Green β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements: cerium and lanthanum

During the past decades, the removal and recovery of Lanthanum (La) and cerium (Ce) have attracted considerable interest owing to their importance in several industrial processes. In the present work, green nanosponge adsorbents have been synthesized from a local and economic source of β-cyclodextri...

Full description

Autores:
Jemli, Sonia
Pinto, Diana
Kanhounnon, Wilfried G.
Ben Amara, Fakhreddine
lotfi, sellaoui
Bonilla-Petriciolet, Adrian
Dhaouadi, Fatma
Ameri, Rihab
Silva Oliveira, Luis Felipe
Bejar, Samir
Dotto, Guilherme Luiz
Badawi, Michael
Tipo de recurso:
Article of investigation
Fecha de publicación:
2023
Institución:
Corporación Universidad de la Costa
Repositorio:
REDICUC - Repositorio CUC
Idioma:
eng
OAI Identifier:
oai:repositorio.cuc.edu.co:11323/10527
Acceso en línea:
https://hdl.handle.net/11323/10527
https://repositorio.cuc.edu.co/
Palabra clave:
Green adsorbent
LREEs
Adsorption
DFT
Isotherms
La
Ce
Rights
closedAccess
License
Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0)
id RCUC2_b63f6270a44363f2272a13acfa580c5f
oai_identifier_str oai:repositorio.cuc.edu.co:11323/10527
network_acronym_str RCUC2
network_name_str REDICUC - Repositorio CUC
repository_id_str
dc.title.eng.fl_str_mv Green β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements: cerium and lanthanum
title Green β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements: cerium and lanthanum
spellingShingle Green β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements: cerium and lanthanum
Green adsorbent
LREEs
Adsorption
DFT
Isotherms
La
Ce
title_short Green β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements: cerium and lanthanum
title_full Green β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements: cerium and lanthanum
title_fullStr Green β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements: cerium and lanthanum
title_full_unstemmed Green β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements: cerium and lanthanum
title_sort Green β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements: cerium and lanthanum
dc.creator.fl_str_mv Jemli, Sonia
Pinto, Diana
Kanhounnon, Wilfried G.
Ben Amara, Fakhreddine
lotfi, sellaoui
Bonilla-Petriciolet, Adrian
Dhaouadi, Fatma
Ameri, Rihab
Silva Oliveira, Luis Felipe
Bejar, Samir
Dotto, Guilherme Luiz
Badawi, Michael
dc.contributor.author.none.fl_str_mv Jemli, Sonia
Pinto, Diana
Kanhounnon, Wilfried G.
Ben Amara, Fakhreddine
lotfi, sellaoui
Bonilla-Petriciolet, Adrian
Dhaouadi, Fatma
Ameri, Rihab
Silva Oliveira, Luis Felipe
Bejar, Samir
Dotto, Guilherme Luiz
Badawi, Michael
dc.subject.proposal.eng.fl_str_mv Green adsorbent
LREEs
Adsorption
DFT
Isotherms
La
Ce
topic Green adsorbent
LREEs
Adsorption
DFT
Isotherms
La
Ce
description During the past decades, the removal and recovery of Lanthanum (La) and cerium (Ce) have attracted considerable interest owing to their importance in several industrial processes. In the present work, green nanosponge adsorbents have been synthesized from a local and economic source of β-cyclodextrin (β-CD), and applied for the first time to La and Ce ion recovery from aqueous solutions. A statistical physics model has been used to analyze adsorption data. This material has shown high adsorption capacities of 625.34 and 773.29 mg g−1 for Ce and La, respectively. Furthermore, a temperature of 298 K has been identified as the best condition to remove these elements from aqueous solutions. Furthermore, DFT simulations have been performed to identify the nature of functional groups involved in removing these rare earth elements. Assessments of the adsorbent regeneration and recycling capacities have also been determined, showing that β-CD nanosponges remain stable and effective for La and Ce adsorption over three desorption-adsorption cycles. Hence, this green, economic, and reusable biomaterial has great potential for recovering light rare earth elements from water. Finally, this study provides new insights for analyzing the adsorption mechanisms of Ce and La under various experimental conditions.
publishDate 2023
dc.date.accessioned.none.fl_str_mv 2023-10-02T14:36:17Z
dc.date.available.none.fl_str_mv 2023-10-02T14:36:17Z
2025-06-15
dc.date.issued.none.fl_str_mv 2023-06-15
dc.type.spa.fl_str_mv Artículo de revista
dc.type.coar.spa.fl_str_mv http://purl.org/coar/resource_type/c_2df8fbb1
dc.type.content.spa.fl_str_mv Text
dc.type.driver.spa.fl_str_mv info:eu-repo/semantics/article
dc.type.redcol.spa.fl_str_mv http://purl.org/redcol/resource_type/ART
dc.type.version.spa.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.coarversion.spa.fl_str_mv http://purl.org/coar/version/c_970fb48d4fbd8a85
format http://purl.org/coar/resource_type/c_2df8fbb1
status_str publishedVersion
dc.identifier.citation.spa.fl_str_mv Sonia Jemli, Diana Pinto, Wilfried G. Kanhounnon, Fakhreddine Ben Amara, Lotfi Sellaoui, Adrian Bonilla-Petriciolet, Fatma Dhaouadi, Rihab Ameri, Luis F.O. Silva, Samir Bejar, Guilherme Luiz Dotto, Michael Badawi, Green β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements: Cerium and lanthanum, Chemical Engineering Journal, Volume 466, 2023, 143108, ISSN 1385-8947, https://doi.org/10.1016/j.cej.2023.143108
dc.identifier.issn.spa.fl_str_mv 1385-8947
dc.identifier.uri.none.fl_str_mv https://hdl.handle.net/11323/10527
dc.identifier.doi.none.fl_str_mv 10.1016/j.cej.2023.143108
dc.identifier.instname.spa.fl_str_mv Corporación Universidad de la Costa
dc.identifier.reponame.spa.fl_str_mv REDICUC - Repositorio CUC
dc.identifier.repourl.spa.fl_str_mv https://repositorio.cuc.edu.co/
identifier_str_mv Sonia Jemli, Diana Pinto, Wilfried G. Kanhounnon, Fakhreddine Ben Amara, Lotfi Sellaoui, Adrian Bonilla-Petriciolet, Fatma Dhaouadi, Rihab Ameri, Luis F.O. Silva, Samir Bejar, Guilherme Luiz Dotto, Michael Badawi, Green β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements: Cerium and lanthanum, Chemical Engineering Journal, Volume 466, 2023, 143108, ISSN 1385-8947, https://doi.org/10.1016/j.cej.2023.143108
1385-8947
10.1016/j.cej.2023.143108
Corporación Universidad de la Costa
REDICUC - Repositorio CUC
url https://hdl.handle.net/11323/10527
https://repositorio.cuc.edu.co/
dc.language.iso.spa.fl_str_mv eng
language eng
dc.relation.ispartofjournal.spa.fl_str_mv Chemical Engineering Journal
dc.relation.references.spa.fl_str_mv [1] I. Anastopoulos, A. Bhatnagar, E.C. Lima, Adsorption of rare earth metals: a review of recent literature, J. Mol. Liq. 221 (2016) 954–962, https://doi.org/10.1016/j. molliq.2016.06.076.
