arXiv subjects

Andreas Hirsch

Publications and source records attributed to Andreas Hirsch.

At least 19 recordsLinked to original sources

arXiv2024

Moir\'e lattice of twisted bilayer graphene as template for non-covalent functionalization

We present a novel approach to achieve spatial variations in the degree of non-covalent functionalization of twisted bilayer graphene (tBLG). The tBLG with twist angles varying between ~ 5{\deg} and 7{\deg} was non-covalently functionalized with 1,4,5,8,9,11-hexaazatriphenylenehexacarbonitrile (HATCN) molecules. Our results show a correlation between the degree of functionalization and the twist angle of tBLG. This correlation was determined through Raman spectroscopy, where areas with larger twist angles exhibited a lower HATCN peak intensity compared to areas with smaller twist angles. We suggest that the HATCN adsorption follows the moir\'e pattern of tBLG by avoiding AA-stacked areas and attach predominantly to areas with a local AB-stacking order of tBLG, forming an overall ABA-stacking configuration. This is supported by density functional theory (DFT) calculations. Our work highlights the role of the moir\'e lattice in controlling the non-covalent functionalization of tBLG. Our approach can be generalized for designing nanoscale patterns on two-dimensional (2D) materials using moir\'e structures as a template.

cond-mat.mtrl-sci↗

arXiv2020

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.

physics.chem-ph↗

arXiv2019

Post Graphene 2D Chemistry: The Emerging Field of Molybdenum Disulfide and Black Phosphorus Functionalization

The current state of the chemical functionalization of three types of single sheet 2D materials, namely, graphene, molybdenum disulfide (MoS2), and black phosphorus (BP) is summarized. Such 2D sheet polymers represent currently an emerging field at the interface of synthetic chemistry, physics, and materials science. Both covalent and non-covalent functionalization of sheet architectures allows for a systematic modification of their properties, i.e. an improvement of solubility and processability, the prevention of re-aggregation or a band gap tuning. Next to successful functionalization concepts also fundamental challenges are addressed. These include the insolubility and polydispersity of most 2D sheet polymers, the development of suitable characterization tools, the identification of effective binding strategies, the chemical activation of the usually rather unreactive basal planes for covalent addend binding, and the regioselectivity of plane addition reactions. Although a number of these questions remain elusive in this review, the first promising concepts to overcome such hurdles have been listed.

physics.chem-ph↗

arXiv2019

Few layer 2D pnictogens catalyze the alkylation of soft nucleophiles with esters

Group 15 elements in zero oxidation state (P, As, Sb and Bi), also called pnictogens, are rarely used in catalysis due to the difficulties associated in preparing well-structured and stable materials. Here, we report on the synthesis of highly exfoliated, few layer 2D phosphorene and antimonene in zero oxidation state, suspended in an ionic liquid, with the native atoms ready to interact with external reagents while avoiding aerobic or aqueous decomposition pathways, and on their use as efficient catalysts for the alkylation of nucleophiles with esters. The few layer pnictogen material circumvents the extremely harsh reaction conditions associated to previous superacid-catalyzed alkylations, by enabling an alternative mechanism on surface, protected from the water and air by the ionic liquid. These 2D catalysts allow the alkylation of a variety of acid-sensitive organic molecules and giving synthetic relevancy to the use of simple esters as alkylating agents.

physics.chem-ph↗

arXiv2019

Lattice Opening Upon Bulk Reductive Covalent Functionalization of Black Phosphorus

The chemical bulk reductive covalent functionalization of thin layer black phosphorus (BP) using BP intercalation compounds has been developed. Through effective reductive activation, covalent functionalization of the charged BP is achieved by organic alkyl halides. Functionalization was extensively demonstrated by means of several spectroscopic techniques and DFT calculations, showing higher functionalization degrees than the neutral routes.

