Pseudohexagonal 2D DNA crystals from double crossover cohesion

Two-dimensional pseudohexagonal trigonal arrays have been constructed by self-assembly from DNA. The motif used is a bulged-junction DNA triangle whose edges and extensions are DNA double crossover (DX) molecules, rather than conventional DNA double helices. Experiments were performed to establish whether the success of this system results from the added stiffness of DX molecules or the presence of two sticky ends at the terminus of each edge. Removal of one sticky end precludes lattice formation, suggesting that it is the double sticky end that is the primary factor enabling lattice formation.     

Dehydroxylation kinetic and exfoliation of large muscovite flakes

The thermal transformations of muscovite flakes are a key point in many applications because besides dehydroxylation a significant exfoliation process occurs. Dehydroxylation kinetic is experimented by isothermal TG analyses in the 700–850°C temperature range and described with the Avrami theory. Hydroxyl condensation predominates at the onset of the process, but water diffusion is the most important process when the transformed fraction is high. The progressive transition between the two transformation stages contrast with the more accentuated transition for a ground muscovite. The activation energy varies weakly (190–214 kJ mol⁻¹) in the whole transformation process that supports the co-existence of hydroxyl condensation and diffusion phenomena. Dehydroxylation kinetic increases strongly with temperature and decreases with the reaction advancement. Exfoliation is correlated with dehydroxylation kinetic and occurs in a narrow transformation and temperature ranges. An in-situ combination process of hydroxyls occurs and water vapor favors the layer expansion.     

A simple self-assembly method for colloidal photonic crystals with a large area

Colloidal photonic crystals were fabricated using polystyrene particles (180 nm) and PMMA particles (450 nm), respectively, with a new and simple self-assembly method without special equipment. SEM images indicate that the prepared samples have ordered structures with few defects. The position of the stop-band scale nicely agrees with the particles' size. The sintering process of the PS photonic crystal film was studied with AFM heating system.     

Ensuring homology between 2D and 3D molecular crystals

Integrated studies using scanning tunneling microscopy and X-ray crystallography have established that 4,5,9,10-tetrahydropyrene-2,7-dicarboxylic acid and pyrene-2,7-dicarboxylic acid crystallize in 2D and 3D with striking homology. Different behavior is shown by related biphenyls that lack the planarizing conformational constraints of the pyrenyl core and the directing effects of intermolecular hydrogen bonding. The results of these studies show that molecules specifically designed to engage in multiple strong directional interadsorbate interactions are promising tools for imposing particular nanopatterns on surfaces and for revealing subtle aspects of crystallization.     

Macroporous Au materials prepared from colloidal crystals as templates

In this paper, we reported the preparation of macroporous Au materials using organic colloidal crystals as templates and their catalytic activity for electroless copper deposition. The poly(styrene-methyl methacrylate-acrylic acid) (P(St-MMA-AA)) copolymer colloids were deposited in an orderly manner onto the silicon surface, together with the infiltration of the Au nanoparticles into the interspaces of the colloids. The formed hybrid colloidal crystal subsequently was sintered at approximately 550 degrees C to remove the organic components fully to obtain a macroporous Au framework with three-dimensional ordered porous structure. The pore diameter was around 310 nm and almost monodisperse. It was demonstrated that the macroporous Au materials exhibit catalytic activity and can induce electroless copper deposition.     

Functionalization of 2D materials by intercalation

Since the discovery of graphene many studies focused on its functionalization by different methods. These strategies aim to find new pathways to overcome the main drawback of graphene, a missing band-gap, which strongly reduces its potential applications, particularly in the domain of nanoelectronics, despite its huge and unequaled charge carrier mobility. The necessity to contact this material with a metal has motivated a lot of studies of metal/graphene interactions and has led to the discovery of the intercalation process very early in the history of graphene. Intercalation, where the deposited atoms do not stay at the graphene surface but intercalate between the top layer and the substrate, may happen at room temperature or be induced by annealing, depending of the chemical nature of the metal. This kind of mechanism was already well-known in the earlier Graphite Intercalation Compounds (GICs), particularly famous for one current application, the Lithium-ion Battery, which is simply an application based on the intercalation of Lithium atoms between two sheets of graphene in a graphite anode. Among numerous discoveries the GICs community also found a way to obtain graphite with superconducting properties by using intercalated alkali metals. Graphene is now a playground to “revisit” and understand all these mechanisms and to discover possible new properties of graphene induced by intercalation. For example, the intercalation process may be used to decouple the graphene layer from its substrate, to change its doping level or even, in a more general way, to modify its electronic band structure and the nature of its Dirac fermions. In this paper we will focus on the functionalization of graphene by using intercalation of metal atoms but also of molecules. We will give an overview of the induced modifications of the electronic band structure possibly leading to spin-orbit coupling, superconductivity, …We will see how this concept of functionalization is also now used in the framework of other 2D materials beyond graphene and of van der Waals heterostructures based on these materials.     

