Chemical Tailoring of Functional Graphene-Based Nanocomposites by Simple Stacking, Cutting and Folding

Got your work cut out: Stacking, cutting, and folding have been demonstrated to be a viable approach for the fabrication of robust nanocomposites from large-area graphene films and polymers. This method opens up an effective route towards strong, durable, and multifunctional nanomaterials with fascinating properties

Graphene via Molecule-Assisted Ultrasound-Induced Liquid-Phase Exfoliation: A Supramolecular Approach

Graphene is a two-dimensional (2D) material holding unique optical, mechanical, thermal and electrical properties. The combination of these exceptional characteristics makes graphene an ideal model system for fundamental physical and chemical studies as well as technologically ground breaking material for a large range of applications. Graphene can be produced either following a bottom-up or top-down method. The former is based on the formation of covalent networks suitably engineered molecular building blocks undergoing chemical reaction. The latter takes place through the exfoliation of bulk graphite into individual graphene sheets. Among them, ultrasound-induced liquid-phase exfoliation (UILPE) is an appealing method, being very versatile and applicable to different environments and on various substrate types. In this chapter, we describe the recently reported methods to produce graphene via molecule-assisted UILPE of graphite, aiming at the generation of high-quality graphene. In particular, we will focus on the supramolecular approach, which consists in the use of suitably designed organic molecules during the UILPE of graphite. These molecules act as graphene dispersion-stabilizing agents during the exfoliation. This method relying on the joint effect of a solvent and ad hoc molecules to foster the exfoliation of graphite into graphene in liquid environment represents a promising and modular method toward the improvement of the process of UILPE in terms of the concentration and quality of the exfoliated material. Furthermore, exfoliations in aqueous and organic solutions are presented and discussed separately

Direct Photolithography on Molecular Crystals for High Performance Organic Optoelectronic Devices

Organic crystals are generated via the bottom-up self-assembly of molecular building blocks which are held together through weak noncovalent interactions. Although they revealed extraordinary charge transport characteristics, their labile nature represents a major drawback toward their integration in optoelectronic devices when the use of sophisticated patterning techniques is required. Here we have devised a radically new method to enable the use of photolithography directly on molecular crystals, with a spatial resolution below 300 nm, thereby allowing the precise wiring up of multiple crystals on demand. Two archetypal organic crystals, i.e., p-type 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (Dph-BTBT) nanoflakes and n-type N,N′-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8) nanowires, have been exploited as active materials to realize high-performance top-contact organic field-effect transistors (OFETs), inverter and p–n heterojunction photovoltaic devices supported on plastic substrate. The compatibility of our direct photolithography technique with organic molecular crystals is key for exploiting the full potential of organic electronics for sophisticated large-area devices and logic circuitries, thus paving the way toward novel applications in plastic (opto)electronics

Imine-Based Architectures at Surfaces and Interfaces: From Self-Assembly to Dynamic Covalent Chemistry in 2D

Within the last two decades, dynamic covalent chemistry (DCC) has emerged as an efficient and versatile strategy for the design and synthesis of complex molecular systems in solution. While early examples of supramolecularly assisted covalent synthesis at surfaces relied strongly on kinetically controlled reactions for post-assembly covalent modification, the DCC method takes advantage of the reversible nature of bond formation and allows the generation of the new covalently bonded structures under thermodynamic control. These structurally complex architectures obtained by means of DCC protocols offer a wealth of solutions and opportunities in the generation of new complex materials that possess sophisticated properties. In this focus review we examine the formation of covalently bonded imine-based discrete nanostructures as well as one-dimensional (1D) polymers and two-dimensional (2D) covalent organic frameworks (COFs) physisorbed on solid substrates under various experimental conditions, for example, under ultra-high vacuum (UHV) or at the solid–liquid interface. Scanning tunneling microscopy (STM) was used to gain insight, with a sub-nanometer resolution, into the structure and properties of those complex nanopatterns

