Stepwise structuring of the adsorbed layer modulates the physico-chemical properties of hybrid materials from phyllosilicates interacting with the μ-oxo Fe+3-phenanthroline complex

Bernini, Fabrizio; Castellini, Elena; Malferrari, Daniele; Borsari, Marco; Brigatti, Maria Franca

doi:10.1016/j.micromeso.2015.02.039

Cited by 14 publications

(80 citation statements)

References 46 publications

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“…Function q progressively increases with increasing [CuPhen], to reach a limit value at about 0.65 moles/Kg Mt. Furthermore, as already observed for the adsorption of the μ-oxo dinuclear iron-phenanthroline complex onto Mt (Bernini et al, 2015), an inflection point close to half of the q limit value clearly outlines the presence of two steps in the adsorption process (Fig. 1a).…”

Section: Adsorption Of Cuphen Onto Montmorillonitesupporting

confidence: 70%

“…1a). This adsorption behavior identifies a VI type isotherm (Gregg and Sing, 1982; Sing et al, 1966;Bernini et al, 2015). The inflection point occurs at a q value corresponding to the CEC of Mt (q inflection about 0.31 moles/Kg; CEC = 0.661 eq/Kg = 0.330 moles/Kg).…”

Section: Adsorption Of Cuphen Onto Montmorillonitementioning

confidence: 93%

“…The derived hybrid materials are of great importance not only under the perspective of fundamental investigation, but also for their applications in different fields, from biomedicine and pharmacy to energy storage and environmental protection (Bergaya and Lagaly, 2011). One example of these materials, where the functionalization of the interlayer leads to intriguing properties, is montmorillonite intercalated with a μ-oxo Fe 3+ -phenanthroline complex (Mt-Fe 3+ Phen) (Bernini et al, 2015;Brigatti et al, 2017;Sainz-Díaz et al, 2018). This hybrid material was proved to efficiently trap sulfur-bearing gas phases such as thiols and H 2 S, even at extremely low concentration, with a relevant environmental benefit.…”

Section: Introductionmentioning

confidence: 99%

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A new material based on montmorillonite and Cu(II)-phenanthroline complex for effective capture of ammonia from gas phase

Castellini

Malferrari

Bernini

et al. 2020

Applied Clay Science

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The intercalation of [Cu(Phen)(H 2 O) 2 ] 2+ (CuPhen) in montmorillonite (Mt) produces a stable hybrid material that is very efficient in removing NH 3 from gas phase even at extremely low pressures.The process was studied by elemental analysis, X-ray powder diffraction, thermal analysis coupled with evolved gas mass spectrometry and DR UV-Vis, NMR and X-ray absorption spectroscopy. The adsorption of CuPhen on Mt consists of two consecutive steps. During the first one, CuPhen intercalates alone into Mt through a cation exchange process, afterwards CuPhen and SO 4 2− ions entry jointly into the mineral interlayer. The two-steps adsorption process is described by a VI-type isotherm, successfully fitted by two independent Frumkin isotherms. NH 3 trapping is long-lasting, easy, fast even at extremely low gas pressure and reversible under mild conditions. Mt containing CuPhen always results well performant in removing ammonia from gas phase, but an appreciably higher adsorption capacity of NH 3 is obtained when SO 4 2− ion is absent from the interlayer. This hybrid montmorillonite is thus a promising material to be used in industrial or environmental contexts, as an efficient air-cleaner.

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Section: Adsorption Of Cuphen Onto Montmorillonitesupporting

confidence: 70%

Section: Adsorption Of Cuphen Onto Montmorillonitementioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

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A new material based on montmorillonite and Cu(II)-phenanthroline complex for effective capture of ammonia from gas phase

Castellini

Malferrari

Bernini

et al. 2020

Applied Clay Science

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“…The UV-Vis spectra of Fe 3+ phen in solution, obtained at different concentrations, were reported by Bernini et al [20][21][22]. Fe charge-transfer transition) at λ = 356 nm and two additional bands at 223 and 266 nm attributable to the aromatic ligand.…”

