Covalent Organic Framework Membranes and Water Treatment.

Covalent organic frameworks (COFs) are an emerging class of highly porous crystalline organic polymers comprised entirely of organic linkers connected by strong covalent bonds. Due to their excellent physicochemical properties (e.g., ordered structure, porosity, and stability), COFs are considered ideal materials for developing state-of-the-art separation membranes. In fact, significant advances have been made in the last six years regarding the fabrication and functionalization of COF membranes. In particular, COFs have been utilized to obtain thin-film, composite, and mixed matrix membranes that could achieve effective rejection (mostly above 80%) of organic dyes and model organic foulants (e.g., humic acid). COF-based membranes, especially those prepared by embedding into polyamide thin-films, obtained adequate rejection of salts in desalination applications. However, the claims of ordered structure and separation mechanisms remain unclear and debatable. In this perspective, we analyze critically the design and exploitation of COFs for membrane fabrication and their performance in water treatment applications. In addition, technological challenges associated with COF properties, fabrication methods, and treatment efficacy are highlighted to redirect future research efforts in realizing highly selective separation membranes for scale-up and industrial applications.

Scalable Design of Ru-Embedded Carbon Fabric Using Conventional Carbon Fiber Processing for Robust Electrocatalysts.

Metal-carbon composites are extensively utilized as electrochemical catalysts but face critical challenges in mass production and stability. We report a scalable manufacturing process for ruthenium surface-embedded fabric electrocatalysts (Ru-SFECs) via conventional fiber/fabric manufacturing. Ru-SFECs have excellent catalytic activity and stability toward the hydrogen evolution reaction, exhibiting a low overpotential of 11.9 mV at a current density of 10 mA cm-2 in an alkaline solution (1.0 M aq KOH solution) with only a slight overpotential increment (6.5%) after 10,000 cycles, whereas under identical conditions, that of commercial Pt/C increases 6-fold (from 1.3 to 7.8 mV). Using semipilot-scale equipment, a protocol is optimized for fabricating continuous self-supported electrocatalytic electrodes. Tailoring the fiber processing parameters (tension and temperature) can optimize the structural development, thereby achieving good catalytic performance and mechanical integrity. These findings underscore the significance of self-supporting catalysts, offering a general framework for stable, binder-free electrocatalytic electrode design.

Crystalline Porphyrazine-Linked Fused Aromatic Networks with High Proton Conductivity.

Fused aromatic networks (FANs) have been studied in efforts to overcome the low physicochemical stability of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), while preserving crystallinity. Herein, we describe the synthesis of a highly stable and crystalline FAN (denoted as Pz-FAN) using pyrazine-based building blocks to form porphyrazine (Pz) linkages via an irreversible reaction. Unlike most COFs and FANs, which are synthesized from two different building blocks, the new Pz-FAN is formed using a single building block by self-cyclotetramerization. Controlled and optimized reaction conditions result in a highly crystalline Pz-FAN with physicochemical stability. The newly prepared Pz-FAN displayed a high magnitude (1.16×10-2  S cm-1 ) of proton conductivity compared to other reported FANs and polymers. Finally, the Pz-FAN-based membrane was evaluated for a proton-exchange membrane fuel cell (PEMFC), which showed maximum power and current densities of 192 mW cm-2 and 481 mA cm-2 , respectively.

Synthesis of Saddle-Shape Octaaminotetraphenylene Octahydrochloride.

Apart from being experimentally and theoretically interesting, tetraphenylene has potential applications in different fields, including supramolecular chemistry, material science, and asymmetric catalysis. Although a wide range of substituted tetraphenylenes have been reported, octaamine-based tetraphenylene derivatives have not been reported because of their instability. Here, stable octaaminotetraphenylene octahydrochloride is synthesized from the bromination of tetraphenylene to octabromotetraphenylene, which is subsequently aminated into octaiminotetraphenylene. Finally, the imino derivative is deprotected to yield octaaminotetraphenylene octahydrochloride.

Two-dimensional polyaniline (C3N) from carbonized organic single crystals in solid state.

The formation of 2D polyaniline (PANI) has attracted considerable interest due to its expected electronic and optoelectronic properties. Although PANI was discovered over 150 y ago, obtaining an atomically well-defined 2D PANI framework has been a longstanding challenge. Here, we describe the synthesis of 2D PANI via the direct pyrolysis of hexaaminobenzene trihydrochloride single crystals in solid state. The 2D PANI consists of three phenyl rings sharing six nitrogen atoms, and its structural unit has the empirical formula of C3N. The topological and electronic structures of the 2D PANI were revealed by scanning tunneling microscopy and scanning tunneling spectroscopy combined with a first-principle density functional theory calculation. The electronic properties of pristine 2D PANI films (undoped) showed ambipolar behaviors with a Dirac point of -37 V and an average conductivity of 0.72 S/cm. After doping with hydrochloric acid, the conductivity jumped to 1.41 × 10(3) S/cm, which is the highest value for doped PANI reported to date. Although the structure of 2D PANI is analogous to graphene, it contains uniformly distributed nitrogen atoms for multifunctionality; hence, we anticipate that 2D PANI has strong potential, from wet chemistry to device applications, beyond linear PANI and other 2D materials.

