Step-scheme perylenediimide supramolecular nanosheet and TiO2 nanoparticle composites for boosted water splitting performance

Adjusting the band gap of organic-inorganic composites by chemical bonding can effectively construct Step-scheme (S-scheme) heterojunctions, featuring properties of fast photogenerated charge migration and excellent photocatalytic performance. In this work, a novel perylene-3, 4, 9, 10-tetracarboxylicdiimide (PDI)-titanium dioxide (TiO₂) heterojunction is elaborately synthesized through simple solvent compounding method. The monodispersed spherical TiO₂ nanoparticles was prepared with the capping agents of oleylamine and oleic acid, and suffered by a ligand exchange process with nitrosonium tetrafluoroborate (NOBF₄) to remove oleylamine and oleic acid. The NOBF₄ ligands were further replaced by PDI super molecular nanosheets to obtain two dimensional (2D)-zero dimensional (0D) PDI-TiO₂ composites. TiO₂ nanoparticles are evenly anchored on the surface of PDI nanosheets with intimate contact. The PDI-TiO₂ composites has emerged considerably superior activity in hydrogen evolution. The highest hydrogen evolution rate for PDI-TiO₂composites with the PDI weight percentage of 2.4% was 9766 μmol h^?1 g^?1 under solar light irradiation, which is 2.56 times of TiO₂-NOBF₄ catalyst. Moreover, PDI-TiO₂ composites possess stoichiometric overall water splitting performance with H₂ and O₂ release rates of 238.20 and 114.18 μmol h^?1 g^?1. The superior photocatalytic performance of PDI-TiO₂ composites can be attributed to the dramatic increase in visible and NIR light absorption caused by π-π stacking structure of PDI, the prevented charge recombination by the S-scheme heterojunction, and the enhanced oxygen evolution by the stronger oxidation capability of PDI. PDI supramolecular nanosheets may work as a novel functional support for many types of semiconductor nanomaterials as graphene, which will display a wide range of application prospects in the energy and environmental fields.     

Synergetic photocatalytic and thermocatalytic aqueous phase reforming of methanol for hydrogen production based on noble metal/photosensitive supports catalysts

To overcome high Gibbs free energy and low reaction rate of thermal catalytic and photocatalytic hydrogen production from methanol-H₂O mixture, photo-thermal synergistic catalysis (PC-TC) reforming has proved to be an effective strategy owing to the photo-assited thermal synergistic effect to accelerate the step controlling kinetic behavior. In order to efficiently produce H₂, proper photosensitive catalysts which absorb light energy and also show efficient thermal catalytic (TC) performance need to be developed. To study the designing principle for catalysts, herein we incorporate Pt/Pd and three different supports which show similar band gaps (ZnO, CeO₂, and P25) through the in-situ photo-deposition, which act as catalysts for PC-TC methanol aqueous reforming. The resultant 0.1%Pt/P25 catalyst exhibits H₂ evolution activity ～3.1 times than that of the TC condition and ～5.5 times than that of the photocatalytic reforming (PC) condition in the proposed PC-TC process; meanwhile 0.1%Pt/ZnO and 01%Pt/CeO₂ under PC-TC condition show ～1.3 times and ～2.0 times than that of the catalytic performance under TC condition. The physical characterizations prove that the metal-support interaction and the supports may be key factors for the catalytic performance. The active intermediate trapping experiments demonstrate possible intermediates in the PC-TC process and established reaction mechanisms to explain the synergetic effect for improved efficiency of hydrogen production. These findings may open up a new avenue of designing catalysts based on semiconductors for the PC-TC reforming of methanol-water to produce hydrogen in a high-efficiency and low-cost way, serving the needs of the future hydrogen economy.     

