Waste-to-energy insight: Coupled photocatalytic amoxicillin degradation and hydrogen evolution with NiFe-LDH

Öz

In this study, a nickel–iron layered double hydroxide (NiFe-LDH) photocatalyst was synthesized via a co-precipitation method and applied for the simultaneous degradation of amoxicillin (AMX) and hydrogen (H2) generation under visible light irradiation. NiFe-LDH was characterized by SEM, FTIR, XRD, and BET analyses, confirming its layered structure, homogeneous elemental distribution, and a specific surface area of 7.56 m2/g. The photocatalytic performance of NiFe-LDH was systematically evaluated by varying solution pH, catalyst loading, and initial AMX concentration. The optimal AMX degradation (~90%) and hydrogen evolution (58.2 μmol) were achieved at pH 7 with a catalyst loading of 2 g/L and an initial AMX concentration of 5 ppm. Total organic carbon (TOC) and chemical oxygen demand (COD) removal efficiencies reached 65.8% and 84.9%, respectively, under these conditions. The results demonstrate that NiFe-LDH exhibits a promising dual functionality in pollutant mineralization and clean energy production, offering a sustainable waste-to-energy pathway for water treatment applications.

Anahtar Kelimeler

• Amoxicillin
• hydrogen
• NiFe-LDH
• photocatalysis
• wastewater treatment

Atıktan enerji üretimine yönelik bir yaklaşım: NiFe-LDH kullanılarak fotokatalitik amoksisilin giderimi ve hidrojen üretiminin birlikte gerçekleştirilmesi

Öz

Bu çalışmada, nikel–demir tabakalı çift hidroksit (NiFe-LDH) fotokatalizörü çöktürme yöntemiyle sentezlenmiş ve görünür ışık altında amoksisilin (AMX) giderimi ile eşzamanlı hidrojen (H2) üretimi için kullanılmıştır. NiFe-LDH; SEM, FTIR, XRD ve BET analizleriyle karakterize edilmiş, tabakalı yapısı, homojen element dağılımı ve 7,56 m2/g özgül yüzey alanına sahip olduğu doğrulanmıştır. NiFe-LDH’nin fotokatalitik performansı, çözeltinin pH’ısı, katalizör yüklemesi ve başlangıç AMX konsantrasyonu değiştirilerek sistematik olarak değerlendirilmiştir. En yüksek AMX giderimi (~%90) ve hidrojen üretimi (58.2 μmol) pH 7, 2 g/L katalizör yüklemesi ve 5 ppm başlangıç AMX konsantrasyonunda elde edilmiştir. Bu koşullarda toplam organik karbon (TOK) ve kimyasal oksijen ihtiyacı (KOİ) giderim verimleri sırasıyla %65.8 ve %84.9 olarak belirlenmiştir. Elde edilen sonuçlar, NiFe-LDH’nin kirletici mineralizasyonu ve temiz enerji üretimi açısından çift işlevli bir potansiyele sahip olduğunu ortaya koymakta ve su arıtım uygulamaları için sürdürülebilir bir atıktan enerjiye dönüşüm yolu sunduğunu göstermektedir.

Anahtar Kelimeler

• Amoksisilin
• Hidrojen
• NiFe-LDH
• Fotokataliz
• Atık su arıtımı

Kaynakça

1. Orak, C. Application of response surface methodology for bioenergy generation in a yeast-based microbial fuel cell. RSC Advances, 14, 34356–61, (2024).
2. Mirzaei, A., Chen, Z., Haghighat, F., Yerushalmi, L. Magnetic fluorinated mesoporous g-C3N4 for photocatalytic degradation of amoxicillin: Transformation mechanism and toxicity assessment. Applied Catalysis B: Environmental, 242, 337–48, (2019).
3. Verma M, Haritash AK. Photocatalytic degradation of Amoxicillin in pharmaceutical wastewater: A potential tool to manage residual antibiotics. Environmental Technology & Innovation, 20, 101072, (2020).
4. Dou, M., Wang, J., Gao, B., Xu, C., Yang, F. Photocatalytic difference of amoxicillin and cefotaxime under visible light by mesoporous g-C3N4: Mechanism, degradation pathway and DFT calculation. Chemical Engineering Journal, 383, 123134, (2020).
5. Kanakaraju, D., Kockler, J., Motti, C.A., Glass, B.D., Oelgemöller, M. Titanium dioxide/zeolite integrated photocatalytic adsorbents for the degradation of amoxicillin. Applied Catalysis B: Environmental, 166–167, 45–55, (2015).
6. Orak, C, Öcal, B, Yüksel, A. Treatment of Sugar Industry Wastewater by Using Subcritical Water as a Reaction Media. ChemistrySelect, 8, e202203300, (2023).
7. Hansu, TA, Kaya, Ş, Çağlar, A, Akdemir, M, Kivrak, HD, Orak, C, Horoz, S, Kaya, M. Enhanced catalytic performance of Pd/PMAc-g-CNT composite for water splitting and supercapacitor applications. Ionics, 30, 5513–5524, (2024).
8. Orak, C. Enhanced degradation of Procion Red MX-5B using Fe-doped corn cob ash and Fe-doped g-C3N4. Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 46,14244–58, (2024).

