İNDİRGENMİŞ GRAFEN OKSİT DESTEKLİ Fe-Ce BİMETALİK NANOPARTİKÜL KOMPOZİT MALZEMESİNİN SENTEZİ VE p-NİTROFENOLÜN HETEROJEN FENTON-BENZERİ REAKSİYON İLE DEGRADASYONUNDA KATALİZÖR OLARAK KULLANIMI

Year 2021, Volume: 9 , 157 - 172, 30.12.2021

Memduha Ergüt Prof.dr. Ayla Özer

https://doi.org/10.36306/konjes.997618

Abstract

Bu çalışmada, öncelikle modifiye Hummers yöntemi ile grafen oksit (GO) destek malzemesi sentezlenmiş daha sonra birlikte çöktürme yöntemi ile indirgenmiş grafen oksit destekli demir-seryum bimetalik nanopartikül (r-GO/Fe-CeNPs) kompozit malzemesi hazırlanmıştır. Sentezlenen GO’nun ve kompozit malzemenin (r-GO/Fe-CeNPs); FT-IR, XRD, ve SEM analizleri ile karakterizasyonu gerçekleştirilmiştir. r-GO/Fe-CeNPs’nin manyetik davranışı ise VSM analizi ile belirlenmiştir. GO’nun FT-IR ve XRD analiz sonuçlarına göre, GO’ya özgü fonksiyonel gruplar ve karakteristik pikler elde edilmiştir. SEM görüntülerinden ise, GO’nin katmanlı ve homojen bir yüzeye sahip olduğu görülmüştür. r-GO/Fe-CeNPs’nin FT-IR spektrumunda r-GO’ya; CeO ve Fe nanopartiküllerine ait karakteristik bantlar elde edilmiş; XRD spektrumundan yapının amorf özellik gösterdiği belirlenmiştir. Farklı büyütme oranlarında elde edilen r-GO/Fe-CeNPs’lere ait SEM görüntülerinde ise indirgenmiş grafen oksit üzerine dağılmış çiçek benzeri ve aglomere olmuş küresel nanopartiküllerin oluştuğu görülmüştür. Fe-CeNPs’nin ortalama tanecik boyutu SEM görüntülerinden Image J programı ile 70.25 nm olarak belirlenmiştir. r-GO/Fe-CeNPs’nin VSM analiz sonuçlarına göre; katalizörün doygunluk manyetizasyonu (Ms) 40.13 A m2/kg olarak belirlenmiştir. Çalışmanın ikinci bölümünde ise sentezlenen kompozit malzemenin p-nitrofenolün (p-NP) heterojen Fenton-benzeri reaksiyon ile degradasyonunda katalizör olarak kullanılabilirliği ve Fenton-benzeri reaksiyon sürecini etkileyen parametreler olan başlangıç pH’sı, başlangıç p-NP derişimi, katalizör derişimi, H2O2 derişimi, ve sıcaklığın etkisi araştırılmıştır. Optimum ortam koşulları; başlangıç pH’sı 3.0, başlangıç p-NP derişimi 50 mg/L, katalizör derişimi 0.5 g/L, H2O2 derişimi 100 mM ve sıcaklık 65°C olarak belirlenmiştir.

Keywords

İndirgenmiş grafen oksit, Demir-seryum bimetalik nanopartikül, Kompozit malzeme, p-Nitrofenol, Heterojen Fenton-benzeri degradasyon

Supporting Institution

MERSİN ÜNİVERSİTESİ BİLİMSEL ARAŞTIRMA PROJELERİ KOORDİNASYON BİRİMİ (MEÜ-BAP)

Project Number

2020-1-AP7-4088

Thanks

Bu çalışma, Mersin Üniversitesi Bilimsel Araştırma Projeleri Koordinasyon Birimi (MEÜ-BAP) tarafından 2020-1-AP7-4088 numaralı AP 7 Hızlı Destek Araştırma Projesi ile desteklenmiştir.

