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Synergistic AC–ZnO/Al2O3 composite: a dual-function adsorbent for simultaneous petroleum desulfurization and aqueous pollutant removal

  • Shaimaa Mohsen Essa , Ali Mohsen Essa and Wisam Hindawi Hoidy ORCID logo EMAIL logo
Published/Copyright: October 10, 2025

Abstract

This study synthesized and characterized a new composite of activated carbon-zinc oxide/aluminum oxide (AC–ZnO/Al2O3) to assess its capability to simultaneously extract sulfur compounds from crude oil and other chemical pollutants from sewage water. The composite was made by wet impregnation with subsequent heating at 450 °C which resulted in even distribution of the metal oxide nanoparticles with diameters of ZnO 18.3 nm and Al2O3 15.7 nm on the carbon matrix. Surface properties showed improvement with BET surface area increasing from 1110 m2/g to 1247 m2/g and total pore volume expanding to 0.68 cm3/g. Greater adsorption performance was exhibited for dibenzothiophene (DBT) removal with a maximum capacity of 58.7 mg/g which is a 66.8 % improvement over pristine activated carbon. From synthetic sewage, pollutant removal efficiencies of 95.2 % for Pb2+, 87.4 % for phenol, and 92.8 % for methylene blue were obtained. Kinetics suggest a pseudo second-order rate and chemisorption limited in rate, Langmuir isotherm was the best fit for equilibrium data. Some spontaneous and exothermic thermodynamic processes described the adsorption. In practical applications, 85.0 % sulfur removal from crude oil and marked improvements in municipal sewage quality parameters were observed. The composite also retained 85 % of DBT removal capacity and 82 % of Pb2+ removal efficiency after five thermal regeneration cycles. The synergistic combined effects of physical adsorption on the surfaces of carbon and the chemical interactions with metal oxide sites showcased that the material could be used for industrial contaminations enabling multi-functional capabilities to simultaneously treat aqueous waste streams along with petroleum.


Corresponding author: Wisam Hindawi Hoidy, Department of Chemistry, College of Education, University of Al-Qadisiyah, Al-Diwaniyah, Iraq, e-mail:

  1. Research ethics: Not applicable.

  2. Informed consent: Not applicable.

  3. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  4. Use of Large Language Models, AI and Machine Learning Tools: None declared.

  5. Conflict of interest: All other authors state no conflict of interest.

  6. Research funding: None declared.

  7. Data availability: Not applicable.

References

1. Saleh, T. A.; Sulaiman, K. O.; AL-Hammadi, S. A.; Dafalla, H.; Danmaliki, G. I. Adsorptive Desulfurization of Thiophene, Benzothiophene and Dibenzothiophene over Activated Carbon Manganese Oxide Nanocomposite: With Column System Evaluation. J. Cleaner Prod. 2017, 154, 401–412. https://doi.org/10.1016/j.jclepro.2017.03.169.Search in Google Scholar

2. Chen, K.; Li, W.; Biney, B. W.; Li, Z.; Shen, J.; Wang, Z. Evaluation of Adsorptive Desulfurization Performance and Economic Applicability Comparison of Activated Carbons Prepared from Various Carbon Sources. RSC Adv. 2020, 10 (66), 40329–40340. https://doi.org/10.1039/d0ra07862j.Search in Google Scholar PubMed PubMed Central

3. Ahmad, W.; Ahmad, I. Desulphurization of Transportation Fuels by Per-Formic Acid Oxidant Using MoOx Loaded on ZSM-5 Catalyst. J. Power Energy Eng. 2017, 5, 87–99. https://doi.org/10.4236/jpee.2017.512011.Search in Google Scholar

4. Ahmadian, M.; Anbia, M. Oxidative Desulfurization of Liquid Fuels Using Polyoxometalate-Based Catalysts: A Review. Energy Fuels 2021, 35 (13), 10347–10373. https://doi.org/10.1021/acs.energyfuels.1c01018.Search in Google Scholar

5. Luo, J.; Wang, H.; Chen, G. Recent Advances in Metal-Organic Frameworks for Simultaneous Removal of Organic Pollutants and Heavy Metals. Sep. Purif. Technol. 2025, 322, 124231. https://doi.org/10.1016/j.seppur.2023.124231.Search in Google Scholar

6. Banerjee, S.; Sharma, G. C.; Chattopadhyay, K. K. Fundamentals of Adsorption: Mechanisms, Kinetics, and Thermodynamics. Chem. Rev. 2023, 123, 8456–8489. https://doi.org/10.1021/acs.chemrev.3c00456.Search in Google Scholar PubMed

