Frank Hauke

Covalent bulk functionalization of graphene

Graphene, a truly two-dimensional and fully π-conjugated honeycomb carbon network, is currently evolving into the most promising successor to silicon in micro- and nanoelectronic applications. However, its wider application is impeded by the difficulties in opening a bandgap in its gapless band-structure, as well as the lack of processability in the resultant intrinscially insoluble material. Covalent chemical modification of the π-electron system is capable of addressing both of these issues through the introduction of variable chemical decoration. Although there has been significant research activity in the field of functionalized graphene, most work to date has focused on the use of graphene oxide. In this Article, we report on the first wet chemical bulk functionalization route beginning with pristine graphite that does not require initial oxidative damage of the graphene basal planes. Through effective reductive activation, covalent functionalization of the charged graphene is achieved by organic diazonium salts. Functionalization was observed spectroscopically, and successfully prevents reaggregation while providing solubility in common organic media.

Liquid exfoliation of solvent-stabilized few-layer black phosphorus for applications beyond electronics.

Few-layer black phosphorus (BP) is a new two-dimensional material which is of great interest for applications, mainly in electronics. However, its lack of environmental stability severely limits its synthesis and processing. Here we demonstrate that high-quality, few-layer BP nanosheets, with controllable size and observable photoluminescence, can be produced in large quantities by liquid phase exfoliation under ambient conditions in solvents such as N-cyclohexyl-2-pyrrolidone (CHP). Nanosheets are surprisingly stable in CHP, probably due to the solvation shell protecting the nanosheets from reacting with water or oxygen. Experiments, supported by simulations, show reactions to occur only at the nanosheet edge, with the rate and extent of the reaction dependent on the water/oxygen content. We demonstrate that liquid-exfoliated BP nanosheets are potentially useful in a range of applications from ultrafast saturable absorbers to gas sensors to fillers for composite reinforcement.

Manipulating single-wall carbon nanotubes by chemical doping and charge transfer with perylene dyes

Single-wall carbon nanotubes (SWNTs) are emerging as materials with much potential in several disciplines, in particular in electronics and photovoltaics. The combination of SWNTs with electron donors or acceptors generates active materials, which can produce electrical energy when irradiated. However, SWNTs are very elusive species when characterization of their metastable states is required. This problem mainly arises because of the polydispersive nature of SWNT samples and the inevitable presence of SWNTs in bundles of different sizes. Here, we report the complete and thorough characterization of an SWNT radical ion-pair state induced by complexation with a perylene dye, which combines excellent electron-accepting and -conducting features with a five-fused ring π-system. At the same time, the perylene dye enables the dispersion of SWNTs by means of π–π interactions, which gives individual SWNTs in solution. This work clears a path towards electronic and optoelectronic devices in which regulated electrical transport properties are important. Using carbon nanotubes in electronic or photovoltaic devices generates active metastable states. These elusive species are hard to characterize because of the polydisperse and aggregate nature of nanotube bundles. A complete characterization of the radical–ion pair state has now been achieved using a range of techniques.

Wet Chemical Functionalization of Graphene

The fullerenes, carbon nanotubes, and graphene have enriched the family of carbon allotropes over the last few decades. Synthetic carbon allotropes (SCAs) have attracted chemists, physicists, and materials scientists because of the sheer multitude of their aesthetically pleasing structures and, more so, because of their outstanding and often unprecedented properties. They consist of fully conjugated p-electron systems and are considered topologically confined objects in zero, one, or two dimensions. Among the SCAs, graphene shows the greatest potential for high-performance applications, in the field of nanoelectronics, for example. However, significant fundamental research is still required to develop graphene chemistry. Chemical functionalization of graphene will increase its dispersibility in solvents, improve its processing into new materials, and facilitate the combination of graphenes unprecedented properties with those of other compound classes. On the basis of our experience with fullerenes and carbon nanotubes, we have described a series of covalent and noncovalent approaches to generate graphene derivatives. Using water-soluble perylene surfactants, we could efficiently exfoliate graphite in water and prepare substantial amounts of single-layer-graphene (SLG) and few-layer-graphene (FLG). At the same time, this approach leads to noncovalent graphene derivatives because it establishes efficient π-π-stacking interactions between graphene and the aromatic perylene chromophors supported by hydrophobic interactions. To gain efficient access to covalently functionalized graphene we employed graphite intercalation compounds (GICs), where positively charged metal cations are located between the negatively charged graphene sheets. The balanced combination of intercalation combined with repulsion driven by Coulombic interactions facilitated efficient exfoliation and wet chemical functionalization of the electronically activated graphene sheets via trapping with reactive electrophilic addends. For example, the treatment of reduced graphite with aryl diazonium salts with the elimination of N(2) led to the formation of arylated graphene. We obtained alkylated graphene via related trapping reactions with alkyl iodides. These new developments have opened the door for combining the unprecedented properties of graphene with those of other compound classes. We expect that further studies of the principles of graphene reactivity, improved characterization methods, and better synthetic control over graphene derivatives will lead to a whole series of new materials with highly specific functionalities and enormous potential for attractive applications.

