隨著全球工業化與都市化加速發展，水體污染問題日益嚴峻，其中尤以新興汙染物(emerging contaminants, ECs)與含重金屬廢水最具挑戰。新興汙染物包括抗生素、個人護理用品、農藥與微塑膠等，其共同特徵為持久性強、處理困難、易在環境中累積並透過食物鏈傳遞。另一方面，工業製程所排放之六價鉻廢水因毒性強、致癌致突變性高，即使低濃度亦對生態與人體造成威脅。傳統處理技術往往侷限於單一污染物，對於複雜二元體系難以同時有效處理，故開發兼具高效能與穩定性的光觸媒材料成為環境修復的重要方向。
光催化技術具有能利用太陽能、反應條件溫和、不產生二次污染等優勢，是處理難降解污染物的前沿技術。然而傳統光觸媒如TiO2因能隙寬(約3.2 eV)、僅能吸收紫外光、電子-電洞對復合率高等問題，導致光利用效率有限。本研究以生物碳與生物質為基底，結合金屬氧化物，又或是利用共價有機骨架結合傳統半導體，設計新型複合光觸媒，以期提升可見光吸收能力與電荷分離效率，並兼顧材料的循環穩定性與實際應用性。首先，以咖啡渣為碳源熱解製備生物碳，並與氧化亞銅(Cu2O)複合，獲得Cu2O/BC光觸媒。透過 XRD、SEM、TEM、XPS 與 BET 分析確認結構與表面性質。實驗顯示，該材料於可見光下降解磺胺甲噁唑(SMX)的效率顯著優於純Cu2O。其關鍵在於生物碳提供為導電載體，有效抑制電子-電洞復合，促進超氧自由基(•O2-)與空穴(h⁺)的生成與反應。瞬態光電流、電化學阻抗譜與 EPR 結果均證實其電荷分離與活性物種生成的優勢。
其次，合成Cu-Cu2O-CTs複合光觸媒，應用於氟喹諾酮類抗生素恩諾沙星(ENR)的降解。在模擬太陽光下，降解效率接近完全(99.99%)，並於四次循環後仍保持超過 70% 活性，展現良好穩定性。殼聚醣提供氨基官能團，增進材料表面反應性與電荷分離能力。透過 LC-MS 與 DFT 計算，確認 ENR 哌嗪環氮原子為主要反應位點，揭示選擇性降解機理。毒理學模擬顯示中間產物毒性普遍降低，強化其環境應用潛力。
最後，本研究構築TrPa/TiO2-NH2 Z型異質結構，以處理四環素(TC)與Cr(VI)的二元污染系統。結果顯示，該光觸媒能同時高效降解TC與還原Cr(VI)，效能顯著優於單一系統。機制結果指出，TC與Cr(VI)分別作為電洞與電子的消耗劑，協同抑制載流子復合，提升量子效率。EPR 與捕獲實驗確認•O2-、•OH與h⁺共同參與TC降解，而Cr(VI)還原則主要依賴光生電子。DFT 計算不只指出TC在去質子化狀態的反應點位，更進一步揭示電子優先還原Cr(VI)，後續再將O2還原成•O2-進而降解TC。
綜合而言，本研究具以下創新：其一，利用廢棄生物質與可調式無機架構物，並與金屬氧化物複合，開發具備可見光響應的新型光觸媒；其二，結合多種光電化學與光譜技術，完整揭示光生載流子行為及活性物種生成；其三，透過 DFT 理論計算，解析污染物分子反應位點、反應趨勢變化與中間產物毒性；其四，實證材料具備優異循環穩定性，展現實際應用潛力。
本研究奠基於綠色化學工程理念，建立了一套兼具材料創新、機理揭示與應用驗證的整合性研究模式。透過將廢棄生物質資源化與共價有機骨架導入光電催化系統，不僅突破了傳統光觸媒的侷限，也提供了同時處理新興有機污染物與重金屬廢水的新思路。研究成果不僅深化了對複合光觸媒作用機制的理解，也為新興有機污染物與含鉻廢水的同步治理提供可行途徑，在光催化技術應用於實際廢水治理與環境保護具有重要意義。

The intensification of global industrialization and urbanization has aggravated the problem of water pollution, with emerging contaminants (ECs) and heavy metal wastewater posing particular challenges. Emerging pollutants include antibiotics, personal care products, pesticides and microplastics, which are persistent, difficult to treat, easily accumulate in the environment, and can be transferred through the food chain. Meanwhile, wastewater containing hexavalent chromium (Cr(VI)) generated in many industrial production processes is highly toxic, carcinogenic and mutagenic, and even at trace concentrations, it can threaten ecosystems and human health. Conventional treatment methods are often limited to single pollutants and fail to address such complex systems. Thus, the development of photocatalytic materials with both high efficiency and stability is a crucial strategy for environmental remediation. Photocatalysis offers unique advantages, including the use of solar energy, mild operating conditions, and minimal secondary pollution. This study focuses on designing novel composite photocatalysts by integrating biochar, biomass and covalent organic frameworks with conventional semiconductors, aiming to enhance visible-light utilization, charge separation, and material stability.
The biochar prepared from waste coffee grounds was combined with cuprous oxide (Cu2O) to synthesize Cu2O/BC photocatalyst. Compared with pristine Cu2O, the composite exhibited superior degradation efficiency of sulfamethoxazole (SMX) under visible light. This improvement was attributed to the conductive role of biochar, which suppressed electron-hole recombination and facilitated the formation of reactive species such as superoxide radicals (•O2-) and holes (h⁺).
A Cu-Cu2O-CTs composite photocatalyst was synthesized for the degradation of enrofloxacin (ENR). The degradation efficiency reached nearly 99.99% and retained more than 70% activity after four cycles under simulated solar irradiation. LC-MS combined with density functional theory (DFT) calculations identified the piperazine nitrogen atom in ENR as the key reaction site, thus explaining its selective degradation pathway. Toxicological simulations further indicated reduced toxicity of degradation intermediates.
A TrPa/TiO2-NH2 Z-type heterojunction was constructed for the simultaneous degradation of tetracycline (TC) and reduction of hexavalent chromium (Cr(VI)). Mechanistic studies revealed that TC and Cr(VI) acted as hole and electron scavengers, respectively, effectively suppressing carrier recombination and improving quantum efficiency. DFT calculations demonstrated that deprotonated TC species influenced reaction energetics, while Cr(VI) reduction was thermodynamically prioritized, subsequently enhancing O2 reduction to •O2- and accelerating TC degradation.
This research is based on the principles of green chemistry and sustainable engineering and establishes a comprehensive research framework that integrates material innovation, mechanism analysis and application verification. By valorizing waste biomass into functional photocatalysts and incorporating COFs into photocatalytic systems, the study not only overcomes the limitations of conventional photocatalysts but also provides new strategies for the simultaneous treatment of ECs and Cr(VI) containing wastewater. These findings advance our understanding of composite photocatalytic mechanisms and provide practical implications for wastewater remediation. This research highlights the role of photocatalysis as a sustainable technology in environmental protection and public health.

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