FeOOH and (Fe,Zn)OOH hybrid anion exchange adsorbents for phosphate recovery: A determination of Fe-phases and adsorption–desorption mechanisms

C. Belloni; L Korving; Geert Jan Witkamp; E. Brück; P. de Jager; A.I. Dugulan

doi:10.1016/j.cej.2023.145287

FeOOH and (Fe,Zn)OOH hybrid anion exchange adsorbents for phosphate recovery: A determination of Fe-phases and adsorption–desorption mechanisms

C. Belloni, L Korving, Geert Jan Witkamp, E. Brück, P. de Jager, A.I. Dugulan

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

Hybrid anion exchange adsorbents (HAIX) seem promising to prevent eutrophication and recover phosphate (P). HAIX consist of an anion exchange resin (AIX) backbone, promoting anion physisorption (outer-sphere complex), impregnated with iron (hydr)oxide nanoparticles (NPs), for selective P chemisorption (inner-sphere complex). In this work, for the first time, as far as we know, Zn-doped iron (hydr)oxide NPs were embedded in AIX, and the performances compared with conventional HAIX, both commercial and synthesized. Zn-doped HAIX displayed improved P adsorption performances. Mössbauer spectroscopy (MS) revealed the goethite nature of the NPs, against the “amorphous hydrous ferric oxide” claimed in literature. The P adsorption comparisons, made in synthetic solution and real wastewater, underlined the crucial role of the NPs for selective P adsorption, while improving the understanding on the competition between physisorption and chemisorption. In pure P synthetic solutions, especially at high P concentrations, physisorption can “hide” chemisorption. This depends also on the anion form of the AIX, due to their higher affinity for multivalent anions, which affects HAIX adsorption selectivity and P desorption. In fact, a mild alkaline regeneration over three adsorption–desorption cycles revealed a complex interaction between the regenerant OH− and the adsorbed P. OH− molecules are consumed to transform phosphate speciation, causing (stronger) P re-adsorption and preventing desorption. Finally, Mössbauer spectroscopy revealed NPs agglomeration/growth after the three cycles plus final regeneration at pH 14. This study provides further understanding on the P adsorption–desorption mechanism in HAIX, drawing attention on the choice of experimental conditions for reliable performance assessment, and questioning HAIX consistent P removal and efficient P recovery in the long-term.

Original language	English (US)
Pages (from-to)	145287
Journal	Chemical Engineering Journal
Volume	473
DOIs	https://doi.org/10.1016/j.cej.2023.145287
State	Published - Aug 14 2023

Bibliographical note

KAUST Repository Item: Exported on 2023-09-06
Acknowledgements: This work was performed in the cooperation framework of Wetsus, European Centre of Excellence for Sustainable Water Technology (www.wetsus.nl). Wetsus is co-funded by the Dutch Ministry of Economic Affairs and Ministry of Infrastructure and Environment, the European Union Regional, Development Fund, the Province of Fryslân and the Northern Netherlands Provinces. This research received funding from the Netherlands Organization for Scientific Research (NWO) in the framework of the Innovation Fund for Chemistry, and from the Ministry of Economic Affairs and Climate Policy in the framework of the TKI/PPS-Toeslagregeling. The authors thank the participants of the research theme “Phosphate recovery” for the interest, fruitful discussions, and financial support. A special thanks goes to Raimonda Buliauskaitė (Aquacare) for the frequent knowledge exchange and interest in the research, Michel Steenvoorden and Maxim Ariens (TU Delft) for the support with Mössbauer spectroscopy related matters, Antony Cyril Arulrajan, Thomas Prot, Wokke Wijdeveld, Amanda Larasati, Sam Rutten, Daniele Chinello, Qingdian Shu (Wetsus) for the brainstorming sessions and insightful discussions, Gwendolina van der Linden for the work done together.

ASJC Scopus subject areas

Environmental Chemistry
General Chemical Engineering
General Chemistry
Industrial and Manufacturing Engineering

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10.1016/j.cej.2023.145287

https://repository.kaust.edu.sa/bitstream/10754/694118/1/1-s2.0-S1385894723040184-main.pdf

