Nanoporous Surface High-Entropy Alloys as Highly Efficient Multisite Electrocatalysts for Nonacidic Hydrogen Evolution Reaction

Electrocatalytic hydrogen evolution in alkaline and neutral media offers the possibility of adopting platinum-free electrocatalysts for large-scale electrochemical production of pure hydrogen fuel, but most state-of-the-art electrocatalytic materials based on nonprecious transition metals operate at high overpotentials. Here, a monolithic nanoporous multielemental CuAlNiMoFe electrode with electroactive high-entropy CuNiMoFe surface is reported to hold great promise as cost-effective electrocatalyst for hydrogen evolution reaction (HER) in alkaline and neutral media. By virtue of a surface high-entropy alloy composed of dissimilar Cu, Ni, Mo, and Fe metals offering bifunctional electrocatalytic sites with enhanced kinetics for water dissociation and adsorption/desorption of reactive hydrogen intermediates, and hierarchical nanoporous Cu scaffold facilitating electron transfer/mass transport, the nanoporous CuAlNiMoFe electrode exhibits superior nonacidic HER electrocatalysis. It only takes overpotentials as low as ≈240 and ≈183 mV to reach current densities of ≈1840 and ≈100 mA cm⁻² in 1 m  KOH and pH 7 buffer electrolytes, respectively; ≈46- and ≈14-fold higher than those of ternary CuAlNi electrode with bimetallic Cu–Ni surface alloy. The outstanding electrocatalytic properties make nonprecious multielemental alloys attractive candidates as high-performance nonacidic HER electrocatalytic electrodes in water electrolysis.     

Relaxor behavior and energy storage density induced by B-sites substitutions in (Ca0.28Ba0.72)2.1Na0.8Nb5O15 Tungsten bronze ceramics

Lead-free relaxor ferroelectrics (Ca_0.28Ba_0.72)_2.1Na_0.8Nb_5-xSb_xO₁₅ (CBNNS) and (Ca_0.28Ba_0.72)_2.1Na_0.8Nb_5-yTa_yO₁₅ (CBNNT) with tungsten bronze structure were fabricated via solid-state reactions. The obtained CBNNS and CBNNT ceramics showed different dielectric behaviors. Only the CBNNS ceramics revealed an intensified diffusion and relaxor-like characteristics, which could be verified by the modified Curie–Weiss law. The relaxor behaviors in CBNNS were attributed to the radii difference between Sb⁵⁺ and Nb⁵⁺ ions co-occupying in B-sites. For the substitution of Nb⁵⁺ by Sb⁵⁺ in CBNNS ceramics, the change from macroscopic polarization to local polarization could also give rise to the obvious relaxor behavior. The Raman spectra verified a larger off-centering of the cation and a higher distortion degree for BO₆ octahedron in the ab plane for CBNNS ceramics when compared with those of CBNNT. In addition, the ferroelectric properties of CBNNS ceramics further indicated the relaxor ferroelectric nature, and also confirmed that the relaxor behavior helped to improve the energy-storage performance.     

A broadband filter with two transmission zeros adopting a new design method

A new design method was proposed in this article to insert transmission zeros in the broadband filters. In this method, the coupling line was connected to a certain position on the resonator. And then the coupling strength was adjusted by the connecting position. The open end of the resonator was hung and then the cross‐coupling was introduced to realize transmission zeros. This coupling method could add an adjustable parameter to improve the freedom of design and convenient to insert the transmission zeros. To verify this method, a highly selective coupled‐line microstrip filter with two transmission zeros was designed, fabricated, and measured. The measured results were in good agreement with the simulated ones. The return and insertion losses of the broadband filter were better than 18 and 2 dB, respectively. The relative bandwidth of the filter (FBW) was more than 68%. The rectangular coefficient (30 dB:1 dB) was less than 1.21.     

Isolation and identification of two major acylated anthocyanins from purple sweet potato (Ipomoea batatas L. cultivar Eshu No. 8) by UPLC‐QTOF‐MS/MS and NMR

In recent years, researches on the isolation and preparation of monomeric anthocyanins have intensified because of the requirements of quantitative and structure–bioactivity relationship analyses. However, simple and effective methods about the scale of monomeric anthocyanins from the natural purple sweet potato powder are rarely reported. In this study, high molecular weight acylated monomeric anthocyanins were isolated from purple sweet potato (Ipomoea batatas L. cultivar Eshu No. 8) via the combination of column chromatography and semi‐preparative HPLC technology and identified mainly by ultra‐high‐performance liquid chromatography quadrupole time‐of‐flight tandem mass spectrometry/mass spectrometry (UPLC‐QTOF‐MS/MS) and ¹H and ¹³C nuclear magnetic resonance (NMR). Two major acylated anthocyanins were unambiguously determined as peonidin 3‐O‐(6‐O‐(E)‐caffeoyl‐(2‐O‐(6‐O‐p‐hydroxybenzoyl)‐β‐D‐glucopyranosyl)‐β‐D‐glucopyranoside)‐5‐O‐(β‐D‐glucopyranoside) and peonidin 3‐O‐(6‐O‐(E)‐caffeoyl‐(2‐O‐(6‐O‐(E)‐feruloyl)‐β‐D‐ glucopyranosyl)‐β‐D‐glucopyranoside)‐5‐O‐(β‐D‐glucopyranoside). The results of this study may help promote the purification of high molecular weight acylated anthocyanins from purple sweet potato as well as from other plant materials in nature.     