Dual functions of three-dimensional hierarchical architecture on improving the rate capability and cycle performance of LiNi0.8Co0.1Mn0.1O2 cathode material for lithium-ion battery

The main obstacles in lithium-ion battery are limited by rate performance and the rapid capacity fading of LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811). Herein, a novel three-dimensional (3D) hierarchical coating material has been fabricated by in situ growing carbon nanotubes (CNTs) on the surfaces of Ni–Al double oxide (Ni–Al-LDO) sheets (named as LDO&CNT) with Ni–Al double hydroxide (Ni–Al-LDH) as both the substrate and catalyst precursor. The resultant LDO&CNT nanocomposites are uniformly coated on the surfaces of NCM811 by the physical mixing method. The rate capability of the resultant cathode material retains to 78.80% at a current rate of 3C. Its capacity retention increases by 6.7–14.42% compared with pristine NCM811 after 100 cycles within a potential range of 2.75–4.3 V at 0.5C. The improved rate capability and cycle performance of NCM811 are assigned to the synergistic effects between Ni–Al-LDO and CNTs. The hierarchical LDO&CNT nanocomposites coating on the surface of NCM811 avoids the aggregation of conductive CNTs and the stacking of Ni–Al-LDO nanosheets. Furthermore, it accelerates Li⁺ and electrons shuttle and reduces the reaction of Li₂O with H₂O and CO₂ in air, which results in Li₂CO₃ and LiOH alkali formation on the NCM811 surface.     

Silica-based ceramics toward electromagnetic microwave absorption

Silica-based ceramics have been explored extensively as a class of versatile materials for various applications in architecture, catalysis, energy, machinery, and biomedical engineering. Nevertheless, comprehensive information on silica-based ceramic and electromagnetic microwave (EMW) absorption is scarce, although excellent progress has been made in this field. Here, recent progress in the investigation of silica-based ceramics toward EMW absorption is reviewed. We first introduced the basis of ceramics (characteristics, classification, synthetic methods, potential applications). Subsequently, the silica-based ceramics, including Si-based oxides and alloys, SiOC/SiC/Si₃N₄/SiCN-based composite, Ti₃SiC₂ and composite for EMW absorption were systematically summarized. Notably, the fabrication strategies, absorption properties, and mechanisms of silica-based ceramics are described in detail, with a focus on structure and component design. Lastly, the prospects and ongoing challenges of this field in the future are presented. This review is expected to learn from the past and achieve progress toward the future of silica-based ceramic for EMW absorption.     

The effect of the exposed crystal plane on the antioxidant activity of nanoceria

Previous reports have noted that exposed crystal planes could affect the antioxidant activity of nanocerias, although the synthesized nanocerias used in those studies had different exposed crystal planes, as well as different sizes and morphologies. In order to better understand the effect of the crystal planes on the antioxidant activity of the materials, two types of nanocerias with similar morphology and size distribution but different crystal planes were synthesized using the hydrothermal method (CeO₂–H) and the ultrasonic template method (CeO₂–U). The antioxidant activities of the nanocerias were further explored within different ·OH concentrations in the reaction system. The experimental results showed that there is an obvious difference in the antioxidant activity of the two types of nanocerias in the lower free radical concentration system due to the effects of exposed crystal planes. CeO₂–U, with more active crystal planes (100), had stronger antioxidant activity. However, with the increase in the ·OH concentration in the reaction system, the difference in the antioxidant activity of the two nanocerias decreased. This research will increase our understanding of the antioxidant activity of the exposed crystal planes on nanocerias.     

Deep-blue thermally activated delayed fluorescence emitter with a very high fluorescence rate