Cite this

@article{5ac52a82efa1461c894edc83fd62d82d,

title = "FeOOH and (Fe,Zn)OOH hybrid anion exchange adsorbents for phosphate recovery: A determination of Fe-phases and adsorption–desorption mechanisms",

abstract = "Hybrid anion exchange adsorbents (HAIX) seem promising to prevent eutrophication and recover phosphate (P). HAIX consist of an anion exchange resin (AIX) backbone, promoting anion physisorption (outer-sphere complex), impregnated with iron (hydr)oxide nanoparticles (NPs), for selective P chemisorption (inner-sphere complex). In this work, for the first time, as far as we know, Zn-doped iron (hydr)oxide NPs were embedded in AIX, and the performances compared with conventional HAIX, both commercial and synthesized. Zn-doped HAIX displayed improved P adsorption performances. M{\"o}ssbauer spectroscopy (MS) revealed the goethite nature of the NPs, against the “amorphous hydrous ferric oxide” claimed in literature. The P adsorption comparisons, made in synthetic solution and real wastewater, underlined the crucial role of the NPs for selective P adsorption, while improving the understanding on the competition between physisorption and chemisorption. In pure P synthetic solutions, especially at high P concentrations, physisorption can “hide” chemisorption. This depends also on the anion form of the AIX, due to their higher affinity for multivalent anions, which affects HAIX adsorption selectivity and P desorption. In fact, a mild alkaline regeneration over three adsorption–desorption cycles revealed a complex interaction between the regenerant OH− and the adsorbed P. OH− molecules are consumed to transform phosphate speciation, causing (stronger) P re-adsorption and preventing desorption. Finally, M{\"o}ssbauer spectroscopy revealed NPs agglomeration/growth after the three cycles plus final regeneration at pH 14. This study provides further understanding on the P adsorption–desorption mechanism in HAIX, drawing attention on the choice of experimental conditions for reliable performance assessment, and questioning HAIX consistent P removal and efficient P recovery in the long-term.",

author = "C. Belloni and L Korving and Witkamp, {Geert Jan} and E. Br{\"u}ck and {de Jager}, P. and A.I. Dugulan",

note = "KAUST Repository Item: Exported on 2023-09-06 Acknowledgements: This work was performed in the cooperation framework of Wetsus, European Centre of Excellence for Sustainable Water Technology (www.wetsus.nl). Wetsus is co-funded by the Dutch Ministry of Economic Affairs and Ministry of Infrastructure and Environment, the European Union Regional, Development Fund, the Province of Frysl{\^a}n and the Northern Netherlands Provinces. This research received funding from the Netherlands Organization for Scientific Research (NWO) in the framework of the Innovation Fund for Chemistry, and from the Ministry of Economic Affairs and Climate Policy in the framework of the TKI/PPS-Toeslagregeling. The authors thank the participants of the research theme “Phosphate recovery” for the interest, fruitful discussions, and financial support. A special thanks goes to Raimonda Buliauskaitė (Aquacare) for the frequent knowledge exchange and interest in the research, Michel Steenvoorden and Maxim Ariens (TU Delft) for the support with M{\"o}ssbauer spectroscopy related matters, Antony Cyril Arulrajan, Thomas Prot, Wokke Wijdeveld, Amanda Larasati, Sam Rutten, Daniele Chinello, Qingdian Shu (Wetsus) for the brainstorming sessions and insightful discussions, Gwendolina van der Linden for the work done together.",

year = "2023",

month = aug,

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doi = "10.1016/j.cej.2023.145287",

language = "English (US)",

volume = "473",

pages = "145287",

journal = "Chemical Engineering Journal",

issn = "1385-8947",

publisher = "Elsevier",

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TY - JOUR

T1 - FeOOH and (Fe,Zn)OOH hybrid anion exchange adsorbents for phosphate recovery: A determination of Fe-phases and adsorption–desorption mechanisms

AU - Belloni, C.

AU - Korving, L

AU - Witkamp, Geert Jan

AU - Brück, E.

AU - de Jager, P.

AU - Dugulan, A.I.

N1 - KAUST Repository Item: Exported on 2023-09-06 Acknowledgements: This work was performed in the cooperation framework of Wetsus, European Centre of Excellence for Sustainable Water Technology (www.wetsus.nl). Wetsus is co-funded by the Dutch Ministry of Economic Affairs and Ministry of Infrastructure and Environment, the European Union Regional, Development Fund, the Province of Fryslân and the Northern Netherlands Provinces. This research received funding from the Netherlands Organization for Scientific Research (NWO) in the framework of the Innovation Fund for Chemistry, and from the Ministry of Economic Affairs and Climate Policy in the framework of the TKI/PPS-Toeslagregeling. The authors thank the participants of the research theme “Phosphate recovery” for the interest, fruitful discussions, and financial support. A special thanks goes to Raimonda Buliauskaitė (Aquacare) for the frequent knowledge exchange and interest in the research, Michel Steenvoorden and Maxim Ariens (TU Delft) for the support with Mössbauer spectroscopy related matters, Antony Cyril Arulrajan, Thomas Prot, Wokke Wijdeveld, Amanda Larasati, Sam Rutten, Daniele Chinello, Qingdian Shu (Wetsus) for the brainstorming sessions and insightful discussions, Gwendolina van der Linden for the work done together.

