Removal of Some Phenolic Pollutions from Aqueous Solutions by Magnetic Nanoparticles Containing Imidazole-Derivatized Calix[4]arene

Abstract

In this paper, it was aimed to synthesize imidazole-derived calix[4]arenes, immobilize these compounds to [3-(2,3-epoxypropoxy)-propyl]-trimetoxysilane (EPPTMS) modified Fe3O4 nanoparticles and to investigate adsorption properties of the obtained nanoparticles for some phenolic pollutants. For this purpose, firstly, a series of calix[4]arene derivatives (1, 2, 3, 4, 5, 6, 8) were synthesized according to the literature procedures and their structures were verified to synthesize the target compounds. Compound 6 among of these compounds was reacted with imidazole by the Mannich reaction to achieve target 7. On the other hand, calix[4]arene derivative bearing two distal bromo groups 8 was also reacted with imidazole to achive other target compound 9. The structure of both compounds was confirmed by 1H NMR spectroscopy. Thus, two different calix[4]arene derivatives were prepared from both the lower region and the upper region of the calix[4]arene with functional imidazole groups. These compounds were then immobilized to the EPPTMS modified Fe3O4 nanoparticle to obtain calix[4] arene-bonded new magnetic nanoparticles (C-7-BMN and C-9-BMN) bearing the imidazole group. These new nanoparticles were used as adsorbents in the adsorption of phenol (PHE), p-chlorophenol (pCF) and p-nitrophenol (pNP) from the aqueous solution. Concentrations of solution were determined by HPLC and adsorption results were calculated. The results revealed that C-9-BMN performed the highest adsorption for pCF at pH 6, while C-7-BMN showed no remarkable adsorption for any phenolic species. It has been understood that electrostatic interactions and hydrogen bond interactions are particularly important in the adsorption process and they are closely related to the structure of the adsorbent species depending on the ambient conditions. As a result, using the C-9-BMN adsorbent prepared in this study, the adsorption method, pCF, which is a toxic phenolic species, was removed from the aqueous solutions in a remarkable efficiency.

Keywords

• Calixarene
• Phenolic pollution
• Magnetic nanoparticle
• Adsorption

BAZI FENOLİK KİRLİLİKLERİN İMİDAZOL TÜREVLİ KALİKS[4]AREN İÇEREN MANYETİK NANOPARTİKÜLLER KULLANARAK SULU ÇÖZELTİLERDEN UZAKLAŞTIRILMASI

Abstract

Bu çalışmada imidazol türevli kaliks[4]arenlerin sentezi, bu bileşiklerin [3-(2,3-epoksipropoksi)- propil]-trimetoksisilan (EPPTMS) modifiyeli Fe3O4 nanopartikülüne immobilize edilmesi ve elde edilen nanaparitküllerin bazı fenolik kirleticiler için adsorpsiyon özelliklerinin incelenmesi amaçlanmıştır. Bu amaçla ilk olarak hedef bileşikleri sentezlemek üzere bir dizi kaliks[4]aren türevi (1, 2, 3, 4, 5, 6, 8) literatür prosedürüne göre sentezlenmiş ve yapıları doğrulanmıştır. Bu bileşiklerden 6 nolu bileşik Mannich reaksiyonu ile imidazol ile etkileştirilerek hedef bileşik 7 elde edilmiştir. Diğer taraftan 8 nolu karşılıklı iki adet bromo grubu taşıyan kaliks[4]aren türevi yine imidazol ile etkileştirilerek diğer hedef bileşik olan 9 bileşiği sentezlenmiştir. Bu bileşikler daha sonra EPPTMS modifiyeli Fe3O4 nanopartikülüne immobilize edilerek imidazol grubu taşıyan kaliks[4]aren bağlı yeni manyetik nanopartiküller (K-7-BMN ve K-9-BMN) elde edilmiştir. Bu yeni nanopartiküller fenol (FEN), p- klorofenol (pKF) ve p-nitrofenol (pNF)’ün sulu çözeltiden adsorpsiyonunda adsorban olarak kullanılmıştır. Sonuçlar K-9-BMN’nin pH 6 da pKF için en yüksek adsorpsiyonu gerçekleştirdiğini, K-7- BMN’nin ise hiçbir fenolik tür için kayda değer bir adsorpsiyon göstermediğini ortaya çıkarmıştır. Adsorpsiyon sürecinde elektrostatik etkileşimler ve hidrojen bağı etkileşimlerinin özellikle önemli olduğu ve bunların ortam şartlarına bağlı olarak adsorban türlerinin yapısıyla yakından ilgili olduğu anlaşılmıştır.

Keywords

• Kaliksaren
• Fenolik kirlilik
• Manyetik nanopartikül
• Adsorpsiyon

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