Fundamental Insights into the Covalent Silane Functionalization of NiFe Layered Double Hydroxides

Carrasco, Jose A.; Silva, Álvaro Seijas-Da; Oestreicher, Víctor; Romero, Jorge; Márkus, B. G.; Simón, F.; Vieira, Bruno J. C.; Waerenborgh, J.C.; Abellán, Gonzalo; Coronado, Eugenio

doi:10.1002/chem.201905397

Cited by 16 publications

(17 citation statements)

References 95 publications

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“…The APTES molecules embodied on PIN/MTs formed slight conglobation (appearing as a cloud-like darker region) due to the covalent grafting of APTES. 52,53 Also, the TEM micrograph is in good agreement with the SEM micrographs (Fig. 2b and c).…”

Section: Resultssupporting

confidence: 80%

Multiwalled carbon nanotube nanofiller-polyindole polymer matrix-based efficient biosensor for the rapid detection of swine flu

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Section: Resultssupporting

confidence: 80%

Multiwalled carbon nanotube nanofiller-polyindole polymer matrix-based efficient biosensor for the rapid detection of swine flu

et al. 2022

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“…These systems usually show spontaneous magnetization below a certain temperature, T M , which is lower than ca. 15 K. Still, the influence of the interlamellar spacing on the magnetic properties has shown to be very limited, with only subtle modifications by different d BS , [16] or complex multistep covalent functionalization [17] . This may be due to the electrostatic nature of the interaction between the magnetic layers and the organic spacers.…”

Section: Methodsmentioning

confidence: 99%

The Missing Link in the Magnetism of Hybrid Cobalt Layered Hydroxides: The Odd–Even Effect of the Organic Spacer

Oestreicher

Hunt

Dölle

et al. 2020

Chemistry A European J

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A dramatic change in the magnetic behaviour, which solely depends on the parity of the organic linker molecules, has been found in a family of layered CoII hydroxides covalently functionalized with dicarboxylic molecules. These layered hybrid materials have been synthesized at room temperature using a one‐pot procedure through the epoxide route. While hybrids connected by odd alkyl chains exhibit coercive fields (Hc) below ca. 3500 Oe and show spontaneous magnetization at temperatures (TM) below 20 K, hybrids functionalized with even alkyl chains behave as hard magnets with Hc>5500 Oe and display a TM higher than 55 K. This intriguing behaviour was studied by density functional theory with the incorporation of a Hubbard term (DFT+U) calculations, unveiling the structural subtleties underlying this observation. Indeed, the different molecular orientation exhibited by the even/odd alkyl chains, and the orientation of the covalently linked carboxylic groups modify the intensity of the magnetic coupling of both octahedral and tetrahedral in‐plane sublattices, thus strongly affecting the magnetic properties of the hybrid. These findings offer an outstanding level of tuning in the molecular design of hybrid magnetic materials based on layered hydroxides.

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“…In the search of new levels of functionality and complexity, different functionalization strategies have been explored, mainly based in the covalent functionalization (e.g., sylilation) of the interface, resulting in improved absorption properties but slight modifications of the magnetic or electrochemical properties. [ 18 ]…”

Section: Methodsmentioning

confidence: 99%

The Role of Covalent Functionalization in the Thermal Stability and Decomposition of Hybrid Layered Hydroxides

Oestreicher

Abellán

Coronado

2020

Physica Rapid Research Ltrs

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Hybrid organic-inorganic materials represent one of the hottest research topics in materials science. The close structureproperty relationship exhibited in these materials gives rise to a wide variety of applications in fields ranging from biomedicine, catalysis or magnetism to energy storage and conversion. [1-4] Layered and 2D systems, especially those based on earthabundant metals, are playing a key role in the hybrid materials family. The possibility of combining their physical, chemical, and mechanical properties, and the precise control over their structures, placed them in a privileged position. [5-12] Among others, layered hydroxides (LHs) offer a broad range of possibilities due to their tunable chemistry, which allows to modify at will both the inorganic layers and (in)organic intercalated anions. [13] Layered double hydroxides (LDHs) constitute the most famous member of the LHs family exhibiting purely electrostatic sheet/anion interactions. These lamellar systems display hydrotalcite-like structures composed of positive charged sheets where both M II and M III octahedral cations can be tuned. [14] In line with that, hybrid LDHs have been proposed, among others, used for stimuli-responsive materials, or as a precursor for the synthesis of carbon-based nanocomposites of interest in energy storage and conversion. [15-17] In all cases, the main properties are governed by the chemical nature of both components (inorganic host and organic guest) and the interaction between them, which is always electrostatic. In the search of new levels of functionality and complexity, different functionalization strategies have been explored, mainly based in the covalent functionalization (e.g., sylilation) of the interface, resulting in improved absorption properties but slight modifications of the magnetic or electrochemical properties. [18] Along this front, α-Co II hydroxides (or simonkolleite-like structures) are positioned as key members in the LHs family, because they can be considered as naturally occurring covalently functionalized LHs. They present two coordination environments, octahedral centers-Co II (O h)-within the layers, as in the case of LDHs and tetrahedral ones-Co II (T d)-attached to both sides by 3OH bridges. The fourth position can be used to graft different inorganic to organic ligands (Scheme 1). [19] The electronic and magnetic properties can be tuned by changing ligand and/or Co II (T d) ratio, resulting in more conductive systems (mainly by ligand to metal charge transfer) with higher magnetization temperatures (T M) as to the related LDHs. [20-22] Moreover, as recently reported by our group, in hybrid α-Co II hydroxydicarboxylates, Co 5 (OH) 8 [(CH 2) n (COO) 2 ] with n ranging from 1 to 8, the magnetic behavior can be dramatically modified by changing the parity of the organic linker: whereas odd members present T M < 20 K the even ones have T M > 55 K. [23] These results demonstrate that the nature of the interaction between the inorganic layers and the organic guest is crucial for determinin...

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Fundamental Insights into the Covalent Silane Functionalization of NiFe Layered Double Hydroxides

Cited by 16 publications

References 95 publications

Multiwalled carbon nanotube nanofiller-polyindole polymer matrix-based efficient biosensor for the rapid detection of swine flu

Multiwalled carbon nanotube nanofiller-polyindole polymer matrix-based efficient biosensor for the rapid detection of swine flu

The Missing Link in the Magnetism of Hybrid Cobalt Layered Hydroxides: The Odd–Even Effect of the Organic Spacer

The Role of Covalent Functionalization in the Thermal Stability and Decomposition of Hybrid Layered Hydroxides

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