Section: Dr Uv-vis Measurementsmentioning

confidence: 52%

“…Some previous studies dealing with the intercalation of lamellar layered silicates, such as montmorillonite, with cationic metal complexes, specifically Fe 3+ phenanthroline, showed that modifications by ion exchange reactions provide larger spacing between layers [20,21]. In these layer silicates, Fe…”

Section: Introductionmentioning

confidence: 99%

Structural properties of adsorbent phyllosilicates rule the entrapping ability of intercalated iron-phenanthroline complex towards thiols

Castellini

Malferrari

Bernini

et al. 2019

Microporous and Mesoporous Materials

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The interaction of volatile organic sulfur derivatives, such as 1-heptanethiol (C 7 H 16 S), with clay minerals treated with a μ-oxo Fe 3+-phenanthroline 1:1 complex results strongly affected by crystal chemical properties of pristine mineral phases. In particular, two sepiolite clays with different structural features demonstrated significantly different ability to immobilize the Fe 3+-phenanthroline complex at two pH values (pH = 5.4 and pH = 2.3). The most effective binding was obtained with sepiolite with higher structural disorder at pH 5.4. Accordingly, the resulting hybrid material showed also the greatest efficiency in removal of thiol in gas phase. A direct correlation can be established between the adsorption of the Fe 3+-phenanthroline complex and the gas binding process at room temperature. In fact, 1-heptanethiol entrapping occurs via redox reactions between Fe 3+ and a first thiol molecule to give the reduced Fe 2+-phenanthroline complex and disulfide, followed by the binding of further thiols to the reduced metal centre. The extremely high amount of thiol immobilized by the hybrid material also suggests the co-presence of a catalytic mechanism that guarantees the reoxidation of Fe +2 to Fe +3 and the restoration of redox reactions with thiol. Investigation and conclusions were supported by the several experimental techniques: elemental analysis, X-ray powder diffraction analyses, UV-Vis measurements, FT-IR and NMR spectroscopies, thermogravimetric analyses.

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Crystal chemical characterization and computational modeling of a μ-oxo Fe(III) complex with 1,10-phenanthroline clarify its interaction and reactivity with montmorillonite

Brigatti

Díaz

Borsari

et al. 2017

Rend. Fis. Acc. Lincei

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This work provides a systematic study of the μ-oxo-di-fac-[triaqua-(1,10-phenanthroline-κ2N,N′)-iron(III)]bis(sulfate), [(OH2)3(phen)FeOFe(phen)(OH2)3] (SO4)2 (phen = phenanthroline). Crystal structure is determined by single-crystal X-ray diffraction data and refined to R = 0.039. The crystal structure is monoclinic (Z = 2), space group P21 with unit cell dimensions a = 8.5157(3), b = 17.6434(5), c = 9.9678(3) Å, β = 90.133(2)°, V = 1497.62(8) Å3. The triaqua(1,10-phenanthroline)iron(III) parts are linked through one oxo-bridge. Both Fe(III) cations show a distorted octahedral coordination. The single-crystal data are complemented by computational chemistry modeling at quantum mechanical level, X-ray powder diffraction at room and high temperature conditions and by thermal analysis. Molecular modeling suggests that the role of the crystallization water molecules is critical to establish the intermolecular interactions for the stability of the crystal structure

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Stepwise structuring of the adsorbed layer modulates the physico-chemical properties of hybrid materials from phyllosilicates interacting with the μ-oxo Fe+3-phenanthroline complex

Cited by 14 publications

References 46 publications

A new material based on montmorillonite and Cu(II)-phenanthroline complex for effective capture of ammonia from gas phase

A new material based on montmorillonite and Cu(II)-phenanthroline complex for effective capture of ammonia from gas phase

Structural properties of adsorbent phyllosilicates rule the entrapping ability of intercalated iron-phenanthroline complex towards thiols

Crystal chemical characterization and computational modeling of a μ-oxo Fe(III) complex with 1,10-phenanthroline clarify its interaction and reactivity with montmorillonite

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