9. Orak, C. Treatment of sugar industry wastewater via Fenton oxidation with zero-valent iron. Cumhuriyet Science Journal, 45, 100–4, (2024).
10. Orak, C., Oğuz, T., Horoz, S. Facile synthesis of Mn-doped CdS nanoparticles on carbon quantum dots: towards efficient photocatalysis. Journal of the Australian Ceramic Society, 60, 1657-1667, (2024).
11. Haste, Z.Ö., Horoz, S., Orak, C., Biçer, E. Green-synthesized SnO2 derived from Kombucha tea and assessment of its photocatalytic activity for the degradation of Procion Red MX-5B. ChemistrySelect, 9 (43), e202403264, (2024).
12. Bakır, R., Orak, C. Stacked machine learning approach for predicting evolved hydrogen from sugar industry wastewater. International Journal of Hydrogen Energy 85, 75–87, (2024).
13. Bakır, R., Orak, C., Yüksel, A. A machine learning ensemble approach for predicting solar-sensitive hybrid photocatalysts on hydrogen evolution. Physica Scripta, 99, 076015, (2024).
14. Arabacı, B., Bakır, R., Orak, C., Yüksel, A. Predictive modeling of photocatalytic hydrogen production: Integrating experimental insights with machine learning on Fe/g-C3N4 catalysts. Industrial & Engineering Chemistry Research, 64, 5184–5199, (2025).
15. Jabeen, A., Salem Alsaiari, N., MohammedSaleh Katubi, K., Shakir, I., Alrowaili, Z.A., Al-Buraihi, M.S., Warsi, M.F. Synthesis and characterisation of MXene based-LDH photocatalytic materials for the removal of toxic pharmaceutical effluents. Journal of Molecular Liquids, 405, 125066, (2024).
16. Chen, Y., Haihua, X., Khan, M.S., Shiqi, H., and Zhu, S. Recent advances in layered double hydroxides for pharmaceutical wastewater treatment: A critical review. Critical Reviews in Environmental Science and Technology, 1-27, (2025).
17. Ren, L., Wang, C., Li, W., Dong, R., Sun, H., Liu, N., et al. Heterostructural NiFe-LDH@Ni3S2 nanosheet arrays as an efficient electrocatalyst for overall water splitting. Electrochimica Acta, 318, 42–50, (2019).
18. Khataee, A., Rad, T.S., Nikzat, S., Hassani, A., Aslan, M.H., Kobya, M., Demirbaş, E. Fabrication of NiFe layered double hydroxide/reduced graphene oxide (NiFe-LDH/rGO) nanocomposite with enhanced sonophotocatalytic activity for the degradation of moxifloxacin. Chemical Engineering Journal, 375, 122102, (2019).
19. Liu, X., Zhou, Y., Sun, S., Bao, S. Study on the behavior and mechanism of NiFe-LDHs used for the degradation of tetracycline in the photo-Fenton process. RSC Advances, 13, 31528–31540, (2023).
20. Keşir, M.K., Sökmen, M., Bıyıklıoğlu, Z. Photocatalytic efficiency of metallo phthalocyanine sensitized TiO2 (MPc/TiO2) nanocomposites for Cr(VI) and antibiotic amoxicillin. Water, 13, 2174, (2021).
21. Ataklti, A., Alemu, K., Abebe, B. Study of the self-association of amoxicillin, thiamine and the hetero-association with biologically active compound chlorogenic acid. African Journal of Pharmacy and Pharmacology, 10, 393–402, (2016).
22. Hrioua, A., Aghris, S., Ajermoun, N., Ettadili, F., Farahi, A., Lahrich, S., et al. Electrochemical investigation of amoxicillin interaction with some metal ions related to complexation process. Journal of The Electrochemical Society, 167, 126501, (2020).
23. Li, X., Hao, X., Wang, Z., Abudula, A., Guan, G. In-situ intercalation of NiFe LDH materials: An efficient approach to improve electrocatalytic activity and stability for water splitting. Journal of Power Sources, 347, 193–200, (2017).