Synthesis of Reduced Graphene Oxide Supported Fe-Ce Bimetallic Nanoparticle Composite Material and Usage as a Catalyst in the Degradation of p-Nitrophenol by Heterogeneous Fenton-Like Reaction

Abstract

In this study; firstly, graphene oxide (GO) support material was synthesized by the modified Hummers method and then reduced graphene oxide supported iron-cerium bimetallic nanoparticle (r-GO/Fe-CeNPs) composite material was prepared by co-precipitation method. Characterization of synthesized GO and composite material (r-GO/Fe-CeNPs) was performed by FT-IR, XRD, and SEM analyzes. The magnetic behavior of r-GO/Fe-CeNPs was determined by VSM analysis. According to GO’s FT-IR and XRD analysis results, GO-specific functional groups and characteristic peaks were obtained. From the SEM images, it was determined that GO has a layered and homogeneous surface. According to FT-IR spectrum of r-GO/Fe-CeNPs; characteristic bands of r-GO; CeO, and Fe nanoparticles were obtained; it was determined from the XRD spectrum that the structure showed amorphous properties. In the SEM images of r-GO/Fe-CeNPs obtained at different magnifications, it was observed that flower-like and agglomerated spherical nanoparticles dispersed on the reduced graphene oxide were formed. The average particle size of Fe-CeNPs was determined as 70.25 nm from the SEM images with the Image J program. According to the VSM analysis result of r-GO/Fe-CeNPs; the saturation magnetization (Ms) of the catalyst was determined as 40.13 A m2/kg. In the second part of the study, the usability of the synthesized composite material as a catalyst in the degradation of p-nitrophenol (p-NP) by heterogeneous Fenton-like reaction and the parameters affecting the Fenton-like reaction process, such as initial pH, initial p-NP concentration, catalyst concentration, H2O2 concentration, and the effect of temperature were investigated. Optimum environmental conditions were determined as the initial pH 3.0, the initial p-NP concentration 50 mg/L, the catalyst concentration 0.5 g/L, the H2O2 concentration 100 mM, and the temperature 65°C.

Keywords

Reduced graphene oxide, Iron-cerium bimetallic nanoparticle, Composite material, p-Nitrophenol, Heterogeneous Fenton-like degradation

