EXAFS and FTIR studies of selenite and selenate sorption by alkoxide-free sol–gel generated Mg–Al–CO 3 layered double hydroxide with very labile interlayer anions

Natalia Chubar

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71 Scopus citations


© the Partner Organisations 2014. Current research on Layered Double Hydroxides (LDHs, also known as hydrotalcites, HTs) is predominantly focused on their intercalations, but the industrial application of LDHs for anion exchange adsorption has not yet been achieved. It was recently recognized that, to develop LDH applications, these materials should be produced using methods other than direct co-precipitation. Mg-Al-CO3LDH produced using an alkoxide-free sol-gel synthesis showed exceptional removal properties for aqueous selenium species. Se K-edge EXAFS/XANES and FTIR studies (supporting the data by XRD patterns) were performed to explain the unusual adsorptive performance of Mg-Al LDH by revealing the molecular-level mechanism of HSeO3 -, SeO4 2-and {HSeO3 -+ SeO4 2-} uptake at pH 5, 7 and 8.5. The role of inner-sphere complexation (exhibited by inorganic adsorbents with good performance) in adsorption of both selenium aqueous species was not confirmed. However, Mg-Al LDH fully met the other expectations regarding the involvement of the interlayer anions. The interlayer carbonate (due to its favorable speciation and generous HT hydration) gave a "second breath" to selenite sorption and was the only mechanism that controlled the removal of Se(vi). Because inner sphere complexation was the leading mechanism for selenite removal, ion exchange via surface OH-and interlayer CO3 2-species was the only mechanism for selenate removal; both of these species were easily bound to Mg-Al LDH (on its surface and gently parked into the interlayer forming a multilayer without violation of the structure of Mg-Al-CO3LDH). This work provides the first theoretical explanation of why it is more difficult to sorb selenate than selenite and which material should be used for this purpose. This journal is
Original languageEnglish (US)
Pages (from-to)15995-16007
Number of pages13
JournalJ. Mater. Chem. A
Issue number38
StatePublished - 2014
Externally publishedYes

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledged KAUST grant number(s): KUK-C1-017-12
Acknowledgements: A major part of the work was funded by King Abdullah University of Science and Technology (KAUST) through Center-in-Development award no. KUK-C1-017-12. The EXAFS research at DUBBLE at ESRF was funded by NWO (Dutch Ministry of Scientific Research). The authors gratefully thank Dr Harrison (University of Aberdeen) and Prof. Krivovichev (St. Petersburg State University) for providing the crystallography data.
This publication acknowledges KAUST support, but has no KAUST affiliated authors.


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