Punctured Two-Dimensional Sheets for Harvesting Blue Energy

The challenges of global climate change and the world’s growing demand for energy have brought the need for new renewable energy sources to the top of the international community’s agenda. We have known for many centuries that energy is released upon mixing seawater and freshwater, yet it was just a few decades ago that it became clear how this energy can be converted into electricity instead of heat. As a result, the blue energy rush has raised and set new strategies in different science and technology sectors, leading to the construction of a new generation of plants and other technological investments. Among many approaches, pressure-retarded osmosis has emerged as a promising method to collect the largest amount of produced blue energy. In this Perspective, we highlight the advances in the development of ultrathin membranes based on two-dimensional materials. We discuss the most relevant synthetic methods devised to generate atomically thin membranes for pressure-retarded osmosis and retarded electrodialysis applications, and we provide some critical views on the greatest challenges in this thrilling research area

2D materials beyond graphene for high-performance energy storage applications

Energy crisis is one of the most urgent and critical issues in our modern society. Currently, there is an increasing demand for efficient, low-cost, light-weight, flexible and environmentally benign, small-, medium-, and large-scale energy storage devices, which can be used to power smart grids, portable electronic devices, and electric vehicles. Novel electrode materials, with a high energy density at high power are urgently needed for realizing high-performance energy storage devices. The recent development in the field of 2D materials, including both graphene and other layered systems, has shown promise for a wide range of applications. In particular, graphene analogues, due to their remarkable electrochemical properties, have shown great potential in energy-related applications. This review aims at providing an overview of current research and important advances on the development of 2D materials beyond graphene for supercapacitors and batteries. The major challenges to be tackled, and more generally the future directions in the field, are also highlighted

Direct Patterning of Organic Functional Polymers through Conventional Photolithography and Noninvasive Cross-Link Agents

A new technique for direct patterning of functional organic polymers using commercial photolithography setups with a minimal loss of the materials' performances is reported. This result is achieved through novel cross-link agents made by boron- and fluorine-containing heterocycles that can react between themselves upon UV- and white-light exposure

Self-organization of amino-acid-derived NDI assemblies into a nanofibrillar superstructure with humidity sensitive n-type semiconducting properties

The hierarchical self-assembly of L-tyrosine substituted naphthalenediimide has been explored in solution by NMR spectroscopy and in the solid-state by atomic force microscopy. Spontaneous non-covalent polymerisation led to the formation of a three-dimensional fibre-like supramolecular polymer with n-type semiconducting properties

Concentration-dependent supramolecular patterns of C3 and C2 symmetric molecules at the solid/liquid interface

Here we report on a scanning tunnelling microscopy (STM) investigation on the self-assembly of C3- and C2-symmetric molecules at the solution/graphite interface. 1,3,5-tris((E)-2-(pyridin-4-yl)vinyl)benzene and 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethane are used as model systems. These molecules displayed a concentration dependent self-assembly behaviour on graphite, resulting in highly ordered supramolecular structures, which are stabilized jointly by van der Waals substrate-adsorbate interactions and in-plane intermolecular H-bonding. Denser packing is obtained when applying a relatively high concentration solution to the basal plane of the surface whereas a less dense porous network is observed upon lowering the concentration. We show that the molecular conformation does not influence the stability of the self-assembly and a twisted molecule can pack into dense and porous architectures under the concentration effect

High-Performance Phototransistors Based on PDIF-CN2 Solution-Processed Single Fiber and Multifiber Assembly

Here we describe the fabrication of organic phototransistors based on either single or multifibers integrated in three-terminal devices. These self-assembled fibers have been produced by solvent-induced precipitation of an air stable and solution-processable perylene di-imide derivative, i.e., PDIF-CN2. The optoelectronic properties of these devices were compared to devices incorporating more disordered spin-coated PDIF-CN2 thin-films. The single-fiber devices revealed significantly higher field-effect mobilities, compared to multifiber and thin-films, exceeding 2 cm2 V–1 s–1. Such an efficient charge transport is the result of strong intermolecular coupling between closely packed PDIF-CN2 molecules and of a low density of structural defects. The improved crystallinity allows efficient collection of photogenerated Frenkel excitons, which results in the highest reported responsivity (R) for single-fiber PDI-based phototransistors, and photosensitivity (P) exceeding 2 × 103 AW–1, and 5 × 103, respectively. These findings provide unambiguous evidence for the key role played by the high degree of order at the supramolecular level to leverage the material’s properties toward the fabrication of light-sensitive organic field-effect transistors combining a good operational stability, high responsivity and photosensitivity. Our results show also that the air-stability performances are superior in devices where highly crystalline supramolecularly engineered architectures serve as the active layer