Mechanical mixing of molecular crystals

Supramolecular reactions between crystalline materials can be exploited to prepare both hydrogen bonded co-crystals and coordination networks. Mechanical mixing of molecular crystals as well as kneading provide an alternative, solvent-free, route to novel materials hence these methods represent a green route to supramolecular solid-state chemistry.     

Dielectrophoretic assembly of grain-boundary-free 2D colloidal single crystals

Dielectrophoresis (DEP) force-assisted assembly of a colloidal single photonic-crystal monolayer in a microfluidic chamber was demonstrated. Negative DEP force with a high-frequency AC electric field induced the compression of colloidal microspheres to form a colloidal crystal domain at the center of a hexapolar-shaped electrode. While typical assembly by monotonic DEP force forms multicrystalline domains containing crystal defects, repetitions of the DEP/relaxation cycle significantly facilitated crystal growth of 10μm monodispersed polystyrene microspheres, allowing a grain-boundary-free single-crystal monolayer domain of ca. 200μm in size. Microsphere size as well as size distribution affected the formation of the single-crystal domain. A simple method was used to immobilize the single-crystal domain on the glass substrate without losing its crystallinity.     

Polystyrene@TiO2 core-shell microsphere colloidal crystals and nonspherical macro-porous materials

High-quality and stable PS@TiO(2) core-shell microsphere colloidal crystals were prepared by electrostatic colloid stabilization combined with two-substrate vertical deposition method. The polyelectrolyte stabilized colloids self-assembled into face-centered cubic arrays with the (111) face perpendicular to the substrate. These colloidal crystals are gifted with high mechanical stability toward the flow of solution. Structure-property correlations were made using scanning electron microscopy and UV-vis-NIR spectroscopy. Optical spectra showed the presence of an L-stopband peak in the photonic band structure. Besides, these PS@TiO(2) colloidal crystals can be used as templates to fabricate the nonspherical macro-porous materials, and complete band gaps can be more easily obtained from such structure than from their spherical counterparts due to their lower symmetries. This work will hold the promise of enhanced photonic band gap materials.     

2D framework materials for energy applications

In recent years a massive increase in publications on conventional 2D materials (graphene, h-BN, MoS₂) is documented, accompanied by the transfer of the 2D concept to porous (crystalline) materials, such as ordered 2D layered polymers, covalent-organic frameworks, and metal–organic frameworks. Over the years, the 3D frameworks have gained a lot of attention for use in applications, ranging from electronic devices to catalysis, and from information to separation technologies, mostly due to the modular construction concept and exceptionally high porosity. A key challenge lies in the implementation of these materials into devices arising from the deliberate manipulation of properties upon delamination of their layered counterparts, including an increase in surface area, higher diffusivity, better access to surface sites and a change in the band structure. Within this minireview, we would like to highlight recent achievements in the synthesis of 2D framework materials and their advantages for certain applications, and give some future perspectives.

In recent years the 2D concept has been transferred from conventional 2D materials to porous 2D framework materials. This minireview takes a closer look onto the preparation of 2D framework materials and their merits for energy applications.     

Strain of 2D materials via substrate engineering

Two-dimensional(2D) materials have received extensive attention in the fields of electronics, optoelectronics, and magnetic devices attributed to their unique electronic structures and physical properties. The application of strain is a simple and effective strategy to change the lattice structure of 2D materials thus modulating their physical properties, which further facilitate their applications in carrier mobility transistor, magnetic sensor, single-photon emitter etc. In this short review, ...     

Roll‐to‐Roll fabrication of large area functional organic materials

With the prospect of extremely fast manufacture of very low cost devices, organic electronics prepared by thin film processing techniques that are compatible with roll‐to‐roll (R2R) methods are presently receiving an increasing interest. Several technologies using organic thin films are at the point, where transfer from the laboratory to a more production‐oriented environment is within reach. In this review, we aim at giving an overview of some of the R2R‐compatible techniques that can be used in such a transfer, as well the current status of R2R application within some of the existing research fields such as organic photovoltaics, organic thin film transistors, light‐emitting diodes, polymer electrolyte membrane fuel cells, and electrochromic devices. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Janus 2D materials via asymmetric molecular functionalization

Janus two-dimensional materials (2DMs) are a novel class of 2DMs in which the two faces of the material are either asymmetrically functionalized or are exposed to a different local environment. The diversity of the properties imparted to the two opposing sides enables the design of new multifunctional materials for applications in a broad variety of fields including opto-electronics, energy storage, and catalysis. In this perspective, we summarize the most enlightening experimental methods for the asymmetric chemical functionalization of 2DMs with tailored made (macro)molecules by means of a supratopic binding (one side) or antaratopic binding (two sides) process. We describe the emergence of unique electrical and optical characteristics resulting from the asymmetric dressing of the two surfaces. Representative examples of Janus 2DMs towards bandgap engineering, enhanced photoresponse and photoluminescence are provided. In addition, examples of Janus 2DMs for real applications such as energy storage (batteries and supercapacitors) and generation (photovoltaics), opto-electronics (field-effect transistors and photodetectors), catalysis, drug delivery, self-healing materials, chemical sensors and selective capture and separation of small molecules are also described. Finally, we discuss the future directions, challenges, and opportunities to expand the frontiers of Janus 2DMs towards technologies with potential impact in environmental science and biomedical applications.