High Population of Individualized SWCNTs through the Adsorption of Water-Soluble Perylenes

The aqueous dispersion of SWCNTs in the presence of the water-soluble perylene derivatives 1-3 is reported. Significantly, even very low concentrations of the perylenes such as 0.01 wt% of the amphiphilic derivative 3, cause an efficient dissolution of the SWCNTs in water accompanied by a very pronounced individualization. The individualization of SWCNTs in water after ultrasonication in the presence of water-soluble aromatic perylenes was investigated in detail by absorption, emission, and Raman spectroscopy as well as by AFM and cryo-TEM. These studies also revealed that the individualization of the SWCNTs caused by the adsorption of 3 is much more effective than that induced by SDBS, which is the most frequently used surfactant for SWCNT dispersion in water. The pi-pi-stacking interaction and the electronic interaction between the perylene unit and the nanotube surface is reflected, for example, by the distinct absorption and emission features in the UV/vis/nIR, which differ significantly from those observed for SWNTs dispersed in the presence of SDBS and by the quenching of the perylene fluorescence of 3 when being in contact with the tubes.

Nanotube Surfactant Design: The Versatility of Water‐Soluble Perylene Bisimides

The synthesis of perylene-based single-walled carbon nanotube (SWCNT) surfactants and the dispersion and exfoliation of SWCNTs in water by a variety of designed surfactants is investigated. The quality of the nanotube dispersions is evaluated by optical absorption and emission spectroscopy, zeta-potential measurements and statistical atomic force microscopy (AFM). Significantly the dispersion efficiency can be increased at higher pH, as water solubility of the surfactants is ensured by peripheral derivatization with carboxyl-functionalized first- and second-order Newkome dendrimers. Even at very low perylene concentrations of 0.1 g L(-1) and a nanotube-to-surfactant ratio of 1:1, the nanotube supernatant after centrifugation contains up to 73% of the pristine material with exfoliation degrees (the number of fractions of individualized nanotubes N(I)/N(T)) of up to 76%. The adsorption of the perylene core to the nanotube scaffold is indicated by red-shifted perylene-absorption and SWCNT-emission features except for the smallest perylene amphiphile, where solubilization is presumably based on a micellar arrangement. The nanotube fluorescence is significantly altered and reduced in intensity compared to nanotubes dispersed in sodium dodecylbenzene sulfonate (SDBS) being strongly dependent on the structure of the perylene surfactant. We attribute this observation to the homogeneity of the surfactant coverage, e.g., the supramolecular arrangement onto the nanotube backbone. This study represents a step forward in understanding the structure-property relationship of nanotube surfactants. Furthermore high-quality nanotube dispersions with increased degrees of exfoliation are highly desirable, as the efficiency of nanotube separation techniques relies on highly individualized samples.

Non‐Covalent Chemistry of Graphene: Electronic Communication with Dendronized Perylene Bisimides

Graphene is the youngest representative of synthetic carbon allotropes. Since its discovery in 2004, [ 1 ] a series of outstanding physical properties has been revealed. As a consequence, this single-layer graphite is considered to be one of the most promising materials for high-performance applications, [ 2 ] for example in the fi eld of molecular electronics. Although chemistry on graphene and highly dispersed graphite offers unprecedented opportunities, wet chemical functionalization of intact graphene [ 3 ] remains almost completely unexplored. Wet chemistry of graphene is highly attractive because: a) its unique properties can be combined with those of other compound classes, b) solubility and processability can be increased, c) fi ne tuning of the electronic characteristics (doping) can be achieved, d) synthetic routes to novel macromolecular architectures, for instance, graphanes as 2D-polymers, can be provided, and e) the inherent principles of graphene reactivity can be revealed. Herein, we report for the fi rst time on the electronic communication between graphene with the perylene bisimide (PBI) 1 [ 4 ] ( Figure 1 ) when both are deposited on a surface or dispersed in homogeneous solution. This interaction is provided by the non-covalent binding of their conjugated π -systems. Recently we have shown that amphiphilic PBIs, which are related to 1 but contain deprotected carboxylic acid groups, are very effi cient for the exfoliation of single-walled carbon nanotubes (SWNTs) [ 4 , 5 ] and graphite [ 6 ] in water. Moreover, we have demonstrated that the π – π -stacking interaction of electrondefi cient PBIs with SWNTs in water is accompanied by a p -doping of the tubes. [ 7 ] So far, evidence for graphene-dye interactions has been obtained for the solid state, exclusively, for instance, after gas-phase deposition of the dye in ultrahigh vacuum on epitaxial graphene, [ 8 ] after soaking mechanically exfoliated Kish graphite in a dye solution, [ 9 ] on gold or silver colloids, [ 10 ] and on H-passivated substrates. [ 11 ]

Basal-Plane Functionalization of Chemically Exfoliated Molybdenum Disulfide by Diazonium Salts

Although transition metal dichalcogenides such as MoS2 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 MoS2 surface via covalent C-S bonds. This is based on lithium intercalation, chemical exfoliation and subsequent quenching of the negative charges residing on the MoS2 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-MoS2. We show that, unlike both chemically exfoliated and pristine MoS2, the functionalized MoS2 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) MoS2 is energetically favorable and that S-C bonds are formed.

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 ID/IG 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 ID/IG histograms. The Raman results correlate nicely with parallel thermogravimetric analysis (TGA) coupled with mass spectrometry (MS) studies.

The Potential of Perylene Bisimide Derivatives for the Solubilization of Carbon Nanotubes and Graphene

Carbon nanotubes and graphene are outstanding materials of the 21st century with a broad spectrum of applications. However, major challenges are faced such as the intrinsically low solubility of both sp2 carbon allotropes. To overcome this hurdle the potential of noncovalent functionalization is summarized with a special focus on the establishment of the perylene bisimide unit as aromatic anchor to the graphitic surface. Rational surfactant design is unmasked as the key to solubilization of the carbon allotropes, while at the same time tailoring their surface properties, or even electronic properties in a fully reversible fashion.