Tailored Design of a Water-Based Nanoreactor Technology for Producing Processable Sub-40 Nm 3D COF Nanoparticles at Atmospheric Conditions.

Covalent organic frameworks (COFs) are crystalline materials with intrinsic porosity that offer a wide range of potential applications spanning diverse fields. Yet, the main goal in the COF research area is to achieve the most stable thermodynamic product while simultaneously targeting the desired size and structure crucial for enabling specific functions. While significant progress is made in the synthesis and processing of 2D COFs, the development of processable 3D COF nanocrystals remains challenging.

Covalent transfer of chemical gradients onto a graphenic surface with 2D and 3D control.

Control over the functionalization of graphenic materials is key to enable their full application in electronic and optical technologies. Covalent functionalization strategies have been proposed as an approach to tailor the interfaces' structure and properties. However, to date, none of the proposed methods allow for a covalent functionalization with control over the grafting density, layer thickness and/or morphology, which are key aspects for fine-tuning the processability and performance of graphenic materials.

Iron Oxyhydroxide-Covalent Organic Framework Nanocomposite for Efficient As(III) Removal in Water.

The presence of heavy metal ions in water is an environmental issue derived mainly from industrial and mineral contamination. Metal ions such as Cd(II), Pb(II), Hg(II), or As(III) are a significant health concern worldwide because of their high toxicity, mobility, and persistence. Covalent organic frameworks (COFs) are an emerging class of crystalline organic porous materials that exhibit very interesting properties such as chemical stability, tailored design, and low density.

Synthesis of 2D Porous Crystalline Materials in Simulated Microgravity.

To date, crystallization studies conducted in space laboratories, which are prohibitively costly and unsuitable to most research laboratories, have shown the valuable effects of microgravity during crystal growth and morphogenesis. Herein, an easy and highly efficient method is shown to achieve space-like experimentation conditions on Earth employing custom-made microfluidic devices to fabricate 2D porous crystalline molecular frameworks. It is confirmed that experimentation under these simulated microgravity conditions has unprecedented effects on the orientation, compactness and crack-free generation of 2D porous crystalline molecular frameworks as well as in their integration and crystal morphogenesis.

Macroscopic Ultralight Aerogel Monoliths of Imine-based Covalent Organic Frameworks.

The use of covalent organic frameworks (COFs) in practical applications demands shaping them into macroscopic objects, which remains challenging. Herein, we report a simple three-step method to produce COF aerogels, based on sol-gel transition, solvent-exchange, and supercritical CO drying, in which 2D imine-based COF sheets link together to form hierarchical porous structures. The resultant COF aerogel monoliths have extremely low densities (ca.

Exfoliation of Alpha-Germanium: A Covalent Diamond-Like Structure.

2D materials have opened a new field in materials science with outstanding scientific and technological impact. A largely explored route for the preparation of 2D materials is the exfoliation of layered crystals with weak forces between their layers. However, its application to covalent crystals remains elusive.

SERS Barcode Libraries: A Microfluidic Approach.

Microfluidic technologies have emerged as advanced tools for surface-enhanced Raman spectroscopy (SERS). They have proved to be particularly appealing for in situ and real-time detection of analytes at extremely low concentrations and down to the 10 × 10 m level. However, the ability to prepare reconfigurable and reusable devices endowing multiple detection capabilities is an unresolved challenge.

Green synthesis of imine-based covalent organic frameworks in water.

Dynamic covalent bonds have been advantageously used to direct the synthesis of crystalline porous covalent organic frameworks (COFs). Unlike the standard synthetic protocols that involve harsh conditions, this work provides a high-yield "one-pot" green synthesis of imine-based COFs in water. Additionally, this aqueous synthesis can be performed under microwave conditions, considerably reducing the reaction time.

Biomimetic Synthesis of Sub-20 nm Covalent Organic Frameworks in Water.

Covalent organic frameworks (COFs) are commonly synthesized under harsh conditions yielding unprocessable powders. Control in their crystallization process and growth has been limited to studies conducted in hazardous organic solvents. Herein, we report a one-pot synthetic method that yields stable aqueous colloidal solutions of sub-20 nm crystalline imine-based COF particles at room temperature and ambient pressure.

Processing of covalent organic frameworks: an ingredient for a material to succeed.

Covalent organic frameworks (COFs) are an emerging class of new organic polymers showing tuneable permanent porosity and crystallinity. They are formed, using modular chemistry concepts, by condensation reactions between their molecular precursors based on the formation of dynamic bonds. Despite much effort having been devoted towards the design of the physical and/or chemical properties of these materials by selecting their initial building blocks, the importance of processability for their applications has only recently emerged.