[2] A. Negrea, A. Gabor, C.M. Davidescu, M. Ciopec, P. Negrea, N. Duteanu, A. Barbulescu, Rare earth elements removal from water using natural polymers, Sci. Rep. 8 (2018) 1–11.
[3] J. Navarro, F. Zhao, Life-cycle assessment of the production of rare-earth elements for energy applications: a review, Front. Energy Res. 2 (2014) 45.
[4] Q. Tan, J. Li, X. Zeng, Rare earth elements recovery from waste fluorescent lamps: a review, Crit. Rev. Environ. Sci. Technol. 45 (7) (2015) 749–776.
[5] L. Omodara, S. Pitk¨ aaho, E.-M. Turpeinen, P. Saavalainen, K. Oravisj¨ arvi, R. L. Keiski, Recycling and substitution of light rare earth elements, cerium, lanthanum, neodymium, and praseodymium from end-of-life applications - a review, J. Clean. Prod. 236 (2019) 117573, https://doi.org/10.1016/j. jclepro.2019.07.048.
[6] V. Balaram, Rare earth elements: a review of applications, occurrence, exploration, analysis, recycling, and environmental impact, Geosci. Front. 10 (2019) 1285–1303, https://doi.org/10.1016/j.gsf.2018.12.005.
[7] W. Yantasee, G.E. Fryxell, R.S. Addleman, R.J. Wiacek, V. Koonsiripaiboon, K. Pattamakomsan, V. Sukwarotwat, J. Xu, K.N. Raymond, Selective removal of lanthanides from natural waters, acidic streams and dialysate, J. Hazard. Mater. 168 (2-3) (2009) 1233–1238.
[8] G. Pagano, P.J. Thomas, A. Di Nunzio, M. Trifuoggi, Human exposures to rare earth elements: present knowledge and research prospects, Environ. Res. 171 (2019) 493–500.
[9] W. Gwenzi, L. Mangori, C. Danha, N. Chaukura, N. Dunjana, E. Sanganyado, Sources, behaviour, and environmental and human health risks of high-technology rare earth elements as emerging contaminants, Sci. Total Environ. 636 (2018) 299–313.
[10] A.V. Paiva, M.S. de Oliveira, S.N. Yunes, L.G. de Oliveira, J.B. Cabral-Neto, C.E. B. de Almeida, Effects of lanthanum on human lymphocytes viability and DNA strand break, Bull. Environ. Contam. Toxicol. 82 (4) (2009) 423–427.
[11] G. Pagano, M. Guida, F. Tommasi, R. Oral, Health effects and toxicity mechanisms of rare earth elements—knowledge gaps and research prospects, Ecotoxicol. Environ. Saf. 115 (2015) 40–48.
[12] A. Kotelnikova, I. Fastovets, O. Rogova, D.S. Volkov, V. Stolbova, Toxicity assay of lanthanum and cerium in solutions and soil, Ecotoxicol. Environ. Saf. 167 (2019) 20–28, https://doi.org/10.1016/j.ecoenv.2018.09.117.
[13] Y.R. Smith, D. Bhattacharyya, T. Willhard, M. Misra, Adsorption of aqueous rare earth elements using carbon black derived from recycled tires, Chem. Eng. J. 296 (2016) 102–111.
[14] S. Iftekhar, D.L. Ramasamy, V. Srivastava, M.B. Asif, M. Sillanp¨ a¨ a, Understanding the factors affecting the adsorption of lanthanum using different adsorbents: a critical review, Chemosphere 204 (2018) 413–430, https://doi.org/10.1016/j. chemosphere.2018.04.053.
[15] M. Sethurajan, E.D. van Hullebusch, D. Fontana, A. Akcil, H. Deveci, B. Batinic, J. P. Leal, T.A. Gasche, M. Ali Kucuker, K. Kuchta, I.F.F. Neto, H.M.V.M. Soares, A. Chmielarz, Recent advances on hydrometallurgical recovery of critical and precious elements from end of life electronic wastes-a review, Crit. Rev. Environ. Sci. Technol. 49 (3) (2019) 212–275.
[16] T. Ogata, H. Narita, M. Tanaka, Adsorption behavior of rare earth elements on silica gel modified with diglycol amic acid, Hydrometallurgy 152 (2015) 178–182.
