双酚A（Bisphenol A, BPA）和布洛芬（Ibuprofen, IBU）分别作为增塑剂与常用药在生产生活中广泛使用，是典型的新污染物。两者用量大，在水环境中流失严重，有一定蓄积性，近年来在地表水、地下水、海洋中被频繁检出。目前，已有报道表明，BPA与IBU长期暴露对环境生态安全以及人类健康构成潜在威胁。现有技术对BPA和IBU的处理存在成本高，能效低，二次污染严重等方面的缺陷，因此，亟待开发新的环境友好、高选择性、高效低耗的水污染控制技术。

基于过一硫酸盐（Peroxymonosulfate，PMS）的高级氧化技术具有高活性、高选择性、环境友好的技术优势，受到了研究者的广泛关注。过渡金属催化剂常被用于PMS活化，其优势在于活化能力强且无需施加外部能量，便于在修复现场展开。然而，如何充分利用过渡金属催化活性位点，提高催化剂的原子经济性是值得思考的问题。单原子催化剂（SACs）可充分暴露活性位点，最大化提高原子利用效率，成为过渡金属催化剂研究领域的热点。然而如何有效调节和优化活性位点及催化剂的表面几何参数，以进一步改善SACs催化活性和选择性则是悬而未解的技术和理论问题。基于以上分析，本文以BPA和IBU为目标污染物，通过热聚合工艺制备多种碳基SACs，并构建SACs/PMS活化体系，考察不同催化活化体系对污染物的降解性能、阐明活化机理，并对其实际应用潜力进行了初步评估。本论文主要研究内容和结论总结如下：

（1）为改善Fe SACs的原子经济性和活性物种产率，以铁（Fe）盐和尿素为前驱体制备了Fe掺杂碳氮化物（CN），再经盐酸刻蚀制备出一系列存在不同N空位缺陷Fe₁-C₃N₄催化剂（记为Fe-CNW），该催化剂具有优异的PMS活化能力，可以高效去除BPA（伪一级反应动力学常数k_BPA = 2.51 min^–1，3 min内对BPA去除率超过99 %）。X射线光电子能谱（XPS）、电子自旋波谱仪（ESR）以及X射线吸收光谱（XAS）等表征手段证明，酸刻蚀导致催化剂中Fe₁-N₄结构重构为Fe₁-C₂N₁结构，该结构提供的活性位点更有利于PMS活化，并且极大地降低了产生单线态氧（¹O₂）的活化能垒。通过酸刻蚀Fe-CN实现了对配位环境的精确调控，BPA的降解速率常数比Fe₁-N₄配位结构提高29倍。

（2）进一步对钴（Co）和镍（Ni）掺杂的Co-CN和Ni-CN催化剂进行类似的酸刻蚀处理。研究发现，酸刻蚀后的Co/Ni-CN催化剂上主导活性物种的类型发生了改变，从硫酸根自由基（SO₄^•-）和羟基自由基（·OH）主导的低选择性氧化体系转变为¹O₂为主导的高选择性氧化体系。通过ESR、XPS等表征，发现酸刻蚀同样造成了Co/Ni-CNW（酸刻蚀后的Co-CN）结构中N空位缺陷的产生。结合综合物性分析（PPMS）可知，N空位诱导Co/Ni-CNW由高自旋态转变为低自旋态，促使PMS分子的S-O键断裂，吸附在低自旋位点的*OO，进一步产生¹O₂。

（3）通过对铜（Cu）-MOF前驱体与不同比例N源进行煅烧，制备了高度分散的Cu₁-NC催化剂，并考察PMS吸附状态对PMS活化的影响。实验结果显示，当前驱体与N源质量比为1:10时，所制备的Cu₁-NC-4催化剂表现出良好的PMS活化能力和较高BPA去除效率（k_BPA = 0.997 min⁻¹，3 min内对BPA的去除率超过99.9 %以上）。综合实验评估、材料表征以及密度泛函理论（DFT）模拟计算结果，认为适宜的N元素配比优化了Cu位点分布，导致Cu SAC原子间的间距发生变化，而这种间距调节对PMS分子吸附构型有重要影响，可以诱导PMS以桥式吸附模式与Cu活性位点结合。该吸附构型在热力学上更稳定，可增强电子从供体上的抽离效应，选择性分解BPA。

