Porous CoNiOOH nanosheets derived from the well-mixed MOFs as stable and highly efficient electrocatalysts for water oxidation

The development of efficient and stable electrocatalysts is of great significance for improving water splitting. Among them, transition metal oxyhydroxides show excellent performance in oxygen evolution reactions (OER), but there are certain difficulties in direct preparation. Recently, Metal–organic frameworks (MOFs) as precatalysts or precursors have shown promising catalytic performance in OER and can be decomposed under alkaline conditions. Therefore, using a mild and controllable way to convert MOFs into oxyhydroxides and retaining the original structural advantages is crucial for improving the catalytic activity. Herein, a rapid electrochemical strategy is used to activate well-mixed MOFs to prepare Co/Ni oxyhydroxide nanosheets for efficient OER catalysts, and the structural transformation in this process was investigated in detail by using scanning electron microscope, X-ray diffraction, Raman, X-ray photoelectron spectroscopy and electrochemical methods. It is discovered that electrochemical activation can promote ligand substitution of well-mixed MOFs to form porous oxyhydroxide nanosheets and tune the electronic structure of the metal (Co and Ni), which can lead to more active site exposure and accelerate charge transfer. In addition, the change of structure also improves hydrophilicity, as well as benefiting from the strong synergistic effect between multiple species, the optimal a-MCoNi–MOF/NF has excellent OER performance and long-term stability. More obviously, the porous CoNiOOH nanosheets are formed in situ during electrochemical activation process through structural transformation and acts as the active centers. This work provides new insights for mild synthesis of MOFs derivatives and also provides ideas for the preparation of highly efficient catalysts.     

Recent insights in synthesis and energy storage applications of porous carbon derived from biomass waste: A review

In the last few decades, global warming, environmental pollution, and an energy shortage of fossil fuel may cause a severe economic crisis and health threats. Storage, conversion, and application of regenerable and dispersive energy would be a promising solution to release this crisis. The development of porous carbon materials from regenerated biomass are competent methods to store energy with high performance and limited environmental damages. In this regard, bio-carbon with abundant surface functional groups and an easily tunable three-dimensional porous structure may be a potential candidate as a sustainable and green carbon material. Up to now, although some literature has screened the biomass source, reaction temperature, and activator dosage during thermochemical synthesis, a comprehensive evaluation and a detailed discussion of the relationship between raw materials, preparation methods, and the structural and chemical properties of carbon materials are still lacking. Hence, in this review, we first assess the recent advancements in carbonization and activation process of biomass with different compositions and the activity performance in various energy storage applications including supercapacitors, lithium-ion batteries, and hydrogen storage, highlighting the mechanisms and open questions in current energy society. After that, the connections between preparation methods and porous carbon properties including specific surface area, pore volume, and surface chemistry are reviewed in detail. Importantly, we discuss the relationship between the pore structure of prepared porous carbon with surface functional groups, and the energy storage performance in various energy storage fields for different biomass sources and thermal conversion methods. Finally, the conclusion and prospective are concluded to give an outlook for the development of biomass carbon materials, and energy storage applications technologies. This review demonstrates significant potentials for energy applications of biomass materials, and it is expected to inspire new discoveries to promote practical applications of biomass materials in more energy storage and conversion fields.     

Deduction of a facile method to construct Antheraea mylitta silk fibroin/gelatin blend films for prospective biomedical applications

Blend films of two types (I and II) were prepared by mixing Antheraea mylitta silk fibroin (AMF) and gelatin solution in various blend ratios via the solution casting method. Two different crosslinkers, namely glutaraldehyde and genipin, were used during blend preparation. The structural characteristics and thermal properties of the blend films were examined by Fourier transform infrared (FTIR) spectroscopy, X‐ray diffraction (XRD), Thermogravimetric analysis (TGA) and Diffrential scanning calorimetery (DSC). The FTIR spectra showed conformational alterations in type I blend films while type II films attained high β‐sheet crystallinity. The XRD diffractograms presented a high degree of crystallinity in type II blend films compared to type I, which showed an almost amorphous structure. Further, thermal and biological studies were conducted on type II films. According to the TGA thermograms, the degradation temperature of the crosslinked blend films shifted compared to pure gelatin and pure AMF films. Partial miscibility of the two components was indicated by DSC thermograms of the blends. The high water uptake capacity of type II blend films was found to imitate hydrogel behaviour. The blend films did not show any toxicity in 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide (MTT) assay and supported L929 fibroblast cell spreading and proliferation. The biodegradation of the blend films was significantly faster than the pure silk film. © 2020 Society of Industrial Chemistry     

