锌（Zn）是电镀和电池领域中的关键战略资源，然而，其生产和使用过程中产生的含锌废水给环境和公众健康带来了严重威胁。高效回收电镀废水中的锌，是同步解决锌资源短缺与污染问题的有效手段。电容去离子（Capacitive Deionization，CDI）是一种新型的重金属离子回收技术，具有高效、稳定、绿色和节能等特点。然而，传统的CDI技术因碳电极缺乏特定离子的选择性，在处理复杂废水时效果欠佳，难以大规模应用。近年来基于离子脱嵌机制的法拉第电极因其独特的选择性而逐渐收到关注，本论文制备了对Zn2+具有选择吸附性的氟磷酸钒钠（Na3V2(PO4)2F3, NVPF）材料，并将其作为CDI阴极，与钌铱钛阳极（Dimensionally Stable Anode, DSA）结合组成非对称CDI系统，实现对废水中锌离子的高效选择性去除与回收。本文主要研究内容及结论如下：（1）采用溶胶-凝胶合成法制备碳包覆的氟磷酸钒钠（NVPF@C），并首次将此钒基材料用作CDI的阴极，与活性炭对电极共同组成电容去离子系统（NVPF@C//AC-HCDI），探究对废水中Zn2+去除和回收的选择性。在1.2V外加电压、50 mg/L Zn2+的初始浓度下，NVPF@C对Zn2+的吸附容量为24.2 mg/g，显著高于商用活性炭对Zn2+的吸附容量（15.3 mg/g），且在反接1.2 V外加电压条件下可实现90%以上的解吸附率。NVPF@C对于Zn2+、Na+混合溶液的选择性系数为βZn/Na=133.2，对比活性炭（βZn/Na=6.46）表现出更优的选择性。（2）进一步利用循环伏安曲线和密度泛函理论揭示了NVPF@C选择性去除Zn2+的机制，主要是通过离子在NASICON结构中的插层脱嵌机理。（3）实际废水中锌通常以络合态形式存在，电吸附效率不佳。本论文以乙二胺四乙酸（EDTA）结合态锌离子的络合物为处理目标，设计了一种耦合电催化氧化与电阴极吸附的非对称CDI系统（NVPF@C//DSA）：钌铱钛DSA作为阳极，用于对EDTA-Zn络合物破络合；NVPF@C作为阴极，用于选择性去除和回收锌离子。实验结果表明，DSA所具有的析氯功能可有效氧化降解EDTA；在电压3.6 V和7.7 mM Cl- 浓度下, NVPF@C//DSA体系对锌的吸附容量为 23.9 mg/g，完全避免了络合物的影响。本论文创新性地将电池材料NVPF@C应用于电容去离子技术中，显著提高了选择性锌离子回收能力，同时耦合钌铱钛DSA组成非对称CDI系统，减轻锌污染的同时满足了锌资源回收的需求，为重金属废水处理提供了一个有效的解决方案。

Zinc (Zn) holds a strategic significance in electro-plating and battery sectors, but the resultant zinc-laden wastewater presents environmental and public health threats. The effective recovery of zinc from wastewater serves as a viable solution to address both the scarcity of zinc resources and pollution issues. Capacitive deionization (CDI) is an emergent technology for heavy metal ion recovery, celebrated for its efficiency, stability, eco-friendliness, and energy-saving attributes. Traditional CDI systems typically employ carbon electrodes, which lack selectivity for certain ions, rendering them less effective in practical wastewater with diverse contaminants, thus impeding large-scale application. Recently, Faradaic electrodes that display selective ion intercalation mechanisms have garnered attention. In this thesis, sodium vanadium fluorophosphate (Na3V2(PO4)2F3, NVPF) materials with selective adsorption for Zn2+ were fabricated and utilized as the cathode in a CDI system, coupled with ruthenium-iridium titanium anodes (Dimensionally Stable Anode, DSA) to form an asymmetric CDI system. This system was designed for efficient and selective removal and recovery of zinc ions from wastewater. The main research content and conclusions of this thesis are as follows:(1) Carbon-coated sodium vanadium fluorophosphate (NVPF@C) was synthesized using the sol-gel method, and for the first time, this vanadium-based material was employed as the cathode in a CDI system, in conjunction with activated carbon to form a Capacitive Deionization System (NVPF@C//AC-HCDI), exploring selectivity for the removal and recovery of Zn2+ from wastewater. Under an applied voltage of 1.2V with an initial Zn2+ concentration of 50 mg/L, NVPF@C exhibited an adsorption capacity for Zn2+ of 24.2 mg/g, significantly higher than the commercial activated carbon capacity for Zn2+ (15.3 mg/g). Furthermore, over 90% desorption efficiency was achieved upon reversing the applied voltage of 1.2V. The selectivity coefficient for Zn2+ in the presence of Na+ for NVPF@C was βZn/Na=133.2, showing superior selectivity compared to activated carbon (βZn/Na=6.46). (2) Cyclic voltammetry and density functional theory further elucidated the mechanism of selective Zn2+ removal by NVPF@C, with the NASICON structure's ion intercalation/deintercalation being the predominant action. (3) In real wastewater scenarios, zinc often exists in a complexed form, which is inefficiently adsorbed. This thesis targeted the EDTA-bound zinc complexes, designing an asymmetric CDI system (NVPF@C//DSA) that integrates electrocatalytic oxidation with cathodic adsorption: ruthenium-iridium DSA serving as the anode to break EDTA-Zn complexes and NVPF@C as the cathode for selective removal and recovery of zinc ions. Experimental results demonstrated that the chlorination functionality of DSA effectively degrades EDTA. At an applied voltage of 3.6V and a chloride concentration of 7.7 mM, the NVPF@C//DSA asymmetric CDI system exhibited a zinc adsorption capacity of 23.9 mg/g, circumventing the influence of the complex.This thesis innovatively applies the battery material NVPF@C to capacitive deionization technology, significantly enhancing selective zinc ion recovery capabilities. It also combines it with ruthenium-iridium DSA to form an asymmetric CDI system, which addresses zinc pollution while meeting zinc resource recovery needs, providing an effective solution for heavy metal wastewater treatment.