Project Number

2020-1-AP7-4088

References

• Ali, M. M., Mahdi, H. S., Parveen, A., & Azam, A., 2018, “Optical properties of cerium oxide (CeO2) nanoparticles synthesized by hydroxide mediated method”, In AIP Conference Proceedings, Cilt 1953, Sayı 1, ss. 030044.
• Babuponnusami, A., & Muthukumar, K., 2014, “A review on Fenton and improvements to the Fenton process for wastewater treatment”, Journal of Environmental Chemical Engineering, Cilt 2, Sayı 1, ss. 557-572.
• Belachew, N., Fekadu, R., & Ayalew Abebe, A., 2020, “RSM-BBD optimization of Fenton-like degradation of 4-nitrophenol using magnetite impregnated kaolin”, Air, Soil and Water Research, Cilt 13, ss. 1178622120932124.
• Cihanoğlu, A., Gündüz, G., Dükkancı, M., 2015, “Degradation of acetic acid by heterogeneous Fenton-like oxidation over iron-containing ZSM-5 zeolites”, Applied Catalysis B-Environmental, Cilt 165, ss. 687-69.
• Compeán-Jasso, M. E., Ruiz, F., Martínez, J. R., & Herrera-Gómez, A., 2008, “Magnetic properties of magnetite nanoparticles synthesized by forced hydrolysis”, Materials Letters, Cilt 62, Sayı 27, ss.4248-4250.
• Dong, C. D., Huang, C. P., Nguyen, T. B., Hsiung, C. F., Wu, C. H., Lin, Y. L., & Hung, C. M., 2019, “The degradation of phthalate esters in marine sediments by persulfate over iron–cerium oxide catalyst”, Science of The Total Environment, Cilt 696, ss.133973.
• Ensafi, A. A., Noroozi, R., Zandi, N., & Rezaei, B., 2017, “Cerium (IV) oxide decorated on reduced graphene oxide, a selective and sensitive electrochemical sensor for fenitrothion determination”, Sensors and Actuators B: Chemical, Cilt 245, ss. 980-987.
• Erişim., Su Kirliliği Kontrolü Yönetmeliğinde Değişiklik Yapılmasına Dair Yönetmelik. Çevre ve Orman Bakanlığı, 2008, http://www.resmigazete.gov.tr, ziyaret tarihi: 10.09.2021
• Guo, S., Zhang, G., Guo, Y., & Jimmy, C. Y., 2013, “Graphene oxide–Fe2O3 hybrid material as highly efficient heterogeneous catalyst for degradation of organic contaminants”, Carbon, Cilt 60, ss.437-444.
• Johra, F.T., Lee, J. W., & Jung, W. G., 2014, “Facile and safe graphene preparation on solution based platform”, Journal of Industrial and Engineering Chemistry, Cilt 20, Sayı 5, ss. 2883-2887.
• Liu, M., Jia, Z., Li, P., Liu, Y., Zhao, M., Yang, Y., ...& Yu, C., 2019, “High Catalytic Activity of Fe3− x Cu xO4/Graphene Oxide (0≤ x≤ 0.1) Nanocomposites as Heterogeneous Fenton Catalysts for p-Nitrophenol Degradation”, Water, Air, & Soil Pollution, Cilt 230, Sayı 3, ss.1-15.
• Liu, Q., Zhou, L., Liu, L., Li, J., Wang, S., Znad, H., & Liu, S., 2020, “Magnetic ZnO@ Fe3O4 composite for self-generated H2O2 toward photo-Fenton-like oxidation of nitrophenol”, Composites Part B: Engineering, Cilt 200, ss.108345.
• Min, L., Zhang, P., Fan, M., Xu, X., Wang, C., Tang, J., & Sun, H., 2021, “Efficient degradation of p-nitrophenol by Fe@ pomelo peel-derived biochar composites and its mechanism of simultaneous reduction and oxidation process”, Chemosphere, Cilt 267, ss.129213.
• Mirzaei, A., Chen, Z., Haghighat, F., Yerushalmi, L., 2017, “Removal of pharmaceuticals from water by homo/heterogonous Fenton-type processes–A review”, Chemosphere, Cilt 174, ss. 665-688.
• Nor, W. F. K. N., Soh, S. K. C., Azmi, A. A. A., Yusof, M. S. M., & Shamsuddin, M., 2017, “Synthesis and physicochemical properties of magnetite nanoparticles (Fe3O4) as potential solid support for homogeneous catalysts”, Malaysian Journal of Analytical Sciences, Cilt 2, Sayı 5, ss.768-774.
• Pai, A. R., & Nair, B., 2013, “Synthesis of reduced graphene oxide using novel exfoliation technique and its characterizations”, Journal Of Nano-And Electronıc Physıcs, Cilt 5, Sayı 2, ss. 02032.
