Layered double hydroxides (LDHs) are a class of ionic lamellar compounds made up of positively charged brucite-like layers with an interlayer region containing charge compensating anions and solvation molecules. Delamination of LDHs is an interesting route for producing positively charged thin platelets with a thickness of a few atomic layers, which can be used as nanocomposites for polymers or as building units for making new designed organic-inorganic or inorganic-inorganic nanomaterials. The synthesis of nanosized LDH platelets can be generally classified into two approaches, bottom-up and top-down. It requires modification of the LDH interlamellar environment and then selection of an appropriate solvent system. In DDS intercalated LDHs, the aliphatic tails of the DDS- anions exhibit a high degree of interdigitation in order to maximize guest-guest dispersive interactions. Bellezza reported that the LDH colloids can also been obtained by employing a reverse microemulsion approach.

Recent advances in the synthesis and application of layered double hydroxide (LDH) nanosheets.

https://dr.ntu.edu.sg/bitstream/10356/96770/1/30.%20Application%20of%20Layered%20Double%20Hydroxides%20for%20Removal%20of%20Oxyanions.pdf

Application of layered double hydroxides for removal of oxyanions: A review

PROMETHEE: A comprehensive literature review on methodologies and applications

Halloysite clay minerals are ubiquitous in soils and weathered rocks where they occur in a variety of particle shapes and hydration states. Diversity also characterizes their chemical composition, cation exchange capacity and potassium selectivity. This review summarizes the extensive but scattered literature on halloysite, from its natural occurrence, through its crystal structure, chemical and morphological diversity, to its reactivity toward organic compounds, ions and salts, involving the various methods of differentiating halloysite from kaolinite. No unique test seems to be ideal to distinguish these 1:1 clay minerals, especially in soils. The occurrence of 2:1 phyllosilicate contaminants appears, so far, to provide the best explanation for the high charge and potassium selectivity of halloysite. Yet, hydration properties of the mineral probably play a major role in ion sorption. Clear trends seem to relate particle morphology and structural Fe. However, future work is required to understand the possible mechanisms linking chemical, morphological, hydration and charge properties of halloysite.

Halloysite clay minerals — a review

The aim of this review article on recent developments of mechanochemistry (nowadays established as a part of chemistry) is to provide a comprehensive overview of advances achieved in the field of atomistic processes, phase transformations, simple and multicomponent nanosystems and peculiarities of mechanochemical reactions. Industrial aspects with successful penetration into fields like materials engineering, heterogeneous catalysis and extractive metallurgy are also reviewed. The hallmarks of mechanochemistry include influencing reactivity of solids by the presence of solid-state defects, interphases and relaxation phenomena, enabling processes to take place under non-equilibrium conditions, creating a well-crystallized core of nanoparticles with disordered near-surface shell regions and performing simple dry time-convenient one-step syntheses. Underlying these hallmarks are technological consequences like preparing new nanomaterials with the desired properties or producing these materials in a reproducible way with high yield and under simple and easy operating conditions. The last but not least hallmark is enabling work under environmentally friendly and essentially waste-free conditions (822 references).

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Hallmarks of mechanochemistry: From nanoparticles to technology

The difference in the local environment of CO32−, NO3−, SO42−, and ClO4− in Mg/Al-hydrotalcite compared to the free anions was studied by infrared and Raman spectroscopy. In comparison to free CO32− a shift toward lower wavenumbers was observed. A band around 3000–3200 cm−1 has been attributed to the bridging mode H2O-CO32−. The IR spectrum of CO3− hydrotalcite clearly shows the split ν3 band around 1365 and 1400 cm−1 together with weak ν2 and ν4 modes around 870 and 667 cm−1. The ν1 mode is activated and observed as a weak band around 1012 cm−1. The Raman spectrum shows a strong ν1 band at 1053 cm−1 plus weak ν3 and ν4 modes around 1403 and 695 cm−1. The symmetry of the carbonate anions is lowered from D 3 h to C 2 s resulting in activation of the IR inactive ν1 mode around 1050–1060 cm−1. In addition, the ν3 shows a splitting of 30–60 cm−1. Although NO3-hydrotalcite has incorporated some CO32− the IR shows a strong ν3 mode at 1360 cm−1 with a weak band at 827 cm−1, and the ν4 band is observed at 667 cm−1, although it is largely obscured by the hydrotalcite lattice modes. The Raman spectrum shows a strong ν1 mode at 1044 cm−1 with a weaker ν4 band at 712 cm−1. The ν3 mode at 1355 cm−1 is obscured by a broad band due to the presence of CO32−. The symmetry of NO3− did not change when incorporated in hydrotalcite. The IR spectrum of SO4-hydrotalcite shows a strong ν3 at 1126, ν4 at 614 and a weak ν1 mode at 981 cm−1. The Raman spectrum is characterized by a strong ν1 mode at 982 cm−1 plus medium ν2 and ν4 bands at 453 and 611 cm−1; ν3 cannot be identified as a separate band, although a broad band can be seen around 1134 cm−1. The site symmetry of SO42− is lowered from T d to C 2 v . The distortion of ClO4− in the interlayer of hydrotalcite is reflected in the IR spectrum with both ν3 and ν4 bands split around 1096 and 1145 cm−1 and 626 and 635 cm−1, respectively. A weak ν1 band is observed at 935 cm−1. The Raman spectrum shows a strong ν1 mode at 936 cm−1 plus ν2 and ν4 bands at 461 and 626 cm−1, respectively. A ν3 mode cannot be clearly recognized, but a broad band is visible around 1110 cm−1. These data indicative a lowering of symmetry from T d to C s .

