Interfacial Proton Supply/Filtration Regulates the Dynamics of Electrocatalytic Nitrogen Reduction Reaction: A Perspective

As a promising energy carrier, ammonia synthesis by electrocatalytic nitrogen reduction reaction (eNRR) is a promising green and low-carbon ammonia synthesis strategy that can replace the traditional Haber–Bosch process. However, the development of eNRR processes is mainly severely constrained by competitive hydrogen evolution reaction (HER), and the corresponding strategies to inhibit this adverse side reaction to obtain high eNRR selectivity are still limited. In addition, for this complex reaction involving gas–liquid–solid three-phase interface and proton/electron transfer, it is great significance to analyze and summarize the existing inhibition HER strategies from the viewpoint of dynamics. In view of this, this work reviews proton supply/filtration regulation strategy in catalytic system, allowing a systematic survey of the literature focusing on interface membrane regulation (inorganic membrane and organic membrane), electrolyte regulation (metal-mediated strategy and electrolyte ion regulation strategy) and system device design (electrode structure design and electrolytic cell device design). Constructive catalytic system design guidance is also suggested to inhibit hydrogen evolution and improve NH₃ selectivity, aiming for scalable and economically feasible applications.     

Amine Coordinated Electron-Rich Palladium Nanoparticles for Electrochemical Hydrogenation of Benzaldehyde

Electrocatalytic hydrogenation (ECH) is a burgeoning strategy for the sustainable utilization of hydrogen. However, how to effectively suppress the competitive hydrogen evolution reaction (HER) is a big challenge to ECH catalysis. In this study, amine (NH₂ R)-coordinated Pd nanoparticles loaded on carbon felt (Pd@CF) as a catalyst is successfully synthesized by a one-step solvothermal reduction method using oleylamine as the reducing agent. An exceptional ECH reactivity on benzaldehyde is achieved on the optimal Pd@CF catalyst in terms of a high conversion (89.7%) and selectivity toward benzyl alcohol (89.8%) at −0.4 V in 60 min. Notably, the Faradaic efficiency for producing benzyl alcohol is up to 90.2%, much higher than that catalyzed by Pd@CF-without N-group (41.1%) and thecommercial Pd/C (20.9%). The excellent ECH performance of Pd@CF can be attributed to the enriched electrons on Pd surface resulted from the introduction of NH₂ R groups, which strengthens both the adsorption of benzaldehyde and the adsorbed hydrogen (H_ads) on Pd, preventing the combination of H_ads to form H₂, that is, inhibiting the HER. This study gives a new insight into design principles of highly efficient electrocatalysts for the hydrogenation of unsaturated aldehydes molecules.     

Fast Li+ Transport via Silica Network-Driven Nanochannels in Ionomer-in-Framework for Lithium Metal Batteries

For the development of all-solid-state lithium metal batteries (LMBs), a high-porous silica aerogel (SA)-reinforced single-Li⁺ conducting nanocomposite polymer electrolyte (NPE) is prepared via two-step selective functionalization. The mesoporous SA is introduced as a mechanical framework for NPE as well as a channel for fast lithium cation migration. Two types of monomers containing weak-binding imide anions and Li⁺ cations are synthesized and used to prepare NPEs, where these monomers are grafted in SA to produce SA-based NPEs (SANPEs) as ionomer-in-framework. This hybrid SANPE exhibits high ionic conductivities (≈10⁻³ S cm⁻¹), high modulus (≈10⁵ Pa), high lithium transference number (0.84), and wide electrochemical window (>4.8 V). The resultant SANPE in the lithium symmetric cell possesses long-term cyclic stability without short-circuiting over 800 h under 0.2 mA cm⁻². Furthermore, the LiFePO₄|SANPE|Li solid-state batteries present a high discharge capacity of 167 mAh g⁻¹ at 0.1 C, good rate capability up to 1 C, wide operating temperatures (from −10 to 40 °C), and a stable cycling performance with 97% capacity retention and 100% coulombic efficiency after 75 cycles at 1 C and 25 °C. The SANPE demonstrates a new design principle for solid-state electrolytes, allowing for a perfect complex between inorganic silica and organic polymer, for high-energy-density LMBs.     

