近幾年來，科學家們致力於研究環境水體中之新興污染物，主要項目包含農藥、工業用品、介面活性劑、藥物與個人保健用品等，而藥物與個人保健用品例如藥水、抗生素、針劑中存在數種會影響身體內分泌系統之干擾物質。布洛芬(Ibuprofen)為生活中廣泛使用的抗生素並且屬於非類固醇抗消炎藥(non-steroidal anti-inflammatory drugs)，主要用於緩解各種疾病所引起的疼痛。由於布洛芬很難通過自然降解和傳統的廢污水處理程序中去除，因此可以在廢水、地下水及地表水中檢測出微量殘留。目前主要應用於去除新興污染物的技術包括活性炭吸附、高級氧化法、微生物系統和薄膜處理。但上述方法都需要大量的時間和高成本，有鑒於此，本研究以觸媒活化過一硫酸氫鉀(PMS)程序應用於降解布洛芬，可提供快速且環境友善處理新興汙染物的方式之一。在本研究中通過快速、簡便的共沉澱方法製備一系列金屬氧化物，以SEM、TEM、XRD、FT-IR、XPS、Raman、BET等進行物化特性分析，並探討所製備觸媒降解布洛芬效能的差異。在批次實驗結果中顯示，負載鈣、鎂、鋇等鹼土金屬氧化物中，修飾氧化鈣於氧化銅的複合金屬氧化物具有較多的表面官能基、氧空位與三價銅能有效活化PMS，因此有最佳的降解布洛芬效能，並進一步改變修飾氧化鈣的含量(1~20%)以探討其最適含量，結果發現在氧化鈣含量5%的條件下，有較穩定的球狀結構、均勻分布的氧化鈣與較多的Cu-OH鍵結，因此具有最好降解效能(6分鐘內達到99.9%的布洛芬去除率)。進一步研究不同的操作條件下(觸媒濃度、布洛芬含量、PMS劑量、溫度、pH值及不同淬滅劑)，對5%氧化鈣/氧化銅的複合金屬氧化物觸媒降解效能的影響。最後透過液相層析質譜儀分析布洛芬的降解中間產物，並結合EPR及淬滅劑實驗，發現此反應之主要機制是由單線氧為主的非自由基系統。

In the recent years, scientists have devoted to the research of emerging contaminants (ECs) in the water body environment. The ECs consist of pesticides, industrial chemicals, surfactants and pharmaceuticals and personal care products (PPCPs) such as antibiotics, syrups, and injections. Among the ECs, endocrine disrupting substances are commonly known as environmental hormones. Ibuprofen (IBF), regarded as one kind of pharmaceuticals, personal care products and non-steroidal anti-inflammatory drugs (NSAID), is applied to relieve pain caused by toothache, headache, muscle pain, arthritis, or physical pain. Because it is hard to remove by natural degradation and traditional wastewater treatment systems, it can be found in effluent water, surface water and groundwater. Current technologies for treating ECs include activated carbon adsorption, membrane treatments, biological treatments, and advanced oxidation. However, all the above methods require a lot of time and high cost. Therefore, using catalysts to activate the peroxymonosulfate for degrading ibuprofen may be a feasible and eco-friendly strategy. In this research, a series of metal oxides were prepared via a fast and facile coprecipitation method. The morphologies and physicochemical properties of the catalysts were analyzed by SEM, TEM, FT-IR, XPS, Raman, XRD and BET analyses. The degradation of IBF was carried out in a batch reactor under magnetic stirring and their corresponding degradation performance of IBF via prepared catalysts is also studied. The experimental results show that among the alkaline earth metal oxides such as MgO, CaO and BaO, the decoration of CaO onto CuO possess more surface functional groups, more oxygen vacancies and more Cu3+ species which can degrade IBF most effectively. In terms of different CaO ratios (1~20%) onto CuO, the CaOCuO catalysts (5% CaO) have the best degradation efficiency (IBF removal efficiency = ca. 99.9%) within 6 min because of more complete sphere structure, uniform dispersion of CaO and more Cu-OH bondings. The effects of different operating conditions (catalyst, IBF concentrations, peroxymonosulfate dosages, temperature, pH, and quenchers) on catalyst performance are also discussed. The intermediate products of the degraded IBF and its mechanism were also analyzed by liquid chromatography mass spectrometer, EPR and quenching tests. The results show that the 1O2 is the main reactive species involved in the degradation of IBF via the CaOCuO (5%)/PMS system.