The asymmetric molecular functionalization of two-dimensional materials on one (supratopic) or both (antaratopic) faces enables the design of new multifunctional Janus materials for applications in opto-electronics, energy storage, and catalysis.     

2D mapping by Kohonen networks of the air quality data from a large city

The 15-variable environmental data (7 concentrations: CO, SO2, O3, NOx, NO, NO2, particulate matter smaller than 10 micron (PM10), and 8 weather data: cloudiness, rainfall, insolation factor (Isfi), temperature, pressure at two locations, and wind intensity with direction) in a period of 45 days with 1-h intervals were extracted from a larger database of concentrations recorded in minute intervals for the same time period. The monitoring site was located in the City of Buenos Aires in a relatively heavy traffic crossroad of two avenues. The data required special pretreatment where the hourly content of rain, wind intensity, wind velocity, and cloudiness were concerned. The new variable named insolation factor (relative UV radiation) calculated on the basis of the general meteorological data, the geographic position of the monitoring site, cloudiness, date, and the time of the recording was composed. The relative intensity of UV radiation was modeled by a Gaussian function, multiplied by a cloudiness factor. Based on the 14-variable input and the 1-variable output (ozone) data, first, the clustering of all 980 data records was made. The top map clustering showing the ozone concentration was related to the maps of all 14 variables. The link between O3 clusters, NO2, and Isfi weight levels is shown and discussed. As a preliminary result of this study some of the most interesting correlations between the maps and remaining variables are given.     

Self-assembled colloidal crystals from ZrO2 nanoparticles

Ordered three-dimensional (3-D) assemblies of nanocrystalline zirconia were synthesized from aqueous suspensions of ZrO(2) nanoparticles without the need for hydrocarbon surfactants or solvents to control colloidal crystal growth. Nanoparticles were suspended in mild acid and subsequently titrated from low to neutral pH. The solubility was reduced as the surfaces were neutralized, promoting assembly of the nanoparticles into ordered monoliths. TEM measurements indicated the formation of three-dimensional, hexagonal faceted, micrometer-sized colloidal crystals composed of 4 nm diameter ZrO(2) nanoparticles. Lacking organic surfactants, the colloidal crystals were exceptionally robust and were sintered at high temperatures (300-500 degrees C) for further stability. Small-angle X-ray scattering (SAXS) measurements demonstrate that the samples become progressively more amorphous above 350 degrees C, although some ordered domains of nanoparticles persist. Additionally, the heat treatment dramatically increases the surface area of the colloidal crystals as water and residual organics are desorbed, revealing highly controlled interstitial spaces and pores.     

Formation of extraordinarily large nanosheets from K4Nb6O17 crystals

Exfoliated K4Nb6O17 bilayer nanosheets in extraordinarily large size (ca. 100 microns) were prepared by the direct reaction of K4Nb6O17.3H2O crystals with an aqueous solution of propylamine; the size was extremely larger than that of exfoliated nanosheets (several microns) reported previously.     

Recent progress in 2D materials for flexible supercapacitors

High performance supercapacitors coupled with mechanical flexibility are needed to drive flexible and wearable electronics that have anesthetic appeal and multi-functionality. Two dimensional (2D) materials have attracted attention owing to their unique physicochemical and electrochemical properties, in addition to their ability to form hetero-structures with other nanomaterials further improving mechanical and electrochemical properties. After a brief introduction of supercapacitors and 2D materials, recent progress on flexible supercapacitors using 2D materials is reviewed. Here we provide insights into the structure–property relationships of flexible electrodes, in particular free-standing films. We also present our perspectives on the development of flexible supercapacitors.     

Stimuli-responsive 2D polyelectrolyte photonic crystals for optically encoded pH sensing

A versatile photonic crystal sensing motif based on a two-dimensional (2D) inverse opal monolayer of stimuli-responsive polyelectrolyte gel with tunable optical properties is reported. The photonic membrane shows prompt response to pH and can be readily read out from either its optical spectra or interference colours.     

High surface area V-Mo-N materials synthesized from amine intercalated foams

Nanocrystalline ternary V-Mo nitrides were prepared via nitridation of amine intercalated oxide foams or bulk ternary oxides. Specific surface areas were in the range between 40 and 198 m² g⁻¹ and strongly depended on the preparation method (foam or bulk oxide). Foamed precursors were favorable for vanadium rich materials, while for molybdenum rich samples bulk ternary oxides resulted in higher specific surface areas. The materials were characterized via nitrogen physisorption at 77 K, X-ray diffraction patterns, electron microscopy, and elemental analysis.