ZIF-Induced d-Band Modification in a Bimetallic Nanocatalyst: Achieving Over 44 % Efficiency in the Ambient Nitrogen Reduction Reaction

The electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance owing to preferential catalyst–H formation and the consequential hydrogen evolution reaction (HER). Now, the Pt/Au electrocatalyst d-band structure is electronically modified using zeolitic imidazole framework (ZIF) to achieve a Faradaic efficiency (FE) of >44 % with high ammonia yield rate of >161 μg mg_cat⁻¹ h⁻¹ under ambient conditions. The strategy lowers electrocatalyst d-band position to weaken H adsorption and concurrently creates electron-deficient sites to kinetically drive NRR by promoting catalyst–N₂ interaction. The ZIF coating on the electrocatalyst doubles as a hydrophobic layer to suppress HER, further improving FE by >44-fold compared to without ZIF (ca. 1 %). The Pt/Au-N_ZIF interaction is key to enable strong N₂ adsorption over H atom.     

Covalent Organic Framework for Improving Near‐Infrared Light Induced Fluorescence Imaging through Two‐Photon Induction

Fluorescent materials exhibiting two‐photon induction (TPI) are used for nonlinear optics, bioimaging, and phototherapy. Polymerizations of molecular chromophores to form π‐conjugated structures were hindered by the lack of long‐range ordering in the structure and strong π–π stacking between the chromophores. Reported here is the rational design of a benzothiadiazole‐based covalent organic framework (COF) for promoting TPI and obtaining efficient two‐photon induced fluorescence emissions. Characterization and spectroscopic data revealed that the enhancement in TPI performance is attributed to the donor‐π‐acceptor‐π‐donor configuration and regular intervals of the chromophores, the large π‐conjugation domain, and the long‐range order of COF crystals. The crystalline structure of TPI‐COF attenuates the π–π stacking interactions between the layers, and overcomes aggregation‐caused emission quenching of the chromophores for improving near‐infrared two‐photon induced fluorescence imaging.     

Flame retardancy and smoke suppression of silicone foams with microcapsulated aluminum hypophosphite and zinc borate

The flame‐retardant microcapsules were successfully fabricated with an aluminum hypophosphite (AHP) core. Fourier transform infrared (FTIR) and X‐ray photoelectron spectroscopy (XPS) were used to verify that AHP was encapsulated in the microcapsules, and thermogravimetry analysis showed that microencapsulated AHP (MAHP) possessed higher thermal stability than that of AHP. Then, a flame‐retardant and smoke suppression system for silicone foams (SiFs) was obtained through a synergistic effect of MAHP and zinc borate (2ZnO·3B₂O₃·3.5H₂O). The mechanical properties, flame retardance, and smoke suppression of SiFs with MAHP and zinc borate were tested using the tensile test, limiting oxygen index (LOI) test, UL‐94 test, and cone calorimeter test. The mechanical properties indicated that the tensile strength and elongation at break of SiFs could evidently improve with the incorporation of MAHP. Compared with pure SiF, SiF8 with 4.5‐wt% MAHP and 1.5‐wt% zinc borate could achieve an LOI value of 30.7 vol% and an UL‐94 V‐0 rating, the time to ignition amplified almost six times, the peak heat release rate and total heat release were 51.10% and 46.00% less than that of pure SiF, respectively, the fire performance index increased nearly 13 times, and the fire growth index value was only 13.18% of pure SiF. Moreover, the partial substitution of zinc borate imparted a substantial improvement in both flame retardancy and smoke suppression. Especially, the peak smoke production rate and total smoke production of SiF8 were merely 38.46% and 38.84% of pure SiF.     

The effect of polymer dispersions on the early hydration of calcium sulfoaluminate cement

The influence of three polymer dispersions [styrene–butadiene copolymer (SB), styrene–acrylic ester copolymer (SA) and polyacrylic ester (PA)] on the hydration of calcium sulfoaluminate (CSA) cement within 72 h was investigated by using isothermal conduction calorimetry, X-ray diffraction analysis and thermal gravimetric analysis. The results indicate that these three polymer dispersions perform different influences on the hydration heat flow of CSA cement during different periods, they all postpone the occurrence time of the maxima peaks, and its extent is mainly dependent on the addition amount. Polymer dispersions manifest great retardation on the initial hydration of CSA cement, and the effect is much more significant within 1 h. In this stage, the generation of ettringite is strongly delayed; however, the formation of ettringite is accelerated by these polymer dispersions at and after 2 h. Among these three polymer dispersions, PA demonstrates the highest acceleration effect on the hydration degree.

