9 research outputs found
Defect Engineering of Two-dimensional Molybdenum Disulfide
Two-dimensional (2D) molybdenum disulfide (MoS2) holds great promise in
electronic and optoelectronic applications owing to its unique structure and
intriguing properties. The intrinsic defects such as sulfur vacancies (SVs) of
MoS2 nanosheets are found to be detrimental to the device efficiency. To
mitigate this problem, functionalization of 2D MoS2 using thiols has emerged as
one of the key strategies for engineering defects. Herein, we demonstrate an
approach to controllably engineer the SVs of chemically exfoliated MoS2
nanosheets using a series of substituted thiophenols in solution. The degree of
functionalization can be tuned by varying the electron withdrawing strength of
substituents in thiophenols. We find that the intensity of 2LA(M) peak
normalized to A1g peak strongly correlates to the degree of functionalization.
Our results provide a spectroscopic indicator to monitor and quantify the
defect engineering process. This method of MoS2 defect functionalization in
solution also benefits the further exploration of defect free MoS2 for a wide
range of applications
Scanning-Raman-Microscopy for the Statistical Analysis of Covalently Functionalized Graphene
We report on the introduction of a systematic method for the quantitative and reliable characterization of covalently functionalized graphene based on Scanning-Raman-Microscopy (SRM). This allows for recording and analyzing several thousands of Raman spectra per sample and straightforward display of various Raman properties and their correlations with each other in histograms or coded 2D-plots. In this way, information about the functionalization efficiency of a given reaction, the reproducibility of the statistical analysis, and the sample homogeneity can be easily deduced. Based on geometric considerations, we were also able to provide, for the first time, a correlation between the mean defect distance of densely packed point defects and the Raman <i>I</i><sub>D</sub>/<i>I</i><sub>G</sub> ratio directly obtained from the statistical analysis. This proved to be the prerequisite for determining the degree of functionalization, termed θ. As model compounds, we have studied a series of arylated graphenes (GPh) for which we have developed new synthetic procedures. Both graphite and graphene grown by chemical vapor deposition (CVD) were used as starting materials. The best route toward GPh consisted of the initial reduction of graphite with a Na/K alloy in 1,2-dimethoxyethane (DME) as it yields the highest overall homogeneity of products reflected in the widths of the Raman <i>I</i><sub>D</sub>/<i>I</i><sub>G</sub> histograms. The Raman results correlate nicely with parallel thermogravimetric analysis (TGA) coupled with mass spectrometry (MS) studies
Topology-Driven Reductive Silylation of Synthetic Carbon Allotropes
Herein, the combined application
of characterization tools, such as Raman spectroscopy, thermal gravimetric
analysis coupled with mass spectrometry, and optical and atomic force
microscopy, confirms the reductive silylation of synthetic carbon
allotropes as a new covalent functionalization strategy for the formation
of heteroatom–carbon bonds. In particular, our study gives
interesting insights into the topology-driven retrofunctionalization
of nanotubide and graphenide derivatives
Basal-Plane Functionalization of Chemically Exfoliated Molybdenum Disulfide by Diazonium Salts
Although transition metal dichalcogenides such as MoS<sub>2</sub> have been recognized as highly potent two-dimensional nanomaterials, general methods to chemically functionalize them are scarce. Herein, we demonstrate a functionalization route that results in organic groups bonded to the MoS<sub>2</sub> surface <i>via</i> covalent C–S bonds. This is based on lithium intercalation, chemical exfoliation and subsequent quenching of the negative charges residing on the MoS<sub>2</sub> by electrophiles such as diazonium salts. Typical degrees of functionalization are 10–20 atom % and are potentially tunable by the choice of intercalation conditions. Significantly, no further defects are introduced, and annealing at 350 °C restores the pristine 2H-MoS<sub>2</sub>. We show that, unlike both chemically exfoliated and pristine MoS<sub>2</sub>, the functionalized MoS<sub>2</sub> is very well dispersible in anisole, confirming a significant modification of the surface properties by functionalization. DFT calculations show that the grafting of the functional group to the sulfur atoms of (charged) MoS<sub>2</sub> is energetically favorable and that S–C bonds are formed