10.57647/jnsc.2025.1501.03

3D Print-Based Polypyrrole /TiVCTx/UiO-66 Composites for Effective Adsorption of Combined Pollutants in Water Media

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  • Tao Wu1,
  • Yan Li2,
  • Zhouxiang Zhang3,
  • Dongxing Zhang2,
  • Elena Niculina Dragoi4,
  • Hassan Karimi-Maleh*5,
  1. School of Resources and Environment, University of Electronic Science and Technology of China, Xiyuan Ave, Chengdu, China
  2. Shenzhen Institute for Advanced Study, University of Electronic Science and Technology of China, Yesun Industry Zone, Guanlan Street, Shenzhen, Guangdong, China
  3. Yangtze Delta Region Institute (Huzhou), University of Electronic Science and Technology of China, Huzhou, China
  4. “Cristofor Simionescu” Faculty of Chemical Engineering and Environmental Protection, “Gheorghe Asachi” Technical University, Iasi, Bld. D Mangeron, Romania
  5. Engineering Research Center for Endoscope Instrument and Technology Development, Biosensor group, The Quzhou Affiliated Hospital of Wenzhou Medical University, Quzhou People’s Hospital, Quzhou, Zhejiang, PR China
3D Print-Based Polypyrrole /TiVCTx/UiO-66 Composites for Effective Adsorption of Combined Pollutants in Water Media

Received: 09-01-2025

Revised: 01-02-2025

Accepted: 25-02-2025

Published in Issue 28-02-2025

Copyright (c) -1 Tao Wu, Yan Li, Zhouxiang Zhang, Dongxing Zhang, Elena Niculina Dragoi, Hassan Karimi-Maleh (Author)

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This work is licensed under a Creative Commons Attribution 4.0 International License.

How to Cite

Wu, T., Li, Y., Zhang, Z., Zhang, D., Dragoi, E. N., & Karimi-Maleh, H. (2025). 3D Print-Based Polypyrrole /TiVCTx/UiO-66 Composites for Effective Adsorption of Combined Pollutants in Water Media. Journal of Nanostructure in Chemistry, 15(1 (February 2025). https://doi.org/10.57647/jnsc.2025.1501.03
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Abstract

The presence of heavy metals and dyes in contaminated water systems at the same time poses significant threats to the integrity of the environment as well as to the health of the general public. Therefore, a novel TiVCTx/UiO-66 composite was prepared by in-situ growth synthesis in this paper. The risk of difficult separation and recovery of powder materials in water medium and easy secondary pollution is considered. 3D printing technology is used to design and prepare 3D structures (3DS) with high porosity and connectivity. Immediately, a novel monolithic adsorbent (PPy/TiVCTx/UiO-66/3DS) was synthesized by combining polypyrrole (PPy) with TiVCTx/UiO-66 and fixing it on the surface of the 3D structure. The adsorption performance of monolithic adsorbents was assessed through single-factor batch adsorption tests conducted within single and combined pollutant systems. According to the findings, the adsorbent demonstrates remarkable separation and recovery characteristics, as it is able to efficiently remove Congo red (CR) and Cr(Ⅵ) from aqueous solutions. The maximum adsorption capacities reached 230.96 mg/g for CR and 40.84 mg/g for Cr(VI). Interestingly, the presence of trace Cr(VI) (20 ppm) induced a 9.84% enhancement in CR adsorption capacity. After five successive regeneration cycles, the adsorbent retained 97.65% and 67.84% removal efficiencies for CR and Cr(VI). In addition, the fixed bed column can effectively dynamically remove CR and Cr(Ⅵ) of about 600mL and 360mL. The ongoing advancement of 3D printing technology increases efficiency in producing large-scale models. This trend indicates that monolithic adsorbents created using 3D printing possess substantial potential for practical application in wastewater treatment processes.