PY - 2023/8/14

Y1 - 2023/8/14

N2 - Hybrid anion exchange adsorbents (HAIX) seem promising to prevent eutrophication and recover phosphate (P). HAIX consist of an anion exchange resin (AIX) backbone, promoting anion physisorption (outer-sphere complex), impregnated with iron (hydr)oxide nanoparticles (NPs), for selective P chemisorption (inner-sphere complex). In this work, for the first time, as far as we know, Zn-doped iron (hydr)oxide NPs were embedded in AIX, and the performances compared with conventional HAIX, both commercial and synthesized. Zn-doped HAIX displayed improved P adsorption performances. Mössbauer spectroscopy (MS) revealed the goethite nature of the NPs, against the “amorphous hydrous ferric oxide” claimed in literature. The P adsorption comparisons, made in synthetic solution and real wastewater, underlined the crucial role of the NPs for selective P adsorption, while improving the understanding on the competition between physisorption and chemisorption. In pure P synthetic solutions, especially at high P concentrations, physisorption can “hide” chemisorption. This depends also on the anion form of the AIX, due to their higher affinity for multivalent anions, which affects HAIX adsorption selectivity and P desorption. In fact, a mild alkaline regeneration over three adsorption–desorption cycles revealed a complex interaction between the regenerant OH− and the adsorbed P. OH− molecules are consumed to transform phosphate speciation, causing (stronger) P re-adsorption and preventing desorption. Finally, Mössbauer spectroscopy revealed NPs agglomeration/growth after the three cycles plus final regeneration at pH 14. This study provides further understanding on the P adsorption–desorption mechanism in HAIX, drawing attention on the choice of experimental conditions for reliable performance assessment, and questioning HAIX consistent P removal and efficient P recovery in the long-term.

AB - Hybrid anion exchange adsorbents (HAIX) seem promising to prevent eutrophication and recover phosphate (P). HAIX consist of an anion exchange resin (AIX) backbone, promoting anion physisorption (outer-sphere complex), impregnated with iron (hydr)oxide nanoparticles (NPs), for selective P chemisorption (inner-sphere complex). In this work, for the first time, as far as we know, Zn-doped iron (hydr)oxide NPs were embedded in AIX, and the performances compared with conventional HAIX, both commercial and synthesized. Zn-doped HAIX displayed improved P adsorption performances. Mössbauer spectroscopy (MS) revealed the goethite nature of the NPs, against the “amorphous hydrous ferric oxide” claimed in literature. The P adsorption comparisons, made in synthetic solution and real wastewater, underlined the crucial role of the NPs for selective P adsorption, while improving the understanding on the competition between physisorption and chemisorption. In pure P synthetic solutions, especially at high P concentrations, physisorption can “hide” chemisorption. This depends also on the anion form of the AIX, due to their higher affinity for multivalent anions, which affects HAIX adsorption selectivity and P desorption. In fact, a mild alkaline regeneration over three adsorption–desorption cycles revealed a complex interaction between the regenerant OH− and the adsorbed P. OH− molecules are consumed to transform phosphate speciation, causing (stronger) P re-adsorption and preventing desorption. Finally, Mössbauer spectroscopy revealed NPs agglomeration/growth after the three cycles plus final regeneration at pH 14. This study provides further understanding on the P adsorption–desorption mechanism in HAIX, drawing attention on the choice of experimental conditions for reliable performance assessment, and questioning HAIX consistent P removal and efficient P recovery in the long-term.

UR - http://hdl.handle.net/10754/694118

UR - https://linkinghub.elsevier.com/retrieve/pii/S1385894723040184

UR - http://www.scopus.com/inward/record.url?scp=85167967336&partnerID=8YFLogxK

U2 - 10.1016/j.cej.2023.145287

DO - 10.1016/j.cej.2023.145287

M3 - Article

SN - 1385-8947

VL - 473

SP - 145287

JO - Chemical Engineering Journal

JF - Chemical Engineering Journal

ER -

FeOOH and (Fe,Zn)OOH hybrid anion exchange adsorbents for phosphate recovery: A determination of Fe-phases and adsorption–desorption mechanisms

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