Layered double hydroxides (LDHs) have been known for a considerable time and have been widely studied. The basic features of their structure, involving positively charged brucite-like layers together with charge-balancing anions and water in interlayer galleries are well understood, but some detailed aspects of their structure have been the subject of controversy in the literature. In this article we review the wide range of experimental and theoretical studies of the structure of LDHs, highlighting areas of consensus and currently unresolved issues. We focus on the range of composition for which LDHs may be formed, possible layer stacking polytypes, arrangement of guest species in the interlayer galleries and the extent of order-disorder phenomena, both long-range and short-range, in the layers and interlayer galleries.

Structural aspects of layered double hydroxides

Raman spectroscopy for fluid inclusion analysis

Early hydration and setting of Portland cement monitored by IR, SEM and Vicat techniques

Direct adoption of metal-organic frameworks (MOFs) as electrode materials shows impoverished electrochemical performance owing to low electrical conductivity and poor chemical stability. In this study, we demonstrate self-templated pseudomorphic transformation of MOF into surface chemistry rich hollow framework that delivers highly reactive, durable, and universal electrochemically active energy conversion and storage functionalities. In situ pseudomorphic transformation of MOF-derived hollow rhombic dodecahedron template and sulfurization of nickel cobalt layered double hydroxides (NiCo-LDHs) lead to the construction of interlayered metal sulfides (NiCo-LDH/Co9S8) system. The embedment of metal sulfide species (Co9S8) at the LDH intergalleries offers optimal interfacing of the hybrid constituent elements and materials stability. The hybrid NiCo-LDH/Co9S8 system collectively presents an ideal porous structure, rich redox chemistry, and high electrical conductivity matrix. This leads to a significant enhancement in its complementary electrocatalytic hydrogen evolution and supercapacitive energy storage properties. This work establishes the potential of MOF derived scaffold for designing of novel class hybrid inorganic–organic functional materials for electrochemical applications and beyond.

In Situ Transformation of MOFs into Layered Double Hydroxide Embedded Metal Sulfides for Improved Electrocatalytic and Supercapacitive Performance

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 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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Leisel Hickey

Papers

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

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

The effects of synthesis pH and hydrothermal treatment on the formation of zinc aluminum hydrotalcites

The effect of varying synthesis conditions on zinc chromium hydrotalcite: a spectroscopic study

Heating stage Raman and infrared emission spectroscopic study of the dehydroxylation of synthetic Mg-hydrotalcite