Lanthanide-organic-frameworks modified ZnIn2S4 for boosting hydrogen generation under UV–Vis and visible light

Novel Ln-MOF with microrods shape were successfully combined with ZnIn₂S₄ (ZIS) microsphere and used for photocatalytic hydrogen generation under UV–Vis and visible light. The Ln-MOFs/ZIS system comprises lanthanide-carboxylate coordination networks (Tm and Gd as metal ions, and 1,3,5-benzenetricarboxylic acid (BTC) as the organic linker) deposited on ZnIn₂S₄ microspheres. Effect of the amount of ((Tm,Gd)-BTC) (1, 5, 10 wt%) on the optical properties and photocatalytic hydrogen evolution performance was investigated. ZIS microsphere shows the marigold flower-like morphology and hexagonal polytopic crystal form. Our results proved that the combination of ZIS microsphere, Ln-MOF and Pt nanoparticles (NPs) caused significant enhancement in hydrogen generation. Amount of formed hydrogen was raised from 196.3 to 7782.1 μmol g^?1 for pristine ZIS and ZIS decorated with 1% (Tm, Gd)-BTC/Pt under UV–Vis light, respectively.     

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.     

Nanoraspberry-like palladium/spongy nickel oxide for electrooxidation of five light fuels

The spongy nickel oxide (SNO) was synthesized the solution combustion method. The SNO was selected as a promoter to boost the catalytic activity of nanoraspberry-like palladium (NRPd) toward electrooxidation of five light fuels (LFs): methanol, ethanol, formaldehyde, formic acid, and ethylene glycol. The X-ray powder diffraction, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy, and field emission scanning electron microscope techniques were used for the materials characterization. In comparison with nonpromoted Pd, the NRPd-SNO electrocatalyst shown an excellent efficiency in parameters like the electrochemical active surface area and anti-CO poisoning behavior. The turnover data and the parameters, including reaction order, activation energy, and the coefficients of electron transfer and diffusion, were evaluated for the each process of LFs electrooxidation. The outcome for NRPd-SNO activity toward LFs electrooxidation was compared to some reported electrodes. The SNO increases the removal of intermediates created in the oxidation of LFs that can poison the surface of palladium catalyst. This is due to the presence of the lattice oxygens in SNO structure and Ni switching between its high and low valances. The compatibility of the adsorption process of LFs on the surface of the NRPd-SNO catalyst with different isotherms was determined by studying the Tafel polarization and calculating the surface coverage.     

Fabrication of barium titanate ceramics via digital light processing 3D printing by using high refractive index monomer

A digital light processing (DLP) technology has been developed for 3D printing lead-free barium titanate (BTO) piezoelectric ceramics. By comparing the curing and rheological properties of slurries with different photosensitive monomer, a high refractive index monomer acryloyl morpholine (ACMO) was chosen, and a design and preparation method of BTO slurry with high solid content, low viscosity and high curing ability was proposed. By further selecting the printing parameters, the single-layer exposure time was reduced and the forming efficiency has been greatly improved. Sintered specimens were obtained after a nitrogen-air double-step debinding and furnace sintering process, and the BTO ceramics fabricated with 80 wt% slurry shows the highest relative density (95.32 %) and piezoelectric constant (168.1 pC/N). Furthermore, complex-structured BTO ceramics were prepared, impregnated by epoxy resin and finally assembly made into hydrophones, which has significance for the future design and manufacture of piezoelectric ceramic-based composites that used in functional devices.     

Freeze-drying and mechanical redispersion of aqueous PEDOT:PSS

Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films are attracting famous applications in antistatic coating, energy storage and conversion, printed electronics, and biomedical fields due to their conductivity, optical transparency and flexibility. However, PEDOT:PSS has poor dispersion stability during long-term storage and transport. Moreover, the dried PEDOT:PSS films are insoluble in any solvent and cannot be redispersed again. In comparison to bake drying, here, a feasible strategy to achieve mechanically redispersed PEDOT:PSS with the help of freeze-drying process was reported. The redispersed PEDOT:PSS can recover not only the initial characters such as pH, chemical composition, viscosity, and particle size under similar solid contents, but also conductivity and surface morphology of treated films. In addition, the treated film exhibits self-healing properties similar to pristine film in terms of mechanical and electrical properties. This technology enables reuse and overcomes the technical problems of PEDOT:PSS dispersion, realizing real-time processing to meet variable applications.     

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.     

Determinants of the intention to use non-medical insertable digital devices: The case of Chile and Colombia

In the past, thinking of carrying electronic devices inside our bodies was only posed by non-real scenarios. The emergence of insertable devices has changed this. Since this technology is still in its initial development stages, few studies have investigated factors that influence its acceptance. This paper analyzes the predictors of the intention to use non-medical insertable devices in two Latin American contexts. We used partial least squares structural equation modeling to examine whether six constructs predicted intention to use insertable devices. A questionnaire was administered to undergraduate students located in Colombia and Chile (n = 672). We also examined whether these predictors influenced intention differently for both of them. Four common constructs significantly and positively influenced both Chilean and Colombian respondents to use insertable devices (hedonic motivation, habit, performance expectancy, and social influence). Also, the habit has a complementary mediating effect on the relationship between social influence and behavioral intention. By contrast, effort expectations were a positive and significant predictor, but only among Chilean respondents. Findings suggest that when technologies are emerging, well-known predictors of intention (e.g., performance and effort expectations) are less influential than predictors related to self-efficacy (e.g., habit and hedonic motivation). The use of insertable devices has a significant impact on society. Thus, a better understanding of what motivates their use has implications for both academia and industry.