Keywords

  • MXene,
  • Metal-organic frame,
  • Pollutant,
  • Monolithic adsorbent,
  • 3D printing,
  • Water treatment
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References

  1. Qin, W.H., Li M.X., Zhang, Y.B., Li, W., Jia R., Xiong, Y.S., Lu, H.Q., Zhang, S.Y.: High capacity and selective adsorption of Congo red by cellulose-based aerogel with mesoporous structure: Adsorption properties and statistical data simulation. Int. J. Biol. Macromol. 259, 129137 (2024).
  2. Tian, Y., Wei, L., Yu, T., Shen, H., Zhao, W., Chu, X.: Adsorption of Cr(VI) and Cr(III) on layered pipe scales and the effects of disinfectants in drinking water distribution systems. J. Hazard. Mater. 474, 134745 (2024).
  3. Deng, H., Hu, Q., Zhu, P., Sun, A., Yang, S.: A study on soil remediation of hexavalent chromium pollution using nano-sized zinc oxide and Miscanthus lutarioriparius. Alex. Eng. J. 105, 292-299 (2024).
  4. Zeng, X., Zhang, G., Wen, J., Li, X., Zhu, J., Wu, Z.: Simultaneous removal of aqueous same ionic type heavy metals and dyes by a magnetic chitosan/polyethyleneimine embedded hydrophobic sodium alginate composite: Performance, interaction and mechanism. Chemosphere. 318, 137869 (2023).
  5. Dhiman, P., Goyal, D., Rana, G., Kumar, A., Sharma, G., Kumar, L.G: Recent advances on carbon-based nanomaterials supported single-atom photo-catalysts for waste water remediation. J. Nanostruct. Chem. 14, 21-52 (2022).
  6. S.A. Moosaviyan, M.R. Baezzat, M. Ghaedi, H. Abbasi-Asl, Photocatalytic decomposition of methylene blue and rhodamine B using Ag–Ag2SeO3/Ppy nano‑photocatalyst from aqueous solutions: experimental design optimization. J. Nanostruct. Chem. 14, 419-436 (2023).
  7. Li, Z., Li, R., Liu, R., Zhang, W.J., Wan, Y., Sun, Y.Z., Yang, L., Long, Y.Z.: A beaded g-C3N4/CoFe2O4 nanofibers for efficient adsorbing and catalytical degrading multiple pollutants. Carbon Lett. 35, 1187–1203 (2025).
  8. Sun, C., Xing, X., Li, J., Xiong, W., Li, H.: Recent advances in carbon-based catalysts for electrocatalytic nitrate reduction to ammonia. Carbon Lett. 35, 1-19 (2024).
  9. Xu, T., Huang, Y., Ye, W., Wang, M., Chen, Y., Yang, H., Ren, B.: Process study of ceramic membrane treatment for water treatment residuals from lake and reservoir water purification plants in severe cold regions. Carbon Lett. 34, 2399-2410 (2024).
  10. Mehta, J., Dhaka, R.K., Dilbaghi, N., Lim, D.K., Hassan, A.A., Kim, K.H., Kumar, S.: Recent advancements in adsorptive removal of organophosphate pesticides from aqueous phase using nanomaterials. J. Nanostruct. Chem. 14, 53-70 (2022).
  11. Lin, G., Zeng, B., Li, J., Wang,Z., Wang, S., Hu, T., Zhang, L.: A systematic review of metal organic frameworks materials for heavy metal removal: Synthesis, applications and mechanism. Chem. Eng. J. 460, 141710 (2023).
  12. Shi, X., Gao, M., Hu, W., Luo, D., Hu, S., Huang, T., Zhang, N., Wang,Y.: Largely enhanced adsorption performance and stability of MXene through in-situ depositing polypyrrole nanoparticles. Sep. Purif. Technol. 287, 120596 (2022).
  13. Lee, G., Ahmed, I., Lee, H.J., Jhung, S.H.: Adsorptive removal of organic pollutants with a specific functional group from water by using metal–organic frameworks (MOFs) or MOF-derived carbons: A review. Sep. Purif. Technol. 347, 127602 (2024).