[17] Y. Zhu, Y. Zheng, A. Wang, A simple approach to fabricate granular adsorbent for adsorption of rare elements, Int. J. Biol. Macromol. 72 (2015) 410–420.
[18] I. Bouchmila, B. Bejaoui Kefi, R. Souissi, M. Abdellaoui, Desorption of La3+ and Ce3+ from treated’ chert’a siliceous byproduct of the phosphate mining industry of Gafsa-Metlaoui Basin (Southwestern Tunisia), Chem. Africa 2 (1) (2019) 89–101.
[19] S.J.R. Vargas, J.C. Quint˜ ao, G.M.D. Ferreira, L.H.M. Da Silva, M.C. Hespanhol, Lanthanum and cerium separation using an aqueous two-phase system with ionic liquid, J. Chem. Eng. Data 64 (10) (2019) 4239–4246.
[20] N. Das, D. Das, Recovery of rare earth metals through biosorption: an overview, J. Rare Earths 31 (10) (2013) 933–943.
[21] M. Torab-Mostaedi, M. Asadollahzadeh, A. Hemmati, A. Khosravi, Biosorption of lanthanum and cerium from aqueous solutions by grapefruit peel: equilibrium, kinetic and thermodynamic studies, Res. Chem. Intermed. 41 (2015) 559–573.
[22] N.K. Gupta, A. Gupta, P. Ramteke, H. Sahoo, A. Sengupta, Biosorption-a green method for the preconcentration of rare earth elements (REEs) from waste solutions: a review, J. Mol. Liq. 274 (2019) 148–164.
[23] C. Li, H. Ma, S. Venkateswaran, B.S. Hsiao, Sustainable carboxylated cellulose filters for efficient removal and recovery of lanthanum, Environ. Res. 188 (2020) 109685.
[24] T.B. da Costa, M.G.C. da Silva, M.G.A. Vieira, Biosorption of lanthanum using sericin/alginate/polyvinyl alcohol beads as a natural cation exchanger in a continuous fixed-bed column system, Colloids Surf. A Physicochem. Eng. Asp. 627 (2021) 127233.
[25] R. Han, J. Li, H.-D. Shin, R.R. Chen, G. Du, L. Liu, J. Chen, Recent advances in discovery, heterologous expression, and molecular engineering of cyclodextrin glycosyltransferase for versatile applications, Biotechnol. Adv. 32 (2) (2014) 415–428.
[26] B.G. Poulson, Q.A. Alsulami, A. Sharfalddin, E.F. El Agammy, F. Mouffouk, A.- H. Emwas, L. Jaremko, M. Jaremko, Cyclodextrins: structural, chemical, and physical properties, and applications, Polysaccharides 3 (2021) 1–31.
[27] G. Narayanan, J. Shen, I. Matai, A. Sachdev, R. Boy, A.E. Tonelli, Cyclodextrinbased nanostructures, Prog. Mater. Sci. 124 (2022) 100869.
[28] S.V. Kurkov, T. Loftsson, Cyclodextrins, Int. J. Pharm. 453 (1) (2013) 167–180.
[29] L. Dahabra, G. Broadberry, A. Le Gresley, M. Najlah, M. Khoder, Sunscreens containing cyclodextrin inclusion complexes for enhanced efficiency: a strategy for skin cancer prevention, Molecules 26 (2021) 1698.
[30] E. Einafshar, A.H. Asl, A.H. Nia, M. Mohammadi, A. Malekzadeh, M. Ramezani, New cyclodextrin-based nanocarriers for drug delivery and phototherapy using an irinotecan metabolite, Carbohydr. Polym. 194 (2018) 103–110.
[31] A. Matencio, A. Rubin Pedrazzo, A. Difalco, S. Navarro-Orcajada, Y. Khazeai Monfared, I. Conesa, A. Rezayat, J.M. Lopez-Nicol ´ ´ as, F. Trotta, Advances and classification of cyclodextrin-based polymers for food-related issues, Polymers 13 (2021) 4226.
[32] Y. Hu, C. Qiu, Y. Qin, X. Xu, L. Fan, J. Wang, Z. Jin, Cyclodextrin–phytochemical inclusion complexes: promising food materials with targeted nutrition and functionality, Trends Food Sci. Technol. 109 (2021) 398–412.
[33] W. Tang, C. Zou, C. Da, Y. Cao, H. Peng, A review on the recent development of cyclodextrin-based materials used in oilfield applications, Carbohydr. Polym. 240 (2020) 116321.
[34] W.-F. Lai, A.L. Rogach, W.-T. Wong, Chemistry and engineering of cyclodextrins for molecular imaging, Chem. Soc. Rev. 46 (20) (2017) 6379–6419.
[35] G. Liu, L. Li, D. Xu, X. Huang, X. Xu, S. Zheng, Y. Zhang, H. Lin, Metal–organic framework preparation using magnetic graphene oxide–β-cyclodextrin for neonicotinoid pesticide adsorption and removal, Carbohydr. Polym. 175 (2017) 584–591.
[36] Q. Liu, Y. Zhou, J. Lu, Y. Zhou, Novel cyclodextrin-based adsorbents for removing pollutants from wastewater: a critical review, Chemosphere 241 (2020) 125043.
[37] B. Tian, S. Hua, Y.u. Tian, J. Liu, Cyclodextrin-based adsorbents for the removal of pollutants from wastewater: a review, Environ. Sci. Pollut. Res. 28 (2) (2021) 1317–1340.
[38] J. Jia, Y. Liu, D. Wu, J. Yu, T. Gao, F. Li, Water-insoluble β-Cyclodextrin-based nanocubes as cost-effective adsorbents for dyeing wastewater remediation with high selectivity, Chem. Eng. J. 457 (2023) 141331.
