Deintercalation of Zero-Valent Metals from Two-Dimensional Layered Chalcogenides

Abstract

A general solution-based approach to deintercalate zero-valent tin and copper from two-dimensional layered chalcogenides is presented using a one-step comproportionation reduction–oxidation reaction. The reaction is performed between the intercalated zero-valent metal and high oxidation state metal cations (Sn4+ and Cu2+) dissolved in acetone. This chemistry is shown to work for a variety of layered chalcogenides with differing morphologies and crystallinity. Copper and tin are deintercalated from powders of MoS2, MoSe2, NbSe2, and WS2 and crystalline nanoribbons of Bi2Se3, In2Se3, and GeS. This chemistry achieves a general route to remove zero-valent tin and copper from 2D layered chalcogenides.

Enhancing Light–Matter Interactions in MoS2 by Copper Intercalation

“…[ 13,14 ] In the case of ionic intercalation, self‐intercalation of Cu +1 has improved the electronic transport in layered metal–chalcogen compounds. [ 15 ] These techniques have resulted in a vast array of chemically tunable behaviors including ambipolar optoelectronics in SnS 2 , [ 16 ] chemochromism in MoO 3 , [ 17 ] tunable enhanced transparency in Bi 2 Se 3 , [ 18,19 ] enhanced catalytic and energy storage behaviors in oxides, [ 20,21 ] tunable mechanical properties, [ 22 ] and enhanced thermoelectric performance in bismuth telluride. [ 23,24 ] The ability to chemically tune material properties—including optical and electronic properties—through intercalation opens a vast space of new physical and chemical behaviors.…”

Intercalation Strategy in 2D Materials for Electronics and Optoelectronics

“…Typically, numerous zerovalent metal atoms, such as Ag, Au, Cu, and Sn, are intercalated into the vdW gaps of host materials utilizing a series of disproportionation reactions. [ 73–77 ] A summary of these solution‐based methods is presented in Table 2 . Zerovalent metal atoms are more stable in the vdW gaps than keeping dissociative in dilute solution.…”

In Situ Dynamics during Heating of Copper-Intercalated Bismuth Telluride

“…13 Because of their wide utility, a variety of synthetic pathways have been developed to grow layered materials. 14,15 Furthermore, as the individual layers are separated by a vdW gap, several solid-state, 16 chemical, [17][18][19][20][21] and electrochemical [22][23][24][25][26] techniques have been developed to intercalate species into the gap. Although the main focus of intercalation in layered materials has been on intercalating ionic species for energy storage, [27][28][29][30] other benefits such as tuning of optoelectronic 17,31 and electrical 32 properties can also be achieved through intercalation without deleterious structural or chemical changes to the host lattice.…”

“…14,15 Furthermore, as the individual layers are separated by a vdW gap, several solid-state, 16 chemical, [17][18][19][20][21] and electrochemical [22][23][24][25][26] techniques have been developed to intercalate species into the gap. Although the main focus of intercalation in layered materials has been on intercalating ionic species for energy storage, [27][28][29][30] other benefits such as tuning of optoelectronic 17,31 and electrical 32 properties can also be achieved through intercalation without deleterious structural or chemical changes to the host lattice. Recently, intercalation within layered materials has also been shown to be a pathway for creating entirely new materials, including the stabilization of atomically thin metals, 33 as well as using self-intercalation 34 to generate covalently bonded bilayers.…”