Nanostructuring Graphene by Dense Electronic Excitation

The ability to manufacture tailored graphene nanostructures is a key factor to fully exploit its enormous technological potential. We have investigated nanostructures created in graphene by swift heavy ion induced folding. For our experiments, single layers of graphene exfoliated on various substrates and freestanding graphene have been irradiated and analyzed by atomic force and high resolution transmission electron microscopy as well as Raman spectroscopy. We show that the dense electronic excitation in the wake of the traversing ion yields characteristic nanostructures each of which may be fabricated by choosing the proper irradiation conditions. These nanostructures include unique morphologies such as closed bilayer edges with a given chirality or nanopores within supported as well as freestanding graphene. The length and orientation of the nanopore, and thus of the associated closed bilayer edge, may be simply controlled by the direction of the incoming ion beam. In freestanding graphene, swift heavy ion irradiation induces extremely small openings, offering the possibility to perforate graphene membranes in a controlled way.Comment: 16 pages, 5 figures, submitted to Nanotechnolog

Rhodium-Complex-Functionalized and Polydopamine-Coated CdSe@CdS Nanorods for Photocatalytic NAD+ Reduction

[Image: see text] We report on a photocatalytic system consisting of CdSe@CdS nanorods coated with a polydopamine (PDA) shell functionalized with molecular rhodium catalysts. The PDA shell was implemented to enhance the photostability of the photosensitizer, to act as a charge-transfer mediator between the nanorods and the catalyst, and to offer multiple options for stable covalent functionalization. This allows for spatial proximity and efficient shuttling of charges between the sensitizer and the reaction center. The activity of the photocatalytic system was demonstrated by light-driven reduction of nicotinamide adenine dinucleotide (NAD(+)) to its reduced form NADH. This work shows that PDA-coated nanostructures present an attractive platform for covalent attachment of reduction and oxidation reaction centers for photocatalytic applications

Water-soluble ionic carbon nitride as unconventional stabilizer for highly catalytically active ultrafine gold nanoparticles

Ultrafine metal nanoparticles (NPs) hold promise for applications in many fields, including catalysis. However, ultrasmall NPs are typically prone to aggregation, which often leads to performance losses, such as severe deactivation in catalysis. Conventional stabilization strategies (e.g., immobilization, embedding, or surface modification by capping agents) are typically only partly effective and often lead to loss of catalytic activity. Herein, a novel type of stabilizers based on water-soluble ionic (K$^+$ and Na$^+$ containing) polymeric carbon nitride (i.e., K,Na-poly(heptazine imide) = K,Na-PHI) is reported that enables effective stabilization of highly catalytically active ultrafine (size of ∼2–3 nm) gold NPs. Experimental and theoretical comparative studies using different structural units of K,Na-PHI (i.e., cyanurate, melonate, cyamelurate) indicate that the presence of functionalized heptazine moieties is crucial for the synthesis and stabilization of small Au NPs. The K,Na-PHI-stabilized Au NPs exhibit remarkable dispersibility and outstanding stability even in solutions of high ionic strength, which is ascribed to more effective charge delocalization in the large heptazine units, resulting in more effective electrostatic stabilization of Au NPs. The outstanding catalytic performance of Au NPs stabilized by K,Na-PHI is demonstrated using the selective reduction of 4-nitrophenol to 4-aminophenol by NaBH$_4$ as a model reaction, in which they outperform even the benchmark “naked” Au NPs electrostatically stabilized by excess NaBH$_4$. This work thus establishes ionic carbon nitrides (PHI) as alternative capping agents enabling effective stabilization without compromising surface catalysis, and opens up a route for further developments in utilizing PHI-based stabilizers for the synthesis of high-performance nanocatalysts

Giant persistent photoconductivity in monolayer MoS2 field-effect transistors

Monolayer transition metal dichalcogenides (TMD) have numerous potential applications in ultrathin electronics and photonics. The exposure of TMD-based devices to light generates photo-carriers resulting in an enhanced conductivity, which can be effectively used, e.g., in photodetectors. If the photo-enhanced conductivity persists after removal of the irradiation, the effect is known as persistent photoconductivity (PPC). Here we show that ultraviolet light (λ = 365 nm) exposure induces an extremely long-living giant PPC (GPPC) in monolayer MoS2 (ML-MoS2) field-effect transistors (FET) with a time constant of ~30 days. Furthermore, this effect leads to a large enhancement of the conductivity up to a factor of 107. In contrast to previous studies in which the origin of the PPC was attributed to extrinsic reasons such as trapped charges in the substrate or adsorbates, we show that the GPPC arises mainly from the intrinsic properties of ML-MoS2 such as lattice defects that induce a large number of localized states in the forbidden gap. This finding is supported by a detailed experimental and theoretical study of the electric transport in TMD based FETs as well as by characterization of ML-MoS2 with scanning tunneling spectroscopy, high-resolution transmission electron microscopy, and photoluminescence measurements. The obtained results provide a basis for the defect-based engineering of the electronic and optical properties of TMDs for device applications