Defect-Free Encapsulation of Fe0 in 2D Fused Organic Networks as a Durable Oxygen Reduction Electrocatalyst.

Because they provide lower cost but comparable activity to precious platinum (Pt)-based catalysts, nonprecious iron (Fe)-based materials, such as Fe/Fe3C and Fe-N-C, have gained considerable attention as electrocatalysts for the oxygen reduction reaction (ORR). However, their practical application is hindered by their poor stability, which is attributed to the defective protection of extremely unstable Fe nanoparticles. Here, we introduce a synthesis strategy for a stable Fe-based electrocatalyst, which was realized by defect-free encapsulation of Fe nanoparticles using a two-dimensional (2D) phenazine-based fused aromatic porous organic network (Aza-PON). The resulting Fe@Aza-PON catalyst showed electrocatalytic activity (half-wave potential, 0.839 V; Tafel slope, 60 mV decade-1) comparable to commercial Pt on activated carbon (Pt/C, 0.826 V and 90 mV decade-1). More importantly, the Fe@Aza-PON displayed outstanding stability (zero current loss even after 100 000 cycles) and tolerance against contamination (methanol and CO poisoning). In a hybrid Li-air battery test, the Fe@Aza-PON demonstrated performance superior to Pt/C.

Molybdenum-Based Carbon Hybrid Materials to Enhance the Hydrogen Evolution Reaction.

Hydrogen is considered a future energy carrier that could improve energy storage of intermittent solar/wind power to solve energy and environmental problems. Based on such demand, development of electrocatalysts for hydrogen generation has been actively pursued. Although Pt is the most efficient catalyst for the hydrogen evolution reaction (HER), it has limits for widespread application, mainly its low abundance and high cost. Thus, developing an efficient catalyst from non-precious metals that are abundant and inexpensive remains an important challenge to replacement of Pt. Transition metals have been considered possible candidates to replace Pt-based catalysts. In this review, among the transition metals, we focus on recently developed molybdenum-carbon (Mo-C) hybrid materials as electrocatalysts for HER. In particular, the synthesis strategy for Mo-C hybrid electrocatalysts and the role of various carbon nanocomposites in Mo-C hybrid systems are highlighted.

A Robust 3D Cage-like Ultramicroporous Network Structure with High Gas-Uptake Capacity.

A three-dimensional (3D) cage-like organic network (3D-CON) structure synthesized by the straightforward condensation of building blocks designed with gas adsorption properties is presented. The 3D-CON can be prepared using an easy but powerful route, which is essential for commercial scale-up. The resulting fused aromatic 3D-CON exhibited a high Brunauer-Emmett-Teller (BET) specific surface area of up to 2247 m2 g-1 . More importantly, the 3D-CON displayed outstanding low pressure hydrogen (H2 , 2.64 wt %, 1.0 bar and 77 K), methane (CH4 , 2.4 wt %, 1.0 bar and 273 K), and carbon dioxide (CO2 , 26.7 wt %, 1.0 bar and 273 K) uptake with a high isosteric heat of adsorption (H2 , 8.10 kJ mol-1 ; CH4 , 18.72 kJ mol-1 ; CO2 , 31.87 kJ mol-1 ). These values are among the best reported for organic networks with high thermal stability (ca. 600 °C).

Direct Synthesis of a Covalent Triazine-Based Framework from Aromatic Amides.

There have been extensive efforts to synthesize crystalline covalent triazine-based frameworks (CTFs) for practical applications and to realize their potential. The phosphorus pentoxide (P2 O5 )-catalyzed direct condensation of aromatic amide instead of aromatic nitrile to form triazine rings. P2 O5 -catalyzed condensation was applied on terephthalamide to construct a covalent triazine-based framework (pCTF-1). This approach yielded highly crystalline pCTF-1 with high specific surface area (2034.1 m2 g-1 ). At low pressure, the pCTF-1 showed high CO2 (21.9 wt % at 273 K) and H2 (1.75 wt % at 77 K) uptake capacities. The direct formation of a triazine-based COF was also confirmed by model reactions, with the P2 O5 -catalyzed condensation reaction of both benzamide and benzonitrile to form 1,3,5-triphenyl-2,4,6-triazine in high yield.

Porous Cobalt Phosphide Polyhedrons with Iron Doping as an Efficient Bifunctional Electrocatalyst.