physics.app-ph↗

arXiv2019

Monolayer black phosphorus by sequential wet-chemical surface oxidation

We report a straightforward chemical methodology for controlling the thickness of black phosphorus flakes down to the monolayer limit by layer-by-layer oxidation and thinning, using water as solubilizing agent. Moreover, the oxidation process can be stopped at will by two different passivation procedures, namely the non-covalent functionalization with perylene diimide chromophores, which prevents the photooxidation, or by using a protective ionic liquid layer. The obtained flakes preserve their electronic properties as demonstrated by fabricating a BP field-effect transistor (FET). This work paves the way for the preparation of BP devices with controlled thickness

physics.app-ph↗

arXiv2018

Effect of TCNQ layer cover on oxidation dynamics of black phosphorus

The puckered surface of black phosphorus represents an ideal substrate for an unconventional arrangement of physisorbed species and the resulting specific two-dimensional chemistry of this system. This opens the way to investigate the chemical and physical properties of locally confined areas of black phosphorus without the necessity for further physical downscaling of the material. We have evaporated TCNQ on top of black phosphorus under over-saturation non-equilibrium conditions in vacuum. The evolution of linear density and height of droplets formed through oxidation during exposure to air was studied time-dependently by scanning-force microscopy. Our study suggests that the TCNQ molecules spontaneously arrange in a thin layer of the order of a few nm height, which, however, is fragmented with a periodicity of about 100 nm. It is shown that within the confined space separating the layer fragments the chemical dynamics of the oxidation process is remarkably different than on a bare black phosphorus surface.

cond-mat.mtrl-sci↗

arXiv2018

Optimized single-layer MoS2 field-effect transistors by non-covalent functionalisation

Field-effect transistors (FETs) with non-covalently functionalised molybdenum disulfide (MoS2) channels grown by chemical vapour deposition (CVD) on SiO2 are reported. The dangling-bond-free surface of MoS2 was functionalised with a perylene bisimide derivative to allow for the deposition of Al2O3 dielectric. This allowed the fabrication of top-gated, fully-encapsulated MoS2 FETs. Furthermore, by the definition of vertical contacts on MoS2, devices, in which the channel area was never exposed to polymers, were fabricated. The MoS2 FETs showed high mobilities for transistors fabricated on SiO2 with Al2O3 as top-gate dielectric. Thus, gate-stack engineering using innovative chemistry is a promising approach for the fabrication of reliable electronic devices based on 2D materials.

physics.app-ph↗

arXiv2018

Statistical-Raman-Microscopy and Atomic-Force-Microscopy on Heterogeneous Graphene Obtained after Reduction of Graphene Oxide

Graphene oxide can be used as a precursor to graphene but the quality of graphene flakes is highly heterogeneous. Scanning-Raman-Microscopy (SRM) is used to characterize films of graphene derived from flakes of graphene oxide with an almost intact carbon framework (ai-GO). The defect density of these flakes is visualized in detail by analyzing the intensity and full-width at half-maximum of the most pronounced Raman peaks. In addition, we superimpose the SRM results with AFM images and correlate the spectroscopic results with the morphology. Furthermore, we use SRM technique to display the amount of defects in a film of graphene. Thus, an area of 250 x 250 {\my}m2 of graphene is probed with a step-size increment of 1 μm. We are able to visualize the position of graphene flakes, edges and the substrate. Finally, we alter parameters of measurement to analyze the quality of graphene fast and reliable. The described method can be used to probe and visualize the quality of graphene films.

physics.chem-ph↗

arXiv2018

Chemistry with Graphene and Graphene Oxide - Challenges for Synthetic Chemists

The chemical production of graphene as well as its controlled wet- chemical modification is a challenge for synthetic chemists and the characterization of reaction products requires sophisticated analytic methods. In this review we first describe the structure of graphene and graphene oxide. We then outline the most important synthetic methods which are used for the production of these carbon based nanomaterials. We summarize the state-of-the-art for their chemical functionalization by non-covalent and covalent approaches. We put special emphasis on the differentiation of the terms graphite, graphene, graphite oxide and graphene oxide. An improved fundamental knowledge about the structure and the chemical properties of graphene and graphene oxide is an important prerequisite for the development of practical applications.