[39] M.T. Sikder, M.M. Rahman, M. Jakariya, T. Hosokawa, M. Kurasaki, T. Saito, Remediation of water pollution with native cyclodextrins and modified cyclodextrins: a comparative overview and perspectives, Chem. Eng. J. 355 (2019) 920–941.
[40] I. Krabicov´ a, S.L. Appleton, M. Tannous, G. Hoti, F. Caldera, A. Rubin Pedrazzo, C. Cecone, R. Cavalli, F. Trotta, History of cyclodextrin nanosponges, Polymers 12 (2020) 1122.
[41] D. Chodankar, A. Vora, A. Kanhed, β-cyclodextrin and its derivatives: application in wastewater treatment, Environ. Sci. Pollut. Res. 1–20 (2021).
[42] V.S. Ghorpade, A.V. Yadav, R.J. Dias, Citric acid crosslinked β-cyclodextrin/ carboxymethylcellulose hydrogel films for controlled delivery of poorly soluble drugs, Carbohydr. Polym. 164 (2017) 339–348.
[43] W. Li, H. Liu, L. Li, K. Liu, J. Liu, T. Tang, W. Jiang, Green synthesis of citric acidcrosslinked β-cyclodextrin for highly efficient removal of uranium (VI) from aqueous solution, J. Radioanal. Nucl. Chem. 322 (3) (2019) 2033–2042.
[44] C. Cecone, G. Hoti, I. Krabicova, ´ S.L. Appleton, F. Caldera, P. Bracco, M. Zanetti, F. Trotta, Sustainable synthesis of cyclodextrin-based polymers by exploiting natural deep eutectic solvents, Green Chem. 22 (17) (2020) 5806–5814.
[45] F. Ben Amara, M. Bouzid, M. Sahnoun, Y. Ben Nasr, B. Jaouadi, S. Bejar, S. Jemli, Valorization of potato peels starch for efficient β-cyclodextrin production and purification through an eco-friendly process, Starch-St¨ arke 74 (2022) 2200037.
[46] S. Jemli, E.B. Messaoud, D. Ayadi-Zouari, B. Naili, B. Khemakhem, S. Bejar, A βcyclodextrin glycosyltransferase from a newly isolated Paenibacillus pabuli US132strain: purification, properties and potential use in bread-making, Biochem. Eng. J. 34 (2007) 44–50.
[47] W. Huang, Y. Hu, Y. Li, Y. Zhou, D. Niu, Z. Lei, Z. Zhang, Citric acid-crosslinked β-cyclodextrin for simultaneous removal of bisphenol A, methylene blue and copper: the roles of cavity and surface functional groups, J. Taiwan Inst. Chem. Eng. 82 (2018) 189–197.
[48] J. VandeVondele, M. Krack, F. Mohamed, M. Parrinello, T. Chassaing, J. Hutter, Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach, Comput. Phys. Commun. 167 (2005) 103–128, https://doi.org/10.1016/j.cpc.2004.12.014.
[49] G. Lippert, J. Hutter, M. Parrinello, A hybrid Gaussian and plane wave density functional scheme, Mol. Phys. 92 (1997) 477–487, https://doi.org/10.1080/ 00268979709482119.
[50] C. Hartwigsen, S. Goedecker, J. Hutter, Relativistic separable dual-space Gaussian pseudo-potentials from H to {Rn}, Phys. Rev. B 58 (1998) 3641–3662, https://doi. org/10.1103/PhysRevB.58.3641.
[51] R. Khatib, E.H.G. Backus, M. Bonn, M.-J. Perez-Haro, M.-P. Gaigeot, M. Sulpizi, Water orientation and hydrogen-bond structure at the fluorite/water interface, Sci. Rep. 6 (2016) 24287, https://doi.org/10.1038/srep24287.
[52] F. Mouhat, F.-X. Coudert, M.-L. Bocquet, structure and chemistry of graphene oxide in liquid water from first principles, Nat. Commun. 11 (2020) 1566, https://doi. org/10.1038/s41467-020-15381-y.
[53] F.-X. Coudert, D. Kohen, Molecular insight into CO2 “trapdoor” adsorption in zeolite Na-RHO, Chem. Mater. 29 (7) (2017) 2724–2730.
[54] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77 (1996) 3865.
[55] S. Grimme, J. Antony, S. Ehrlich, H. Krieg, A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu, J. Chem. Phys. 132 (2010) 154104.
[56] J. VandeVondele, J. Hutter, Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases, J. Chem. Phys. 127 (11) (2007) 114105, https://doi.org/10.1063/1.2770708.
[57] R.L. Abarca, F.J. Rodriguez, A. Guarda, M.J. Galotto, J.E. Bruna, Characterization of beta-cyclodextrin inclusion complexes containing an essential oil component, Food Chem. 196 (2016) 968–975.
[58] J. Junthip, Water-insoluble cyclodextrin polymer crosslinked with citric acid for paraquat removal from water, J. Macromol. Sci. A 56 (2019) 555–563.
[59] Y. Zhu, Y. Zheng, A. Wang, Preparation of granular hydrogel composite by the redox couple for efficient and fast adsorption of La (III) and Ce (III), Journal of Environmental, Chem. Eng. 3 (2) (2015) 1416–1425.
[60] M. Najafi Lahiji, A.R. Keshtkar, M.A. Moosavian, Adsorption of cerium and lanthanum from aqueous solutions by chitosan/polyvinyl alcohol/3- mercaptopropyltrimethoxysilane beads in batch and fixed-bed systems, Part. Sci. Technol. 36 (3) (2018) 340–350.
[61] F. Zhao, E. Repo, Y. Meng, X. Wang, D. Yin, M. Sillanpa¨¨ a, An EDTA-β-cyclodextrin material for the adsorption of rare earth elements and its application in preconcentration of rare earth elements in seawater, J. Colloid Interface Sci. 465 (2016) 215–224.
