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Register a new userCovalent functionalization by cycloaddition reactions of pristine, defect-free graphene
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Based on a low temperature scanning tunneling microscopy study, we present a direct visualization of a cycloaddition reaction performed for some specific fluorinated maleimide molecules deposited on graphene. These studies showed that the cycloaddition reactions can be carried out on the basal plane of graphene, even when there are no pre-existing defects. In the course of covalently grafting the molecules to graphene, the sp2 conjugation of carbon atoms was broken and local sp3 bonds were created. The grafted molecules perturbed the graphene lattice, generating a standing-wave pattern with an anisotropy which was attributed to a (1,2) cycloaddition, as revealed by T-matrix approximation calculations. DFT calculations showed that while both (1,4) and (1,2) cycloaddition were possible on free standing graphene, only the (1,2) cycloaddition could be obtained for graphene on SiC(0001). Globally averaging spectroscopic techniques, XPS and ARPES, were used to determine the modification in the elemental composition of the samples induced by the reaction, indicating an opening of an electronic gap in graphene.
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Interfacial thermal transport between electrodes and polymer electrolytes can play a crucial role in the thermal management of solid-state lithium-ion batteries (SLIBs). Modifying the electrode surface with functional molecules can effectively increase the interfacial thermal conductance (ITC) between electrodes and polymers (e.g., electrolytes, separators); however, how they influence the interfacial thermal transport in SLIBs during charge/discharge remains unknown. In this work, we conduct molecular dynamics (MD) simulations to investigate the ITC between charged electrodes and solid-state polymer electrolytes (SPEs) mixed with ionic liquids (ILs). We find that ILs could self assemble at the electrode surface and act as non-covalent functional molecules that could significantly enhance the interfacial thermal transport during charge/discharge because of the formation of a densely packed cationic or anionic layer at the interface. While the electrostatic interactions between the charged electrode and the IL ions are responsible for forming these dense interfacial layers, the enhancement of ITC is mainly contributed by the increased Lennard-Jones (LJ) interactions between the charged electrodes and ILs. This work may provide useful insights into the understanding of interfacial thermal transport between electrodes and electrolytes of SLIBs during charge/discharge.
We investigated theoretically the effect of covalent edge functionalization, with organic functional groups, on the electronic properties of graphene nanostructures and nano-junctions. Our analysis shows that functionalization can be designed to tune electron affinities and ionization potentials of graphene flakes, and to control the energy alignment of frontier orbitals in nanometer-wide graphene junctions. The stability of the proposed mechanism is discussed with respect to the functional groups, their number as well as the width of graphene nanostructures. The results of our work indicate that different level alignments can be obtained and engineered in order to realize stable all-graphene nanodevices.
Electrons in two-dimensional hexagonal materials have valley degree of freedom, which can be used to encode and process quantum information. The valley-selective excitations, governed by the circularly polarised light resonant with the materials band-gap, continues to be the foundation of valleytronics. It is often assumed that achieving valley selective excitation in pristine graphene with all-optical means is not possible due to the inversion symmetry of the system. Here we demonstrate that both valley-selective excitation and valley-selective high-harmonic generation can be achieved in pristine graphene by using the combination of two counter-rotating circularly polarized fields, the fundamental and its second harmonic. Controlling the relative phase between the two colours allows us to select the valleys where the electron-hole pairs and higher-order harmonics are generated. We also describe an all-optical method for measuring valley polarization in graphene with a weak probe pulse. This work offers a robust recipe to write and read valley-selective electron excitations in materials with zero bandgap and zero Berry curvature.
In a pristine monolayer graphene subjected to a constant electric field along the layer, the Bloch oscillation of an electron is studied in a simple and efficient way. By using the electronic dispersion relation, the formula of a semi-classical velocity is derived analytically, and then many aspects of Bloch oscillation, such as its frequency, amplitude, as well as the direction of the oscillation, are investigated. It is interesting to find that the electric field affects the component of motion, which is non-collinear with electric field, and leads the particle to be accelerated or oscillated in another component.
Two-dimensional semiconducting transition metal dichalcogenides (TMDCs) like molybdenum disulfide (MoS2) are generating significant excitement due to their unique electronic, chemical, and optical properties. Covalent chemical functionalization represents a critical tool for tuning the properties of TMDCs for use in many applications. However, the chemical inertness of semiconducting TMDCs has thus far hindered the robust chemical functionalization of these materials. Previous reports have required harsh chemical treatments or converting TMDCs into metallic phases prior to covalent attachment. Here, we demonstrate the direct covalent functionalization of the basal planes of unmodified semiconducting MoS2 using aryl diazonium salts without any pretreatments. Our approach preserves the semiconducting properties of MoS2, results in covalent C-S bonds, is applicable to MoS2 derived from a range of different synthesis methods, and enables a range of different functional groups to be tethered directly to the MoS2 surface. Using density functional theory calculations including van der Waals interactions and atomic-scale scanning probe microscopy studies, we demonstrate a novel reaction mechanism in which cooperative interactions enable the functionalization to propagate along the MoS2 basal plane. The flexibility of this covalent chemistry employing the diverse aryl diazonium salt family is further exploited to tether active proteins to MoS2, suggesting future biological applications and demonstrating its use as a versatile and powerful chemical platform for enhancing the utility of semiconducting TMDCs
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