-Al bimetallic composite ionic liquid on W electrode under different scanning rates

v/(mV?s^-1)	E $p a a 1$ /V	E $p / 2 a 1$ /V	I_a1/(mA?cm^-2)	E $p a a 2$ /V	E $p / 2 a 2$ /V	I_a2/(mA?cm^-2)	∣I_c2/I_a2∣
100	0.50	0.33	12.81	-0.31	-0.54	21.98	0.57
200	0.53	0.39	14.95	-0.23	-0.49	26.50	0.58
300	0.58	0.44	17.51	-0.12	-0.42	31.68	0.64
400	0.67	0.52	19.52	-0.09	-0.37	34.68	0.65
500	0.70	0.54	21.54	-0.02	-0.35	38.25	0.66
600	0.80	0.62	23.91	0.05	-0.32	41.72	0.69
average	—	—	—	—	—	—	0.63

表3 铜铝双金属复合离子液体在W盘工作电极上不同扫描速率下的CV曲线的还原峰数据

Table 3 Data of reduction peaks of CV curves of Cu-Al bimetallic composite ionic liquid on W electrode under different scanning rates

v/(mV?s^-1)	E $p c c 1$ /V	E $p / 2 c 1$ /V	I_c1/(mA?cm^-2)	E $p c c 2$ /V	E $p / 2 c 2$ /V	I_c2/(mA?cm^-2)	α_c2	D₀/(10^-6cm²?s^-1)
100	-0.08	0.11	-8.53	-1.32	-1.17	-12.44	0.31	2.41
200	-0.17	0.05	-13.32	-1.37	-1.24	-15.44	0.37	1.86
300	-0.33	-0.08	-19.21	-1.44	-1.29	-20.17	0.33	2.11
400	-0.41	-0.12	-21.74	-1.50	-1.34	-22.42	0.30	1.96
500	-0.43	-0.14	-24.85	-1.55	-1.38	-25.41	0.28	2.01
600	-0.47	-0.17	-27.20	-1.63	-1.42	-28.60	0.23	2.12
average	—	—	—	—	—	—	0.30	2.08

表3 铜铝双金属复合离子液体在W盘工作电极上不同扫描速率下的CV曲线的还原峰数据

Table 3 Data of reduction peaks of CV curves of Cu-Al bimetallic composite ionic liquid on W electrode under different scanning rates

v/(mV?s^-1)	E $p c c 1$ /V	E $p / 2 c 1$ /V	I_c1/(mA?cm^-2)	E $p c c 2$ /V	E $p / 2 c 2$ /V	I_c2/(mA?cm^-2)	α_c2	D₀/(10^-6cm²?s^-1)
100	-0.08	0.11	-8.53	-1.32	-1.17	-12.44	0.31	2.41
200	-0.17	0.05	-13.32	-1.37	-1.24	-15.44	0.37	1.86
300	-0.33	-0.08	-19.21	-1.44	-1.29	-20.17	0.33	2.11
400	-0.41	-0.12	-21.74	-1.50	-1.34	-22.42	0.30	1.96
500	-0.43	-0.14	-24.85	-1.55	-1.38	-25.41	0.28	2.01
600	-0.47	-0.17	-27.20	-1.63	-1.42	-28.60	0.23	2.12
average	—	—	—	—	—	—	0.30	2.08

图4 铜铝双金属复合离子液体在Cu丝电极上的电流-时间暂态曲线

Fig.4 Current-time transient of Cu-Al bimetallic composite ionic liquid on Cu wire electrode

图5 铜铝双金属复合离子液体不同电压下电流-时间暂态无量纲曲线实验与理论对比

Fig.5 Comparison of the dimensionless experimental current-time transient of Cu-Al bimetallic composite ionic liquid with the theoretical curves for instantaneous nucleation and progressive nucleation

表4 铜铝双金属复合离子液体长周期电沉积过程不同时间通过的电量

Table 4 Charge for different time during long-term electrodeposition of Cu-Al bimetallic composite ionic liquid

Potential/V	Time/h	Charge/C
-2.60	0.5	40.1
-2.60	1.0	39.1
-2.60	1.5	37.7
-2.60	2.0	38.4
-2.60	2.5	37.0
-2.60	3.0	37.4
-2.60	3.5	34.1
-2.60	4.0	33.9
-2.60	4.5	34.1
-2.60	5.0	33.7
-2.60	5.5	33.9
-2.60	6.0	32.7
-2.60	6.5	32.0
-2.60	7.0	32.5
-2.60	7.5	32.4
-2.60	8.0	31.7

图6 铜铝双金属复合离子液体8 h长周期实验过程Cu(Ⅰ)浓度随时间的变化

Fig.6 Trend of Cu(Ⅰ) concentration for Cu-Al bimetallic composite ionic liquid during long-term electrodeposition

图7 铜铝双金属复合离子液体不同电压下获得的阴极沉积物的SEM图

Fig.7 SEM images of electrodeposits of Cu-Al bimetallic composite ionic liquid under different potentials

图8 -2.60 V下得到的镀层EDX面扫描谱图

Fig.8 EDX mapping images of electrodeposits at the potential of -2.60 V with the elements of Cu, Al, Ag, Cl and O

图9 铜铝双金属复合离子液体在不同电势(-1.20、-1.70、-2.60 V， vs Pt)下的电沉积产物的XRD谱图

Fig.9 XRD patterns of cathodic electrodeposits from Cu-Al bimetallic composite ionic liquid on the silver electrode at the potentials of -1.20, -1.70 and -2.60 V （vs. Pt）

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