摘 要

我国拥有丰富的钼矿资源，其储量居世界之首。其中，辉钼矿约占钼矿资源总量的99%，因此，推动辉钼矿的高质量资源化利用具有重要的战略意义。辉钼矿是一种层状过渡金属硫化矿物，具有窄带隙半导体特性，在光催化领域具备潜在的应用前景。然而，天然辉钼矿存在光生电荷易复合、价带氧化还原电势不足等缺陷，限制了其催化性能的充分发挥。本文通过液相超声法对辉钼矿进行剥离，制备了少层辉钼矿。再与不同铁基材料复合，制备了不同结构的辉钼矿基光－芬顿复合材料。以含有四环素水溶液为目标污染物，研究了辉钼矿基复合材料降解抗生素废水的性能，探究了辉钼矿基光－芬顿复合材料用于处理地下抗生素污染废水的可行性、适用性和实用性，拓展了辉钼矿材料的应用领域，对于辉钼矿资源的高效利用具有重要的指导意义。以下是主要的研究内容和结论：

（1）确定了辉钼矿在光－芬顿体系中能够提高Fe²⁺再生率的可行性。以天然辉钼矿为原料，采用液相超声剥离－煅烧法制备了Fe/少层辉钼矿非均相复合材料，并对其进行了表征。以水溶液中的四环素为目标污染物，考察了复合材料的催化性能。结果表明，Fe/少层辉钼矿复合材料的光－芬顿性能明显高于少层辉钼矿，光－芬顿反应100 min，15%Fe/少层辉钼矿对四环素的氧化降解效率可达89.4%，一级动力学速率常数为0.022 min^-1，是原始少层辉钼矿（0.007 min^-1）的3.1倍。辉钼矿与Fe复合后，加速了光生电荷的迁移与分离效率，促进了Fe³⁺的还原。此外，少层辉钼矿表面的S^2-易与溶液中的H⁺形成H₂S，暴露出活泼Mo⁴⁺有效加速芬顿反应中的Fe³⁺/ Fe²⁺循环，进一步促进反应活性的提高。本研究为进一步构筑不同性能的辉钼矿基光－芬顿复合材料奠定了基础。

（2）构筑了高效的Z型少层辉钼矿/Fe/Bi₂MoO₆光－芬顿复合材料。由于少层辉钼矿窄的带隙和较高的电荷复合率阻碍了其光生电子对Fe³⁺的还原，将具有合适价带位置的宽带隙Bi₂MoO₆与少层辉钼矿复合，采用水热法合成了三元Z型少层辉钼矿/Fe/Bi₂MoO₆复合材料。结果表明，在可见光照射下，少层辉钼矿/Fe/Bi₂MoO₆-3复合材料对四环素的光－芬顿催化降解效果显著提高，在120 min，四环素的去除率达到92.05%。经历四个循环反应后，少层辉钼矿/Fe/Bi₂MoO₆的光－芬顿降解效率均超过85%。Fe介导在Bi₂MoO₆和少层辉钼矿之间，促进了Bi₂MoO₆和少层辉钼矿两相界面处的电子传递，增强了Fe³⁺/Fe²⁺循环，促进了H₂O₂的分解，从而进一步提高了光－芬顿降解效率。

（3）设计合成了一种宽pH适用范围的少层辉钼矿/MIL101(Fe)光－芬顿复合材料。针对Fe基光－芬顿催化剂适用pH工作范围窄、易产生含Fe污泥的问题，通过水热法制备了少层辉钼矿/MIL101(Fe)光－芬顿复合材料，并将其应用于四环素降解。结果表明，经过2 h，4%少层辉钼矿/MIL101(Fe)纳米复合材料对四环素的去除率高达93.6%。这是由于少层辉钼矿/MIL101(Fe)框架中Fe-O团簇促进了Fe³⁺/Fe²⁺的循环，加速了光－芬顿反应的进行。此外，得益于MIL101(Fe)的固体酸催化剂功能，少层辉钼矿/MIL101(Fe)光－芬顿复合材料对四环素降解的pH适用范围显著拓宽，在pH值为3-9的范围内，少层辉钼矿/MIL101(Fe)对四环素的去除率均高于81%，三次循环后四环素的去除率均在72%以上。少层辉钼矿/MIL101(Fe)复合材料具有良好的pH使用范围，有效解决了传统芬顿氧化工艺pH低、范围窄的问题。

（4）制备了一种可磁性回收的少层辉钼矿/MnFe₂O₄光－芬顿材料。针对复杂体系反应中催化材料的难回收利用问题，采用水热法制备了少层辉钼矿/MnFe₂O₄复合材料。在四环素浓度20 mg/L，催化剂用量为0.2 g/L，pH = 6，双氧水浓度为6 mmol/L，反应120 min，15%少层辉钼矿/MnFe₂O₄复合材料对四环素的降解效率为92.7%。循环实验表明，四次循环后，15%少层辉钼矿/MnFe₂O₄复合材料仍能达到87.4%降解率，且材料表面的官能团和晶相均未发生明显变化。此外，15%少层辉钼矿/MnFe₂O₄材料具有磁性分离能力，可通过磁性实现催化材料与反应体系的快速分离，其在环境修复中具有很大的应用潜力。

