Atomic Ni Anchored Covalent Triazine Framework as High Efficient Electrocatalyst for Carbon Dioxide Conversion

Electrochemically driven carbon dioxide (CO₂) conversion is an emerging research field due to the global warming and energy crisis. Carbon monoxide (CO) is one key product during electroreduction of CO₂; however, this reduction process suffers from tardy kinetics due to low local concentration of CO₂ on a catalyst's surface and low density of active sites. Herein, presented is a combination of experimental and theoretical validation of a Ni porphyrin‐based covalent triazine framework (NiPor‐CTF) with atomically dispersed NiN₄ centers as an efficient electrocatalyst for CO₂ reduction reaction (CO₂RR). The high density and atomically distributed NiN₄ centers are confirmed by aberration‐corrected high‐angle annular dark field scanning transmission electron microscopy and extended X‐ray absorption fine structure. As a result, NiPor‐CTF exhibits high selectivity toward CO₂RR with a Faradaic efficiency of >90% over the range from ?0.6 to ?0.9 V for CO conversion and achieves a maximum Faradaic efficiency of 97% at ?0.9 V with a high current density of 52.9 mA cm^?2, as well as good long‐term stability. Further calculation by the density functional theory method reveals that the kinetic energy barriers decreasing for *CO₂ transition to *COOH on NiN₄ active sites boosts the performance.     

Covalent 0D–2D Heterostructuring of Co9S8–MoS2 for Enhanced Hydrogen Evolution in All pH Electrolytes

Ultrasmall Co₉S₈ nanoparticles are introduced on the basal plane of MoS₂ to fabricate a covalent 0D–2D heterostructure that enhances the hydrogen evolution reaction (HER) activity of electrochemical water splitting. In the heterostructure, separate phases of Co₉S₈ and MoS₂ are formed, but they are connected by Co–S–Mo type covalent bonds. The charge redistribution from Co to Mo occurring at the interface enhances the electron‐doped characteristics of MoS₂ to generate electron‐rich Mo atoms. Besides, reductive annealing during the synthesis forms S defects that activates adjacent Mo atoms for further enhanced HER activity as elucidated by the density functional theory (DFT) calculation. Eventually, the covalent Co₉S₈–MoS₂ heterostructure shows amplified HER activity as well as stability in all pH electrolytes. The synergistic effect is pronounced when the heterostructure is coupled with a porous Ni foam (NF) support to form Co₉S₈–MoS₂/NF that displays superior performance to those of the state‐of‐the‐art non‐noble metal electrocatalysts, and even outperforms a commercial Pt/C catalyst in a practically meaningful, high current density region in alkaline (>170 mA cm^?2) and neutral (>60 mA cm^?2) media. The high HER performance and stability of Co₉S₈–MoS₂ heterostructure make it a promising pH universal alternative to expensive Pt‐based electrocatalysts for practical water electrolyzers.     

Photonic Vitrimer Elastomer with Self-Healing,High Toughness,Mechanochromism, and Excellent Durability based on Dynamic Covalent Bond

Vitrimers, with their unique dynamic covalent bonds, possess attractive self-healability and mechanical robustness, providing an intriguing opportunity to construct functional soft materials. However, their potential for function recovery, especially optical function, is underexplored. Harnessing the synergistic effect of photonic crystals and vitrimers, a novel photonic vitrimer with light regulating and self-healing capabilities is presented. The resulting photonic vitrimer exhibits a large tensile strain (>1000%), high toughness (21.2 kJ m⁻³), bright structural color, and mechanochromism. Notably, the structural color remains constant even after 10 000 stretching/releasing cycles, showing superior mechanical stability, creep-resistance, and excellent durability. More importantly, the exchange of dynamic covalent bonds imparts the photonic vitrimer with a self-healing ability (>95% efficiency), enabling the recovery of its optical function. Benefiting from the above merits, the photonic vitrimer has been successfully used as a sensor for human motion detection, which demonstrates visualized interactive sensibility even after self-repairing. This material design provides a general strategy for optical functionalization of vitrimers. The photonic vitrimer elastomers present great potential as resilient functional soft materials for diverse flexible devices and a novel optical platform for soft robotics, smart wearable devices, and human-machine interaction.     

Thiol-Functionalized Covalent Organic Frameworks as Thermal History Indictor for Temperature and Time History Monitoring

Various products, including foods and pharmaceuticals, are sensitive to temperature fluctuations. Thus, temperature monitoring during production, transportation, and storage is critical. Facile indicators are required to monitor temperature conditions via color changes in real time. This study aimed to prepare and apply thiol-functionalized covalent organic frameworks (COFs) as a novel indicator for monitoring thermal history and temperature abuse. The COFs underwent obvious color changes from bright yellow to purple after exposure to different temperatures for varying durations. The reaction kinetics are analyzed under isothermal conditions, which reveal that the order of reaction rates is k_−20°C < k_4°C < k_20°C < k_35°C < k_55°C. The activation energy (E_a) of the COFs is calculated using the Arrhenius equation as 50.71 kJ moL⁻¹. The COFs are capable of sensitive color changes and offer a broad temperature tracking range, thereby demonstrating their application potential for the monitoring of temperature and time exposure history during production, transportation, and storage. This excellent performance thermal history indicator also shows promise for expanding the application field of COFs.     