Vapor Phase Dealloying Derived Nanoporous Co@CoO/RuO2 Composites for Efficient and Durable Oxygen Evolution Reaction (Adv. Funct. Mater. 17/2023)

The development of low-cost and effective oxygen evolution reaction (OER) electrocatalysts to expedite the slow kinetics of water splitting is crucial for increasing the efficiency of energy conversion from electricity to hydrogen fuel. Herein, 3D bicontinuous nanoporous Co@CoO/RuO₂ composites with tunable sizes and chemical compositions are fabricated by introducing vapor phase dealloying of cobalt-based alloys. The influence of physical parameters on the formation of nanoporous Co substrates with various feature ligament sizes is systematically investigated. The CoO/RuO₂ shell is constructed by integrating a thin layer of RuO₂ on the inner surface of nanoporous Co, where the CoO interlayer is formed by annealing oxidization. The composite catalyst delivers an ultralow overpotential of 198 mV at 10 mA cm⁻², Tafel slope of 57.1 mV dec⁻¹, and long-term stability of 50 h. The superior OER activity and fast reaction kinetics are attributed to charge transfer through the coupling of Co O Ru bonds at the interface and the excellent nanopore connectivity, while the durability originates from the highly stable CoO/RuO₂ interface.     

Freely Tailorable Yolk-Shell Encapsulation: Versatile Applications in Ultralow-k Dielectric,Drug Delivery Systems,and Catalysts

Herein, a facile, controllable, and versatile method is reported to prepare monodisperse yolk-shell and yolk-multishell silica nanoparticles (NPs) with mesoporous shells by a novel selective etching strategy. The mechanism of selective etching based on fluoride-silica chemistry is investigated in detail and thus provides a fundamentally novel principle for the fabrication of yolk-shell NPs. Specifically, this unprecedented and versatile synthesis strategy can be used to encapsulate essentially any silica-based, carbon-based, metal, metal oxide, or other possible NPs. Noteworthy is that most of the yolk-shell mesoporous silica (mSiO₂) NPs are prepared for the first time. To demonstrate the major structural and compositional advantages of the designed yolk-shell NPs, their applications in the fields of ultralow-dielectric constant (k) materials, drug delivery systems, and catalysts were explored. In detail, the lowest k value of the prepared yolk-shellordered mesoporous silica@mSiO₂/fluorinated polybenzoxazole composite films is 2.02; The obtained yolk-shell mSiO₂/C@mSiO₂/C NPs possess high hydrophilicity and pH-responsive sensitivity; The conversion of the catalytic reaction of the designed magnetic yolk-shell hollow Fe₃O₄@SiO₂/Au@mSiO₂ NPs at 20 min is 97% with a high conversion rate (92%) and recyclability even after 10 reuses. This innovative work lays a solid foundation for freely tailorable yolk-shell encapsulation and will greatly stimulate more efforts devoted to relevant research and development.     

可控震源重锤-活塞杆动态行为规律与扰动控制研究

针对工程应用中可控震源振动器扰动量大、信噪比低等问题,结合重锤运动轨迹检测试验,通过理论计算与数值模拟,开展了重锤-活塞杆动态行为规律研究;在此基础上,开展振动器扰动控制研究,提出竖直进油方式振动器,与横向进油时的结果开展对比仿真分析,并进行竖直进油振动器扰动试验验证。结果表明:横向进油方式下,重锤受绕z轴的转动力矩作用且活塞杆存在变形,导致重锤上某点的运动轨迹为空间曲线,增大了振动器的扰动量,因此,横向进油方式是导致振动器扰动大的直接原因;竖直进油方式下,重锤不再受转动力矩影响且活塞杆变形得到极大改善,有效降低了振动器扰动量。研究结果对改善输出信号品质、提高输出信号分辨率具有重要的工程意义,建议在振动器的设计中采用竖直进油方式。     