（4）为灵活有效地针对水中污染物的化学稳定性控制氧化反应深度，受Cu-NC-4/PMS催化活化反应机理启发，以Cu-NC、Co-NC、Ni-NC催化剂作为颗粒电极，以钌铱（Ti/RuIr）阳极以及钛（Ti）阴极共同组成电解池体系，研究该体系对BPA和IBU的去除能力。结果表明，在电诱导条件下IBU的去除均有不同程度的提高（动力学常数分别提高4.88倍、3.40倍和1.89倍），电诱导协同因子大小顺序为：Cu-NC > Ni-NC > Co-NC。通过一系列实验也证明了电诱导可以强化自由基的产生（SO₄^•- 和·OH）促使SACs/PMS体系的主导活性物种反应过程在非自由基过程和自由基过程之间灵活转化，可以有效降解IBU等非自由基过程难以去除的有机污染物。同时，研究表明使用三维颗粒电极体系活化PMS可显著提高传质效率，而且在一定程度上降低能耗。

（5）最后，综合考察了所制备催化剂的稳定性、反应体系的鲁棒性并且对催化剂应用潜力进行了初步评估。研究结果表明，Fe-CNW3（酸刻蚀3次的Fe-CN）/PMS、CuNC-4/PMS的催化体系在较为宽泛的pH值范围（3–10）内表现出良好的活性和稳定性，抗无机离子干扰能力较强。而电诱导下的催化反应体系则对pH适应范围较窄，但具有较高的矿化能力。此外，所有体系中，几乎所有的SACs经历10–12次循环使用，对污染物的去除效率始终保持在85 %以上。进一步地，将SACs负载于膜表面制备反应活性膜体系，或者作为颗粒电极在流化床反应器中进行连续流实验测试，结果表明，Fe-CNW3反应活性膜装置出水中BPA的去除率保持在90 %以上（170 h），二级出水中BPA去除率也稳定在75 %以上；对于电化学诱导条件下的颗粒电极体系来说，装置连续运行170 h内，出水中BPA和IBU的去除率分别保持在85–95 %和85–90 %以上；以实际地表水进行模拟研究，结果显示当BPA和IBU的初始浓度在5 mg L^–1，两者的去除率均在90 %以上。对电诱导体系进行比能耗（SEC）计算，证明电诱导催化活化体系的能耗更低，具有一定的技术优势。

Bisphenol A (BPA) and ibuprofen (IBU) are widely used as plasticizers and common drugs in production and daily life, and are typical emerging pollutants. both substances are used in large quantities and prone to severe loss in aquatic environments. They have certain accumulation characteristics and have been frequently detected in surface water, groundwater, and oceans in recent years. Currently, it has been reported that long-term exposure to BPA and IBU poses potential threats to environmental ecology and human health. The existing technologies for the treatment of BPA and IBU has high cost, low energy efficiency and serious secondary pollution, so it is urgent to develop new environmentally friendly, high selectivity, high efficiency and low consumption targeted technologies to control aquatic pollution.

Peroxymonosulfate (PMS) based advanced oxidation technology has attracted significant attention from researchers due to its advantages of high activity, high selectivity and environmental friendliness. Transition metal catalysts are commonly used for PMS activation, which have the advantage of strong activation ability and the absence of external energy, making it convenient for on-site remediation. However, it is worth thinking about how to fully utilize the active sites of transition metal catalysts and improve their atomic economy. Single-atom catalysts (SACs) can fully expose active sites and maximize the atomic utilization efficiency, becoming a hot topic in the field of transition metal catalyst research. Nevertheless, However, how to effectively adjust and optimize the active site and the surface geometry parameters of the catalyst to further improve the catalytic activity and selectivity of SACs is an unresolved technical and theoretical problem. Based on the above analysis, this paper focused on BPA and IBU as target pollutants, prepared a variety of carbon-based SACs by hot polymerization process, and constructed SACs /PMS activation systems. The degradation performance of different catalytic activation systems for pollutants was investigated, the activation mechanism was clarified, and the potential practical application of was preliminarily evaluated. The main research contents and major conclusions of this paper are summarized as follows:

(1) To enhance the atomic economy and yield of active species for Fe Single-Atom Catalysts (SACs), a series of Fe-doped carbon nitride (CN) catalysts with various N-vacancy defects, referred to as Fe-CNW, were synthesized using iron (Fe) salts and urea as precursors, followed by etching with hydrochloric acid. The catalysts exhibited excellent PMS activation ability and could effectively remove BPA (pseudo-first-order reaction rate constant, k_BPA= 2.51 min^–1, removal efficiency over 99 % within 3 min). Characterization techniques such as X-ray photoelectron spectroscopy (XPS), electron spin resonance spectroscopy (ESR), and X-ray absorption spectroscopy (XAS) confirmed that acid etching resulted in the structural reconstruction of Fe₁-N₄ into Fe₁-C₂N₁, which provided more favorable active sites for PMS activation and significantly reduced the energy barrier for generating ¹O₂. Acid etching of Fe-CN achieved precise control over the coordination environment, and the degradation rate constant of BPA was 29 times higher than that of Fe₁-N₄.