Iron (Fe)-doped porous cobalt phosphide polyhedrons are designed and synthesized as an efficient bifunctional electrocatalyst for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The synthesis strategy involves one-step route for doping foreign metallic element and forming porous cobalt phosphide polyhedrons. With varying doping levels of Fe, the optimized Fe-doped porous cobalt phosphide polyhedron exhibits significantly enhanced HER and OER performances, including low onset overpotentials, large current densities, as well as small Tafel slopes and good electrochemical stability during HER and OER.

Unusually Stable Triazine-based Organic Superstructures.

Solid-state reactions have been rapidly gaining popularity in organic chemistry owing to their simplicity, efficiency, and selectivity compared to liquid-phase reactions. Herein, we describe the formation of superstructures through the solid-state reaction of an organic single-crystal. The superstructure of 5,5',5''-(1,3,5-triazine-2,4,6-triyl)triisophthalonitrile (TIPN) can be formed by cyclotrimerization of 1,3,5-tricyanobenzene (TCB) single crystals. The TIPN superstructure was confirmed by single crystal X-ray diffraction and visualized by transmission electron microscopy. The superstructure has hexagonally packed 1-dimensional (1D) channels along the crystal axis. Furthermore, the superstructure arises from interdigitated nitrile interactions in the crystal lattice, and thus has electron-beam tolerance and very high thermal stability.

Edge-carboxylated graphene nanosheets via ball milling.

Low-cost, high-yield production of graphene nanosheets (GNs) is essential for practical applications. We have achieved high yield of edge-selectively carboxylated graphite (ECG) by a simple ball milling of pristine graphite in the presence of dry ice. The resultant ECG is highly dispersable in various solvents to self-exfoliate into single- and few-layer (≤ 5 layers) GNs. These stable ECG (or GN) dispersions have been used for solution processing, coupled with thermal decarboxylation, to produce large-area GN films for many potential applications ranging from electronic materials to chemical catalysts. The electrical conductivity of a thermally decarboxylated ECG film was found to be as high as 1214 S/cm, which is superior to its GO counterparts. Ball milling can thus provide simple, but efficient and versatile, and eco-friendly (CO(2)-capturing) approaches to low-cost mass production of high-quality GNs for applications where GOs have been exploited and beyond.

Preparation and characterization of hybrid polypyrrole nanoparticles as a conducting polymer with controllable size.

Hybrid polypyrrole (PPy) nanoparticles were prepared using a low-temperature oxidative polymerization process in an acidic solution with polyethyleneimine (PEI) as a template and amine source. The results showed that the nanoparticles have an amorphous structure in the X-ray diffractogram and exhibited good dispersibility in water, uniform size, and a specific conductivity ranging from 0.1 to 6.9 S/cm. The particle size could be tuned from 85 to 300 nm by varying the reactant concentration. Undoping the samples with sodium hydroxide (NaOH) solution altered the optical absorption properties and surface roughness of the particles. However, it did not affect the particle size. The nanoparticles also exhibited optical sensing properties based on their UV-vis absorption changes with the pH. Moreover, nanoparticles could have potential applications in gene delivery and bio-adsorption for contaminant removal. This work demonstrates a simple and effective method for preparing hybrid polypyrrole nanoparticles with controllable size, dispersibility, and conductivity for various nanotechnology, biotechnology, and environmental engineering purposes.

Triboelectric Energy Harvesting from Highly Conjugated Fused Aromatic Ladder Structure Under Extreme Environmental Conditions.

Practical application of triboelectric nanogenerators (TENGs) has been challenging, particularly, under harsh environmental conditions. This work proposes a novel 3D-fused aromatic ladder (FAL) structure as a tribo-positive material for TENGs, to address these challenges. The 3D-FAL offers a unique materials engineering platform for tailored properties, such as high specific surface area and porosity, good thermal and mechanical stability, and tunable electronic properties. The fabricated 3D-FAL-based TENG reaches a maximum peak power density of 451.2 µW cm-2 at 5 Hz frequency. More importantly, the 3D-FAL-based TENG maintains stable output performance under harsh operating environments, over wide temperature (-45-100 °C) and humidity ranges (8.3-96.7% RH), representing the development of novel FAL for sustainable energy generation under challenging environmental conditions. Furthermore, the 3D-FAL-based TENG proves to be a promising device for a speed monitoring system engaging reconstruction in virtual reality in a snowy environment.

Solution-Processable Semiconducting Conjugated Planar Network.

After the emergence of graphene in the material science field, top-down and bottom-up studies to develop semiconducting organic materials with layered structures became highly active. However, most of them have suffered from poor processability, which hampers device fabrication and frustrates practical applications. Here, we suggest an unconventional approach to fabricating semiconducting devices, which avoids the processability issue. We designed a soluble amorphous network using a solution process to form a thin film on a substrate. We then employed heat treatment to develop a flattened organic structure in the thin film, as an active layer for organic thin-film transistors (TFTs). The fabricated TFTs showed good performance in both horizontal and vertical charge transport, suggesting a versatile and useful approach for the development of organic semiconductors.

