Layered zinc hydroxide monolayers by hydrolysis of organozincs

Abstract

Organometallic precursors provide a new and clean route to solutions of 2D materials relevant for applications including catalysis, electronics and sensing.

From Chain‐ to Graphene‐like Hydroxyl‐terminated (ZnO)n Clusters with n≤6 Obtained via Zinc Dimethoxide Hydrolysis and Condensation: Ab initio Structural, Electronic, Vibrational and Optical Properties Calculations

“…In addition, single‐layered and aggregates of layered graphene‐like ZnO synthesized by a hydrothermal technique using zinc nitrate as precursor in an aqueous medium were also reported to be stable at room temperature [36] . Moreover, other preparation techniques such as the hydrolysis of diethyl zinc and zinc carboxylate mixtures at room temperature have yielded a series of layered zinc hydroxides coordinated by aliphatic carboxylate ligands [37] . On the other hand, the size confinement towards 1D nanostructures has been explored theoretically, such as the case of ZnO nanowires with ∼2 nm diameter still maintaining a Wurtzite structure, revealing large piezoelectric coefficients and polarity inversion [38,39] .…”

“…[36] Moreover, other preparation techniques such as the hydrolysis of diethyl zinc and zinc carboxylate mixtures at room temperature have yielded a series of layered zinc hydroxides coordinated by aliphatic carboxylate ligands. [37] On the other hand, the size confinement towards 1D nanostructures has been explored theoretically, such as the case of ZnO nanowires with~2 nm diameter still maintaining a Wurtzite structure, revealing large piezoelectric coefficients and polarity inversion. [38,39] However, although successful experimental results of further confinement of 1D nanostructures down to the atomic-scale have been reported for titanium oxide employing alkoxide precursor sol-gel methodology in organic medium, [40] to the best of our knowledge, atomic-scale 1D ZnO wires have not been reported experimentally yet.…”

Layered Zinc Hydroxide Dihydrate, Zn5(OH)10·2H2O, from Hydrothermal Conversion of ε-Zn(OH)2 at Gigapascal Pressures and its Transformation to Nanocrystalline ZnO

“… 4 , 5 Further, terminating layers with hydrophobic long-chain carboxylate ions lead to unique architectures of layer assemblies, which can be subsequently exfoliated. 8 − 10 Films of LZHs may be prepared by electrodeposition 4 or liquid–liquid biphasic synthesis. 11 Using hydrophilic substrates allows the fabrication of films of upright-standing nanosheets of LZHs that are stacked parallel to the substrate.…”

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

“…The carboxylate‐intercalated LZH‐R materials, where R 1 −n = alkyl ether chains, O 2 C(CH 2 O((CH 2 ) 2 O) n CH 3 ( n = 0, 1, 2, and 4), R 2 = 5‐hexenoate and R 3 = 9‐anthracenecarboxylate, were synthesized by modifying the previously reported synthesis ( Scheme ). [ 16 ] Diethyl zinc was added to a solution of the appropriate carboxylic acid at a molar ratio of [COOR]/[Zn] of 0.6; a slight excess of the acid is added relative to the stoichiometry of [Zn 5 (OH) 8 A 2 ] ([A]/[Zn] = 0.4) to deliver the LZH free from any detectable zinc oxide. The reaction between diethyl zinc and carboxylic acids proceeds via the formation of pentanuclear clusters, [Zn 5 (Et) 4 (COOR) 6 ], with the excess diethyl zinc rapidly exchanging with the coordinated zinc ethyl groups.…”

“…[ 15 ] In 2018, our group applied a related organozinc hydrolysis method to make LZH nanosheets: the hydrolysis of diethyl zinc in the presence of alkyl zinc carboxylate complexes produced a series of alkyl carboxylate intercalated LZH. [ 16 ] The oleate‐intercalated LZH nanosheets showed good solubility in toluene. Here, we aim to transform this initial result into a general principle, showing that exfoliated LZHs can be rendered both functional and soluble in a range of solvents, including common polar solvents such as ethanol and water.…”