Bimetallic reduced graphene oxide/zeolitic imidazolate framework hybrid aerogels for efficient heavy metals removal

Abstract

Graphene oxide is a promising adsorption material. However, it has been difficult to recycle and separate graphene oxide in the solution. To alleviate this problem, graphene oxide was thermally reduced to produce porous hydrogel which was then functionalized with polydopamine. The functional groups act as not only adsorption sites but also nucleation sites for in situ crystallization of cobalt-doped zeolitic-imidazolate-framework-8 nano-adsorbents. The effects of cobalt-doping contents on the physicochemical and adsorption properties of the resulting aerogel were also evaluated by varying the cobalt concentration. For instance, the reduced graphene oxide-polydopamine/50cobalt-zeolitic-imidazolate-framework-8 aerogel exhibited a high surface area of 900 m²·g^–1 and maintained the structure in water after ten days. The as-synthesized aerogels showed an ultrahigh adsorption capacity of 1217 ± 24.35 mg·g^–1 with a removal efficiency of > 99% of lead, as well as excellent adsorption performance toward other heavy metals, such as copper and cadmium with adsorption capacity of 1163 ± 34.91 and 1059 ± 31.77 mg·g^–1, respectively. More importantly, the lead adsorption stabilized at 1023 ± 20.5 mg·g^–1 with a removal efficiency of > 80% after seven cycles, indicating their potential in heavy metal removal from industrial wastewater.

Graphical abstract

Keywords

rGO / Co-doped ZIF-8 / heavy metals / adsorption / aerogel

References

[1] Azimi A , Azari A , Rezakazemi M , Ansarpour M . Removal of heavy metals from industrial wastewaters: a review. ChemBioEng Reviews, 2017, 4(1): 37–59

[2] Zou Y , Wang X , Khan A , Wang P , Liu Y , Alsaedi A , Hayat T , Wang X . Environmental remediation and application of nanoscale zero-valent iron and its composites for the removal of heavy metal ions: a review. Environmental Science & Technology, 2016, 50(14): 7290–7304

[3] Li X , Wang B , Cao Y , Zhao S , Wang H , Feng X , Zhou J , Ma X . Water contaminant elimination based on metal-organic frameworks and perspective on their industrial applications. ACS Sustainable Chemistry & Engineering, 2019, 7(5): 4548–4563

[4] Mariana M , Abdul A K , Mistar E M , Yahya E B , Alfatah T , Danish M , Amayreh M . Recent advances in activated carbon modification techniques for enhanced heavy metal adsorption. Journal of Water Process Engineering, 2021, 43: 102221

[5] Rahman N S A , Yhaya M F , Azahari B , Ismail W R . Utilisation of natural cellulose fibres in wastewater treatment. Cellulose (London, England), 2018, 25(9): 4887–4903

[6] Ihsanullah I , Sajid M , Khan S , Bilal M . Aerogel-based adsorbents as emerging materials for the removal of heavy metals from water: progress, challenges, and prospects. Separation and Purification Technology, 2022, 291: 120923

[7] Chandra V , Park J , Chun Y , Lee J W , Hwang I C , Kim K S . Water-dispersible magnetite-reduced graphene oxide composites for arsenic removal. ACS Nano, 2010, 4(7): 3979–3986

[8] Stankovich S , Piner R D , Chen X , Wu N , Nguyen S T , Ruoff R S . Stable aqueous dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite oxide in the presence of poly(sodium 4-styrenesulfonate). Journal of Materials Chemistry, 2006, 16(2): 155–158

[9] Xu Y , Wu Q , Sun Y , Bai H , Shi G . Three-dimensional self-assembly of graphene oxide and DNA into multifunctional hydrogels. ACS Nano, 2010, 4(12): 7358–7362

[10] Chen T , Wei X , Chen Z , Morin D , Alvarez S V , Yoon Y , Huang Y . Designing energy-efficient separation membranes: Knowledge from nature for a sustainable future. Advanced Membranes, 2022, 2: 100031

[11] Muschi M , Serre C . Progress and challenges of graphene oxide/metal-organic composites. Coordination Chemistry Reviews, 2019, 387: 262–272

[12] Saliba D , Ammar M , Rammal M , Al-Ghoul M , Hmadeh M . Crystal growth of ZIF-8, ZIF-67, and their mixed-metal derivatives. Journal of the American Chemical Society, 2018, 140(5): 1812–1823

[13] Kaur G , Rai R K , Tyagi D , Yao X , Li P Z , Yang X C , Zhao Y , Xu Q , Singh S K . Room-temperature synthesis of bimetallic Co-Zn based zeolitic imidazolate frameworks in water for enhanced CO₂ and H₂ uptakes. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2016, 4(39): 14932–14938

[14] Zaręba J K , Nyk M , Samoć M . Co/ZIF-8 heterometallic nanoparticles: control of nanocrystal size and properties by a mixed-metal approach. Crystal Growth & Design, 2016, 16(11): 6419–6425

[15] Mazlan N A , Butt F S , Lewis A , Krishnamoorthi R , Chen S , Radacsi N , Huang Y . Robust reduced graphene oxide-PDA/ZIF-8 aerogel composite for cyclic, high-capacity dye adsorption. Separation and Purification Technology, 2024, 334: 126005

