Carbonate–Hydrogenocarbonate Coexistence and Dynamics in Layered Double Hydroxides

Abstract

Carbonated layered double hydroxides were fully characterized by vibrational spectroscopies, powder X-ray diffraction and solid-state NMR tuning the cations, the layer charge density, and the preparation method to get original structural and dynamical features within the materials. It clearly appears that carbonate and hydrogenocarbonate coexist in the same interlayer after contact with air and also that the hydrogenocarbonate quantity is correlated to the M II /M III molar ratio constituting a strong pH probe of the interlayer space. Likewise, these two species are involved in an exchange process with atmospheric carbon dioxide, and hydrogenocarbonate proves to be the key parameter of exchange kinetics. These crucial results, extended to various cationic couples, could lead to new alternatives for carbon dioxide storage.

Chemical Heterogeneities within the Disordered Mineral domains of Aragonite Platelets in Nacre from the European Abalone Haliotis tuberculata

“…It is worth noticing that our experimentally determined CSA parameters are in accordance with previous data reported in the literature for various calcium carbonates phases , and, in particular, for aragonite for which the Δ CSA and η CSA are very close (−53.5 ppm and 0.2, respectively), confirming the aragonitic environment around resonance A and B. Concerning, resonance C, we observe a Δ CSA much lower than the reference compound (+43 vs +62 ppm for NaHCO 3 ) that can be explained by the relatively poor S / N and the difficulty to determine precise experimental Δ CSA value for resonance C. Finally, we note that such approach consisting in the careful examination of the spinning sideband manifold of slow MAS 13 C NMR spectra for carbonate/bicarbonate differentiation has already been used to evidence the partition of carbon dioxide into CO 3 2– or HCO 3 – inside layered double hydroxide materials . Our results confirm that the disordered mineral domain in nacre is different from a biogenic ACC for which one homogeneous single broad resonance is observed .…”

“…Concerning, resonance C, we observe a Δ CSA much lower than the reference compound (+43 vs +62 ppm for NaHCO 3 ) that can be explained by the relatively poor S/N and the difficulty to determine precise experimental Δ CSA value for resonance C. Finally, we note that such approach consisting in the careful examination of the spinning sideband manifold of slow MAS 13 C NMR spectra for carbonate/bicarbonate differentiation has already been used to evidence the partition of carbon dioxide into CO 3 2− or HCO 3 − inside layered double hydroxide materials. 86 Our results confirm that the disordered mineral domain in nacre is different from a biogenic ACC for which one homogeneous single broad resonance is observed. 87 and more structurally disordered HCO 3 − possessing a distribution of 13 C chemical shifts.…”

Probing the Dynamics of Layered Double Hydroxides by Solid-State 27Al NMR Spectroscopy

“…behind this breathing phenomenon 8. This type of behavior bears some potential for the development of carbon dioxide storage materials.In several papers,Kirkpatrick et al.…”

“…The opportunity to tune the composition, the structure, and the texture leads to the design of refined materials with desired properties for various applications such as catalysis, drug delivery, and environmental remediation. , Furthermore, these materials are of considerable geological relevance because of their anion exchange capacity, which can affect the mobility of chemical species in the environment. In recent papers by Ishihara et al, it has been shown not only that LDH materials have the capacity to store CO 2 under the form of carbonate anions captured in cationic mineral layers but also that this type of material literally breathes and exchanges the interlayer anionic carbonate with the atmosphere. , More information was very recently revealed on the exchange mechanism that lies behind this breathing phenomenon . This type of behavior bears some potential for the development of carbon dioxide storage materials.…”

NMR Crystallography Reveals Carbonate Induced Al‐Ordering in ZnAl Layered Double Hydroxide

“…[13,14] Carbon species in the interlayers of carbonate-intercalated ZnAl LDHs (ZnAl-CO3) have been investigated with NMR spectroscopy, revealing two types of 13 C signals assigned to either exchangeable carbonate and hydrogen carbonate species or to two carbon species interacting with the LDH layer or with impurities present. [15][16][17] Unambiguous assignment of the 13 C NMR signals observed in carbonate intercalated LDHs also remains a topic of debate. LDH materials are typically synthesized by co-precipitation in a pH stated medium at pH between 8 and 10.…”