Identification and Quantification of Defects in the Cation Ordering in Mg/Al Layered Double Hydroxides

Cadars, Sylvian; Layrac, Géraldine; Gérardin, Corine; Deschamps, Michaël; Yates, Jonathan R.; Tichit, Didier; Massiot, Dominique

doi:10.1021/cm200029q

Cited by 119 publications

(201 citation statements)

References 55 publications

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“…Cadars et al then argued based on their 1 H double quantum (DQ) MAS NMR spectroscopy results that even within a largely ordered structure, a small concentration of defects, for example, MgAl 2 OH, could exist in Al rich LDHs. [ 13 ] Cation ordering was further supported by the 25 Mg NMR data obtained by Sideris et al at an ultrahigh magnetic fi eld, where it was argued that the presence of defects in some samples was likely a consequence of the synthesis method. [ 14,15 ] Large 1 H-1 H homonuclear dipolar couplings are present in these systems, [ 17 ] and ultrafast spinning rates (i.e., >40 kHz) [ 18 ] were required for the NO 3 − -containing LDHs to allow resolution of the major resonances.…”

Section: Introductionmentioning

confidence: 86%

“…[ 11 ] Despite this, compelling evidence for cation local ordering is only just starting to emerge. [12][13][14][15] Solid-state NMR spectroscopy is a powerful tool with which to probe local environments on an atomic length scale. Although 27 Al magic angle spinning (MAS) NMR experiments have long been used to track Al coordination changes on thermal treatment of LDHs, they are not sensitive to intralayer cation distributions.…”

Section: Introductionmentioning

confidence: 99%

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Investigating Local Structure in Layered Double Hydroxides with ¹⁷O NMR Spectroscopy

Zhao

Blanc

et al. 2013

Adv Funct Materials

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Section: Introductionmentioning

confidence: 86%

Section: Introductionmentioning

confidence: 99%

Investigating Local Structure in Layered Double Hydroxides with ¹⁷O NMR Spectroscopy

Zhao

Blanc

et al. 2013

Adv Funct Materials

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“…The physico-chemical properties of a particular LDHs are believed to be determined by the nature of its cationic ordering. Cadars et al [73] studied the nature of the Al/Mg ordering in LDHs. In these materials, X-ray diffraction provides no information on the local ordering of the cations.…”

Section: Other Spectroscopiesmentioning

confidence: 99%

“…In these materials, X-ray diffraction provides no information on the local ordering of the cations. However, using [73]. Copyright c 2011 the American Chemical Society.…”

Section: Other Spectroscopiesmentioning

confidence: 99%

Density functional theory in the solid state

Hasnip

Refson

Probert

et al. 2014

Phil. Trans. R. Soc. A.

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288

168

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Density functional theory (DFT) has been used in many fields of the physical sciences, but none so successfully as in the solid state. From its origins in condensed matter physics, it has expanded into materials science, high-pressure physics and mineralogy, solid-state chemistry and more, powering entire computational subdisciplines. Modern DFT simulation codes can calculate a vast range of structural, chemical, optical, spectroscopic, elastic, vibrational and thermodynamic phenomena. The ability to predict structure–property relationships has revolutionized experimental fields, such as vibrational and solid-state NMR spectroscopy, where it is the primary method to analyse and interpret experimental spectra. In semiconductor physics, great progress has been made in the electronic structure of bulk and defect states despite the severe challenges presented by the description of excited states. Studies are no longer restricted to known crystallographic structures. DFT is increasingly used as an exploratory tool for materials discovery and computational experiments, culminating in ex nihilo crystal structure prediction, which addresses the long-standing difficult problem of how to predict crystal structure polymorphs from nothing but a specified chemical composition. We present an overview of the capabilities of solid-state DFT simulations in all of these topics, illustrated with recent examples using the CASTEP computer program.

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“…Evidence in favor of cation ordering is provided by an array of techniques such as extended X-ray absorption fine structure (Vucelic et al, 1997;Bigey et al, 1997;Roussel et al, 2000Roussel et al, , 2001, magic angle spinningnuclear magnetic resonance (Sideris et al, 2008(Sideris et al, , 2012Cadars et al, 2011), and X-ray diffraction (XRD) (Krivovichev et al, 2010;Radha and Kamath, 2013). Cation ordering generates a large unit cell with a = Hn6a o (n = 3 for x = 0.33) (Hofmeister and Platen, 1992).…”

Section: Introductionmentioning

confidence: 99%

Relative Humidity-Induced Reversible Hydration Of Sulfate-Intercalated Layered Double Hydroxides

Radha

Jayanthi

Breu

et al. 2014

Clays and clay miner.

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Abstract-Layered double hydroxides (LDH) are extremely important materials for industrial processes and in the environment, and their physical-chemical behavior depends in large part on their hydration state, but the characterization of these hydration effects on their properties are incomplete. The present study was designed to explore the interpolytype transitions induced by variation in the ambient humidity among LDHs. The cooperative behavior of intercalated water molecules resulted in a sudden, single-step, reversible dehydration of the [Zn-Cr-SO 4 ] LDH. The [Zn-Al-SO 4 ] LDH provided an interesting contrast with (1) the coexistence of the end members of the hydration cycle over the 40À20% relative humidity range during the dehydration cycle, and (2) a random interstratified intermediate in the hydration cycle. These observations showed that the [Zn-Al-SO 4 ] LDH offered sites having a range of hydration enthalpies, whereby, at critical levels of hydration (20À40%), the non-uniform swelling of the structure resulted in an interstratified phase. The variation in domain size during reversible hydration was also responsible for the differences observed in the hydration vs. the dehydration pathways. This behavior was attributed to the distortion in the array of hydroxyl ions which departs from hexagonal symmetry on account of cation ordering as shown by structure refinement by the Rietveld method. This distortion was much less in the [Zn-Cr-SO 4 ] LDH, whereby the nearly hexagonal array of hydroxyl ions offered sites of uniform hydration enthalpy for the intercalated water molecules. In this case, all the water molecules experienced the same force of attraction and dehydrated reversibly in a single step. The changes in basal spacing were also accompanied by interpolytype transitions, involving the rigid translations of the metal hydroxide layers relative to one another.

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Identification and Quantification of Defects in the Cation Ordering in Mg/Al Layered Double Hydroxides

Cited by 119 publications

References 55 publications

Investigating Local Structure in Layered Double Hydroxides with ¹⁷O NMR Spectroscopy

Investigating Local Structure in Layered Double Hydroxides with ¹⁷O NMR Spectroscopy

Density functional theory in the solid state

Relative Humidity-Induced Reversible Hydration Of Sulfate-Intercalated Layered Double Hydroxides

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Identification and Quantification of Defects in the Cation Ordering in Mg/Al Layered Double Hydroxides

Cited by 119 publications

References 55 publications

Investigating Local Structure in Layered Double Hydroxides with 17O NMR Spectroscopy

Investigating Local Structure in Layered Double Hydroxides with 17O NMR Spectroscopy

Density functional theory in the solid state

Relative Humidity-Induced Reversible Hydration Of Sulfate-Intercalated Layered Double Hydroxides

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Investigating Local Structure in Layered Double Hydroxides with ¹⁷O NMR Spectroscopy

Investigating Local Structure in Layered Double Hydroxides with ¹⁷O NMR Spectroscopy