[16] Yang Q , Lu R , Ren S S , Chen C , Chen Z , Yang X . Three dimensional reduced graphene oxide/ZIF-67 aerogel: effective removal cationic and anionic dyes from water. Chemical Engineering Journal, 2018, 348: 202–211

[17] Tang L , Dang J , He M , Li J , Kong J , Tang Y , Gu J . Preparation and properties of cyanate-based wave-transparent laminated composites reinforced by dopamine/POSS functionalized Kevlar cloth. Composites Science and Technology, 2019, 169: 120–126

[18] Chen T , Butt F S , Zhang M , Wei X , Lewis A , Radacsi N , Semiao A J C , Han J , Huang Y . Ultra-permeable zeolitic imidazolate frameworks-intercalated graphene oxide membranes for unprecedented ultrafast molecular separation. Chemical Engineering Journal, 2021, 419: 129507

[19] Huang H H , De Silva K K H , Kumara G R A , Yoshimura M . Structural evolution of hydrothermally derived reduced graphene oxide. Scientific Reports, 2018, 8(1): 6849

[20] Xi Z Y , Xu Y Y , Zhu L P , Wang Y , Zhu B K . A facile method of surface modification for hydrophobic polymer membranes based on the adhesive behavior of poly(DOPA) and poly(dopamine). Journal of Membrane Science, 2009, 327(1–2): 244–253

[21] Luan Tran B , Chin H Y , Chang B K , Chiang A S . Dye adsorption in ZIF-8: the importance of external surface area. Microporous and Mesoporous Materials, 2019, 277: 149–153

[22] Ren H , Kulkarni D D , Kodiyath R , Xu W , Choi I , Tsukruk V V . Competitive adsorption of dopamine and rhodamine 6G on the surface of graphene oxide. ACS Applied Materials & Interfaces, 2014, 6(4): 2459–2470

[23] Maharsi R , Arif A F , Ogi T , Widiyandari H , Iskandar F . Electrochemical properties of TiO_x/rGO composite as an electrode for supercapacitors. RSC Advances, 2019, 9(48): 27896–27903

[24] Han X , Zhang L , Li C . Preparation of polydopamine-functionalized graphene-Fe₃O₄ magnetic composites with high adsorption capacities. RSC Advances, 2014, 4(58): 30536–30541

[25] Abuzalat O , Tantawy H , Basuni M , Alkordi M H , Baraka A . Designing bimetallic zeolitic imidazolate frameworks (ZIFs) for aqueous catalysis: Co/Zn-ZIF-8 as a cyclic-durable catalyst for hydrogen peroxide oxidative decomposition of organic dyes in water. RSC Advances, 2022, 12(10): 6025–6036

[26] Zou R , Liu F , Hu N , Ning H , Jiang X , Xu C , Fu S , Li Y , Zhou X , Yan C . Carbonized polydopamine nanoparticle reinforced graphene films with superior thermal conductivity. Carbon, 2019, 149: 173–180

[27] Zhao M , Tesfay Reda A , Zhang D . Reduced graphene oxide/ZIF-67 aerogel composite material for uranium adsorption in aqueous solutions. ACS Omega, 2020, 5(14): 8012–8022

[28] Liu Y , Fu J , He J , Wang B , He Y , Luo L , Wang L , Chen C , Shen F , Zhang Y . Synthesis of a superhydrophilic coral-like reduced graphene oxide aerogel and its application to pollutant capture in wastewater treatment. Chemical Engineering Science, 2022, 260: 117860

[29] Park H , Amaranatha Reddy D , Kim Y , Ma R , Choi J , Kim T K , Lee K S . Zeolitic imidazolate framework-67 (ZIF-67) rhombic dodecahedrons as full-spectrum light harvesting photocatalyst for environmental remediation. Solid State Sciences, 2016, 62: 82–89

[30] Zhu G , Li H , Deng S , Zhang C , Kang K , Zhang X , Li K . In situ growth of bimetallic Co/Zn-ZIF within wood scaffold for enhanced adsorption capacity and improved flame retardancy. Wood Science and Technology, 2022, 56(6): 1657–1673

[31] Kobielska P A , Howarth A J , Farha O K , Nayak S . Metal-organic frameworks for heavy metal removal from water. Coordination Chemistry Reviews, 2018, 358: 92–107

[32] Nundy S , Ghosh A , Nath R , Paul A , Tahir A A , Mallick T K . Reduced graphene oxide (rGO) aerogel: efficient adsorbent for the elimination of antimony (III) and (V) from wastewater. Journal of Hazardous Materials, 2021, 420: 126554

[33] Ha Y M , Kim Y N , Jung Y C . Rapid and local self-healing ability of polyurethane nanocomposites using photothermal polydopamine-coated graphene oxide triggered by near-infrared laser. Polymers, 2021, 13(8): 1274

[34] Wang L , Zhao X , Zhang J , Xiong Z . Selective adsorption of Pb(II) over the zinc-based MOFs in aqueous solution-kinetics, isotherms, and the ion exchange mechanism. Environmental Science and Pollution Research International, 2017, 24(16): 14198–14206