Ahmed, M. J., & Theydan, S. K. (2012). Adsorption of cephalexin onto activated carbons from Albizia lebbeck seed pods by microwave-induced KOH and K2CO3 activations. Chemical Engineering Journal, 211-212, 200-207.
Almamoori, A., Lawson, S., Rownaghi, A., & Rezaei, F. (2019). Improving Adsorptive Performance of CaO for High Temperature CO2 Capture through Fe and Ga Doping. Energy & Fuels, 33.
Anipsitakis, G. P., & Dionysiou, D. D. (2004). Radical Generation by the Interaction of Transition Metals with Common Oxidants. Environmental Science & Technology, 38(13), 3705-3712.
Ansari, M., & Jahan, N. (2021). Structural and Optical Properties of BaO Nanoparticles Synthesized by Facile Co-precipitation Method. Materials Highlights, 2.
Bolobajev, J., Trapido, M., & Goi, A. (2016). Effect of iron ion on doxycycline photocatalytic and Fenton-based autocatatalytic decomposition. Chemosphere, 153, 220-226.
Borghi, A. A., Silva, M. F., Al Arni, S., Converti, A., & Palma, M. S. A. (2015). Doxycycline Degradation by the Oxidative Fenton Process. Journal of Chemistry, 2015, 492030.
Cabrita, I., Ruiz, B., Mestre, A. S., Fonseca, I. M., Carvalho, A. P., & Ania, C. O. (2010). Removal of an analgesic using activated carbons prepared from urban and industrial residues. Chemical Engineering Journal, 163(3), 249-255.
Carr, D. L., Morse, A. N., Zak, J. C., & Anderson, T. A. (2011). Biological Degradation of Common Pharmaceuticals and Personal Care Products in Soils with High Water Content. Water, Air, & Soil Pollution, 217(1), 127-134.
Cheng, H., Rogers, J. D., Demetriades, J. L., Holland, S. D., Seibold, J. R., & Depuy, E. (1994). Pharmacokinetics and Bioinversion of Ibuprofen Enantiomers in Humans. Pharmaceutical Research, 11(6), 824-830.
Cho, H.-H., Huang, H., & Schwab, K. (2011). Effects of Solution Chemistry on the Adsorption of Ibuprofen and Triclosan onto Carbon Nanotubes. Langmuir, 27(21), 12960-12967.
Chopra, S., & Kumar, D. (2020). Ibuprofen as an emerging organic contaminant in environment, distribution and remediation. Heliyon, 6(6), e04087.
Deng, Y., Handoko, A. D., Du, Y., Xi, S., & Yeo, B. S. (2016). In Situ Raman Spectroscopy of Copper and Copper Oxide Surfaces during Electrochemical Oxygen Evolution Reaction: Identification of CuIII Oxides as Catalytically Active Species. ACS Catalysis, 6(4), 2473-2481.
Ding, M., Chen, W., Xu, H., Shen, Z., Lin, T., Hu, K., . . . Xie, Z. (2020). Novel α-Fe2O3/MXene nanocomposite as heterogeneous activator of peroxymonosulfate for the degradation of salicylic acid. Journal of Hazardous Materials, 382, 121064.
Ekhagen, M., Martin, M., & Ryding, S.-O. (2016). Procurement of pharmaceuticals in an environmental context and its inclusion into the CSR Compass. A study within the UN 10YFP SPP Programme on Promoting Supply Chain´s Sustainability.
