Electrically driven NiFeMn LDH/CNTs/PVDF film electrode for selective extraction of tungstate ions

doi:10.11949/0438-1157.20241421

Abstract

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

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

CLC Number:

TQ 150.5

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.

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.

Figures/Tables 16

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

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

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

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

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

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

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

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

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

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

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	—	—	—

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

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

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

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

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

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

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

References 31

[1]	周永敏. 炼油技术开发现状及发展趋势[J]. 石化技术, 2019, 26(12): 120, 115.
	Zhou Y M. Present situation and development trend of refining technology development[J]. Petrochemical Industry Technology, 2019, 26(12): 120, 115.
[2]	赵中伟, 孙丰龙, 杨金洪, 等. 我国钨资源、技术和产业发展现状与展望[J]. 中国有色金属学报, 2019, 29(9): 1902-1916.
	Zhao Z W, Sun F L, Yang J H, et al. Status and prospect for tungsten resources, technologies and industrial development in China[J]. The Chinese Journal of Nonferrous Metals, 2019, 29(9): 1902-1916.
[3]	Serdyukov S I, Kniazeva M I, Sizova I A, et al. A new precursor for synthesis of nickel-tungsten sulfide aromatic hydrogenation catalyst[J]. Molecular Catalysis, 2021, 502: 111357.
[4]	Haack A, Hillenbrand J, van Gastel M, et al. Spectroscopic and theoretical study on siloxy-based molybdenum and tungsten alkylidyne catalysts for alkyne metathesis[J]. ACS Catalysis, 2021, 11(15): 9086-9101.
[5]	Dawood K M, Nomura K. Recent developments in Z-selective olefin metathesis reactions by molybdenum, tungsten, ruthenium, and vanadium catalysts[J]. Advanced Synthesis & Catalysis, 2021, 363(8): 1970-1997.
[6]	Bonassi F, Ravelli D, Protti S, et al. Decatungstate photocatalyzed acylations and alkylations in flow via hydrogen atom transfer[J]. Advanced Synthesis & Catalysis, 2015, 357(16/17): 3687-3695.
[7]	Yan S Q, Tong T, Li Y, et al. Production of biodiesel through esterification reaction using choline exchanging polytungstoboronic acids as temperature-responsive catalysts[J]. Catalysis Surveys from Asia, 2017, 21(4): 151-159.
[8]	Zhao C, Wang C Y, Wang X R, et al. Recovery of tungsten and titanium from spent SCR catalyst by sulfuric acid leaching process[J]. Waste Management, 2023, 155: 338-347.
[9]	Wang B, Yang Q W. Optimization of roasting parameters for recovery of vanadium and tungsten from spent SCR catalyst with composite roasting[J]. Processes, 2021, 9(11): 1923.
[10]	Moon G, Kim J H, Lee J Y, et al. Leaching of spent selective catalytic reduction catalyst using alkaline melting for recovery of titanium, tungsten, and vanadium[J]. Hydrometallurgy, 2019, 189: 105132.
[11]	张邦胜, 肖连生, 张启修. 沉淀法分离钨钼的研究进展[J]. 江西有色金属, 2001, 15(2): 26-29.
	Zhang B S, Xiao L S, Zhang Q X. Progress in W/Mo separation by precipitation[J]. Jiangxi Nonferrous Metals, 2001, 15(2): 26-29.
[12]	关文娟, 张贵清, 高从堦, 等. 双氧水络合萃取分离钨钼的前驱体料液的制备[J]. 中南大学学报(自然科学版), 2013, 44(5): 1766-1774.
	Guan W J, Zhang G Q, Gao C J, et al. Preparation of precursor solution for solvent separation of Mo and W by H₂O₂-complexation[J]. Journal of Central South University (Science and Technology), 2013, 44(5): 1766-1774.
[13]	袁斌, 邓舜勤. 用离子交换法从钨溶液中分离钼[J]. 湿法冶金, 2003, 22(2): 69-78.