  14. Song, X., Dai, R., Zhu, T., Zhang, S., Liu, J., Zhang, S., Zhang, L.: A novel iron metal organic framework-based nanocomposite for the synergistic degradation and adsorption of organic pollutants and Cr (Ⅵ) under visible light. J. Clean. Prod. 456, 142337 (2024).
  15. Saini, K., Singh, J., Malik, S., Saharan, Y., Goyat, R., Umar, A., Akbar, S., Ibrahim, A.A., Baskoutas, S.: Metal-Organic Frameworks: A promising solution for efficient removal of heavy metal ions and organic pollutants from industrial wastewater. J. Mol. Liq. 399, 124365 (2024).
  16. Jiang, S., Lyu, Y., Zhang, J., Zhang, X., Yuan, M., Zhang, Z., Jin, G., He, B., Xiong, W., Yi, H.: Continuous adsorption removal of organic pollutants from wastewater in a UiO-66 fixed bed column. J. Environ. Chem. Eng. 12, 111951(2024).
  17. Li, Y., Zhang, J., Cheng, Y., Feng, K., Li, J., Yang, L., Yin, S.: Stable TiVCTx/poly-o-phenylenediamine composites with three-dimensional tremella-like architecture for supercapacitor and Li-ion battery applications. Chem. Eng. J. 433, 134578 (2022).
  18. Lv, T., Wu, F., Zhang, Z., Liu, Z., Zhao, Y., Yu, L., Zhang, J., Yu, C., Zhao, C., Xing, G.: TiVCTX MXene/Graphene Nanosheet-Based Aerogels for Removal of Organic Contaminants from Wastewater. ACS Appl. Nano Mater. 7, 7312-7326 (2024).
  19. Li, Q., Zhang, X., Ren, Y., Liu, N., Yu, F., Ma, J.: Atomically selective oxidation of double transition-metal TiVCTX MXene for highly selective Mg2+/Ca2+ separation. Sep. Purif. Technol. 361, 131295 (2025).
  20. Luo, X., Wang, H., Ren, X., Liu, G., Luo, H., Zheng, Z., Wu, F.: Effective adsorptive removal of heavy metal anion Cr(Ⅵ) and dye cation methylene blue by the novel 2D material TiVCTx MXene. J. Alloy. Compd. 1010, 177409 (2025).
  21. Gong, K., Yin, L., Wu, Z., Zhou, K., Yu, W.W.: MXene nanohybrids assembled with phytic acid-modified UiO-66 toward mechanically reinforced, fire-resistant and smoke-suppressed epoxy composites. Chem. Eng. J. 505,159605 (2025).
  22. Wang, R., Yao, C., Peng, C., Qiu, J., Wang, Q., Liu, X., Meng, J., Wang, W.: Ultra-strong adsorption of organic dyes and antibiotic onto the alk-MXene/ZIF adsorbents with a specific intercalation structure. Chem. Eng. J. 485, 149916 (2024).
  23. Ren, X., Fang, L., Hu, Y., Wu, F., Liu, G., Zhang, S., Luo, H.: Enhancing both the long-term stability and methylene blue adsorption performance of TiVCTxvia a facile antioxidation treatment. Nanoscale. 17, 10065-10081 (2025).
  24. Peng, S., Ji, X., Dong, H., Guo, Z., Ma, H., Han, R., Pang, K., Chen, X., Wang, X.: Designing MOFs/CuCo-LDHs hybrid-based superhydrophobic sponge for speedy eliminating microplastics, dyes, and oils from high-salinity water. Colloid. Surfaces A. 692, 133996 (2024).
  25. Yousefzadeh, Y., Izadkhah, V., Sobhanardakani, S., Lorestani, B., Alavinia, S.: UiO-66-NH2/guanidine-functionalized chitosan: A new bio-based reusable bifunctional adsorbent for removal of methylene blue from aqueous media. Int. J. Biol. Macromol. 254, 127391 (2024).
  26. Yang, H., Zhang, P., Zheng, Q., Hameed, M.U., Raza, S.: Synthesis of cellulose cotton-based UiO-66 MOFs for the removal of rhodamine B and Pb(II) metal ions from contaminated wastewater. Int. J. Biol. Macromol. 253, 126986 (2023).
  27. Gonçalves, N.P.F., Olhero, S.M., Labrincha, J.A., Novais, R.M.: 3D-printed red mud/metakaolin-based geopolymers as water pollutant sorbents of methylene blue. J. Clean. Prod. 383, 135315 (2023).