Molecularly engineered black phosphorus heterostructures with improved ambient stability and enhanced charge carrier mobility

Overcoming the intrinsic instability and preserving unique electronic properties are key challenges for the practical applications of black phosphorus (BP) under ambient conditions. Here, it is demonstrated that molecular heterostructures of BP and hexaazatriphenylene derivatives (BP/HATs) enable improved environmental stability and charge transport properties. The strong interfacial coupling and charge transfer between the HATs and the BP lattice decrease the surface electron density and protect BP sheets from oxidation, resulting in an excellent ambient lifetime of up to 21 d. Importantly, HATs increase the charge scattering time of BP, contributing to an improved carrier mobility of 97 cm2 V-1 s-1, almost three times of the pristine BP films, based on noninvasive THz spectroscopic studies. The film mobility is an order of magnitude larger than previously reported values in exfoliated 2D materials. The strategy opens up new avenues for versatile applications of BP sheets and provides an effective method for tuning the physicochemical properties of other air-sensitive 2D semiconductors

Assessment techniques, database design and software facilities for thermodynamics and diffusion

The purpose of this article is to give a set of recommendations to producers of assessed thermodynamic data, who may be involved in either the critical evaluation of limited chemical systems or the creation and dissemination of larger thermodynamic databases. Also, it is hoped that reviewers and editors of scientific publications in this field will find some of the information useful. Good practice in the assessment process is essential, particularly as datasets from many different sources may be combined together into a single database. With this in mind, we highlight some problems that can arise during the assessment process and we propose a quality assurance procedure. It is worth mentioning at this point, that the provision of reliable assessed thermodynamic data relies heavily on the availability of high quality experimental information. The different software packages for thermodynamics and diffusion are described here only briefly

Microscopic View on Short-Range Wetting at the Free Surface of the Binary Metallic Liquid Gallium-Bismuth: An X-ray Reflectivity and Square Gradient Theory Study

We present an x-ray reflectivity study of wetting at the free surface of the binary liquid metal gallium-bismuth (Ga-Bi) in the region where the bulk phase separates into Bi-rich and Ga-rich liquid phases. The measurements reveal the evolution of the microscopic structure of wetting films of the Bi-rich, low-surface-tension phase along different paths in the bulk phase diagram. A balance between the surface potential preferring the Bi-rich phase and the gravitational potential which favors the Ga-rich phase at the surface pins the interface of the two demixed liquid metallic phases close to the free surface. This enables us to resolve it on an Angstrom level and to apply a mean-field, square gradient model extended by thermally activated capillary waves as dominant thermal fluctuations. The sole free parameter of the gradient model, i.e. the so-called influence parameter, $\kappa$, is determined from our measurements. Relying on a calculation of the liquid/liquid interfacial tension that makes it possible to distinguish between intrinsic and capillary wave contributions to the interfacial structure we estimate that fluctuations affect the observed short-range, complete wetting phenomena only marginally. A critical wetting transition that should be sensitive to thermal fluctuations seems to be absent in this binary metallic alloy.Comment: RevTex4, twocolumn, 15 pages, 10 figure

Conversion of self-assembled monolayers into nanocrystalline graphene: Structure and electric transport

Graphene-based materials have been suggested for applications ranging from nanoelectronics to nanobiotechnology. However, the realization of graphene-based technologies will require large quantities of free-standing two-dimensional (2D) carbon materials with tuneable physical and chemical properties. Bottom-up approaches via molecular self-assembly have great potential to fulfil this demand. Here, we report on the fabrication and characterization of graphene made by electron-radiation induced cross-linking of aromatic self-assembled monolayers (SAMs) and their subsequent annealing. In this process, the SAM is converted into a nanocrystalline graphene sheet with well defined thickness and arbitrary dimensions. Electric transport data demonstrate that this transformation is accompanied by an insulator to metal transition that can be utilized to control electrical properties such as conductivity, electron mobility and ambipolar electric field effect of the fabricated graphene sheets. The suggested route opens broad prospects towards the engineering of free-standing 2D carbon materials with tuneable properties on various solid substrates and on holey substrates as suspended membranes.Comment: 30 pages, 5 figure