[62] S¸ . Sert, C. Kütahyali, S. ˙ Inan, Z. Talip, B. Çetinkaya, M. Eral, Biosorption of lanthanum and cerium from aqueous solutions by Platanus orientalis leaf powder, Hydrometallurgy 90 (2008) 13–18, https://doi.org/10.1016/j. hydromet.2007.09.006.
dc.relation.citationendpage.spa.fl_str_mv 10
dc.relation.citationstartpage.spa.fl_str_mv 1
dc.relation.citationvolume.spa.fl_str_mv 466
dc.rights.eng.fl_str_mv © 2023 Elsevier B.V. All rights reserved.
dc.rights.license.spa.fl_str_mv Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0)
dc.rights.uri.spa.fl_str_mv https://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.accessrights.spa.fl_str_mv info:eu-repo/semantics/closedAccess
dc.rights.coar.spa.fl_str_mv http://purl.org/coar/access_right/c_14cb
rights_invalid_str_mv Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0)
© 2023 Elsevier B.V. All rights reserved.
https://creativecommons.org/licenses/by-nc-nd/4.0/
http://purl.org/coar/access_right/c_14cb
eu_rights_str_mv closedAccess
dc.format.extent.spa.fl_str_mv 10 páginas
dc.format.mimetype.spa.fl_str_mv application/pdf
dc.publisher.spa.fl_str_mv Elsevier
dc.publisher.place.spa.fl_str_mv Netherlands
dc.source.spa.fl_str_mv https://www.sciencedirect.com/science/article/pii/S1385894723018399
institution Corporación Universidad de la Costa
bitstream.url.fl_str_mv https://repositorio.cuc.edu.co/bitstreams/7356872b-110a-422b-8312-b316b46fef12/download
https://repositorio.cuc.edu.co/bitstreams/58b06556-57c0-47f0-a547-8e9ec1c61dbf/download
https://repositorio.cuc.edu.co/bitstreams/1d3eb14a-bf7c-463c-b9c4-3a5afdefc012/download
https://repositorio.cuc.edu.co/bitstreams/37b5f970-988b-4540-baad-df55c6a29e16/download
bitstream.checksum.fl_str_mv 50369120cea64026ed4e22645daa06f7
2f9959eaf5b71fae44bbf9ec84150c7a
c0ed7a0135822c7f7a25aca72f1329d2
10a02cca2290b1ca2695564b1866103f
bitstream.checksumAlgorithm.fl_str_mv MD5
MD5
MD5
MD5
repository.name.fl_str_mv Repositorio de la Universidad de la Costa CUC
repository.mail.fl_str_mv repdigital@cuc.edu.co
_version_ 1811760745054994432
spelling Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0)© 2023 Elsevier B.V. All rights reserved.https://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/closedAccesshttp://purl.org/coar/access_right/c_14cbJemli, SoniaPinto, DianaKanhounnon, Wilfried G.Ben Amara, Fakhreddinelotfi, sellaouiBonilla-Petriciolet, AdrianDhaouadi, FatmaAmeri, RihabSilva Oliveira, Luis FelipeBejar, SamirDotto, Guilherme LuizBadawi, Michael2023-10-02T14:36:17Z2025-06-152023-10-02T14:36:17Z2023-06-15Sonia Jemli, Diana Pinto, Wilfried G. Kanhounnon, Fakhreddine Ben Amara, Lotfi Sellaoui, Adrian Bonilla-Petriciolet, Fatma Dhaouadi, Rihab Ameri, Luis F.O. Silva, Samir Bejar, Guilherme Luiz Dotto, Michael Badawi, Green β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements: Cerium and lanthanum, Chemical Engineering Journal, Volume 466, 2023, 143108, ISSN 1385-8947, https://doi.org/10.1016/j.cej.2023.1431081385-8947https://hdl.handle.net/11323/1052710.1016/j.cej.2023.143108Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/During the past decades, the removal and recovery of Lanthanum (La) and cerium (Ce) have attracted considerable interest owing to their importance in several industrial processes. In the present work, green nanosponge adsorbents have been synthesized from a local and economic source of β-cyclodextrin (β-CD), and applied for the first time to La and Ce ion recovery from aqueous solutions. A statistical physics model has been used to analyze adsorption data. This material has shown high adsorption capacities of 625.34 and 773.29 mg g−1 for Ce and La, respectively. Furthermore, a temperature of 298 K has been identified as the best condition to remove these elements from aqueous solutions. Furthermore, DFT simulations have been performed to identify the nature of functional groups involved in removing these rare earth elements. Assessments of the adsorbent regeneration and recycling capacities have also been determined, showing that β-CD nanosponges remain stable and effective for La and Ce adsorption over three desorption-adsorption cycles. Hence, this green, economic, and reusable biomaterial has great potential for recovering light rare earth elements from water. Finally, this study provides new insights for analyzing the adsorption mechanisms of Ce and La under various experimental conditions.10 páginasapplication/pdfengElsevierNetherlandshttps://www.sciencedirect.com/science/article/pii/S1385894723018399Green β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements: cerium and lanthanumArtículo de revistahttp://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/version/c_970fb48d4fbd8a85Chemical Engineering Journal[1] I. Anastopoulos, A. Bhatnagar, E.C. Lima, Adsorption of rare earth metals: a review of recent literature, J. Mol. Liq. 221 (2016) 954–962, https://doi.org/10.1016/j. molliq.2016.06.076.