  28. Quan, H., Zhang, T., Xu, H., Luo, S., Nie, J., Zhu, X.: Photo-curing 3D printing technique and its challenges. Bioact. Materials. 5, 110-115 (2020).
  29. Kokkinos, C., Economou, A., Pournara, A., Manos, M., Spanopoulos, I., Kanatzidis, M., Tziotzi, T., Petkov, V., Margariti, A., Oikonomopoulos, P., Papaefstathiou, G.S.: 3D-printed lab-in-a-syringe voltammetric cell based on a working electrode modified with a highly efficient Ca-MOF sorbent for the determination of Hg(II). Sensor. Actuat. B-Chem. 321, 128508 (2020).
  30. Far, H.S., Najafi, M., Hasanzadeh, M., Rabbani, M.: Self-Supported 3D-Printed Lattices Containing MXene/Metal–Organic Framework (MXOF) Composite as an Efficient Adsorbent for Wastewater Treatment, ACS Appl. Mater. Interfaces. 14, 44488-44497 (2022).
  31. Far, H.S., Najafi, M., Hasanzadeh, M., Rahimi, R.: A 3D-printed hierarchical porous architecture of MOF@clay composite for rapid and highly efficient dye scavenging. New J. Chem. 46, 23351-23360 (2022).
  32. Fijoł, N., Mautner, A., Grape, E.S., Bacsik, Z., Inge, A.K., Mathew, A.P.: MOF@Cell: 3D printed biobased filters anchored with a green metal–organic framework for effluent treatment. J. Mater. Chem. A. 11, 12384-12394 (2023).
  33. Wu, T., Karimi-Maleh, H., Li, Y., Zhang, D., Zhang, Z., Zhong, N., Wen, Y., Aminabhavi, T.M.: 3D printed porous chitosan/metal–organic framework composites as effective adsorbents to remove heavy metals from wastewater. Chem. Eng. J. 493, 152780 (2024).
  34. Peñas-Garzón, M., Sampaio, M.J., Manrique, Y., Silva, C.G., Faria, J.L.: Enhanced removal of emerging pollutants through visible light-activated carbon nitride materials immobilized over 3D printed structures. J. Environ. Chem. Eng. 11, 111343 (2023).
  35. Huong, V.T., Duc, B.V., An, N.T., Anh, T.T.P., Aminabhavi, T.M., Vasseghian, Y., Joo, S.W.: 3D-Printed WO3-UiO-66@reduced graphene oxide nanocomposites for photocatalytic degradation of sulfamethoxazole. Chem. Eng. J. 483, 149277 (2024).
  36. Bansiddhi, A., Panomsuwan, G., Hussakan, C., Htet, T.L., Kandasamy, B., Janbooranapinij, K., Choophun, N., Techapiesancharoenkij, R., Pant, H.R., Ang, W.L., Jongprateep, O.: Ecofriendly 3D Printed TiO2/SiO2/Polymer Scaffolds for Dye Removal. Top. Catal. 66, 1662-1673 (2023).
  37. Lawson, S., Li, X., Thakkar, H., Rownaghi, A.A., Rezaei, F.: Recent Advances in 3D Printing of Structured Materials for Adsorption and Catalysis Applications. Chem. Rev. 121, 6246-6291 (2021).
  38. Scaffaro, R., Gulino, E.F., Citarrella, M.C.: Multifunctional 3D-printed composites based on biopolymeric matrices and tomato plant (Solanum lycopersicum) waste for contextual fertilizer release and Cu(II) ions removal. Adv. Compos. Hybrid Ma. 7, 95 (2024).
  39. Negarestani, M., Shayesteh, H., Kheradmand, A., Pahlevani, F., Mollahosseini, A., Javanshir, S.: Preparation of polypyrrole-functionalized recycled cotton fiber as a renewable and eco-friendly cellulose-based adsorbent for water decolorization: Comprehensive batch and fixed-bed column study. Surf. Interfaces. 48, 104360 (2024).
  40. Ouyang, J., Chen, J., Ma, S., Xing, X., Zhou, L., Liu, Z., Zhang, C.: Adsorption removal of sulfamethoxazole from water using UiO-66 and UiO-66-BC composites. Particuology. 62, 71-78 (2022).