Spray drying for making covalent chemistry II: synthesis of covalent-organic framework superstructures and related composites.

Here we report a method that combines the spray-drying technique with a dynamic covalent chemistry process to synthesize zero-dimensional, spherical and microscale superstructures made from the assembly of imine-based COF nanocrystals. This methodology also enables the integration of other functional materials into these superstructures forming COF-based composites.

Noncovalent Functionalization and Charge Transfer in Antimonene.

Antimonene, a novel group 15 two-dimensional material, is functionalized with a tailormade perylene bisimide through strong van der Waals interactions. The functionalization process leads to a significant quenching of the perylene fluorescence, and surpasses that observed for either graphene or black phosphorus, thus allowing straightforward characterization of the flakes by scanning Raman microscopy. Furthermore, scanning photoelectron microscopy studies and theoretical calculations reveal a remarkable charge-transfer behavior, being twice that of black phosphorus.

Microfluidic-based Synthesis of Covalent Organic Frameworks (COFs): A Tool for Continuous Production of COF Fibers and Direct Printing on a Surface.

Covalent Organic Frameworks (COFs) are a class of porous covalent materials which are frequently synthesized as unprocessable crystalline powders. The first COF was reported in 2005 with much effort centered on the establishment of new synthetic routes for its preparation. To date, most available synthetic methods for COF synthesis are based on bulk mixing under solvothermal conditions.

Ionic Conductivity and Potential Application for Fuel Cell of a Modified Imine-Based Covalent Organic Framework.

We present the novel potential application of imine-based covalent organic frameworks (COFs), formed by the direct Schiff reaction between 1,3,5-tris(4-aminophenyl)benzene and 1,3,5-benzenetricarbaldehyde building blocks in m-cresol or acetic acid, named RT-COF-1 or RT-COF-1Ac/RT-COF-1AcB. The post-synthetic treatment of RT-COF-1 with LiCl leads to the formation of LiCl@RT-COF-1. The ionic conductivity of this series of polyimine COFs has been characterized at variable temperature and humidity, using electrochemical impedance spectroscopy.

Few-Layer Antimonene by Liquid-Phase Exfoliation.

We report on a fast and simple method to produce highly stable isopropanol/water (4:1) suspensions of few-layer antimonene by liquid-phase exfoliation of antimony crystals in a process that is assisted by sonication but does not require the addition of any surfactant. This straightforward method generates dispersions of few-layer antimonene suitable for on-surface isolation. Analysis by atomic force microscopy, scanning transmission electron microscopy, and electron energy loss spectroscopy confirmed the formation of high-quality few-layer antimonene nanosheets with large lateral dimensions.

Antimonene: Mechanical Isolation of Highly Stable Antimonene under Ambient Conditions (Adv. Mater. 30/2016).

On page 6332, J. Gómez-Herrero, F. Zamora, and co-workers describe the isolation of antimonene, a new allotrope of antimony that consists of a single layer of atoms.

Crystalline fibres of a covalent organic framework through bottom-up microfluidic synthesis.

A microfluidic chip has been used to prepare fibres of a porous polymer with high structural order, setting a precedent for the generation of a wide variety of materials using this reagent mixing approach that provides unique materials not accessible easily through bulk processes. The reaction between 1,3,5-tris(4-aminophenyl)benzene and 1,3,5-benzenetricarbaldehyde in acetic acid under continuous microfluidic flow conditions leads to the formation of a highly crystalline and porous covalent organic framework (hereafter denoted as MF-COF-1), consisting of fibrillar micro-structures, which have mechanical stability that allows for direct drawing of objects on a surface.

Mechanical Isolation of Highly Stable Antimonene under Ambient Conditions.

Antimonene fabricated by mechanical exfoliation is highly stable under atmospheric conditions over periods of months and even when immersed in water. Density functional theory confirms the experiments and predicts an electronic gap of ≈1 eV. These results highlight the use of antimonene for optoelectronics applications.

Direct On-Surface Patterning of a Crystalline Laminar Covalent Organic Framework Synthesized at Room Temperature.

We report herein an efficient, fast, and simple synthesis of an imine-based covalent organic framework (COF) at room temperature (hereafter, RT-COF-1). RT-COF-1 shows a layered hexagonal structure exhibiting channels, is robust, and is porous to N2 and CO2 . The room-temperature synthesis has enabled us to fabricate and position low-cost micro- and submicropatterns of RT-COF-1 on several surfaces, including solid SiO2 substrates and flexible acetate paper, by using lithographically controlled wetting and conventional ink-jet printing.