Fused Aromatic Network with Exceptionally High Carrier Mobility.

Recently, studies of 2D organic layered materials with unique electronic properties have generated considerable interest in the research community. However, the development of organic materials with functional electrical transport properties is still needed. Here, a 2D fused aromatic network (FAN) structure with a C5 N basal plane stoichiometry is designed and synthesized, and thin films are cast from C5 N solution onto silicon dioxide substrates. Then field-effect transistors are fabricated using C5 N thin flakes as the active layer in a bottom-gate top-contact configuration to characterize their electrical properties. The C5 N thin flakes, isolated by polydimethylsiloxane stamping, exhibit ambipolar charge transport and extraordinarily high electron (996 cm2 V-1 s-1 ) and hole (501 cm2 V-1 s-1 ) mobilities, surpassing the performance of most pristine organic materials without doping. These results demonstrate their vast potential for applications in thin-film optoelectronic devices.

Vertical two-dimensional layered fused aromatic ladder structure.

Planar two-dimensional (2D) layered materials such as graphene, metal-organic frameworks, and covalent-organic frameworks are attracting enormous interest in the scientific community because of their unique properties and potential applications. One common feature of these materials is that their building blocks (monomers) are flat and lie in planar 2D structures, with interlayer π-π stacking, parallel to the stacking direction. Due to layer-to-layer confinement, their segmental motion is very restricted, which affects their sorption/desorption kinetics when used as sorbent materials. Here, to minimize this confinement, a vertical 2D layered material was designed and synthesized, with a robust fused aromatic ladder (FAL) structure. Because of its unique structural nature, the vertical 2D layered FAL structure has excellent gas uptake performance under both low and high pressures, and also a high iodine (I2) uptake capacity with unusually fast kinetics, the fastest among reported porous organic materials to date.

Two-dimensional amine and hydroxy functionalized fused aromatic covalent organic framework.

Ordered two-dimensional covalent organic frameworks (COFs) have generally been synthesized using reversible reactions. It has been difficult to synthesize a similar degree of ordered COFs using irreversible reactions. Developing COFs with a fused aromatic ring system via an irreversible reaction is highly desirable but has remained a significant challenge. Here we demonstrate a COF that can be synthesized from organic building blocks via irreversible condensation (aromatization). The as-synthesized robust fused aromatic COF (F-COF) exhibits high crystallinity. Its lattice structure is characterized by scanning tunneling microscopy and X-ray diffraction pattern. Because of its fused aromatic ring system, the F-COF structure possesses high physiochemical stability, due to the absence of hydrolysable weak covalent bonds.

Ruthenium anchored on carbon nanotube electrocatalyst for hydrogen production with enhanced Faradaic efficiency.

Developing efficient and stable electrocatalysts is crucial for the electrochemical production of pure and clean hydrogen. For practical applications, an economical and facile method of producing catalysts for the hydrogen evolution reaction (HER) is essential. Here, we report ruthenium (Ru) nanoparticles uniformly deposited on multi-walled carbon nanotubes (MWCNTs) as an efficient HER catalyst. The catalyst exhibits the small overpotentials of 13 and 17 mV at a current density of 10 mA cm-2 in 0.5 M aq. H2SO4 and 1.0 M aq. KOH, respectively, surpassing the commercial Pt/C (16 mV and 33 mV). Moreover, the catalyst has excellent stability in both media, showing almost "zeroloss" during cycling. In a real device, the catalyst produces 15.4% more hydrogen per power consumed, and shows a higher Faradaic efficiency (92.28%) than the benchmark Pt/C (85.97%). Density functional theory calculations suggest that Ru-C bonding is the most plausible active site for the HER.

Fused Aromatic Network Structures as a Platform for Efficient Electrocatalysis.

Fused aromatic network (FAN) structures are a category of ordered porous polymers that permit the specific fusion of building blocks into extended porous network structures with designed skeletons and pores. One significant feature of FANs is that their structures can be tailorable with fused aromatic rings without rotatable single-bond connectivity. As a result, the geometry and space orientation of the building blocks are easily incorporated to guide the topological expansion of the architectural periodicity. The variety of building units and fused linkages make FANs a promising materials platform for constitutional outline and functional design. The stably confined spaces of FAN architectures can be extended for the exchange of photons, ions, electrons, holes, and guest molecules, and exhibit customized chemical, electrochemical and optical properties. Herein, the main progress and advances in the field of 2D and 3D FANs and their utilization as a platform to develop efficient electrocatalysts for energy conversion and storage applications are summarized.