Controllability and observability of multi-agent systems with heterogeneous and switching topologies

ABSTRACT

This paper focuses on controllability and observability of multi-agent systems with heterogeneous and switching topologies, where the first- and the second-order information interaction topologies are different and switching. First, based on the controllable state set, a controllability criterion is obtained in terms of the controllability matrix corresponding to the switching sequence. Next, by virtue of the subspace sequence, two necessary and sufficient algebraic conditions are established for controllability in terms of the system matrices corresponding to all the possible topologies. Furthermore, controllability is considered from the graphic perspective. It is proved that the system is controllable if the union graph of all the possible topologies is controllable. With respect to observability, two sufficient and necessary conditions are derived by taking advantage of the system matrices and the corresponding invariant subspace, respectively. Finally, some simulation examples are worked out to illustrate the theoretical results.     

Preparation of transparent Y2O3 ceramic via gel casting: Realization of high solid volume via surface modification

In this article, isocyanate was adopted to modify Y₂O₃ powder for the purpose of preparing transparent Y₂O₃ ceramics via gel casting. The modification could enhance the hydration resistance of Y₂O₃ powder through the steric hindrance effect. The coating mechanism can be proved by the infrared spectrum of the surface-modified Y₂O₃ powder. Modification could not only prevent Y₂O₃ particles from reacting with water, but also prevents agglomeration between particles. The viscosity of the slurry with a solid content of 52.7 vol% is only 0.48 Pa·s at the shear rate of 100 s⁻¹, which is suitable for preparing high-density compacts by gel casting. The transmittance of the sample (1840°C × 8 h, 1 mm thickness) at 1100 nm reaches 75%. The microstructure of the sintered body is dense with the average grain size of 6.5 μm without obvious impurities nor pores. Five mol% ZrO₂-doped Y₂O₃ transparent ceramic fairing with the diameter of 5 cm without defects was successfully fabricated by gel casting (52.7 vol% solid volume) and vacuum sintering (1840°C × 8 h).     

Multi-Functional Black Bioactive Glasses Prepared via Containerless Melting Process for Tumor Therapy and Tissue Regeneration

Tissue regeneration in complex lesions such as the site of tumors, bacterial infection, and sites lacking blood vessels, has been a huge challenge. Therefore, developing bioactive implantable materials with multi-functional properties such as tumor destruction, bacteria growth inhibition, and angiogenesis promotion is of great significance. In this study, black CaO-SiO₂-TiO₂ (CST) glasses are prepared through the containerless melting approach, by which heterogeneous nucleation can be avoided and thereby glass formation becomes possible via fast quenching. This approach enables the formation of trivalent titanium (Ti³⁺) without using a reducing atmosphere or reducing agents. The black CST glasses are found in this study to possess a strong ability to inhibit bacteria and tumors by their excellent photothermal and photocatalytic effects. Strikingly, these glasses also promote the formation of blood vessels and accelerate the healing of chronic wounds by the synergistic effects of the photothermal effect and Si ions. Thus, this glass system can be a promising multi-functional material for tissue regeneration in complex lesions.     

In-situ self-reconstruction of Ni–Fe–Al hybrid phosphides nanosheet arrays enables efficient oxygen evolution in alkaline

Developing efficient oxygen evolution reaction (OER) electrocatalysts with earth-abundant elements is very important for sustainable H₂ generation via electrochemical water splitting. Here we design a crystalline-amorphous Ni–Fe–Al hybrid phosphides nanosheet arrays grown on NiFe foam for efficient OER application. Dynamic surface reorganization of phosphides at anodic/cathodic polarizations is probed by in situ Raman spectroscopy. The reconstructed amorphous Ni(Fe)OOH species are determined as the active phases that facilitate the OER process. This unique electrode shows highly catalytic activity toward water oxidation, achieving the current densities of 10 and 100 mA cm^?2 at 181 and 214 mV in 1 M KOH, respectively. Meanwhile, it also exhibits excellent stability at a large current density of 100 mA cm^?2 for over 60 h. This work reveals the dynamic structural transformation of pre-catalyst in realistic conditions and highlights the important role of oxyhydroxides as real reactive species in OER process with high activity.