• Rodrigues, C. S., Soares, O. S. G. P., Pinho, M. T., Pereira, M. F. R., & Madeira, L. M., 2017, “p-Nitrophenol degradation by heterogeneous Fenton’s oxidation over activated carbon-based catalysts”, Applied Catalysis B-Environmental, Cilt 219, ss.09-122.
• Ruíz-Baltazar, A., Esparza, R., Rosas, G., & Pérez, R., 2015, “Effect of the surfactant on the growth and oxidation of iron nanoparticles”, Journal of Nanomaterials, Cilt 2015, ss. 1-8.
• Shahriary, L., & Athawale, A. A., 2014, “Graphene oxide synthesized by using modified hummers approach”, International Journal of Renewable Energy and Environmental Engineering, Cilt 2, Sayı, 01, ss.58-63.
• Sodipo, B. K., & Azlan, A. A., 2015, “Superparamagnetic iron oxide nanoparticles incorporated into silica nanoparticles by inelastic collision via ultrasonic field: role of colloidal stability”, In AIP Conference Proceedings, Cilt 657, Sayı 1, ss.100002. AIP Publishing LLC.
• Subbulekshmi, N. L., & Subramanian, E., 2017, “Nano CuO immobilized fly ash zeolite Fenton-like catalyst for oxidative degradation of p-nitrophenol and p-nitroaniline”, Journal of Environmental Chemical Engineering, Cilt 5, Sayı 2, ss.1360-1371.
• Temel, F., 2020, “Merrıfıeld reçinesine desteklenmiş kaliks[4] aren dinitro türevinin sulu ortamdaki fenolik türlere karşı ekstraksiyon özelliklerinin incelenmesi”, Konya Mühendislik Bilimleri Dergisi, Cilt 8, Sayı 1, ss.60-70.
• Thomas, N., Dionysiou, D. D., & Pillai, S. C., 2021, “Heterogeneous Fenton catalysts: A review of recent advances”, Journal of Hazardous Materials, Cilt 404, ss.124082.
• Tian, X., Liu, Y., Chi, W., Wang, Y., Yue, X., Huang, Q., & Yu, C., 2017, “Catalytic degradation of phenol and p-nitrophenol using Fe3O4/MWCNT nanocomposites as heterogeneous Fenton-like catalyst”, Water, Air, & Soil Pollution, Cilt 228, Sayı 8, ss.1-12.
• Uzunoglu, D., Ergüt, M., & Özer, A., 2019, “Heterojen Fenton-benzeri Reaksiyon ile p-nitrofenolün Degradasyonu İçin Katalizör Geliştirilmesi: Fe-Zn Nps/C Kompozit Malzemesi”,Yuzuncu Yıl University Journal of the Institute of Natural and Applied Sciences, Cilt 24, ss.87-89.
• Vasistha, P., & Ganguly, R., 2020, “Water quality assessment of natural lakes and its importance: an overview”, Materials Today: Proceedings, Cilt 32, Sayı 4, ss. 544-552.
• Zhang, A., Wang, N., Zhou, J., Jiang, P., ve Liu, G., 2012, “Heterogeneous Fenton-like catalytic removal of p-nitrophenol in water using acid-activated fly ash”, Journal of Hazardous Materials, Cilt 201, ss. 68-73.
• Wan, D., Li, W., Wang, G., Lu, L., & Wei, X., 2017, “Degradation of p-Nitrophenol using magnetic Fe/FeO/Coke composite as a heterogeneous Fenton-like catalyst”, Science of the Total Environment, Cilt 574, ss.1326-1334.
• Wan, Z., & Wang, J., 2016, “Ce-Fe-reduced graphene oxide nanocomposite as an efficient catalyst for sulfamethazine degradation in aqueous solution”, Environmental Science and Pollution Research, Cilt 23, Sayı, 18, ss.18542-18551.
• Wan, Z., Hu, J., & Wang, J., 2016, “Removal of sulfamethazine antibiotics using CeFe-graphene nanocomposite as catalyst by Fenton-like process”, Journal of Environmental Management, Cilt 182, ss. 284-291.
• Wang, N., Zheng, T., Zhang, G., Wang, P., 2016, “A review on Fenton-like processes for organic wastewater treatment”, Journal of Environmental Chemical Engineering, Cilt 4, Sayı 1, ss.762-787.
• Wen, Z., Lu, J., Zhang, Y., Cheng, G., Huang, S., Chen, J., & Chen, R., 2020, “Facile inverse micelle fabrication of magnetic ordered mesoporous iron cerium bimetal oxides with excellent performance for arsenic removal from water”, Journal of Hazardous Materials, Cilt 383, ss.121172.