An overview on microwave processing of material: A special emphasis on glass melting

Material processing adopting microwave heating has emerged as an alternative tool owing to faster processing, a cleaner environment, and several other advantages. This review provides a summary of recent reports of microwave synthesis of materials. This study reviews the use of microwave energy for application in several material processing technologies apart from food processing. A special emphasis has been made in the processing of glass adopting microwave energy. Melting of glass comprising SiO₂, P₂O₅, B₂O₃ as the main building block has been discussed. It has been revealed that silica, a microwave transparent material as reported earlier, can be heated under microwave heating directly. Microwave absorption of raw materials and different glass system has been discussed. Dielectric properties, particularly loss tangent or loss factor, are presented for some glass composition. Less evaporation of ingredient and low contamination from the crucible wall are noticed during glass melting using microwave heating. Enhanced iron redox ratio (Fe⁺²/∑Fe) in microwave processing may be considered an advantage in the preparation of heat absorbing filter glass. Small-scale glass melting using the microwave heating has a significant impact on energy and time saving. However, the challenges associated with the upscaling glass melting with microwave heating and future scope have been talked about.     

Simultaneous Imaging of Endogenous Survivin mRNA and On‐Demand Drug Release in Live Cells by Using a Mesoporous Silica Nanoquencher

The design of multifunctional drug delivery systems capable of simultaneous target detection, imaging, and therapeutics in live mammalian cells is critical for biomedical research. In this study, by using mesoporous silica nanoparticles (MSNs) chemically modified with a small‐molecule dark quencher, followed by sequential drug encapsulation, MSN capping with a dye‐labeled antisense oligonucleotide, and bioorthogonal surface modification with cell‐penetrating poly(disulfide)s, the authors have successfully developed the first mesoporous silica nanoquencher (qMSN), characterized by high drug‐loading and endocytosis‐independent cell uptake, which is able to quantitatively image endogenous survivin mRNA and release the loaded drug in a manner that depends on the survivin expression level in tumor cells. The authors further show that this novel drug delivery system may be used to minimize potential cytotoxicity encountered by many existing small‐molecule drugs in cancer therapy.     

Rational Design and Synthesis of Extremely Efficient Macroporous CoSe2–CNT Composite Microspheres for Hydrogen Evolution Reaction

Uniquely structured CoSe₂–carbon nanotube (CNT) composite microspheres with optimized morphology for the hydrogen‐evolution reaction (HER) are prepared by spray pyrolysis and subsequent selenization. The ultrafine CoSe₂ nanocrystals uniformly decorate the entire macroporous CNT backbone in CoSe₂–CNT composite microspheres. The macroporous CNT backbone strongly improves the electrocatalytic activity of CoSe₂ by improving the electrical conductivity and minimizing the growth of CoSe₂ nanocrystals during the synthesis process. In addition, the macroporous structure resulting from the CNT backbone improves the electrocatalytic activity of the CoSe₂–CNT microspheres by increasing the removal rate of generated H₂ and minimizing the polarization of the electrode during HER. The CoSe₂–CNT composite microspheres demonstrate excellent catalytic activity for HER in an acidic medium (10 mA cm^?2 at an overpotential of ≈174 mV). The bare CoSe₂ powders exhibit moderate HER activity, with an overpotential of 226 mV at 10 mA cm^?2. The Tafel slopes for the CoSe₂–CNT composite and bare CoSe₂ powders are 37.8 and 58.9 mV dec^?1, respectively. The CoSe₂–CNT composite microspheres have a slightly larger Tafel slope than that of commercial carbon‐supported platinum nanoparticles, which is 30.2 mV dec^–1.