采用响应面法优化光催化降解亚甲基蓝的Ag₃PO₄@ZnO牛皮纸木质素复合材料
Ag₃PO₄@ZnO kraft lignin composite for optimized photocatalytic degradation of methylene blue using response surface methodology.
作者信息
Abdelkader Marwa S, Younis Sherif A, El-Fawal Esraa M, Ali Hager R, Ibrahim Hosny
机构信息
Analysis and Evaluation Department, Egyptian Petroleum Research Institute, Nasr City, 11727, Cairo, Egypt.
Chemistry Department, Faculty of Science, Cairo University, Cairo, Egypt.
出版信息
Sci Rep. 2025 Jun 20;15(1):20165. doi: 10.1038/s41598-025-05597-7.
This research explores the use of kraft lignin (KL), derived from pulping black liquor waste, as a supportive medium for AgPO@ZnO (AZ-NC) p-n heterojunction and design a new cost-effective ternary KL-AgPO@ZnO nanocomposite (AZKL). The aim is to improve its photocatalytic efficiency in treating textile wastewater while tackling environmental issues such as chemical stability, charge carrier separation, and the production of secondary waste during the photocatalytic process. The response surface methodology (RSM) analysis shows that AZKL is highly effective catalyst for methylene blue (MB: 10 - 25 mg/L) dye mineralization, achieving a rapid decolorization (> 98.2% within 40 min) under visible light at a near-neutral pH (7.48) with maintained high catalytic activity across four consecutive cycles. This outstanding performance is driven by the synergistic interplay of AZKL-based photocatalysis and advanced oxidation process using 0.03% HO co-catalyst. Gas chromatography-mass spectrometry analysis reveals that MB dye degrades stepwise into intermediates such as N, N-dimethyl-p-phenylenediamine, hydroquinone, and formic acid, ultimately mineralizing completely into CO₂ and H₂O. The dominant reactive oxygen species driven this multi-step process are identified as hydroxyl radicals (•OH) and photogenerated holes (h⁺), with H₂O₂ and superoxide radicals (•O₂⁻) playing secondary roles. The data also highlights the multifunctional role of KL support, which enhances charge carrier separation, captures dye molecules, and prevents Zn/Ag ion leaching (less than 0.2 ppm) into the treated water during photocatalysis. This is facilitated by the electron-donating polyphenolic hydroxyl groups on the KL surface, which reduce Ag⁺ to metallic silver and stabilize AZ-NC heterojunction under light irradiation, creating Schottky junctions that improve charge transfer efficiency while reducing secondary contamination risks. A practical case study further illustrates the effectiveness of AZKL in treating real textile effluents, as evidenced by the improved biodegradability of residual organic matter, indicated by changes in chemical/biological oxygen demands (COD/BOD) ratios from 2.62 to 1.47 and inhibition tests against E. coli, meeting wastewater discharge standards. The findings emphasize that the AZKL composite could serve as an effective and adaptable photocatalyst for breaking down organic pollutants and treating intricate wastewater systems.
本研究探索了源自制浆黑液废料的硫酸盐木质素(KL)作为AgPO@ZnO(AZ-NC)p-n异质结的支撑介质的用途,并设计了一种新型经济高效的三元KL-AgPO@ZnO纳米复合材料(AZKL)。目的是提高其在处理纺织废水方面的光催化效率,同时解决诸如化学稳定性、电荷载流子分离以及光催化过程中二次废物产生等环境问题。响应面方法(RSM)分析表明,AZKL是用于亚甲基蓝(MB:10 - 25 mg/L)染料矿化的高效催化剂,在近中性pH值(7.48)的可见光下能实现快速脱色(40分钟内> 98.2%),并且在连续四个循环中保持高催化活性。这种出色的性能是由基于AZKL的光催化与使用0.03% H₂O共催化剂的高级氧化过程的协同相互作用驱动的。气相色谱 - 质谱分析表明,MB染料逐步降解为N,N - 二甲基对苯二胺、对苯二酚和甲酸等中间体,最终完全矿化为CO₂和H₂O。驱动这一多步骤过程的主要活性氧物种被确定为羟基自由基(•OH)和光生空穴(h⁺),H₂O₂和超氧自由基(•O₂⁻)起次要作用。数据还突出了KL载体的多功能作用,它增强了电荷载流子分离,捕获染料分子,并在光催化过程中防止Zn/Ag离子浸出(小于0.2 ppm)到处理后的水中。这是由KL表面的供电子多酚羟基促进的,这些羟基将Ag⁺还原为金属银,并在光照下稳定AZ-NC异质结,形成肖特基结,提高电荷转移效率,同时降低二次污染风险。一个实际案例研究进一步说明了AZKL在处理实际纺织废水方面的有效性,残余有机物生物降解性的提高证明了这一点,化学需氧量/生化需氧量(COD/BOD)比值从2.62变为1.47以及对大肠杆菌的抑制试验表明其符合废水排放标准。研究结果强调,AZKL复合材料可作为一种有效且适应性强的光催化剂,用于分解有机污染物和处理复杂的废水系统。
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