Functionalization of MoS2 with 1,2-dithiolanes: toward donor-acceptor nanohybrids for energy conversion

Abstract

The covalent functionalization of exfoliated semiconducting MoS 2 by 1,2-dithiolanes bearing an ethylene glycol alkyl chain terminated to a butoxycarbonyl-protected amine and a photoactive pyrene moiety is accomplished. The MoS 2 -based nanohybrids were fully characterized by complementary spectroscopic, thermal, and microscopy techniques. Markedly, density functional theoretical studies combined with X-ray photoelectron spectroscopy analysis demonstrate preferential edge functionalization, primarily via sulfur addition along partially sulfur saturated zig-zag MoS 2 molybdenum-edges, preserving intact the 2D basal structure of functionalized MoS 2 -based nanohybrids as confirmed by high-resolution transmission electron microscopy and electron energy loss spectroscopy. Furthermore, in the MoS 2 -pyrene hybrid, appreciable electronic interactions at the excited state between the photoactive pyrene and the semiconducting MoS 2 were revealed as inferred by steady-state and time-resolved photoluminescence spectroscopy, implying its high potentiality to function in energy conversion schemes.

Molecular Functionalization of Two‐Dimensional MoS2 Nanosheets

“…[61] The versatility of the 1,2-dithiolane precursor used, a-lipoic acid, offerst he advantage of chemical manipulation at the carboxylic acid unit and the development of diversep hotoactive derivatives. [61] The versatility of the 1,2-dithiolane precursor used, a-lipoic acid, offerst he advantage of chemical manipulation at the carboxylic acid unit and the development of diversep hotoactive derivatives.…”

Simultaneous Fabrication and Functionalization of Nanoparticles of 2D Materials with Hybrid Optical Properties

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biomedicine, [2,3] tribology, [4] photonics, [5] and electrocatalysis, [6] among others. [7] This progress has focused on the functionalization of mono-or few-layer nanosheets with lateral dimensions greater than 100 nm by combining chemical exfoliation, [8][9][10][11][12] micromechanical exfoliation, [13] or liquid exfoliation [14] with the reaction of functionalities. [7] This progress has focused on the functionalization of mono-or few-layer nanosheets with lateral dimensions greater than 100 nm by combining chemical exfoliation, [8][9][10][11][12] micromechanical exfoliation, [13] or liquid exfoliation [14] with the reaction of functionalities.

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Electronic Interactions in Illuminated Carbon Dot/MoS2 Ensembles and Electrocatalytic Activity towards Hydrogen Evolution

“…[2] Exfoliated MoS 2 was spectroscopically evaluated and found to be around 340 nm in lateral size and oligolayers thick. This involved the recently established methodology for the functionalization of chemically exfoliated LTMDCs, based on the high binding affinity of 1,2-dithiolanes for Mo atoms, [7] particularly those located at the edges of exfoliated MoS 2 .F iltration of the reaction mix-ture through ap olytetrafluoroethylene (PTFE)m embrane with a0 .2 mmp ore size and successive washing with dichloromethane guaranteedt hat modified MoS 2 material 2 was free from noncovalently associated organic species. This involved the recently established methodology for the functionalization of chemically exfoliated LTMDCs, based on the high binding affinity of 1,2-dithiolanes for Mo atoms, [7] particularly those located at the edges of exfoliated MoS 2 .F iltration of the reaction mix-ture through ap olytetrafluoroethylene (PTFE)m embrane with a0 .2 mmp ore size and successive washing with dichloromethane guaranteedt hat modified MoS 2 material 2 was free from noncovalently associated organic species.…”

“…Notably,w erecently developedafacile approach that led to exfoliated semiconducting LTMDCst hrough treatment with chlorosulfonic acid; [2] this is in contrast to the BuLi exfoliation process, which gives access predominantly to the metallic poly typestructure. [7] Carbon dots (CDs), since their serendipitous discovery in 2004, [8] have provent ob eavaluable new entry to carbonbased nanomaterials. Hence, functionalization of LTMDCsisimperative for fully harnessing their capabilities and broadening their application in av ariety of fields.H owever, LTMDCs tend to be rather inert-chalcogena toms in the basal plane are saturated and not highly reactive, whereas metal atoms are embeddedb eneath the chalcogen layer,a nd thus, not susceptible to functionalization.…”