	Yuan B, Deng S Q. Remove of molybdenum from tungsten solution by ion exchange[J]. Hydrometallurgy of China, 2003, 22(2): 69-78.
[14]	郭超, 肖连生. 钼酸铵结晶过程中的钨钼分离研究[J]. 稀有金属与硬质合金, 2010, 38(3): 1-4, 15.
	Guo C, Xiao L S. Study on tungsten and molybdenum separation in the ammonium molybdate crystallization process[J]. Rare Metals and Cemented Carbides, 2010, 38(3): 1-4, 15.
[15]	Zhang W J, Li J T, Zhao Z W, et al. Separation of W and Mo from their peroxoacids solutions by thermal decomposition[J]. Transactions of Nonferrous Metals Society of China, 2016, 26(10): 2731-2737.
[16]	王文强, 赵中伟. 钨提取冶金中钨钼分离研究进展——从“削足适履”到“量体裁衣”[J]. 中国钨业, 2015, 30(1): 49-55.
	Wang W Q, Zhao Z W. Research advances of tungsten-molybdenum separation in tungsten extractive metallurgy[J]. China Tungsten Industry, 2015, 30(1): 49-55.
[17]	高凤凤, 杨言言, 杜晓, 等. 电控离子(交换)膜分离技术——从ESIX到ESIPM[J]. 化学进展, 2020, 32(9): 1344-1351.
	Gao F F, Yang Y Y, Du X, et al. Electrically switched ion membrane for ion selective separation and recovery: from ESIX to ESIPM[J]. Progress in Chemistry, 2020, 32(9): 1344-1351.
[18]	Hu W T, Sun B C, Zhang X F, et al. New insights into the ion/electron transfer mechanisms of LiMn₂O₄-based membrane electrodes at different electron fluxes[J]. Small, 2025: 2407656.
[19]	Zeng G L, Ye D N, Zhang X F, et al. A potential-responsive ion-pump system based on nickel hexacyanoferrate film for selective extraction of cesium ions[J]. Chinese Journal of Chemical Engineering, 2023, 63: 51-62.
[20]	Jiang M F, Zhang X F, Du X, et al. An electrochemically induced dual-site adsorption composite film of Ni-MOF derivative/NiCo LDH for selective bromide-ion extraction[J]. Separation and Purification Technology, 2022, 283: 120175.
[21]	Hu Y S, Luo Q L, Du X, et al. Film electrode by incorporating polypyrrole/carbon black into cross-linked binders of chitosan/cationic polyacrylamide for selective chloride extraction in wastewater[J]. Separation and Purification Technology, 2024, 330: 125434.
[22]	Luo J H, Du X, Gao F F, et al. Electrochemically triggered iodide-vacancy BiOI film for selective extraction of iodide ion from aqueous solutions[J]. Separation and Purification Technology, 2021, 259: 118120.
[23]	Song T, Luo Q L, Gao F F, et al. Adsorption and electro-assisted method removal of boron in aqueous solution by nickel hydroxide[J]. Journal of Industrial and Engineering Chemistry, 2023, 118: 372-382.
[24]	Song Y F, He L H, Chen X Y, et al. Removal of tungsten from molybdate solution by Fe-Mn binary oxide adsorbent[J]. Transactions of Nonferrous Metals Society of China, 2017, 27(11): 2492-2502.
[25]	Srivastava R R, Kim M S, Lee J C. Separation of tungsten from Mo-rich leach liquor by adsorption onto a typical Fe-Mn cake: kinetics, equilibrium, mechanism, and thermodynamics studies[J]. Industrial & Engineering Chemistry Research, 2013, 52(49): 17591-17597.
[26]	Chai Q, Yang B, Li X M, et al. A self-driven Ni(OH)₂/CB/PVDF film for highly efficient adsorption of tungsten via hydroxyl ligand exchange[J]. Separation and Purification Technology, 2025, 352: 128163.
[27]	Zhao Z W, Cao C F, Chen X Y. Separation of macro amounts of tungsten and molybdenum by precipitation with ferrous salt[J]. Transactions of Nonferrous Metals Society of China, 2011, 21(12): 2758-2763.
[28]	Zhao Y J, Zhang P J, Liang J R, et al. Unlocking layered double hydroxide as a high-performance cathode material for aqueous zinc-ion batteries[J]. Advanced Materials, 2022, 34(37): 2204320.
[29]	Lu Z Y, Qian L, Tian Y, et al. Ternary NiFeMn layered double hydroxides as highly-efficient oxygen evolution catalysts[J]. Chemical Communications, 2016, 52(5): 908-911.
[30]	Ye D N, Gao F F, Zeng G L, et al. An electroactive BiOBr/PVDF/CB film electrode for electrochemical extraction of bromine ions from brines[J]. Industrial & Engineering Chemistry Research, 2023, 62(22): 8882-8892.
[31]	Yang B, Chai Q, Li X M, et al. A potential-driven FeMnO _x /CNTs film electrode for efficient extraction of WO 4 2 - via electrochemical coordination and inner-sphere complexation[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2024, 699: 134686.