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Infrared and Raman study of interlayer anions CO32–, NO3–, SO42– and ClO4– in Mg/Al-hydrotalcite

Synthetic corundum (Al2O3), gibbsite (Al(OH)3), bayerite (Al(OH)3), boehmite (AlO(OH)) and pseudoboehmite (AlO(OH)) have been studied by high resolution XPS. The chemical compositions based on the XPS survey scans were in good agreement with the expected composition. High resolution Al2p scans showed no significant changes in binding energy, with all values between 73.9 and 74.4 eV. Only bayerite showed two transitions, associated with the presence of amorphous material in the sample. More information about the chemical and crystallographic environment was obtained from the O1s high resolution spectra. Here a clear distinction could be made between oxygen in the crystal structure, hydroxyl groups and adsorbed water. Oxygen in the crystal structure was characterised by a binding energy of about 530.6 eV in all minerals. Hydroxyl groups, present either in the crystal structure or on the surface, exhibited binding energies around 531.9 eV, while water on the surface showed binding energies around 533.0 eV. A distinction could be made between boehmite and pseudoboehmite based on the slightly lower ratio of oxygen to hydroxyl groups and water in pseudoboehmite.

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XPS study of the major minerals in bauxite: gibbsite, bayerite and (pseudo-)boehmite.

Fourier Transform Infrared and Raman Spectroscopic Study of the Local Structure of Mg-, Ni-, and Co-Hydrotalcites

Synthetic Mg/Zn/Al-hydrotalcites with atomic ratios of 6:0:2, 4:2:2, 2:4:2 and 0:6:2 were characterized by FT-Raman and FT-IR spectroscopy. ‘AlOH’ IR translation modes are observed at 419, 427, 559, 616 and 771 cm−1 with two corresponding Raman bands at 465–477 and 547–553 cm−1. ‘MgOH’ IR translation modes are found at 412, 559 and 616 cm−1 with equivalent Raman bands at 464–477 and 547–553 cm−1. The ‘ZnOH’ IR translation mode is found at 445 cm−1 and the Raman modes around 450 and 495 cm−1. The CO32 − group is identified by the ν1(IR) at 1112 cm−1 and a doublet in the Raman around 1045–1055 and 1060 cm−1. ν2(IR) is observed at 874 cm−1. ν3(IR) is a doublet at 1359 and 1381 cm−1. ν4 is observed in both the IR and Raman spectra around 670 and 695–715 cm−1, respectively. In the OH deformation region, a doublet is observed for ‘AlOH’ at 955 and 1033 cm−1 in the IR spectra. The ‘ZnOH’ IR deformation mode is observed at 1462 cm−1. H2O is characterized by a bending mode at 1632 cm−1 and an H-bonded interlayer H2O mode at 3266 cm−1 with a Raman band between 3244 and 3271 cm−1. The OH stretching region is characterized by three bands in the Raman spectra around 3355–3360, 3440–3455 and 3535–3580 cm−1. One band is observed in the IR spectra at 3471 cm−1. Copyright © 2004 John Wiley & Sons, Ltd.

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FT‐Raman and FT‐IR spectroscopic study of synthetic Mg/Zn/Al‐hydrotalcites

Smectites are one of the most important groups of phyllositicates found in soils and sediments, and certainly one of the most difficult to study. New information about the formation mechanisms, impact of structural features on surface properties, and long-term stability of smectites can best be gained from the systematic study of single-phase specimens. In most instances, these specimens can only be obtained through synthesis under controlled conditions. Syntheses of smectites have been attempted (1) at ambient pressure and low-temperature ( 1000~ or pressures >10 kbars), and (4) in the presence of fluoride. Of these approaches, syntheses performed under moderate hydrother- mal conditions are the most numerous and the most successful in terms of smectite yield and phase- purity. Using hydrothermal techniques, high phase-purity can be obtained for beidellites and several transition-metal smectites. However, synthesis of montmorillonite in high purity remains difficult. Starting materials for hydrothermal syntheses include gels, glasses, and other aluminosilicate minerals. The pres- ence of Mg 2+ seems to be essential for the formation of smectites, even for phases such as montmorillonite which contain low amounts of Mg. Highly crystalline smectites can be obtained when extreme temper- atures or pressures are used, but other crystalline impurities are always present. Although the correlation between synthesis stability fields and thermodynamic stability fields is good in many instances, metastable phases are often formed. Few studies, however, include the additional experiments (approach from under- and over-saturation, reversal experiments) needed to ascertain the conditions for formation of thermody- namically stable phases. Thorough characterization of synthetic products by modern instrumental and molecular-scale techniques is also needed to better understand the processes leading to smectite formation.

J. Theo Kloprogge

Papers

Infrared and Raman study of interlayer anions CO32–, NO3–, SO42– and ClO4– in Mg/Al-hydrotalcite

XPS study of the major minerals in bauxite: gibbsite, bayerite and (pseudo-)boehmite.

Fourier Transform Infrared and Raman Spectroscopic Study of the Local Structure of Mg-, Ni-, and Co-Hydrotalcites

FT‐Raman and FT‐IR spectroscopic study of synthetic Mg/Zn/Al‐hydrotalcites

Synthesis of smectite clay minerals; a critical review