24. Tian, M., Liu, C., Neale, Z.G., Zheng, J., Long, D., Cao, G. Chemically Bonding NiFe-LDH Nanosheets on rGO for Superior Lithium-Ion Capacitors. ACS Applied Materials & Interfaces, 11, 35977–86, (2019).
25. Sirisomboonchai, S., Li, S., Yoshida, A., Li, X., Samart, C., Abudula, A., Guan, G. Fabrication of NiO Microflake@NiFe-LDH Nanosheet Heterostructure Electrocatalysts for Oxygen Evolution Reaction. ACS Sustainable Chemistry & Engineering, 7, 2327–34, (2019).
26. Qutob, M., Shakeel, F., Alam, P., Alshehri, S., Ghoneim, M.M., Rafatullah, M. A review of radical and non-radical degradation of amoxicillin by using different oxidation process systems. Environmental Research, 214, 113833, 2022.
27. Elmolla, E.S., Chaudhuri, M. Photocatalytic degradation of amoxicillin, ampicillin and cloxacillin antibiotics in aqueous solution using UV/TiO2 and UV/H2O2/TiO2 photocatalysis. Desalination, 252, 46–52, (2010).
28. Sun, C., Wang, Y., Jiang, B., Hu, S., Wang, Y., Zhang, C., Li, G. Self-catalyst degradation of amoxicillin in alkaline condition driven by superoxide radical. Chemical Engineering Journal, 477, 146942, (2023).
29. Tran, M.L., Fu, C.C., Juang, R.S. Removal of metronidazole and amoxicillin mixtures by UV/TiO2 photocatalysis: an insight into degradation pathways and performance improvement. Environmental Science and Pollution Research, 26, 11846–55, (2019).
30. Li, Y., Du, J., Peng, S., Xie, D., Lu, G., Li, S. Enhancement of photocatalytic activity of cadmium sulfide for hydrogen evolution by photoetching. International Journal of Hydrogen Energy, 33, 2007–2013, (2008).
31. Sreethawong, T., Yoshikawa, S. Comparative investigation on photocatalytic hydrogen evolution over Cu-, Pd-, and Au-loaded mesoporous TiO2 photocatalysts. Catalysis Communications, 6, 661–668, (2005).
32. Shao, L., Cheng, S., Yang, Z., Xia, X., Liu, Y. Nickel aluminum layered double hydroxide nanosheets grown on oxygen vacancy-rich TiO2 nanobelts for enhanced photodegradation of an antibiotic. Journal of Photochemistry and Photobiology A: Chemistry, 411, 113209, (2021).
33. Xiong, J., Zeng, H.Y., Chen, C.R., Li, S., Xu, S., An, D.S. Ag3VO4 anchored ZnTi hydrotalcite microspheres with rosette-like structure for tetracycline degradation. Applied Clay Science, 208, 106118, (2021).
34. Chen, C.R., Zeng, H.Y., Yi, M.Y., Xiao, G.F., Zhu, R.L., Cao, X.J., Shen, S.G., Peng, J.W. Fabrication of Ag2O/Ag decorated ZnAl-layered double hydroxide with enhanced visible light photocatalytic activity for tetracycline degradation. Ecotoxicology and Environmental Safety, 172, 423–431, (2019).
35. Sun, C., Wang, Y., Wu, L., Hu, J., Long, X., Wu, H., Jiao, F. In situ preparation of novel p–n junction photocatalyst MgAl-LDH/(BiO)2CO3 for enhanced photocatalytic degradation of tetracycline. Materials Science Semiconductor Processing, 150, 106939, (2022).
36. Zhu, C., Wang, Y., Qiu, L., Yang, W., Yu, Y., Li, J., Liu, Y. Z-scheme NiFe LDH/Bi4O5I2 heterojunction for photo-Fenton oxidation of tetracycline. Journal of Alloys and Compdounds, 944, 169124, (2023).
37. Wu, Z., Gu, Y., Xin, S., Lu, L., Huang, Z., Li, M., Cui, Y., Fu, R., Wang, S. CuxNiyCo-LDH nanosheets on graphene oxide: an efficient and stable Fenton-like catalyst for dual-mechanism degradation of tetracycline. Chemical Engineering Journal, 434, 134574, (2022).