Feng, Y., Liao, C., Li, H., Liu, C., & Shih, K. (2018). Cu2O-promoted degradation of sulfamethoxazole by α-Fe2O3-catalyzed peroxymonosulfate under circumneutral conditions: synergistic effect, Cu/Fe ratios, and mechanisms. Environmental Technology, 39(1), 1-11.
Guo, S., Wang, H., Yang, W., Fida, H., You, L., & Zhou, K. (2020). Scalable synthesis of Ca-doped α-Fe2O3 with abundant oxygen vacancies for enhanced degradation of organic pollutants through peroxymonosulfate activation. Applied Catalysis B: Environmental, 262, 118250.
Hu, J., Dong, H., Qu, J., & Qiang, Z. (2017). Enhanced degradation of iopamidol by peroxymonosulfate catalyzed by two pipe corrosion products (CuO and δ-MnO2). Water Research, 112, 1-8.
Hu, P., & Long, M. (2016). Cobalt-catalyzed sulfate radical-based advanced oxidation: A review on heterogeneous catalysts and applications. Applied Catalysis B: Environmental, 181, 103-117.
Huang, L., Wang, M., Shi, C., Huang, J., & Zhang, B. (2014). Adsorption of tetracycline and ciprofloxacin on activated carbon prepared from lignin with H3PO4 activation. Desalination and Water Treatment, 52(13-15), 2678-2687.
Huang, Y.-F., & Huang, Y.-H. (2009). Identification of produced powerful radicals involved in the mineralization of bisphenol A using a novel UV-Na2S2O8/H2O2-Fe(II,III) two-stage oxidation process. Journal of Hazardous Materials, 162(2), 1211-1216.
Jaafarzadeh, N., Ghanbari, F., & Ahmadi, M. (2017). Efficient degradation of 2,4-dichlorophenoxyacetic acid by peroxymonosulfate/magnetic copper ferrite nanoparticles/ozone: A novel combination of advanced oxidation processes. Chemical Engineering Journal, 320, 436-447.
Jawad, A., Zhan, K., Wang, H. B., Shahzad, A., Zeng, Z. H., Wang, J., . . . Chen, Z. Q. (2020). Tuning of Persulfate Activation from a Free Radical to a Nonradical Pathway through the Incorporation of Non-Redox Magnesium Oxide. Environmental Science & Technology, 54(4), 2476-2488.
Jia, Y., Yin, L., Khanal, S. K., Zhang, H., Oberoi, A. S., & Lu, H. (2020). Biotransformation of ibuprofen in biological sludge systems: Investigation of performance and mechanisms. Water Res, 170, 115303.
Khan, A., Liao, Z., Liu, Y., Jawad, A., Ifthikar, J., & Chen, Z. (2017). Synergistic degradation of phenols using peroxymonosulfate activated by CuO-Co3O4@MnO2 nanocatalyst. Journal of Hazardous Materials, 329, 262-271.
Lei, Y., Chen, C.-S., Tu, Y.-J., Huang, Y.-H., & Zhang, H. (2015). Heterogeneous Degradation of Organic Pollutants by Persulfate Activated by CuO-Fe3O4: Mechanism, Stability, and Effects of pH and Bicarbonate Ions. Environmental Science & Technology, 49(11), 6838-6845.
Li, H., Gao, Y., Gao, D., & Wang, Y. (2019). Effect of oxide defect on photocatalytic properties of MSnO3 (M = Ca, Sr, and Ba) photocatalysts. Applied Catalysis B: Environmental, 243, 428-437.
Li, X., Wang, Z., Zhang, B., Rykov, A. I., Ahmed, M. A., & Wang, J. (2016). FexCo3−xO4 nanocages derived from nanoscale metal–organic frameworks for removal of bisphenol A by activation of peroxymonosulfate. Applied Catalysis B: Environmental, 181, 788-799.
Liang, H.-y., Zhang, Y.-q., Huang, S.-b., & Hussain, I. (2013). Oxidative degradation of p-chloroaniline by copper oxidate activated persulfate. Chemical Engineering Journal, 218, 384-391.