  41. Taka, A.L., Klink, M.J., Mbianda, X.Y., Naidoo, E.B.: Chitosan nanocomposites for water treatment by fixed-bed continuous flow column adsorption: A review. Carbohyd. Polym. 255, 117398 (2021).
  42. He, Z., Rong, T., Li, Y., Ma, J., Li, Q., Wu, F., Wang, F., Wang, F.: Two-Dimensional TiVC Solid-Solution MXene as Surface-Enhanced Raman Scattering Substrate. ACS Nano. 16, 4072-4083 (2022).
  43. Liu, D., Li, Y., Liu, C., Zhou, Y.: Facile preparation of UiO-66@PPy nanostructures for rapid and efficient adsorption of fluoride: Adsorption characteristics and mechanisms. Chemosphere. 289, 133164 (2022).
  44. Abid, H.R., Ang, H.M., Wang, S.: Effects of ammonium hydroxide on the structure and gas adsorption of nanosized Zr-MOFs (UiO-66). Nanoscale. 4, 3089-3094 (2012).
  45. Cao, Y., Zhao, Y., Lv, Z., Song, F., Zhong, Q.: Preparation and enhanced CO2 adsorption capacity of UiO-66/graphene oxide composites. J. Ind. Eng. Chem. 27, 102-107 (2015).
  46. Ebrahim, A.M., Levasseur, B., Bandosz, T.J.: Interactions of NO2 with Zr-Based MOF: Effects of the Size of Organic Linkers on NO2 Adsorption at Ambient Conditions. Langmuir. 29, 168-174 (2012).
  47. Zhou, T., Liang, Q., Zhou, X., Luo, H., Chen, W.: Enhanced removal of toxic hexavalent chromium from aqueous solution by magnetic Zr-MOF@polypyrrole: performance and mechanism. Environ. Sci. Pollut. R. 28, 13084-13096 (2021).
  48. Liu, Y., Liu, M.: Conductive carboxylated styrene butadiene rubber composites by incorporation of polypyrrole-wrapped halloysite nanotubes. Compos. Sci. Technol. 143, 56-66 (2017).
  49. Yazdanparast, S., Soltanmohammad, S., Fash-White, A., Tucker, G.J., Brennecka, G.L.: Synthesis and Surface Chemistry of 2D TiVC Solid-Solution MXenes. ACS Appl. Mater. Interfaces. 12, 20129-20137 (2020).
  50. Hu, X., Zhang, Y., Li, J., Su, M., Yang, M., Fang, X., Wang, H., Li, G.: Synthesis and performance studies of functionalized metal-organic framework UiO-66 composites in water bodies. J. Taiwan Inst. Chem. E.159, 105512 (2024).
  51. Mirzaei, K., Jafarpour, E., Shojaei, A., Khasraghi, S.S., Jafarpour, P.: An investigation on the influence of highly acidic media on the microstructural stability and dye adsorption performance of UiO-66. Appl. Surf. Sci. 618, 156531(2023).
  52. Healy, C., Patil, K.M., Wilson, B.H., Hermanspahn, L., Harvey-Reid, N.C., Howard, B.I., Kleinjan, C., Kolien, J., Payet, F., Telfer, S.G., Kruger, P.E., Bennett, T.D.: The thermal stability of metal-organic frameworks. Coordin. Chem. Rev. 419, 213388 (2020).
  53. Zhu, Y., Lin, H., Feng, Q., Zhao, B., Lan, W., Li, T., Xue, B., Li, M., Zhang, Z.: Sulfhydryl-modified SiO2 cryogel: A pH-insensitive and selective adsorbent for efficient removal of mercury in waters. Colloid. Surface. A. 617, 126382 (2021).
  54. Ahmad, R., Kumar, R.: Adsorptive removal of congo red dye from aqueous solution using bael shell carbon. Appl. Surf. Sci. 257,1628-1633 (2010).
  55. Qin, H., Xu, L., Qin, L., Kang, B., Zha, F., Wang, Q., Huang, K.: Removal of Cu(II) by sodium hexametaphosphate and nano zero-valent iron modified calcium bentonite: characteristic, adsorption performance and mechanism. J. Environ. Manage. 358, 120866 (2024).
  56. Zhao, J., Yang, X., Yang, Y., Liu, L., Lin, Y., Xie, L., Chai, X., Xu, K., Du, G., Zhang, L.: Biomass polyamine-functionalized nanocellulose-loaded covalent organic framework to construct composite aerogels for highly efficient removal of Cr (VI) and methyl orange. Chem. Eng. J. 486, 150282 (2024).