[35] Yang W , Kong Y , Yin H , Cao M . Study on the adsorption performance of ZIF-8 on heavy metal ions in water and the recycling of waste ZIF-8 in cement. Journal of Solid State Chemistry, 2023, 326: 124217

[36] Ahmad K , Ashfaq M , Shah S S A , Hussain E , Naseem H A , Parveen S , Ayub A . Effect of metal atom in zeolitic imidazolate frameworks (ZIF-8 & 67) for removal of Pb²⁺ & Hg²⁺ from water. Food and Chemical Toxicology, 2021, 149: 112008

[37] Yu C X , Wang K Z , Li X J , Liu D , Ma L F , Liu L L . Highly efficient and facile removal of Pb²⁺ from water by using a negatively charged azoxy-functionalized metal-organic framework. Crystal Growth & Design, 2020, 20(8): 5251–5260

[38] IghaloJ ORangabhashiyamSAdeyanjuC AOgunniyiSAdeniyiA GIgwegbeC A. Zeolitic imidazolate frameworks (ZIFs) for aqueous phase adsorption—a review. Journal of Industrial and Engineering Chemistry, 2022, 105: 34–48

[39] Gao C , Dong Z , Hao X , Yao Y , Guo S . Preparation of reduced graphene oxide aerogel and its adsorption for Pb(II). ACS Omega, 2020, 5(17): 9903–9911

[40] Nazir M A , Najam T , Shahzad K , Wattoo M A , Hussain T , Tufail M K , Shah S S A , Rehman A . Heterointerface engineering of water stable ZIF-8@ZIF-67: adsorption of rhodamine B from water. Surfaces and Interfaces, 2022, 34: 102324

[41] Chen H , Li T , Zhang L , Wang R , Jiang F , Chen J . Pb(II) adsorption on magnetic γ-Fe₂O₃/titanate nanotubes composite. Journal of Environmental Chemical Engineering, 2015, 3(3): 2022–2030

[42] Scheufele F B , Módenes A N , Borba C E , Ribeiro C , Espinoza-Quiñones F R , Bergamasco R , Pereira N C . Monolayer-multilayer adsorption phenomenological model: kinetics, equilibrium and thermodynamics. Chemical Engineering Journal, 2016, 284: 1328–1341

[43] Bulut E , Özacar M , Şengil I A . Adsorption of malachite green onto bentonite: equilibrium and kinetic studies and process design. Microporous and Mesoporous Materials, 2008, 115(3): 234–246

[44] Zubair Y O , Fuchida S , Tokoro C . Insight into the mechanism of arsenic(III/V) uptake on mesoporous zerovalent iron-magnetite nanocomposites: adsorption and microscopic studies. ACS Applied Materials & Interfaces, 2020, 12(44): 49755–49767

[45] Zhao C , Hong P , Li Y , Song X , Wang Y , Yang Y . Mechanism of adsorption of tetracycline-Cu multi-pollutants by graphene oxide (GO) and reduced graphene oxide (rGO). Journal of Chemical Technology and Biotechnology, 2019, 94(4): 1176–1186

[46] Zeng Q , Qi X , Zhang M , Tong X , Jiang N , Pan W , Xiong W , Li Y , Xu J , Shen J . . Efficient decontamination of heavy metals from aqueous solution using pullulan/polydopamine hydrogels. International Journal of Biological Macromolecules, 2020, 145: 1049–1058

[47] Foo K Y , Hameed B H . Insights into the modeling of adsorption isotherm systems. Chemical Engineering Journal, 2010, 156(1): 2–10

[48] Saadi R , Saadi Z , Fazaeli R , Fard N E . Monolayer and multilayer adsorption isotherm models for sorption from aqueous media. Korean Journal of Chemical Engineering, 2015, 32(5): 787–799

[49] Zhang Y , Cao B , Zhao L , Sun L , Gao Y , Li J , Yang F . Biochar-supported reduced graphene oxide composite for adsorption and coadsorption of atrazine and lead ions. Applied Surface Science, 2018, 427: 147–155

[50] Liu Y , Ai K , Lu L . Polydopamine and its derivative materials: synthesis and promising applications in energy, environmental, and biomedical fields. Chemical Reviews, 2014, 114(9): 5057–5115

Competing interests

The authors declare that they have no competing interests.

Acknowledgements

This work was funded by Jiangsu Dingying New Materials Co., Ltd. under Grant Number (C-00005685) and the School of Engineering, the University of Edinburgh. N.A.M. acknowledges the Malaysian Government for awarding a Ph.D. scholarship. The authors would like to thank Fergus Dingwall for his laboratory assistance and we acknowledge the use of the Zeiss Crossbeam Cryo FIB/SEM bought with the EPSRC grant EP/P030564/1 and Fraser Laidlaw for help with image acquisition.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-024-2442-0 and is accessible for authorized users.

Funding note

Funding note not available.

Open Access

This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source. provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

RIGHTS & PERMISSIONS

2024 The Author(s) 2024. This article is published with open access at link.springer.com and journal.hep.com.cn