ABSTRACT

China possesses abundant molybdenum ore resources, ranking first in the world in terms of reserves. Among these, molybdenite accounts for approximately 99% of the total molybdenum ore resources, making the high-quality resource utilization of molybdenite of significant strategic importance. Molybdenite is a layered transition metal sulfide mineral with narrow bandgap semiconductor characteristics, showing potential applications in the field of photocatalysis. However, natural molybdenite has limitations such as easy recombination of photogenerated charges and insufficient oxidation-reduction potential of the valence band, which restrict its full catalytic performance. In this dissertation, few-layer molybdenite was prepared by exfoliating molybdenite through a liquid-phase ultrasonic method. Then, different structures of molybdenite-based photo-Fenton composite materials were synthesized by combining it with various iron-based materials. Using aqueous solution containing tetracycline as the target pollutant, the performance of molybdenite-based composite materials in degrading subterranean organic wastewater was investigated. The feasibility, applicability, and practicality of using molybdenite-based photo-Fenton composite materials for antibiotic wastewater treatment were explored, expanding the application fields of pyromolybdenite materials and providing important guidance for the efficient use of pyromolybdenite resources. The main research contents and conclusions are as follows:

(1) The feasibility of pyromolybdenite in the photo-Fenton system capable of increasing the Fe²⁺ regeneration rate was determined. Using natural molybdenite as a raw material, the Fe/few-layer molybdenite heterogeneous composite material was prepared by a liquid-phase ultrasonic exfoliation-calcination method and characterized. The catalytic properties of the composites were investigated using tetracycline in aqueous solution as the target pollutant. The results showed that the photo-Fenton performance of the Fe/few-layer molybdenite composite material was significantly higher than that of few-layer molybdenite alone. After 100 min of photo-Fenton reaction, the oxidative degradation efficiency of tetracycline by 15%Fe/few-layer molybdenite reached 89.4%, with a first-order kinetic rate constant of 0.022 min^-1, which is 3.1 times that of the original few-layer molybdenite (0.007 min^-1). The combination of molybdenite with Fe accelerated the migration and separation efficiency of photogenerated charges and promoted the reduction of Fe³⁺. Additionally, S^2- on the surface of few-layer molybdenite easily forms H₂S with H⁺ in the solution, exposing active Mo⁴⁺ sites that effectively accelerate the Fe³⁺/Fe²⁺ cycle in the Fenton reaction, further enhancing the reaction activity. This study lays the foundation for the construction of molybdenite-based photo-Fenton composite materials with different properties.

(2) Efficient Z-type few-layer molybdenite/Fe/Bi₂MoO₆ photo-Fenton composites were constructed. Due to the narrow bandgap and high charge recombination rate in few-layer molybdenite, which hinder its photogenerated electrons from reducing Fe³⁺, a wide bandgap Bi₂MoO₆ with an appropriate valence band position was combined with few-layer molybdenite to synthesize the ternary Z-scheme few-layer molybdenite/Fe/Bi₂MoO₆ composite material using a hydrothermal method. The results showed that under visible light irradiation, the few-layer molybdenite/Fe/Bi₂MoO₆-3 composite material significantly improved the photo-Fenton catalytic degradation efficiency of tetracycline, achieving a removal rate of 92.05% after 120 min. After four reaction cycles, the photo-Fenton degradation efficiency of the few-layer molybdenite/Fe/Bi₂MoO₆ remained above 85%. Fe mediation between Bi₂MoO₆ and few-layer molybdenite promoted electron transfer at the interface of the two phases, enhancing the Fe³⁺/Fe²⁺ cycle and promoting the decomposition of H₂O₂, thereby further improving the photo-Fenton degradation efficiency.

(3) A few-layer/MIL101(Fe) photo-Fenton composite with a wide pH suitability range was designed and synthesised. To address the problems of the Fe-based photo-Fenton catalysts, such as the narrow applicable pH working range and the disadvantage of easy generation of Fe-containing sludge, a few-layer molybdenite/MIL101(Fe) photo-Fenton composite was prepared by hydrothermal method and applied to the degradation of tetracycline. The results showed that after 2 h, the 4% few-layer molybdenite/MIL101(Fe) nanocomposite material achieved a tetracycline removal rate of up to 93.6%. This is due to the Fe-O clusters in the few-layer molybdenite/MIL101(Fe) framework promoting the Fe³⁺/Fe²⁺ cycle, accelerating the photo-Fenton reaction. Additionally, thanks to the solid acid catalyst function of MIL101(Fe), the pH application range for tetracycline degradation by the few-layer molybdenite/MIL101(Fe) photo-Fenton composite material was significantly broadened. Within the pH range of 3-9, the removal rates of tetracycline by few-layer molybdenite/MIL101(Fe) were all above 81%, and after three cycles, the removal rates remained above 72%. The few-layer molybdenite/MIL101(Fe) composite material has a good pH range of applicability, effectively solving the problems of low pH and narrow range in traditional Fenton oxidation processes.

(4) A magnetically recyclable few-layer molybdenite/MnFe₂O₄ photo-Fenton material was prepared. To address the difficulty of recycling catalytic materials in complex systems, a few-layer molybdenite/MnFe₂O₄ composite material was prepared using a hydrothermal method. Under the conditions of a tetracycline concentration of 20 mg/L, catalyst dosage of 0.2 g/L, pH = 6, and hydrogen peroxide concentration of 6 mmol/L, after a reaction time of 120 minutes, the 15% few-layer molybdenite/MnFe₂O₄ composite material achieved a degradation rate of 92.7% for tetracycline. Cycling experiments showed that after four cycles, the 15% few-layer molybdenite/MnFe₂O₄ composite material could still achieve a degradation rate of 87.4%, and no significant changes were observed in the functional groups and crystal phase on the material surface. Additionally, the 15% few-layer molybdenite/MnFe₂O₄ material has magnetic separation capability, which can be used to achieve rapid separation of catalytic materials from the reaction system through magnetism, and it has great potential for application in environmental remediation.

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