(2) Further acid etching treatment was applied to cobalt (Co) and nickel (Ni) doped Co-CN and Ni-CN catalysts. It was found that dominant active species on the acid-etched Co/Ni-CN catalysts changed from a low-selectivity oxidation system dominated by sulfate radical (SO₄^•-) and hydroxyl radical (•OH) to a high-selectivity oxidation system dominated by singlet oxygen (¹O₂). ESR, XPS and other characterization revealed that acid etching also induced the generation of N vacancy defects in the Co/Ni-CNW (acid-etched Co-CN) structure. Combined with comprehensive physical property analysis (PPMS) results, it was observed that the N-vacancy induced the transition in Co/Ni-CNW, from a high-spin state to a low-spin state, facilitating the breaking of S-O bonds in PMS molecules and the adsorption of *OO species on low-spin sites, further generating ¹O₂.

(3) Highly dispersed Cu₁-NC catalysts were developed by calcining copper-molecular organic framework (Cu-MOF) precursors with different ratios of nitrogen (N) sources, aiming to investigate the effect of PMS adsorption status on PMS activation. The experimental results showed that the Cu₁-NC-4 catalyst prepared with a precursor to N source mass ratio of 1:10 exhibited excellent PMS activation ability, high BPA removal efficiency, and selectivity (k_BPA= 0.997 min⁻¹, removal efficiency of BPA over 99.9 % in 3 min). Combined experimental evaluation, material characterization, and density functional theory (DFT) simulation results suggested that the appropriate N element ratio optimized the Cu site distribution, resulting in changes in the spacing between Cu SAC atoms. This spacing adjustment had important influence on the adsorption configuration of PMS molecules, inducing bridge adsorption mode of PMS with Cu active sites. This adsorption configuration was thermodynamically more stable and enhanced the electron abstraction effect from the donor, selectively decomposing BPA.

(4) To flexibly and effectively control the depth of oxidation reactions for the chemical stability of waterborne pollutants, inspired by the catalytic activation mechanism of Cu-NC-4/PMS, Cu-NC, Co-NC, and Ni-NC catalysts were utilized as particulate electrodes, in conjunction with a ruthenium-iridium (Ti/RuIr) anode and a titanium (Ti) cathode to form an electrolytic cell system. The removal capabilities of this system for BPA and IBU were investigated. The results showed that under electro-induced conditions, the removal of IBU was significantly enhanced (kinetic rate increased by 4.88 times, 3.4 times, and 1.89 times, respectively), with the electro-induced synergy factors following the order of Cu-NC > Ni-NC > Co-NC. A series of experiments also demonstrated that electro-induced processes could enhance the generation of radicals (SO₄^•- and •OH ), flexible shifting the dominant reactive process in SACs/PMS system from non-radical to radical processes, effectively degrading organic pollutants such as IBU that are difficult to remove by non-radical processes. Additionally, the study showed that activating PMS with a three-dimensional particle electrode system significantly improved mass transfer efficiency and reduced energy consumption to a certain extent.

(5) Finally, a comprehensive evaluation was conducted on the stability of the prepared catalysts, the robustness of the reaction system, and a preliminary assessment of the catalysts' application potential was performed. The results showed that Fe-CNW3 (acid-etched 3 times)/PMS and CuNC-4/PMS catalytic systems exhibited good activity and stability over a wide pH range (3–10), but had high mineralization capacity. Furthermore, in all systems, most of the SACs catalysts maintained a BPA removal efficiency of over 85 % after 10–12 cycles of use. Additionally, SACs were loaded onto the surface of membranes to fabricate a reactive membrane system, or utilized as particulate electrodes in a continuous flow experimental test within a fluidized bed reactor. The outcomes demonstrated that the Fe-CNW3 reactive membrane device consistently achieved a removal efficiency of BPA above 90 % in the effluent (over 170 h), and the removal efficiency of BPA in the secondary effluent was also stably above 75 %. For the electrochemically induced particle electrode system, the removal efficiency of BPA and IBU in the effluent remained above 85–95 % and 85–90 %, respectively, during 170 hours of continuous operation. Simulation studies using actual surface water showed that when the initial concentrations of BPA and IBU were 5 mg L⁻¹, the removal efficiency of both were above 90 % Specific energy consumption (SEC) calculations for the electro-induced system proved that the energy consumption of the electro-induced catalytic activation system was lower, indicating certain technical advantages.