电驱动NiFeMn LDH/CNTs/PVDF膜电极选择性提取钨酸根离子

doi:10.11949/0438-1157.20241421

摘要/Abstract

摘要：

电控离子交换技术（electrochemically switched ion exchange，ESIX）是将电活性离子交换材料（EXIMs）沉积或涂覆在导电基底上，通过电化学控制导电基底上活性材料氧化还原状态实现目标离子置入与释放，从而实现离子的分离。该技术具有痕量提取、无二次污染、速率可控、高选择性等优点。通过共沉淀法制备NiFeMn LDH，并将其与碳纳米管（CNTs）、聚偏二氟乙烯（PVDF）混合涂覆到石墨板上，制得NiFeMn LDH/CNTs/PVDF膜电极。NiFeMn LDH层板上具有丰富的羟基官能团，可与W（Ⅵ）发生羟基配位；层间的阴离子与W（Ⅵ）进行离子交换，可为W（Ⅵ）提供丰富的活性位点。在ESIX系统中，膜电极对W（Ⅵ）的吸附容量可达122.10 mg·g^-1，且W（Ⅵ）与Mo（Ⅵ）、Cl^-、NO $3 -$ 分离因子（α $M o (Ⅵ) W (Ⅵ)$ 、α $C l - W (Ⅵ)$ 、α $N O 3 - W (Ⅵ)$ ）分别为1.25、19.60、35.80，实现了W（Ⅵ）选择性分离。此外，该膜电极具有优异的循环稳定性，为钨的高效分离提供了新的方向。

关键词: 选择性, 电控离子交换技术, 钨酸根离子提取, NiFeMn LDH/CNTs/PVDF膜电极, 电化学驱动

Abstract:

Electrochemically switched ion exchange (ESIX) is a process that entails the deposition or coating of electroactive ion exchange materials (EXIMs) onto a conductive substrate, and electrochemically controlling the redox state of the active material on the conductive substrate to achieve the insertion and release of target ions, thus achieving the separation of the ions. This technology has the advantages of trace extraction, no secondary pollution, controllable rate and high selectivity. NiFeMn LDH were prepared by coprecipitation method, and then mixed with carbon nanotubes (CNTs) and polyvinylidene fluoride (PVDF) and coated on graphite plate to obtain NiFeMn LDH/CNTs/PVDF film electrode. The NiFeMn LDH laminates have abundant hydroxyl functional groups, which can be associated with the hydroxyl coordination with W(‍Ⅵ); the anions in the interlayer are capable of ion exchange with W(‍Ⅵ), which can provide abundant active sites for W(‍Ⅵ). In the ESIX system, the adsorption capacity of the film electrode for W(‍Ⅵ) was up to 122.10 mg·g^-1, and the separation factors of W(‍Ⅵ) and Mo(‍Ⅵ), Cl^-, and NO $3 -$ were 1.25, 19.60 and 35.80, enabling selective separation of W(‍Ⅵ). Additionally, the film electrode showed excellent cycling stability, pointing to a promising new direction for tungsten separation.

Key words: selectivity, electrochemically switched ion exchange, tungstate ion extraction, NiFeMn LDH/CNTs/PVDF film electrode, electrochemically driven

中图分类号:

TQ 150.5

高凤凤, 程慧峰, 杨博, 郝晓刚. 电驱动NiFeMn LDH/CNTs/PVDF膜电极选择性提取钨酸根离子[J]. 化工学报, 2025, 76(7): 3350-3360.

Fengfeng GAO, Huifeng CHENG, Bo YANG, Xiaogang HAO. Electrically driven NiFeMn LDH/CNTs/PVDF film electrode for selective extraction of tungstate ions[J]. CIESC Journal, 2025, 76(7): 3350-3360.

图/表 16

图1 NiFeMn LDH/CNTs/PVDF膜电极的制备过程

Fig.1 Preparation process of NiFeMn LDH/CNTs/PVDF film electrode

图2 不同放大倍数下NiFeMn LDH粉末的扫描电镜图像

Fig.2 Scanning electron microscope images of NiFeMn LDH powders at different magnifications

图3 NiFeMn LDH粉末的XRD谱图(a)以及Mn 2p的XPS谱图(b)

Fig.3 XRD spectra (a) and XPS of Mn 2p (b) of NiFeMn LDH powder

图4 NiFeMn LDH在吸附W(Ⅵ)前后的扫描光谱图(a)和O 1s高分辨光谱(b)

Fig.4 Scanning spectra (a) and O 1s high resolution spectra (b) of NiFeMn LDH before and after adsorption of W(Ⅵ) atoms

图5 (a) NiFeMn LDH/CNTs/PVDF膜电极在不同扫速下的CV曲线；(b)阳极/阴极峰值电流随扫速变化的拟合曲线

Fig.5 (a) CV curves of NiFeMn LDH/CNTs/PVDF at different scan rates; (b) Fitting curves of anode/cathode peak currents with scan rates