     

Investigation on the structure,fluoride vaporization and crystallization behavior of CaF2–CaO–Al2O3–(SiO2) slag for electroslag remelting

Journal of Thermal Analysis and Calorimetry - The structure, vaporization behavior and crystallization of CaF2–CaO–Al2O3 slags with different SiO2 contents for electroslag remelting...     

A Diffusion‐‐Reaction Competition Mechanism to Tailor Lithium Deposition for Lithium‐Metal Batteries

Lithium metal is recognized as one of the most promising anode materials owing to its ultrahigh theoretical specific capacity and low electrochemical potential. Nonetheless, dendritic Li growth has dramatically hindered the practical applications of Li metal anodes. Realizing spherical Li deposition is an effective approach to avoid Li dendrite growth, but the mechanism of spherical deposition is unknown. Herein, a diffusion‐reaction competition mechanism is proposed to reveal the rationale of different Li deposition morphologies. By controlling the rate‐determining step (diffusion or reaction) of Li deposition, various Li deposition scenarios are realized, in which the diffusion‐controlled process tends to lead to dendritic Li deposition while the reaction‐controlled process leads to spherical Li deposition. This study sheds fresh light on the dendrite‐free Li metal anode and guides to achieve safe batteries to benefit future wireless and fossil‐fuel‐free world.     

Covalent Assembly of MoS2 Nanosheets with SnS Nanodots as Linkages for Lithium/Sodium‐Ion Batteries

Weak van der Waals interactions between interlayers of two‐dimensional layered materials result in disabled across‐interlayer electron transfer and poor layered structural stability, seriously deteriorating their performance in energy applications. Herein, we propose a novel covalent assembly strategy for MoS₂ nanosheets to realize unique MoS₂/SnS hollow superassemblies (HSs) by using SnS nanodots as covalent linkages. The covalent assembly based on all‐inorganic and carbon‐free concept enables effective across‐interlayer electron transfer, facilitated ion diffusion kinetics, and outstanding mechanical stability, which are evidenced by experimental characterization, DFT calculations, and mechanical simulations. Consequently, the MoS₂/SnS HSs exhibit superb rate performance and long cycling stability in lithium‐ion batteries, representing the best comprehensive performance in carbon‐free MoS₂‐based anodes to date. Moreover, the MoS₂/SnS HSs also show excellent sodium storage performance in sodium‐ion batteries.     

Highly Efficient Trityl-Nitroxide Biradicals for Biomolecular High-Field Dynamic Nuclear Polarization

Dynamic nuclear polarization (DNP) is a powerful method to enhance the sensitivity of solid-state magnetic nuclear resonance (ssNMR) spectroscopy. However, its biomolecular applications at high magnetic fields (preferably>14 T) have so far been limited by the intrinsically low efficiency of polarizing agents and sample preparation aspects. Herein, we report a new class of trityl-nitroxide biradicals, dubbed SNAPols that combine high DNP efficiency with greatly enhanced hydrophilicity. SNAPol-1, the best compound in the series, shows DNP enhancement factors at 18.8 T of more than 100 in small molecules and globular proteins and also exhibits strong DNP enhancements in membrane proteins and cellular preparations. By integrating optimal sensitivity and high resolution, we expect widespread applications of this new polarizing agent in high-field DNP/ssNMR spectroscopy, especially for complex biomolecules.     

Spectrophotometric Study of Catechol Oxidation by Aerial O2 in Alkaline Aqueous Solutions Containing Mg(II) Ions.

Electronic absorption spectroscopy was employed to study the aerial oxidation of catechol (1,2-benzenediol) in alkaline aqueous solution containing an excess of Mg(II) ions. Graphical analysis by the matrix method of UV spectra recorded at regular time intervals gave a good fit for two absorbing species in solution. Based on this result and our earlier ESR spectroscopic investigations we concluded that two main absorbing species in this system are Mg(II)-spin stabilized o-benzosemiquinone anion radical and C-C dimer formed by the nucleophilic attack of catecholate anion on o-benzoquinone. Although the formation of 1,2,4-benzenetriol during the catechol oxidation has been detected in some ESR studies its presence was not indicated by this analysis probably because of the low and/or stable steady state concentration throughout the experiment.