Lin, X., Ma, Y., Wan, J., & Wang, Y. (2017). LiCoPO4 (LCP) as an effective peroxymonosulfate activator for degradation of diethyl phthalate in aqueous solution without controlling pH: Efficiency, stability and mechanism. Chemical Engineering Journal, 315, 304-314.
Liu, P., Liu, W.-J., Jiang, H., Chen, J.-J., Li, W.-W., & Yu, H.-Q. (2012). Modification of bio-char derived from fast pyrolysis of biomass and its application in removal of tetracycline from aqueous solution. Bioresource Technology, 121, 235-240.
Liu, W., Zhang, J., Zhang, C., & Ren, L. (2011). Sorption of norfloxacin by lotus stalk-based activated carbon and iron-doped activated alumina: Mechanisms, isotherms and kinetics. Chemical Engineering Journal, 171(2), 431-438.
Liu, Y., Guo, H., Zhang, Y., Tang, W., Cheng, X., & Li, W. (2018). Heterogeneous activation of peroxymonosulfate by sillenite Bi25FeO40: Singlet oxygen generation and degradation for aquatic levofloxacin. Chemical Engineering Journal, 343, 128-137.
Luo, R., Li, M., Wang, C., Zhang, M., Nasir Khan, M. A., Sun, X., . . . Li, J. (2019). Singlet oxygen-dominated non-radical oxidation process for efficient degradation of bisphenol A under high salinity condition. Water Research, 148, 416-424.
Luo, Y., Guo, W., Ngo, H. H., Nghiem, L. D., Hai, F. I., Zhang, J., . . . Wang, X. C. (2014). A review on the occurrence of micropollutants in the aquatic environment and their fate and removal during wastewater treatment. Science of The Total Environment, 473-474, 619-641.
Ma, M., Chen, L., Zhao, J., Liu, W., & Ji, H. (2019). Efficient activation of peroxymonosulfate by hollow cobalt hydroxide for degradation of ibuprofen and theoretical study. Chinese Chemical Letters, 30(12), 2191-2195.
Malinowski, J., Dercz, G., Prusik, K., Pajak, L., Pielaszek, R., & Pudlo, W. (2009). Structure studies on nanocrystalline powder of MgO xerogel prepared by sol-gel method. MATERIALS SCIENCE-POLAND, 27, 201-207.
Martins, A. C., Pezoti, O., Cazetta, A. L., Bedin, K. C., Yamazaki, D. A. S., Bandoch, G. F. G., . . . Almeida, V. C. (2015). Removal of tetracycline by NaOH-activated carbon produced from macadamia nut shells: Kinetic and equilibrium studies. Chemical Engineering Journal, 260, 291-299.
Maryam, B., Buscio, V., Odabasi, S. U., & Buyukgungor, H. (2020). A study on behavior, interaction and rejection of Paracetamol, Diclofenac and Ibuprofen (PhACs) from wastewater by nanofiltration membranes. Environmental Technology & Innovation, 18, 100641.
Melo-Guimarães, A., Torner-Morales, F. J., Durán-Álvarez, J. C., & Jiménez-Cisneros, B. E. (2013). Removal and fate of emerging contaminants combining biological, flocculation and membrane treatments. Water Sci Technol, 67(4), 877-885.
Meng, S., Greenlee, L. F., Shen, Y. R., & Wang, E. (2015). Basic science of water: Challenges and current status towards a molecular picture. Nano Research, 8(10), 3085-3110.
Meunier, B. (1992). Metalloporphyrins as versatile catalysts for oxidation reactions and oxidative DNA cleavage. Chemical Reviews, 92(6), 1411-1456.
Oh, W.-D., Dong, Z., & Lim, T.-T. (2016). Generation of sulfate radical through heterogeneous catalysis for organic contaminants removal: Current development, challenges and prospects. Applied Catalysis B: Environmental, 194, 169-201.
