光催化降解染料為近年來熱門的研究主題之一，近年來透過研發新材料以及合成不同的複合結構來改善光生載子複合率高以及增強對於可見光波長光源的吸收率，而本研究除了改善材料對可見光波段光吸收外，另外也利用材料本身特性達到可進行暗降解反應；實驗合成之複合結構為將硫化銅合成於氧化鋅-奈米金之複合結構上；可知硫化銅本身為低能隙且本身可在不照光的情況下催化過氧化氫產生高能自由基在這裡稱其為暗降解，但由於單一材料容易有光生載子複合率高，或是合成時奈米顆粒容易團聚之現象，因此將硫化銅合成於氧化鋅-奈米金之複合結構上，且成長於基板之光觸媒也具有易回收之優勢。實驗之光觸媒主體氧化鋅以兩種不同材料為基板，成長結構為奈米牆與奈米柱；在經由硫化製程時間調整以及改變前驅物濃度後找到最佳硫化參數，由最佳參數之結果顯示複合結構後氧化鋅奈米牆之全日催化降解中之光降解反應速率常數k值由0.0027(min-1)提升至0.0081(min-1)，而其暗降解k值則是由非常低的0.0008(min-1)提升至0.006(min-1)；而氧化鋅奈米柱由全日催化降解中暗降解反應速率常數k值0.0013(min-1)提升至0.017(min-1)；並且透過動力學將樣品之暗降解分析，可發現氧化鋅奈米牆在暗降解反應中幾乎無法作用且其降解結果代入動力模型之相關係數極低，也驗證了硫化銅的暗降解特性。

Metal oxide semiconductor nanomaterials have been extensively studied for photocatalytic water treatment. To enhance their photocatalytic performance, different synthetic methods of heterogeneous photocatalysts have been developed for improving energy harvesting of solar light and carrier utilization nowadays. In this study, we used different substrates to synthesize zinc oxide nanorods and nanowalls. Then, combing zinc oxide, gold nanoparticle, and copper sulfide nanomaterial by photochemical reduction and simple chemical reduction method. After that, adjusting two kinds of parameters with sulfidation time and the concentration of precursor solution, cupper (Ⅱ) sulfide, for modifying copper sulfide nanoparticles and enhancing the reaction rate of photodegradation. After increasing the concentration of precursor, cupper (Ⅱ) sulfate, the copper (Ⅱ) sulfide nanoparticles synthesized on ZnO-Au or ZnO would transform to copper (Ⅰ) sulfide nanoparticles which own suitable band alignment with ZnO-Au and ZnO and lead to decreasing the carrier recombination rate. Moreover, the dark catalytic experiments were implemented by adding hydrogen peroxide which would induce the formation of photocatalytic active hydroxyl radicals by copper sulfide without light irradiation. Pseudo-first-order kinetic model were employed to quantify the photocatalytic activity and the rate constant increased from 0.0027 (min-1) to 0.0081 (min-1) in the photodegradation experiment, and 0.0008 (min-1) to 0.006 (min-1) in the dark degradation experiment of zinc oxide nanowalls and ZnO-Au@CuXS. The results also proved that the decoration of copper sulfide nanoparticles can modify zinc oxide effectively on both photocatalytic and dark catalytic reactions that could be applied for all-day active catalyst.

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