[2] A. Negrea, A. Gabor, C.M. Davidescu, M. Ciopec, P. Negrea, N. Duteanu, A. Barbulescu, Rare earth elements removal from water using natural polymers, Sci. Rep. 8 (2018) 1–11.[3] J. Navarro, F. Zhao, Life-cycle assessment of the production of rare-earth elements for energy applications: a review, Front. Energy Res. 2 (2014) 45.[4] Q. Tan, J. Li, X. Zeng, Rare earth elements recovery from waste fluorescent lamps: a review, Crit. Rev. Environ. Sci. Technol. 45 (7) (2015) 749–776.[5] L. Omodara, S. Pitk¨ aaho, E.-M. Turpeinen, P. Saavalainen, K. Oravisj¨ arvi, R. L. Keiski, Recycling and substitution of light rare earth elements, cerium, lanthanum, neodymium, and praseodymium from end-of-life applications - a review, J. Clean. Prod. 236 (2019) 117573, https://doi.org/10.1016/j. jclepro.2019.07.048.[6] V. Balaram, Rare earth elements: a review of applications, occurrence, exploration, analysis, recycling, and environmental impact, Geosci. Front. 10 (2019) 1285–1303, https://doi.org/10.1016/j.gsf.2018.12.005.[7] W. Yantasee, G.E. Fryxell, R.S. Addleman, R.J. Wiacek, V. Koonsiripaiboon, K. Pattamakomsan, V. Sukwarotwat, J. Xu, K.N. Raymond, Selective removal of lanthanides from natural waters, acidic streams and dialysate, J. Hazard. Mater. 168 (2-3) (2009) 1233–1238.[8] G. Pagano, P.J. Thomas, A. Di Nunzio, M. Trifuoggi, Human exposures to rare earth elements: present knowledge and research prospects, Environ. Res. 171 (2019) 493–500.[9] W. Gwenzi, L. Mangori, C. Danha, N. Chaukura, N. Dunjana, E. Sanganyado, Sources, behaviour, and environmental and human health risks of high-technology rare earth elements as emerging contaminants, Sci. Total Environ. 636 (2018) 299–313.[10] A.V. Paiva, M.S. de Oliveira, S.N. Yunes, L.G. de Oliveira, J.B. Cabral-Neto, C.E. B. de Almeida, Effects of lanthanum on human lymphocytes viability and DNA strand break, Bull. Environ. Contam. Toxicol. 82 (4) (2009) 423–427.[11] G. Pagano, M. Guida, F. Tommasi, R. Oral, Health effects and toxicity mechanisms of rare earth elements—knowledge gaps and research prospects, Ecotoxicol. Environ. Saf. 115 (2015) 40–48.[12] A. Kotelnikova, I. Fastovets, O. Rogova, D.S. Volkov, V. Stolbova, Toxicity assay of lanthanum and cerium in solutions and soil, Ecotoxicol. Environ. Saf. 167 (2019) 20–28, https://doi.org/10.1016/j.ecoenv.2018.09.117.[13] Y.R. Smith, D. Bhattacharyya, T. Willhard, M. Misra, Adsorption of aqueous rare earth elements using carbon black derived from recycled tires, Chem. Eng. J. 296 (2016) 102–111.[14] S. Iftekhar, D.L. Ramasamy, V. Srivastava, M.B. Asif, M. Sillanp¨ a¨ a, Understanding the factors affecting the adsorption of lanthanum using different adsorbents: a critical review, Chemosphere 204 (2018) 413–430, https://doi.org/10.1016/j. chemosphere.2018.04.053.[15] M. Sethurajan, E.D. van Hullebusch, D. Fontana, A. Akcil, H. Deveci, B. Batinic, J. P. Leal, T.A. Gasche, M. Ali Kucuker, K. Kuchta, I.F.F. Neto, H.M.V.M. Soares, A. Chmielarz, Recent advances on hydrometallurgical recovery of critical and precious elements from end of life electronic wastes-a review, Crit. Rev. Environ. Sci. Technol. 49 (3) (2019) 212–275.[16] T. Ogata, H. Narita, M. Tanaka, Adsorption behavior of rare earth elements on silica gel modified with diglycol amic acid, Hydrometallurgy 152 (2015) 178–182.[17] Y. Zhu, Y. Zheng, A. Wang, A simple approach to fabricate granular adsorbent for adsorption of rare elements, Int. J. Biol. Macromol. 72 (2015) 410–420.[18] I. Bouchmila, B. Bejaoui Kefi, R. Souissi, M. Abdellaoui, Desorption of La3+ and Ce3+ from treated’ chert’a siliceous byproduct of the phosphate mining industry of Gafsa-Metlaoui Basin (Southwestern Tunisia), Chem. Africa 2 (1) (2019) 89–101.[19] S.J.R. Vargas, J.C. Quint˜ ao, G.M.D. Ferreira, L.H.M. Da Silva, M.C. Hespanhol, Lanthanum and cerium separation using an aqueous two-phase system with ionic liquid, J. Chem. Eng. Data 64 (10) (2019) 4239–4246.[20] N. Das, D. Das, Recovery of rare earth metals through biosorption: an overview, J. Rare Earths 31 (10) (2013) 933–943.[21] M. Torab-Mostaedi, M. Asadollahzadeh, A. Hemmati, A. Khosravi, Biosorption of lanthanum and cerium from aqueous solutions by grapefruit peel: equilibrium, kinetic and thermodynamic studies, Res. Chem. Intermed. 41 (2015) 559–573.[22] N.K. Gupta, A. Gupta, P. Ramteke, H. Sahoo, A. Sengupta, Biosorption-a green method for the preconcentration of rare earth elements (REEs) from waste solutions: a review, J. Mol. Liq. 274 (2019) 148–164.