Paterakis, N., Chiu, T. Y., Koh, Y. K. K., Lester, J. N., McAdam, E. J., Scrimshaw, M. D., . . . Cartmell, E. (2012). The effectiveness of anaerobic digestion in removing estrogens and nonylphenol ethoxylates. Journal of Hazardous Materials, 199-200, 88-95.
Pouretedal, H. R., & Sadegh, N. (2014). Effective removal of Amoxicillin, Cephalexin, Tetracycline and Penicillin G from aqueous solutions using activated carbon nanoparticles prepared from vine wood. Journal of Water Process Engineering, 1, 64-73.
Ren, Y., Lin, L., Ma, J., Yang, J., Feng, J., & Fan, Z. (2015). Sulfate radicals induced from peroxymonosulfate by magnetic ferrospinel MFe2O4 (M=Co, Cu, Mn, and Zn) as heterogeneous catalysts in the water. Applied Catalysis B: Environmental, 165, 572-578.
Richards, S. M., & Cole, S. E. (2006). A toxicity and hazard assessment of fourteen pharmaceuticals to Xenopus laevis larvae. Ecotoxicology, 15(8), 647-656.
Rodriguez-Narvaez, O. M., Peralta-Hernandez, J. M., Goonetilleke, A., & Bandala, E. R. (2017). Treatment technologies for emerging contaminants in water: A review. Chemical Engineering Journal, 323, 361-380.
Rodriguez Narváez, O., Hernández, J. M., Goonetilleke, A., & Bandala, E. (2017). Treatment Technologies for Emerging Contaminants in water: A review. Chemical Engineering Journal, 323.
Rosenfeld, P. E., & Feng, L. G. H. (2011). 16 - Emerging Contaminants. In P. E. Rosenfeld & L. G. H. Feng (Eds.), Risks of Hazardous Wastes (pp. 215-222). Boston: William Andrew Publishing.
Shukla, P., Wang, S., Singh, K., Ang, H. M., & Tadé, M. O. (2010). Cobalt exchanged zeolites for heterogeneous catalytic oxidation of phenol in the presence of peroxymonosulphate. Applied Catalysis B: Environmental, 99(1), 163-169.
Sotelo, J. L., Rodríguez, A., Álvarez, S., & García, J. (2012). Removal of caffeine and diclofenac on activated carbon in fixed bed column. Chemical Engineering Research and Design, 90(7), 967-974.
Souza, F. S., & Féris, L. A. (2015). Degradation of Caffeine by Advanced Oxidative Processes: O3 and O3/UV. Ozone: Science & Engineering, 37(4), 379-384.
Sui, Q., Huang, J., Deng, S., Chen, W., & Yu, G. (2011). Seasonal variation in the occurrence and removal of pharmaceuticals and personal care products in different biological wastewater treatment processes. Environ Sci Technol, 45(8), 3341-3348.
Tabit, R., Amadine, O., Essamlali, Y., Dânoun, K., Rhihil, A., & Zahouily, M. (2018). Magnetic CoFe 2 O 4 nanoparticles supported on graphene oxide (CoFe 2 O 4/GO) with high catalytic activity for peroxymonosulfate activation and degradation of rhodamine B. RSC Advances, 8(3), 1351-1360.
Tan, C., Gao, N., Deng, Y., Deng, J., Zhou, S., Li, J., & Xin, X. (2014). Radical induced degradation of acetaminophen with Fe3O4 magnetic nanoparticles as heterogeneous activator of peroxymonosulfate. Journal of Hazardous Materials, 276, 452-460.
Torres-Pérez, J., Gérente, C., & Andrès, Y. (2012). Sustainable Activated Carbons from Agricultural Residues Dedicated to Antibiotic Removal by Adsorption. Chinese Journal of Chemical Engineering, 20(3), 524-529.
Vallejo-Rodríguez, R., Murillo-Tovar, M., Navarro-Laboulais, J., León-Becerril, E., & López-López, A. (2014). Assessment of the kinetics of oxidation of some steroids and pharmaceutical compounds in water using ozone. Journal of Environmental Chemical Engineering, 2(1), 316-323.