physics.chem-ph↗

arXiv2018

Investigation of the Thermal Stability of the Carbon Framework of Graphene Oxide

In this study, we use our recently prepared graphene oxide (GO) with an almost intact σ-framework of C-atoms (ai-GO) to probe the thermal stability of the carbon framework for the first time. Ai-GO exhibits few defects only by preventing CO2 formation during synthesis. Ai-GO was thermally treated before chemical reduction and subsequently the resulting defect density in graphene was determined by statistical Raman microscopy. Surprisingly, the carbon framework of ai-GO is stable in thin films up to 100 °C. Furthermore, we find evidence for an increasing quality of ai-GO upon annealing at 50 °C before reduction. The carbon framework of GO prepared according to the popular Hummers method (GO-c)appears to be less stable and decomposition starts at 50 °C what is qualitatively indicated by CO2-trapping experiments in μm-thin films. Information about the stability of GO is important for storing, processing and applying GO in applications.

physics.chem-ph↗

arXiv2018

Novel λ^3-Iodane Based Functionalization of Synthetic Carbon Allotropes (SCAs) - Common Concepts and Quantification of the Degree of Addition

The covalent functionalization of carbon allotropes represents a main topic in the growing field of nano materials. However, the development of functional architectures is impeded by the intrinsic polydispersibility of the respective starting material, the unequivocal characterization of the introduced functional moieties and the exact determination of the degree of functionalization. Based on a novel carbon allotrope functionalization reaction, utilizing λ^3-iodanes as radical precursor systems, we were able to demonstrate the feasibility to separate and to quantify thermally detached functional groups, formerly covalently linked to carbon nanotubes and graphene via TG-GC/MS.

physics.chem-ph↗

arXiv2018

Reductive Arylation of Graphene: Insights into a Reversible Carbon Allotrope Functionalization Reaction

The covalent functionalization of graphene represents a main topic in the growing field of nano materials. The reductive exfoliation of graphite with concomitant functionalization of the respective graphenide intermediates provides a promising approach towards functional graphene derivatives. In this article, we present new insights into the reductive arylation of graphene. Graphite intercalation compounds (GICs) with varying stoichiometries have been used as starting materials. Based on the spectroscopic data obtained by scanning Raman microscopy (SRM) and thermogravimetric analysis coupled to mass spectrometry (TG/MS), a clear correlation between the amount of negative charges - present in the GIC - and the degree of functionalization in the final product could be found. Furthermore, the detailed analysis of the thermal defunctionalization process provided deeper insights into the covalent addend binding.

physics.chem-ph↗

arXiv2018

Polyhydrogenated Graphene - Excited State Dynamics in Photo- and Electroactive 2D-Domains

Understanding the phenomenon of intense photoluminescence in carbon materials such as hydrogenated graphene, graphene nanoribbons, etc. is at the forefront of investigations. In this study, six different types of hydrogenated graphene (phG) produced from different starting materials, were fully characterized in terms of structure and spectroscopy. Comprehensive photoluminescence lifetime analyses of phGs were conducted by combining time-correlated single-photon counting spectroscopy with steady-state fluorescence spectroscopy and femtosecond transient absorption spectroscopy. The conclusion drawn from these assays is that graphene islands with diameters in the range from 1.1 to 1.75 nm reveal band gap photoluminescence between 450 and 800 nm. As a complement, phGs were implemented in hybrids with water-soluble electron accepting perylenediimides (PDI). By virtue of mutual π-stacking and charge transfer interactions with graphene islands, PDIs assisted in stabilizing aqueous dispersion of phG. Implicit in these ground state interactions is the formation of 300 ps lived charge separated states once photoexcited.