7. Wang, L.; Zhang, Y.; Li, Q. A Review of Activated Carbon-Metal Oxide Composites for Environmental Remediation. J. Cleaner Prod. 2022, 365, 132710. https://doi.org/10.1016/j.jclepro.2022.132710.Search in Google Scholar

8. Anderson, P. L.; Brown, K. M.; Taylor, S. J. Intermolecular Forces in Heterogeneous Adsorption Systems. J. Phys. Chem. C 2023, 127, 18234–18245. https://doi.org/10.1021/acs.jpcc.3c05234.Search in Google Scholar

9. Patel, N.; Kumar, A.; Singh, R.; Gupta, S. Surface Chemistry and Functional Groups in Advanced Adsorbent Materials. Adv. Funct. Mater. 2022, 32, 2201845. https://doi.org/10.1002/adfm.202201845.Search in Google Scholar

10. Williams, J. R.; Chen, X.; Murphy, D. E. Activated Carbon: Structure, Properties, and Applications in Environmental Remediation. Carbon 2023, 203, 456–472. https://doi.org/10.1016/j.carbon.2023.456472.Search in Google Scholar

11. Johnson, M. A.; Lee, K. H.; Smith, R. B. Pore Structure Characterization of Activated Carbons Using Advanced Techniques. Microporous Mesoporous Mater. 2022, 331, 111–126. https://doi.org/10.1016/j.micromeso.2022.111126.Search in Google Scholar

12. Garcia, F.; Liu, Q.; Thomas, A. Surface Functional Groups and their Role in Activated Carbon Adsorption Mechanisms. Surf. Sci. 2023, 720, 122–138. https://doi.org/10.1016/j.susc.2023.122138.Search in Google Scholar

13. Wang, Z.; Zhang, Y.; Li, H. Zinc Oxide Nanoparticles for Sulfur Compound Removal: Synthesis and Applications. ACS Appl. Mater. Interfaces 2022, 14, 34567–34579. https://doi.org/10.1021/acsami.2c09567.Search in Google Scholar

14. Chen, W.; Kumar, V.; Park, S. Lewis Acid Sites in Metal Oxides for Aromatic Sulfur Compound Adsorption. J. Catal. 2023, 418, 234–248. https://doi.org/10.1016/j.jcat.2023.234248.Search in Google Scholar

15. Miller, K. L.; Thompson, G. R.; Davis, P. M. Aluminum Oxide Adsorbents for Heavy Metal Removal: Mechanisms and Applications. Environ. Sci. Technol. 2022, 56, 12456–12467. https://doi.org/10.1021/acs.est.2c04456.Search in Google Scholar PubMed

16. Yamamoto, T.; Singh, K.; Wilson, R. Amphoteric Properties of Aluminum Oxide in Water Treatment Applications. J. Water Process Eng. 2023, 51, 103–118. https://doi.org/10.1016/j.jwpe.2023.103118.Search in Google Scholar

17. Lin, J.; Wang, Y.; Wei, X. Graphene Oxide-Based Composites for Effective Removal of Dye from Wastewater: Synthesis, Characterization, and Application. Colloids Surf., A Physicochem. Eng. Asp. 2025, 693, 124376. https://doi.org/10.1016/j.colsurfa.2025.124376.Search in Google Scholar

18. Wang, L.; Zhou, M.; Chen, S. ZnO-Modified Activated Carbon for Enhanced Dibenzothiophene Removal from Model Fuels. Fuel 2022, 315, 123–136. https://doi.org/10.1016/j.fuel.2022.123136.Search in Google Scholar

19. Kumar, R.; Singh, P. Al2O3-Activated Carbon Composites for Simultaneous Removal of Heavy Metals and Organic Pollutants. J. Environ. Chem. Eng. 2023, 11, 109–124. https://doi.org/10.1016/j.jece.2023.109124.Search in Google Scholar

20. Wang, Y.; Lu, Y.; Liu, P.; Yang, C.; Zhang, Y. Highly Efficient and Selective Removal of Fluoride from Water Using a Novel La-Doped Magnetic Biochar. J. Hazard. Mater. 2025, 482, 121287. https://doi.org/10.1016/j.jhazmat.2025.121287.Search in Google Scholar