Conventional thermally activated delayed fluorescence (TADF) molecules achieve small energy differences between the lowest singlet and triplet excited states (ΔE_ST) by enhancing the intramolecular charge transfer, which inevitably leads to a wide emission spectrum and low fluorescence rate. Here, we prepared a deep blue TADF molecule via a small ΔE_ST pyridine-phenol fluoroboron complex as the acceptor. The small ΔE_ST is maintained when carbazole donors are attached to the 4-position of the phenyl rings in the fluoroboron complex. Benefiting from the strong electron coupling between the donor (D) and acceptor (A) moieties, the compound Cz-4-BF exhibits a high fluorescence rate of 4.8 × 10⁸ s⁻¹ and a small D-A dihedral angle change in the excited state. Consequently, a photoluminescence (PL) quantum yield of nearly 100% and a PL spectrum with full-width at half-maximum (FWHM) < 60 nm were obtained in solution and low-concentration doped films. A TADF-sensitized fluorescence (TSF) device containing Cz-4-BF achieves an external quantum efficiency of 21%, which is higher than the devices employing classical fluorescent emitters and multiple resonance-type TADF emitters. The Cz-4-BF-based TSF device shows significantly improved color coordinates of (0.14, 0.10) versus a control device without Cz-4-BF.     

Cold plasma hydrophilization of soy protein isolate and milk protein concentrate enables manufacturing of surfactant-free water suspensions. Part I: Hydrophilization of food powders using cold plasma

In this study, we found that treatment with cold plasma influenced the wetting properties of soy protein isolate and milk protein concentrate powders. Cold plasma treatment significantly decreased the apparent contact angle of the powders, indicating hydrophilization of the powders. Cold radiofrequency low-pressure plasma treatment had a larger effect on powder wettability than corona atmospheric plasma discharge. In addition, cold plasma treatment had a more noticeable effect on the wettability of the hydrophobic milk protein concentrate than on the inherently hydrophilic soy protein isolate. Both the soy protein isolate and milk protein concentrate demonstrated zero hydrophobic recovery over time. Scanning electron microscopy showed that cold air plasma treatment of food powders caused minor surface oxidation, though these changes were not observed using FTIR spectroscopy. We suggest that cold plasma treatment has important implications for the production of stabilizer-free food suspensions.     

Alkali metal ion substitution induced luminescence enhancement of NaLaMgWO6:Eu3+ red phosphor for white light-emitting diodes

Alkali metal ion substitution is an effective strategy to improve the luminescence properties of phosphors. In this work, a series of red-emitting phosphors Na_1-xLi_x/2K_x/2La_0.6Eu_0.4MgWO₆ were prepared by a traditional high-temperature solid-state reaction. Their phase structure, microstructure, luminescence properties and potential application in phosphor-converted white light-emitting diodes (pc-WLEDs) were investigated in detail. X-ray diffraction (XRD) result revealed the formation of a solid solution when x?≤?0.3, which kept monoclinic structure of NaLaMgWO₆. Photoluminescence investigation indicated that the partial substitution of Li⁺/K⁺ ions for Na⁺ ions improved largely the red emission of Eu³⁺. Based on the optimized Na_0.7Li_0.15K_0.15La_0.6Eu_0.4MgWO₆ sample with relatively good thermal stability, a WLED device was fabricated by combining a near-ultraviolet (NUV) chip (~400?nm) with the phosphor mixture of commercial green/blue phosphors and the optimized red phosphor. The results indicated that the optimized red phosphor in this work could be a potential candidate for WLEDs pumped by NUV chips.     

Effects of salt-induced changes in protein network structure on the properties of surimi gels: computer simulation and digestion study

Surimi is considered a new base ingredient in special dietary foods because of its excellent gel formation properties and nutritional value. Cross-linked network structures are the basis for the formation of protein hydrogels. In this work, protein network structure induced by NaCl was investigated to evaluate its effects on texture property and digestibility of surimi gels. Micro-protein frameworks were investigated by scanning electron microscope combined with computer simulation, which indicated that the network structure became fine and smooth as a result of salt treatment. The digestibility of surimi with NaCl was higher than that of blank samples in simulated gastric juice in first 30 min, whereas the digestibility showed no significant difference (P = 0.257) in intestinal juice after 180 min. This work aids in understanding of the contribution of salt to the mechanism of surimi gels formation, and its effects on digestion, thus supporting potential applications in special dietary food.