physics.chem-ph↗

arXiv2018

Basic Insights into Tunable Graphene Hydrogenation

The hydrogenation and deuteration of graphite with potassium intercalation compounds (GICs) as starting materials was investigated. Characterization of the reactions products (hydrogenated and deuterated graphene) was carried out by thermogravimetric analysis coupled with mass spectrometry (TG-MS) and Raman spectroscopy including statistical Raman spectroscopy (SRS) and -microscopy (SRM). The results reveal that the choice of the hydrogen/deuterium source, the nature of the graphite (used as starting material), the potassium concentration in the intercalation compound as well as the choice of the solvent have a great impact on the reaction outcome. Furthermore, it was possible to proof that both mono and few-layer hydrogenated/deuterated graphene can be produced.

physics.chem-ph↗

arXiv2018

Novel EDTA-Ligands Containing an Integral Perylene Bisimide (PBI) Core as Optical Reporter Unit

The synthesis, characterization and metal complexation of a new class of perylene bisimides (PBIs) being an integral part of ethylenediaminetetraacetic acid (EDTA) is reported. The simplest representative, namely derivative 1a, was synthesized both by a convergent as well as a direct approach while the elongated derivatives, 1b and 1c, were obtained only via a convergent synthetic pathway. All these new prototypes of water-soluble perylenes are bolaamphiphiles and were fully characterized by 1H- and 13C-NMR spectroscopy, matrix assisted laser desorption ionization, time of flight (MALDI-TOF) mass spectrometry and IR spectroscopy. In order to acquaint for the behaviour in solution of our PBIs bearing dentritic wedges, the simplest derivative, 1a, was chosen and tested by means of UV/Vis and fluorescence spectroscopy as well as by zeta-potential measurements. A photoexcitation induced intramolecular photo-electron transfer (PET) can be observed in these molecules. Therefore potential applications as sensor can be imagined. Model compound 1a efficiently coordinates trivalent metal cations both in water and in dimethyl sulfoxide (DMSO). Significantly, the effects of the complexation strongly depend on the aggregation state of the PBI molecules in solution. As a matter of fact, in water, the presence of M3+ ions triggers the formation of light emitting supramolecular aggregates (excimers). On the other hand, in DMSO-rich solutions metal complexation leads to the suppression of the PET and leads to a strong fluorescence enhancement.

physics.chem-ph↗

arXiv2018

Alkoxide-intercalated NiFe-layered double hydroxides magnetic nanosheets as efficient water oxidation electrocatalysts

Alkoxide-intercalated NiFe-layered double hydroxides were synthesized via the nonaqueous methanolic route. These nanoplatelets exhibit high crystalline quality as demonstrated by atomic resolution scanning transmission electron microscopy combined with electron energy-loss spectroscopy. Moreover, the presence of the alkoxide moieties has been unambiguously demonstrated by means of thermogravimetric analysis coupled to a mass spectrometer. These NiFe-LDHs can be exfoliated in water or organic solvents and processed into homogeneous ultra-thin films (< 3nm thick) with the assistance of O2-plasma. The study of their behaviour as water oxidation electrocatalysts has shown an outstanding performance at basic pHs (small overpotential of ca. 249 mV and Tafel slopes in the range of 52-55 mV per decade).

physics.chem-ph↗

arXiv2018

Highly Integrated Organic-Inorganic Hybrid Architectures by Non-Covalent Exfoliation of Graphite and Assembly with Zinc Oxide Nanoparticles

Herein, we report an easy, straight forward, and versatile approach to build 0D/2D hybrid nanoparticle/graphene architectures by means of non-covalent chemistry and a modified Layer-by-Layer assembly. Three water soluble perylene diimides were employed to efficiently exfoliate pristine graphite into positively charged few- and multilayer graphene flakes. Further combination of these cationic building blocks with anionic zinc oxide nanoparticles led to the formation of tailor-made hybrid films via electrostatic and van der Waals interactions. These supramolecular hybrid nano-structures were thoroughly characterized by UV/Vis and Raman spectroscopy, AFM as well as electron microscopy, showing outstanding long-range homogeneity and high integrity in the centimetre-scale, uniform nanometric thickness between 60-100 nm and a close contact between the different building blocks. Due to their straightforward assembly. These architectures can be considered as promising candidates for numerous advanced applications especially in the field of energy storage and conversion.

physics.chem-ph↗