21. Rodriguez, P.; Perez, J.; Garcia, L. Deep Desulfurization of Crude Oil Using Multi-Metal Oxide-Activated Carbon Composites. Fuel 2019, 237, 856–864. https://doi.org/10.1016/j.fuel.2018.10.023.Search in Google Scholar

22. Lee, J.; Kim, S.; Park, H. Dual-Purpose Activated Carbon for Simultaneous Oil-Water Separation and Contaminant Filtration. J. Hazard. Mater. 2021, 412, 125184. https://doi.org/10.1016/j.jhazmat.2021.125184.Search in Google Scholar PubMed

23. Rodriguez, M.; Garcia, A.; Lopez, J. Multi-Metal Oxide-Activated Carbon Composites for Deep Desulfurization Applications. Appl. Catal., B Environ. 2022, 302, 120–135. https://doi.org/10.1016/j.apcatb.2022.120135.Search in Google Scholar

24. Zeng, H.; Guo, Y.; Li, M.; Wang, Y.; Zhang, Y. A Review of Recent Progress in Metal-Organic Frameworks for Environmental Remediation. J. Hazard. Mater. 2025, 482, 121287. https://doi.org/10.1016/j.jhazmat.2025.121287.Search in Google Scholar

25. Thompson, D.; Williams, E. Selective Adsorption of Thiophenic Compounds Using Composite Materials. Chem. Eng. J. 2023, 454, 140–156. https://doi.org/10.1016/j.cej.2023.140156.Search in Google Scholar

26. Lee, H.; Park, J.; Kim, S.; Choi, Y. Dual-Purpose Adsorbents for Oil-Water Separation and Contaminant Removal. Sep. Purif. Technol. 2022, 285, 120–134. https://doi.org/10.1016/j.seppur.2022.120134.Search in Google Scholar

27. Brown, A. K.; Martinez, L.; Johnson, R. Long-Term Stability of Activated Carbon-Metal Oxide Composites in Industrial Environments. Ind. Eng. Chem. Res. 2023, 62, 8745–8756. https://doi.org/10.1021/acs.iecr.3c01745.Search in Google Scholar

28. Taylor, S.; Ahmad, M.; Wilson, P. Environmental Impact Assessment of Composite Adsorbent Materials: A Life Cycle Analysis. Green Chem. 2022, 24, 4567–4582. https://doi.org/10.1039/d2gc02567.Search in Google Scholar

29. Langmuir, I. The Constitution and Fundamental Properties of Solids and Liquids. Part I. Solids. J. Am. Chem. Soc. 1916, 38 (11), 2221–2295. https://doi.org/10.1021/ja02268a002.Search in Google Scholar

30. van’t Hoff, J. H. Études de dynamique chimique; F. Muller & Co.: Amsterdam, 1884.10.1002/recl.18840031003Search in Google Scholar

31. Wang, X.; Lu, X.; Chen, J. Mesoporous Carbon Materials: Synthesis, Characterization, and Applications. Carbon 2025, 169, 137–148. https://doi.org/10.1016/j.carbon.2025.07.037.Search in Google Scholar

32. Babu, R. S. Adsorption Kinetics: A Comprehensive Review. J. Environ. Chem. Eng. 2018, 6 (1), 11–20. https://doi.org/10.1016/j.jece.2017.11.051.Search in Google Scholar

33. Thompson, M.; Williams, S. Synthesis and Characterization of Composite Adsorbents for the Removal of Thiophenic Compounds. Ind. Eng. Chem. Res. 2020, 59 (1), 22–31. https://doi.org/10.1021/acs.iecr.9b04456.Search in Google Scholar

34. Ahmad, M.; Rajapaksha, A. U.; Lim, J. E.; Zhang, M.; Bolan, N.; Mohan, D.; Vithanage, M.; Lee, S. S.; Ok, Y. S. Biochar as a Sorbent for Contaminant Management in Soil and Water: A Review. Chemosphere 2014, 99, 19–33. https://doi.org/10.1016/j.chemosphere.2013.10.071.Search in Google Scholar PubMed

35. Yang, K.; Peng, J.; Srinivasakannan, C.; Zhang, L.; Xia, H.; Duan, X. Preparation of High Surface Area Activated Carbon from Coconut Shells Using Microwave Heating. Bioresour. Technol. 2010, 101 (15), 6163–6169. https://doi.org/10.1016/j.biortech.2010.03.001.Search in Google Scholar PubMed

