Efficient Exfoliation of Layered Double Hydroxides; Effect of Cationic Ratio, Hydration State, Anions and Their Orientations

层状双氢氧化物的有效剥离;阳离子比例、水合状态、阴离子及其方向的影响

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作者:Jayakumar Karthikeyan, Helmer Fjellvåg, Silje Bundli, Anja Olafsen Sjåstad

Abstract

The exfoliation ability of nitrate based Mg1-xAlx(OH)2(NO3)x·mH2O layered double hydroxides (Mg-Al LDH) in formamide into single or multilayer nanosheets depends strongly on nitrate anion orientation and layer charge. Our systematic studies used materials that were likely to disclose differences with respect to anion type and their concentrations in the interlayer gallery. We assured to avoid any carbonate incorporation into the galleries for nitrate, chloride, iodide, and sulfate based Mg-Al LDHs. Furthermore, the comparative exfoliation experiments were conducted for fully hydrated samples with as similar particle morphology as possible. The exfoliation of nitrate Mg-Al LDH is far superior to similar clays with carbonate, sulfate, chloride, or iodide as charge balancing anions. Quantitative analysis of exfoliation yield for pre-treated, fully hydrated samples, shows an optimum composition for exfoliation into single nanosheets of around x ≈ 0.25, while double or triple layered sheets are encountered for other x-values. We observe a clear correlation between the expansion of the interlayer gallery due to progressing tilts of nitrate anions and water molecules out of the horizontal interlayer plane, suspension turbidity, and degree of exfoliation. The established correlations extends to nitrate Ni-Al LDH materials. We finally claim that morphology is a dominating parameter, with house-of-card morphology particles exfoliation far less than platelet-like particles. Hence, hydrothermal treatment may be favorable to enhance exfoliation yields.

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