Direct Organometallic Synthesis of Carboxylate Intercalated Layered Zinc Hydroxides for Fully Exfoliated Functional Nanosheets

Abstract

Intercalation of organic anions into 2D materials can enable exfoliation, improve dispersion stability, increase surface area, and provide useful functional groups. In layered metal hydroxides, intercalation of bulk structures is commonly achieved by cumbersome and typically incomplete anion exchange reactions. In contrast, here, a series of carboxylate-intercalated layered zinc hydroxides (LZH-R) are synthesized directly, at room temperature, by reacting an organozinc reagent with a precise sub-stoichiometric quantity of the desired carboxylic acid and water. A range of carboxylic acids are used to make new LZH-R materials which are crystalline, soluble, and functionalized, as established by X-ray diffraction, spectroscopic, and microscopy techniques. When R is an alkyl ether carboxylate, this direct synthesis method results in the spontaneous exfoliation of the LZH-R into monolayer nanosheets with high yields (70-80%) and high solubilities in alcohols and water of up to 180 mg mL −1 . By altering the carboxylate ligand, functional groups suitable for post-synthetic modification or for detection by fluorescence are also introduced. These examples demonstrate a versatile synthetic route for functional exfoliated nanosheets.

Morphology Control Strategy of Bimetallic MOF Nanosheets for Upgrading the Sensitivity of Noninvasive Glucose Detection

“…The peak locating at 1620 cm –1 is attributed to the existence of water molecules in the inner coordination sphere of the metallic center. The coordination of carboxylic acid ligands with bimetals is determined by asymmetric and symmetric carboxylic acid stretching at 1574 and 1430 cm –1 , respectively . The asymmetric vibration of NO 3 – is observed by the sharp peak at 1373 cm –1 .…”

Ultrathin Zn-Gallate Catalyst: A Remarkable Performer in CO2 and Propylene Oxide Polymerization

“…The remarkable enhancement in the catalytic activity of Zngallate can be ascribed to the disintegration of its layered structure during the polymerization reaction (Figure 4a). 45 This disintegration results in the creation of ultrathin Zngallate, generating numerous catalytically active zinc sites, including coordinatively unsaturated zinc sites and Zn−OH sites. The proposed mechanism for PPC formation is based on the catalytic action of ZnGA, with Zn−OH serving as an initiator (Figure 4b).…”

Secured Nanosynthesis–Deposition Aerosol Process for Composite Thin Films Incorporating Highly Dispersed Nanoparticles

“…Note that the ligand may also play a role on the hydrolysis reaction. [ 62 , 63 , 64 ] The synthesis can be performed at 20—25 °C under atmospheric pressure, which are conditions fully compatible with DLRI. Under these conditions, the organometallic precursor is highly reactive at rates compatible with the DLRI.…”