[23] C. Li, H. Ma, S. Venkateswaran, B.S. Hsiao, Sustainable carboxylated cellulose filters for efficient removal and recovery of lanthanum, Environ. Res. 188 (2020) 109685.[24] T.B. da Costa, M.G.C. da Silva, M.G.A. Vieira, Biosorption of lanthanum using sericin/alginate/polyvinyl alcohol beads as a natural cation exchanger in a continuous fixed-bed column system, Colloids Surf. A Physicochem. Eng. Asp. 627 (2021) 127233.[25] R. Han, J. Li, H.-D. Shin, R.R. Chen, G. Du, L. Liu, J. Chen, Recent advances in discovery, heterologous expression, and molecular engineering of cyclodextrin glycosyltransferase for versatile applications, Biotechnol. Adv. 32 (2) (2014) 415–428.[26] B.G. Poulson, Q.A. Alsulami, A. Sharfalddin, E.F. El Agammy, F. Mouffouk, A.- H. Emwas, L. Jaremko, M. Jaremko, Cyclodextrins: structural, chemical, and physical properties, and applications, Polysaccharides 3 (2021) 1–31.[27] G. Narayanan, J. Shen, I. Matai, A. Sachdev, R. Boy, A.E. Tonelli, Cyclodextrinbased nanostructures, Prog. Mater. Sci. 124 (2022) 100869.[28] S.V. Kurkov, T. Loftsson, Cyclodextrins, Int. J. Pharm. 453 (1) (2013) 167–180.[29] L. Dahabra, G. Broadberry, A. Le Gresley, M. Najlah, M. Khoder, Sunscreens containing cyclodextrin inclusion complexes for enhanced efficiency: a strategy for skin cancer prevention, Molecules 26 (2021) 1698.[30] E. Einafshar, A.H. Asl, A.H. Nia, M. Mohammadi, A. Malekzadeh, M. Ramezani, New cyclodextrin-based nanocarriers for drug delivery and phototherapy using an irinotecan metabolite, Carbohydr. Polym. 194 (2018) 103–110.[31] A. Matencio, A. Rubin Pedrazzo, A. Difalco, S. Navarro-Orcajada, Y. Khazeai Monfared, I. Conesa, A. Rezayat, J.M. Lopez-Nicol ´ ´ as, F. Trotta, Advances and classification of cyclodextrin-based polymers for food-related issues, Polymers 13 (2021) 4226.[32] Y. Hu, C. Qiu, Y. Qin, X. Xu, L. Fan, J. Wang, Z. Jin, Cyclodextrin–phytochemical inclusion complexes: promising food materials with targeted nutrition and functionality, Trends Food Sci. Technol. 109 (2021) 398–412.[33] W. Tang, C. Zou, C. Da, Y. Cao, H. Peng, A review on the recent development of cyclodextrin-based materials used in oilfield applications, Carbohydr. Polym. 240 (2020) 116321.[34] W.-F. Lai, A.L. Rogach, W.-T. Wong, Chemistry and engineering of cyclodextrins for molecular imaging, Chem. Soc. Rev. 46 (20) (2017) 6379–6419.[35] G. Liu, L. Li, D. Xu, X. Huang, X. Xu, S. Zheng, Y. Zhang, H. Lin, Metal–organic framework preparation using magnetic graphene oxide–β-cyclodextrin for neonicotinoid pesticide adsorption and removal, Carbohydr. Polym. 175 (2017) 584–591.[36] Q. Liu, Y. Zhou, J. Lu, Y. Zhou, Novel cyclodextrin-based adsorbents for removing pollutants from wastewater: a critical review, Chemosphere 241 (2020) 125043.[37] B. Tian, S. Hua, Y.u. Tian, J. Liu, Cyclodextrin-based adsorbents for the removal of pollutants from wastewater: a review, Environ. Sci. Pollut. Res. 28 (2) (2021) 1317–1340.[38] J. Jia, Y. Liu, D. Wu, J. Yu, T. Gao, F. Li, Water-insoluble β-Cyclodextrin-based nanocubes as cost-effective adsorbents for dyeing wastewater remediation with high selectivity, Chem. Eng. J. 457 (2023) 141331.[39] M.T. Sikder, M.M. Rahman, M. Jakariya, T. Hosokawa, M. Kurasaki, T. Saito, Remediation of water pollution with native cyclodextrins and modified cyclodextrins: a comparative overview and perspectives, Chem. Eng. J. 355 (2019) 920–941.[40] I. Krabicov´ a, S.L. Appleton, M. Tannous, G. Hoti, F. Caldera, A. Rubin Pedrazzo, C. Cecone, R. Cavalli, F. Trotta, History of cyclodextrin nanosponges, Polymers 12 (2020) 1122.[41] D. Chodankar, A. Vora, A. Kanhed, β-cyclodextrin and its derivatives: application in wastewater treatment, Environ. Sci. Pollut. Res. 1–20 (2021).[42] V.S. Ghorpade, A.V. Yadav, R.J. Dias, Citric acid crosslinked β-cyclodextrin/ carboxymethylcellulose hydrogel films for controlled delivery of poorly soluble drugs, Carbohydr. Polym. 164 (2017) 339–348.[43] W. Li, H. Liu, L. Li, K. Liu, J. Liu, T. Tang, W. Jiang, Green synthesis of citric acidcrosslinked β-cyclodextrin for highly efficient removal of uranium (VI) from aqueous solution, J. Radioanal. Nucl. Chem. 322 (3) (2019) 2033–2042.[44] C. Cecone, G. Hoti, I. Krabicova, ´ S.L. Appleton, F. Caldera, P. Bracco, M. Zanetti, F. Trotta, Sustainable synthesis of cyclodextrin-based polymers by exploiting natural deep eutectic solvents, Green Chem. 22 (17) (2020) 5806–5814.[45] F. Ben Amara, M. Bouzid, M. Sahnoun, Y. Ben Nasr, B. Jaouadi, S. Bejar, S. Jemli, Valorization of potato peels starch for efficient β-cyclodextrin production and purification through an eco-friendly process, Starch-St¨ arke 74 (2022) 2200037.[46] S. Jemli, E.B. Messaoud, D. Ayadi-Zouari, B. Naili, B. Khemakhem, S. Bejar, A βcyclodextrin glycosyltransferase from a newly isolated Paenibacillus pabuli US132strain: purification, properties and potential use in bread-making, Biochem. Eng. J. 34 (2007) 44–50.