图6 NiFeMn LDH/CNTs/PVDF膜电极在不同电压和pH下对W(Ⅵ)的吸附性能

Fig.6 Adsorption performance of NiFeMn LDH/CNTs/PVDF film electrode under different voltages and pH

图7 NiFeMn LDH/CNTs/PVDF膜电极在不同金属摩尔比例下的吸附性能

Fig.7 Adsorption properties of NiFeMn LDH / CNTs / PVDF film electrodes at different molar ratios of metal

图8 (a) NiFeMn LDH膜在不同初始浓度下的W(Ⅵ)吸附曲线；不同初始W(Ⅵ)浓度的(b)准一级动力学和(c)准二级动力学曲线

Fig.8 (a) W(Ⅵ) adsorption capacity of NiFeMn LDH film at different initial concentrations; (b) Pseudo-first-order kinetic and (c) pseudo-second-order kinetic curves for different initial W(Ⅵ) concentrations

表1 不同初始浓度下NiFeMn LDH膜吸附W（Ⅵ）的动力学模型模拟相关参数

Table 1 Parameters related to kinetic model simulation of W（Ⅵ） adsorption on NiFeMn LDH films with different initial concentrations

Initial concentration/(mg·L^-1)	Q_exp/(mg·g^-1)	Quasi-first-order kinetic			Quasi-second-order kinetic
Initial concentration/(mg·L^-1)	Q_exp/(mg·g^-1)	k₁/min^-1	Q_cal/(mg·g^-1)	R²	k₂/(g·mg^-1·min^-1)	Q_cal/(mg·g^-1)	R²
100	50.22	0.00863	49.19	0.7687	0.00115	50.46	0.9973
200	90.43	0.01550	90.13	0.9683	0.00048	88.83	0.9946
300	112.64	0.01651	112.26	0.9733	0.00032	110.90	0.9917
400	122.10	0.00972	117.78	0.9564	0.00030	119.20	0.9924

图9 (a)NiFeMn LDH膜在不同温度下的W(Ⅵ)吸附曲线；(b)热力学拟合曲线

Fig.9 (a) W(Ⅵ) adsorption curves of NiFeMn LDH film at different temperatures; (b) Thermodynamic fit curve

表2 NiFeMn LDH膜吸附W（Ⅵ）的热力学计算结果

Table 2 Thermodynamic calculations of W（Ⅵ） adsorption on NiFeMn LDH film

T/K	ΔG/(kJ·mol^-1)	ΔH/(kJ·mol^-1)	ΔS/(J·mol^-1·K^-1)	R²
298	-4.125	—	—	—
303	-4.856	—	—	—
308	-6.101	48.59	176.83	0.9847
313	-6.596	—	—	—
318	-7.675	—	—	—

表3 NiFeMn LDH与阴离子的结合能

Table 3 The binding energy of NiFeMn LDH with anions

NiFeMn LDH types	Binding energy/eV
NiFeMn LDH-WO $4 2 -$	-8.55
NiFeMn LDH-SO $4 2 -$	-8.53
single layer NiFeMn LDH-WO $4 2 -$	-10.06

表3 NiFeMn LDH与阴离子的结合能

Table 3 The binding energy of NiFeMn LDH with anions

NiFeMn LDH types	Binding energy/eV
NiFeMn LDH-WO $4 2 -$	-8.55
NiFeMn LDH-SO $4 2 -$	-8.53
single layer NiFeMn LDH-WO $4 2 -$	-10.06

图10 NiFeMn LDH/CNTs/PVDF膜电极在不同条件下的脱附性能

Fig.10 Desorption performance of NiFeMn LDH/CNTs/PVDF film electrode under different conditions

图11 NiFeMn LDH/CNTs/PVDF膜电极的(a)竞争离子存在下的吸附容量和(b)循环稳定性

Fig.11 (a) Adsorption capacity in the presence of competing ions and (b) cycling stability of NiFeMn LDH/CNTs/PVDF film electrode

表4 NiFeMn LDH/CNTs/PVDF复合膜对不同阴离子的分离因子

Table 4 Separation factors of NiFeMn LDH/CNTs/PVDF composite films for different anions

Anion types	Separation factor
W(Ⅵ)	1.00
Mo(Ⅵ)	1.25
Cl^-	19.60
NO $3 -$	35.80

表4 NiFeMn LDH/CNTs/PVDF复合膜对不同阴离子的分离因子

Table 4 Separation factors of NiFeMn LDH/CNTs/PVDF composite films for different anions

Anion types	Separation factor
W(Ⅵ)	1.00
Mo(Ⅵ)	1.25
Cl^-	19.60
NO $3 -$	35.80

图12 NiFeMn LDH/CNTs/PVDF膜电极的电化学稳定性

Fig.12 Electrochemical stability of NiFeMn LDH/CNTs/PVDF film electrode

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