The influence of carbon atom distribution in precursors with 1:1 carbon to silicon atoms ratio on structure and thermal evolution of obtained silicon oxycarbide based materials

In this work, a number of precursors with 1:1 silicon to carbon atoms ratio and various carbon atom distributions were synthesized and pyrolyzed in order to obtain silicon oxycarbide based materials. The different carbon atom distributions were obtained using both simple monomers with only one silicon atom, as well as large monomers containing either four or sixteen silicon atoms with predefined carbon atom positions. The silicon oxycarbide based materials were investigated using IR, XRD, ²⁹Si MAS NMR and elemental analysis after annealing at various temperatures, as well as TG. The research shows that carbon atom distribution has great impact on the structure of final material and can be used to tailor the material for its projected uses.     

Effect of aluminium acetyl acetonate on the hydrogen and nitrogen permeation of carbon molecular sieves membranes

With a growing interest in hydrogen as energy carrier, the efficient purification of hydrogen from gaseous mixtures is very important. This paper addresses the separation of hydrogen using Carbon Molecular Sieves Membranes (CMSM), which show an attractive combination of high permeability, selectivity and stability. Supported CMSM containing various amounts of aluminium have been prepared from novolac and aluminium acetyl acetonate (Al(acac)₃) as carbon and alumina precursors. The thickness of the CMSM layers depend on the content of Al(acac)₃ in the dipping solution, which also has influence in the pore size and pore size distribution of the membranes. The permeation properties of the membranes against the Al content in the membrane follows a volcano shape, where the membrane containing 4 wt (%) of Al(acac)₃ has the best properties and was stable during 720 h for hydrogen at 150 °C and 6 bar pressure difference. All the CMSM have permeation properties well above the Robeson Upper limit.     

Carbon corrosion mechanism on nitrogen-doped carbon support — A density functional theory study

In this work, density functional theory (DFT) calculations were used to investigate the mechanism of carbon corrosion on nitrogen-doped carbon support. Free energy diagrams were generated based on three proposed reaction pathways to evaluate corrosion mechanisms. The most energetically preferred mechanism on nitrogen-doped carbon was determined. The results show that the step of water dissociation to form ^#OH was the rate-determining step for gra-G-1N (graphene doped with graphitic N) and pyrr-G-1N (graphene doped with pyrrolic N). As for graphene doped with pyridinic N, the step of C^#OC^#O formation was critical. It was found that the control of nitrogen concentration was necessary for precisely designing optimized carbon materials. Abundance of nitrogen moieties aggravated the carbon corrosion. When the high potential was applied, specific types of graphitic N and pyridinic N were found to be favorable carbon modifications to improve carbon corrosion resistance. Moreover, the solvent effect was also investigated. The results provide theoretical insights and design guidelines to improve corrosion resistance in carbon support through material modification by inhibiting the adsorption of surface oxides (OH, O, and OOH).     

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.     

Organic Semiconducting Luminophores for Near-Infrared Afterglow,Chemiluminescence, and Bioluminescence Imaging

Optical imaging has played a pivotal role in deciphering in vivo bioinformatics but is limited by shallow penetration depth and poor imaging performance owing to interfering tissue autofluorescence induced by concurrent photoexcitation. The emergence of near-infrared (NIR) self-luminescence imaging independent of real-time irradiation has timely addressed these problems. There are two main kinds of self-luminescent agents, namely inorganic and organic luminophores. Inorganic luminophores usually suffer from long-term biotoxicity concerns resulting from potential heavy-metal ions leakage and nonbiodegradability, which hinders their further translational application. In contrast, organic luminophores, especially organic semiconducting luminophores (OSLs) with good biodegradable potential, tunable design, and outstanding optical properties, are preferred in biological applications. This review summarizes the recent progress of OSLs used in NIR afterglow, chemiluminescence, and bioluminescence imaging. Molecular manipulation and nanoengineering approaches of OSLs are discussed, with emphasis on strategies that can extend the emission wavelength from visible to NIR range and amplify luminescence signals. This review concludes with a discussion of current challenges and possible solutions of OSLs in the self-luminescence field.     

The Chemistry of DPPH· Free Radical and Congeners

Since the discovery in 1922 of 2,2-diphenyl-1-(2,4,6-trinitrophenyl) hydrazyl stable free radical (DPPH^·), the chemistry of such open-shell compounds has developed continuously, allowing for both theoretical and practical advances in the free radical chemistry area. This review presents the important, general and modern aspects of the chemistry of hydrazyl free radicals and the science behind it.     

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.