Flexible,Mechanically Stable,Porous Self-Standing Microfiber Network Membranes of Covalent Organic Frameworks: Preparation Method and Characterization

Covalent organic frameworks (COFs) show advantageous characteristics, such as an ordered pore structure and a large surface area for gas storage and separation, energy storage, catalysis, and molecular separation. However, COFs usually exist as difficult-to-process powders, and preparing continuous, robust, flexible, foldable, and rollable COF membranes is still a challenge. Herein, such COF membranes with fiber morphology for the first time prepared via a newly introduced template-assisted framework process are reported. This method uses electrospun porous polymer membranes as a sacrificial large dimension template for making self-standing COF membranes. The porous COF fiber membranes, besides having high crystallinity, also show a large surface area (1153 m² g⁻¹), good mechanical stability, excellent thermal stability, and flexibility. This study opens up the possibility of preparation of large dimension COF membranes and their derivatives in a simple way and hence shows promise in technical applications in separation, catalysis, and energy in the future.     

Bifunctional Edge-Rich Nitrogen Doped Porous Carbon for Activating Oxygen and Sulfur

Oxygen reduction reaction (ORR) and sulfur reduction reaction (SRR) play key roles in advanced batteries. However, they both suffer from sluggish reaction kinetics. Here, an interesting nitrogen doped porous carbon material that can simultaneously activate oxygen and sulfur is reported. The carbon precursor is a nitrogen containing covalent organic framework (COF), constituting periodically stacked 2D sheets. The COF structure is well preserved upon pyrolysis, resulting in the formation of edge-rich porous carbon with structure resembling stacked holey graphene. The nitrogen containing groups in the COF are decomposed into graphitic and pyridinic nitrogen during pyrolysis. These edge sites and uniform nitrogen doping endow the carbon product with high intrinsic catalytic activities toward ORR and SRR. The COF derived carbon delivers outstanding performances when assembling as cathodes in the Li-S and Li-O₂ batteries. Simultaneous activation of oxygen and sulfur also enables a new battery chemistry. A proof-of-concept Li-S/O₂ hybrid battery is assembled, delivering a large specific capacity of 2,013 mAh g⁻¹. This study may inspire novel battery designs based on oxygen and sulfur chemistry.     

Macro-Sized All-Graphene 3D Structures via Layer-by-Layer Covalent Growth for Micro-to-Macro Inheritable Electrical Performances

Creating 3D-engineered macroscopic architectures while inheriting the superior properties of individual building blocks remains one of the fundamental challenges in nanotechnology. Stable covalent interconnection between micro/nanoblocks is a desired but underexplored strategy to meet the challenges, rather than current dependently-used weak physical forces or organic cross-linking, which disrupts the continuity of chemical composition and electrical properties. Herein, a novel layer-by-layer covalent growth protocol is developed to construct all-graphene macrostructures (AGM) with micro-to-macro inheritable electrical properties by laser-assisted covalent linkage of polyethersulfone-derived 3D porous graphene microblocks without introducing any catalysts, templates, and additives. Creatively, along with graphene generation and inter-layer bonding, a quality optimization process is integrated into one-step laser irradiation, which is unique and efficient for synthesizing high-crystalline graphene. With the covalently nondestructive bridge and free of non-graphene foreign phase impurities, AGM shows unprecedented electrical conductivity, especially a more than 100-fold improvement in cross-layer conductivity compared with non-covalent assembly. Furthermore, the covalent growth mechanism of AGM is clarified by molecular dynamics simulations. Finally, the application efficacy of AGM with enhanced isotropic conductivity is verified by using it as a supercapacitor electrode. This methodology enables the as-obtained AGM to possess the potential for high-performance-pursuing, multi-disciplinary, or large-scale applications.     

Block Copolymer Permeable Membrane with Visualized High‐Density Straight Channels of Poly(ethylene oxide)

A simple fabrication, scalable to centimeter scale, of a permeable membrane made of block copolymer containing molecular transport channels is demonstrated by coating photo‐crosslinkable liquid‐crystalline block copolymer, consisting of poly(ethylene oxide) (PEO) and poly(methacrylate) (PMA) bearing stilbene (Stb) mesogens in the side chains (PEO₁₁₄‐b‐PMA(Stb)₅₂), onto a sacrificial cellulose acetate film substrate. After thermal annealing, perpendicularly aligned and hexagonally arranged PEO cylindrical domains with a surface density of 10¹¹ cm^?2 were formed and then fixed efficiently by photo‐crosslinking the stilbene moieties in the PMA(Stb) domains by [2 + 2] dimerization. The fully penetrating straight PEO cylindrical domains across the 480‐nm‐thick membrane were well‐defined and visualized as molecule‐transport channels. After exfoliated by removal of the cellulose acetate layer, the membrane could be transferred onto another substrate by either scooping or a horizontal lifting method. Throughout the processes, the fully penetrating PEO channels across the membrane are preserved to open at both ends. A simple permeation experiment demonstrates that rhodamine dyes permeate efficiently through the PEO cylindrical channels of the annealed membrane but not across a non‐annealed one.     

Humidity-Induced Simultaneous Visible and Fluorescence Photonic Patterns Enabled by Integration of Covalent Bonds and Ionic Crosslinks

Stimuli-responsive photonic crystals (PCs) have been extensively studied due to their potential in fabrication of anti-counterfeiting devices and information storage. In this work, using Ca²⁺ ionic crosslinker, a cholesteric liquid crystalline network (CLCN) based PC able to simultaneously present visible and fluorescence pattern by moisture treatment is designed and prepared. The circularly polarized light from helical structure of CLCN makes the reflected pattern distinguishable under different circular polarizer, implying the unique advantage of this novel coating as anti-counterfeiting devices. More importantly, due to the thermochromic property of the liquid crystal monomers, permanent pattern is achievable by chemically crosslinking specific region at different temperature. By integrating chemically crosslinking and physically ionic crosslinking, a permanent pattern and a dynamic humidity responsive pattern can be incorporated in a single device, indicating the great potential of this novel photonic coating in information storage.