  57. Al-Ghouti, M.A., Da'ana, D.A.: Guidelines for the use and interpretation of adsorption isotherm models: A review. J. Hazard. Mater. 393, 122383 (2020).
  58. Chen, R., Gan, C., Cai, B., Liu, R., Xu, W., Yin, W., Li, H., Yu, L., Yong, Q.: Co-adsorption and selective-adsorption of heavy metals and dyes from aqueous solution by bio-based humus/chitosan hydrogels. J. Environ. Sci. 145, 193-204 (2024).
  59. Liu, P., Wu, L., Guo, Y., Huang, X., Guo, Z.: High crystalline LDHs with strong adsorption properties effectively remove oil and micro-nano plastics. J. Clean. Prod. 437, 140628 (2024).
  60. Adeleke, A.O., Omar, R.C., Katibi, K.K., Dele-Afolabi, T.T., Ahmad, A., Quazim, J.O., Amusa, A.A., Alshammari, M.B.: Process optimization of superior biosorption capacity of biogenic oyster shells nanoparticles for Congo red and Bromothymol blue dyes removal from aqueous solution: Response surface methodology, equilibrium isotherm, kinetic, and reusability studies. Alex. Eng. J. 92, 11-23 (2024).
  61. Sepehr, M.N., Sivasankar, V., Zarrabi, M., Kumar, M.S.: Surface modification of pumice enhancing its fluoride adsorption capacity: An insight into kinetic and thermodynamic studies. Chem. Eng. J. 228, 192-204 (2013).
  62. Huang, Y., Zheng, H., Hu, X., Wu, Y., Tang, X., He, Q., Peng, S.: Enhanced selective adsorption of lead(II) from complex wastewater by DTPA functionalized chitosan-coated magnetic silica nanoparticles based on anion-synergism. J. Hazard. Mater. 422, 126856 (2022).
  63. Zhang, F., Tang, X., Huang, Y., Keller, A.A., Lan, J.: Competitive removal of Pb2+ and malachite green from water by magnetic phosphate nanocomposites. Water Res. 150, 442-451 (2019).
  64. Qiu, Y., Zhang, Q., Gao, B., Li, M., Fan, Z., Sang, W., Hao, H., Wei, X.: Removal mechanisms of Cr(VI) and Cr(III) by biochar supported nanosized zero-valent iron: Synergy of adsorption, reduction and transformation. Environ. Pollut. 265, 115018 (2020).
  65. Kizito, S., Wu, S., Wandera, S.M., Guo, L., Dong, R.: Evaluation of ammonium adsorption in biochar-fixed beds for treatment of anaerobically digested swine slurry: Experimental optimization and modeling. Sci. Total Environ. 563-564, 1095-1104 (2016).
  66. Brion-Roby, R., Gagnon, J., Deschênes, J.S., Chabot, B.: Investigation of fixed bed adsorption column operation parameters using a chitosan material for treatment of arsenate contaminated water. J. Environ. Chem. Eng. 6, 505-511 (2018).
  67. Rong, Y., Yan, W., Wang, Z., Hao, X., Guan, G.: An electroactive montmorillonite/polypyrrole ion exchange film: Ultrahigh uptake capacity and ion selectivity for rapid removal of lead ions. J. Hazard. Mater. 437, 129366 (2022).
  68. Wei, X., You, Y., Fan, Z., Sheng, G., Ma, J., Huang, Y., Xu, H.: Controllable integration of nano zero-valent iron into MOFs with different structures for the purification of hexavalent chromium-contaminated water: Combined insights of scavenging performance and potential mechanism investigations. Sci. Total Environ. 935, 173395 (2024).
  69. Chen, J., Hu, X., Lu, L., Shahab, A., Zhang, H., Mo, S.Z., Al-Sharif, M.S.: High-efficient removal of methylene blue by zirconium-based organic frameworks modified with 1,3,5-benzenetricarboxylic acid: Characterization, performances, and mechanisms, Chemosphere, 360, 142381 (2024).