Wang, H., & Zhu, H. (2019). A Comparison Study on the Arsenate Adsorption Behavior of Calcium-Bearing Materials. Materials (Basel), 12(12).
Wang, J., & Wang, S. (2018). Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants. Chemical Engineering Journal, 334, 1502-1517.
Wang, L., Sun, Y.-G., Hu, L.-L., Piao, J.-Y., Guo, J., Manthiram, A., . . . Cao, A.-M. (2017). Copper-substituted Na0.67Ni0.3−xCuxMn0.7O2 cathode materials for sodium-ion batteries with suppressed P2–O2 phase transition. Journal of Materials Chemistry A, 5(18), 8752-8761.
Wang, Q., Shao, Y., Gao, N., Chu, W., Chen, J., Lu, X., . . . An, N. (2017). Activation of peroxymonosulfate by Al2O3-based CoFe2O4 for the degradation of sulfachloropyridazine sodium: kinetics and mechanism. Separation and Purification Technology, 189, 176-185.
Wang, S., Gao, S., Tian, J., Wang, Q., Wang, T., Hao, X., & Cui, F. (2020). A stable and easily prepared copper oxide catalyst for degradation of organic pollutants by peroxymonosulfate activation. Journal of Hazardous Materials, 387, 121995.
Xu, H., Wang, D., Ma, J., Zhang, T., Lu, X., & Chen, Z. (2018). A superior active and stable spinel sulfide for catalytic peroxymonosulfate oxidation of bisphenol S. Applied Catalysis B: Environmental, 238, 557-567.
Yang, S., Xu, C.-Y., Zhang, B.-Y., Yang, L., Hu, S.-P., & Zhen, L. (2017). Ca(II) doped β-In2S3 hierarchical structures for photocatalytic hydrogen generation and organic dye degradation under visible light irradiation. Journal of Colloid and Interface Science, 491, 230-237.
Yao, Y., Cai, Y., Wu, G., Wei, F., Li, X., Chen, H., & Wang, S. (2015). Sulfate radicals induced from peroxymonosulfate by cobalt manganese oxides (CoxMn3−xO4) for Fenton-Like reaction in water. Journal of Hazardous Materials, 296, 128-137.
Yuan, Z., Sui, M. H., Yuan, B. J., Li, P., Wang, J. Y., Qin, J., & Xu, G. Y. (2017). Degradation of ibuprofen using ozone combined with peroxymonosulfate. Environmental Science-Water Research & Technology, 3(5), 960-969.
Zhang, G. L., Ding, Y. B., Nie, W. S., & Tang, H. Q. (2019). Efficient degradation of drug ibuprofen through catalytic activation of peroxymonosulfate by Fe3C embedded on carbon. Journal of Environmental Sciences, 78, 1-12.
Zhang, T., Ding, Y., & Tang, H. (2015). Generation of singlet oxygen over Bi(V)/Bi(III) composite and its use for oxidative degradation of organic pollutants. Chemical Engineering Journal, 264, 681-689.
Zhou, M., Han, D., Liu, X., Ma, C., Wang, H., Tang, Y., . . . Yang, J. (2015). Enhanced visible light photocatalytic activity of alkaline earth metal ions-doped CdSe/rGO photocatalysts synthesized by hydrothermal method. Applied Catalysis B: Environmental, 172-173, 174-184.
Zhou, X., Jawad, A., Luo, M., Luo, C., Zhang, T., Wang, H., . . . Chen, Z. (2021). Regulating activation pathway of Cu/persulfate through the incorporation of unreducible metal oxides: Pivotal role of surface oxygen vacancies. Applied Catalysis B: Environmental, 286, 119914.
Zhu, J., Wang, J., Shan, C., Zhang, J., Lv, L., & Pan, B. (2019). Durable activation of peroxymonosulfate mediated by Co-doped mesoporous FePO4 via charge redistribution for atrazine degradation. Chemical Engineering Journal, 375, 122009.