[47] W. Huang, Y. Hu, Y. Li, Y. Zhou, D. Niu, Z. Lei, Z. Zhang, Citric acid-crosslinked β-cyclodextrin for simultaneous removal of bisphenol A, methylene blue and copper: the roles of cavity and surface functional groups, J. Taiwan Inst. Chem. Eng. 82 (2018) 189–197.[48] J. VandeVondele, M. Krack, F. Mohamed, M. Parrinello, T. Chassaing, J. Hutter, Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach, Comput. Phys. Commun. 167 (2005) 103–128, https://doi.org/10.1016/j.cpc.2004.12.014.[49] G. Lippert, J. Hutter, M. Parrinello, A hybrid Gaussian and plane wave density functional scheme, Mol. Phys. 92 (1997) 477–487, https://doi.org/10.1080/ 00268979709482119.[50] C. Hartwigsen, S. Goedecker, J. Hutter, Relativistic separable dual-space Gaussian pseudo-potentials from H to {Rn}, Phys. Rev. B 58 (1998) 3641–3662, https://doi. org/10.1103/PhysRevB.58.3641.[51] R. Khatib, E.H.G. Backus, M. Bonn, M.-J. Perez-Haro, M.-P. Gaigeot, M. Sulpizi, Water orientation and hydrogen-bond structure at the fluorite/water interface, Sci. Rep. 6 (2016) 24287, https://doi.org/10.1038/srep24287.[52] F. Mouhat, F.-X. Coudert, M.-L. Bocquet, structure and chemistry of graphene oxide in liquid water from first principles, Nat. Commun. 11 (2020) 1566, https://doi. org/10.1038/s41467-020-15381-y.[53] F.-X. Coudert, D. Kohen, Molecular insight into CO2 “trapdoor” adsorption in zeolite Na-RHO, Chem. Mater. 29 (7) (2017) 2724–2730.[54] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77 (1996) 3865.[55] S. Grimme, J. Antony, S. Ehrlich, H. Krieg, A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu, J. Chem. Phys. 132 (2010) 154104.[56] J. VandeVondele, J. Hutter, Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases, J. Chem. Phys. 127 (11) (2007) 114105, https://doi.org/10.1063/1.2770708.[57] R.L. Abarca, F.J. Rodriguez, A. Guarda, M.J. Galotto, J.E. Bruna, Characterization of beta-cyclodextrin inclusion complexes containing an essential oil component, Food Chem. 196 (2016) 968–975.[58] J. Junthip, Water-insoluble cyclodextrin polymer crosslinked with citric acid for paraquat removal from water, J. Macromol. Sci. A 56 (2019) 555–563.[59] Y. Zhu, Y. Zheng, A. Wang, Preparation of granular hydrogel composite by the redox couple for efficient and fast adsorption of La (III) and Ce (III), Journal of Environmental, Chem. Eng. 3 (2) (2015) 1416–1425.[60] M. Najafi Lahiji, A.R. Keshtkar, M.A. Moosavian, Adsorption of cerium and lanthanum from aqueous solutions by chitosan/polyvinyl alcohol/3- mercaptopropyltrimethoxysilane beads in batch and fixed-bed systems, Part. Sci. Technol. 36 (3) (2018) 340–350.[61] F. Zhao, E. Repo, Y. Meng, X. Wang, D. Yin, M. Sillanpa¨¨ a, An EDTA-β-cyclodextrin material for the adsorption of rare earth elements and its application in preconcentration of rare earth elements in seawater, J. Colloid Interface Sci. 465 (2016) 215–224.[62] S¸ . Sert, C. Kütahyali, S. ˙ Inan, Z. Talip, B. Çetinkaya, M. Eral, Biosorption of lanthanum and cerium from aqueous solutions by Platanus orientalis leaf powder, Hydrometallurgy 90 (2008) 13–18, https://doi.org/10.1016/j. hydromet.2007.09.006.101466Green adsorbentLREEsAdsorptionDFTIsothermsLaCePublicationORIGINALGreen β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements.pdfGreen β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements.pdfArtículosapplication/pdf3140106https://repositorio.cuc.edu.co/bitstreams/7356872b-110a-422b-8312-b316b46fef12/download50369120cea64026ed4e22645daa06f7MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-814828https://repositorio.cuc.edu.co/bitstreams/58b06556-57c0-47f0-a547-8e9ec1c61dbf/download2f9959eaf5b71fae44bbf9ec84150c7aMD52TEXTGreen β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements.pdf.txtGreen β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements.pdf.txtExtracted texttext/plain51970https://repositorio.cuc.edu.co/bitstreams/1d3eb14a-bf7c-463c-b9c4-3a5afdefc012/downloadc0ed7a0135822c7f7a25aca72f1329d2MD53THUMBNAILGreen β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements.pdf.jpgGreen β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements.pdf.jpgGenerated Thumbnailimage/jpeg14931https://repositorio.cuc.edu.co/bitstreams/37b5f970-988b-4540-baad-df55c6a29e16/download10a02cca2290b1ca2695564b1866103fMD5411323/10527oai:repositorio.cuc.edu.co:11323/105272024-09-17 10:56:20.926https://creativecommons.org/licenses/by-nc-nd/4.0/© 2023 Elsevier B.V. All rights reserved.open.accesshttps://repositorio.cuc.edu.coRepositorio de la Universidad de la Costa CUCrepdigital@cuc.edu.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