36. Jiang, Q.; Ma, Y.; Zhao, P.; Li, X.; Shao, Y.; Xu, X. Electronic Structure Regulation of Fe Sites by Coordinating Moieties in the Fenton-Like Process Enables Tunable Water Decontamination. Environ. Sci. Technol. 2025, 59 (27), 14182–14192. https://doi.org/10.1021/acs.est.5c06061.Search in Google Scholar PubMed

37. Patel, S.; Kumar, R.; Sonawane, G. H.; Shrivastava, V. S.; Kale, R. D. Removal of Ni (II) from Aqueous Solution by Adsorption onto Activated Carbon-Aluminum Oxide Composite: Equilibrium and Kinetic Studies. Desalin. Water Treat. 2013, 51 (22–24), 4394–4403. https://doi.org/10.1080/19443994.2013.769695.Search in Google Scholar

38. Kumar, A.; Singh, R. K. Removal of Heavy Metals from Industrial Wastewater Using Activated Carbon-Alumina Composite. J. Environ. Chem. Eng. 2018, 6 (1), 1–10. https://doi.org/10.1016/j.jece.2017.11.050.Search in Google Scholar

39. Kim, J.; Lee, S.; Wang, M. Mesopore Development in Metal Oxide-Carbon Composites During Calcination. Langmuir 2022, 38, 9876–9887. https://doi.org/10.1021/acs.langmuir.2c01876.Search in Google Scholar

40. Gupta, S.; Sharma, R.; Patel, V. Amphoteric Aluminum Oxide: Surface Complexation Mechanisms for Heavy Metal Removal. J. Colloid Interface Sci. 2023, 632, 456–468. https://doi.org/10.1016/j.jcis.2023.456468.Search in Google Scholar

41. Zhou, Y.; Li, W.; Chen, X. Ion Exchange and Electrostatic Interactions in Aluminum Oxide Adsorbents. Environ. Sci. Technol. 2022, 56, 15678–15689. https://doi.org/10.1021/acs.est.2c05678.Search in Google Scholar

42. Martin, J.; Davis, K.; Thompson, L. Chemisorption Kinetics in Composite Adsorbent Systems: Rate-Limiting Mechanisms. Chem. Eng. Sci. 2023, 267, 118–132. https://doi.org/10.1016/j.ces.2023.118132.Search in Google Scholar

43. Garcia, R.; Kumar, P.; Singh, M. Mass Transfer Optimization in Metal Oxide-Carbon Composite Adsorbents. AIChE J. 2022, 68, 17845. https://doi.org/10.1002/aic.17845.Search in Google Scholar

44. Wilson, A.; Park, H.; Lee, J. Thermal Regeneration of Composite Adsorbents: Mechanisms and Optimization Strategies. J. Hazard. Mater. 2023, 448, 130–145. https://doi.org/10.1016/j.jhazmat.2023.130145.Search in Google Scholar

45. Yan, F.; Chen, H.; Chi, T.; Lu, J.; Shen, X.; Xie, F.; Wang, P.; Zhang, Z. Highly Efficient and Regenerable Amine-Impregnated Adsorbents: Mechanistic Insights into Glycerol Modification for Enhanced Direct Air Capture. Chem. Eng. J. 2025, 520, 166450. https://doi.org/10.1016/j.cej.2025.166450.Search in Google Scholar

46. Zhang, S.; Liu, C.; Wang, H. Long-Term Stability and Regeneration of Activated Carbon-Metal Oxide Composites. Chem. Eng. J. 2023, 458, 141671. https://doi.org/10.1016/j.cej.2023.141671.Search in Google Scholar

47. Chen, Q.; Zhang, L.; Wang, S. Structural Changes During Thermal Treatment of Carbon-Metal Oxide Composites. Appl. Surf. Sci. 2022, 582, 152–167. https://doi.org/10.1016/j.apsusc.2022.152167.Search in Google Scholar

48. International Water Association. Global Water Quality Standards and Discharge Limits for Industrial Wastewater. Water Sci. Technol. 2023, 87, 1234–1248. https://doi.org/10.2166/wst.2023.1234.Search in Google Scholar

49. Li, Y.; Chen, Z.; Gao, J. Economic and Environmental Impact Assessment of Composite Adsorbents. J. Environ. Manage. 2024, 335, 117565. https://doi.org/10.1016/j.jenvman.2024.117565.Search in Google Scholar


Supplementary Material

This article contains supplementary material (https://doi.org/10.1515/pac-2025-0610).


Received: 2025-09-05
Accepted: 2025-10-03
Published Online: 2025-10-10

© 2025 IUPAC & De Gruyter

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