Toward High-Performance Dihydrophenazine-Based Conjugated Microporous Polymer Cathodes for Dual-Ion Batteries through Donor–Acceptor Structural Design

Recent studies have demonstrated that dihydrophenazine (Pz) with high redox-reversibility and high theoretical capacity is an attractive building block to construct p-type polymer cathodes for dual-ion batteries. However, most reported Pz-based polymer cathodes to date still suffer from low redox activity, slow kinetics, and short cycling life. Herein, a donor–acceptor (D–A) Pz-based conjugated microporous polymer (TzPz) cathode is constructed by integrating the electron-donating Pz unit and the electron-withdrawing 2,4,6-triphenyl-1,3,5-triazine (Tz) unit into a polymer chain. The D–A type structure enhances the polymer conjugation degree and decreases the band gap of TzPz, facilitating electron transportation along the polymer skeletons. Therefore the TzPz cathode for dual-ion battery shows a high reversible capacity of 192 mAh g⁻¹ at 0.2 A g⁻¹ with excellent rate performance (108 mAh g⁻¹ at 30 A g⁻¹), which is much higher than that of its counterpart polymer BzPz produced from 1,3,5-triphenylbenzene (Bz) and Pz (148 and 44 mAh g⁻¹ at 0.2 and 10 A g⁻¹, respectively). More importantly, the TzPz cathode also shows a long and stable cyclability of more than 10 000 cycles. These results demonstrate that the D–A structural design is an efficient strategy for developing high-performance polymer cathodes for dual-ion batteries.     

Embedding carbon dots in Eu3+-doped metal-organic framework for label-free ratiometric fluorescence detection of Fe3+ ions

Fluorescent detection is a new spectroscopic measurement for ions sensing due to the advantages of real-time determination with high selectivity, accuracy, and low cost. However, chemosensors based on fluorescent detection are usually determined by absolute intensity from a monochromatic emission signal, which is easy to be fluctuated by the external environment, especially for Fe³⁺ detection in complex fluids. Herein, we rationally design a dual-emission Eu³⁺: CDs@ZIF-8 to construct a ratiometric fluorescent sensor with self-calibrating ability for Fe³⁺ determination. High efficient carbon dots (CDs) are embedded in europium ions (Eu³⁺)-doped MOF by simple stirring preparation at room temperature. The label-free ratiometric fluorescent probe (I_CDs@ZIF-8/I_Eu) exhibits simultaneous blue and red emission under the same excitation at 365 nm. Remarkably, Eu³⁺: CDs@ZIF-8 displays the superiority of high selectivity to Fe³⁺, which shows ratiometric fluorescence characteristics (I₀/I) in a range of 0-6 μmol\L with a low limit of detection (LOD) of 0.897 μmol\L. Besides, the CDs-MOF nanocomposite holds good aqueous dispersibility and low cytotoxicity, which shows great potential applications in medical aid including biological detection and clinical diagnosis.     

Tunable multicolor upconversion luminescence of Yb3+ sensitized Na3La(VO4)2 crystals

Multicolor upconversion luminescence materials show significantly applications in materials science. In this paper, the novel Yb³⁺-sensitized Na₃La(VO₄)₂ upconversion luminescence crystals are synthesized by the solid-state reaction method. Three primary colors upconversion luminescence are successfully achieved in Na₃La(VO₄)₂:Yb³⁺,Tm³⁺, Na₃La(VO₄)₂:Yb³⁺,Er³⁺, and Na₃La(VO₄)₂:Yb³⁺,Ho³⁺ crystals excited by the single 980 nm LD. Multicolor upconversion luminescence can be obtained by simply adjusting the combination ratios of these three samples. Luminescence mechanisms of the Yb³⁺-sensitized system are discussed in detail. In the Na₃La(VO₄)₂ host material, the Yb³⁺/Ho³⁺ codoped system exhibits unusual red upconversion luminescence based on the short decay time of Ho³⁺ ion ⁵I₆ level, which provides the possibility of three primary color luminescence under 980 nm excitation.     

Constructing magnetically recoverable CdS/CaFe2O4 P–N heterojunctions for enhanced photoelectrochemical properties towards H2 evolution reaction

A novel CdS/CaFe₂O₄ (CS/CFO) heterogeneous p-n junction was created by thermal deposition of CaFe₂O₄ nanoparticles on CdS rods. The CS/CFO hetero-structured photocatalysts exhibited increasingly efficient visible light harvesting compared to the bare CdS. The CS/CFO composites also presented higher photocurrent and slower decay of photoluminescence, suggesting a better separation of the photo-generated electrons and holes. The photocatalytic H₂ evolution quantity on the optimized CS/CFO composite from water in the presence of ethanol was up to 2200 μmol after 3-h visible light illumination, which is more than twice that of the pristine CdS. The chemical interaction between CdS and CaFe₂O₄ was confirmed by the shifts in the XPS peaks, which made it possible for the charge carriers to transfer across the p-n junction interface. This research highlights the importance of forming an interfacial p-n heterojunction between two semiconductors for efficient charge separation and improved photocatalytic performance.     

Far-red-emitting YAl3(BO3)4:Cr3+ phosphors with excellent thermal stability and high luminescent yield for plant growth LEDs

Phosphors-converted LEDs (pc-LEDs) are excellent artificial light sources for indoor plant cultivation, in which the far-red-emitting component (700−780 nm) plays an important role in regulating the photomorphogenesis of plants. Accordingly, highly efficient and thermally stable far-red-emitting phosphors are indispensable for developing high-performance plant cultivation pc-LEDs. Herein, far-red-emitting YAl₃(BO₃)₄:Cr³⁺ (YAB:Cr³⁺) phosphors were synthesized by solid-state reaction, and their photoluminescence characteristics, thermal quenching, quantum yield (QY), and application in pc-LEDs were systematically investigated. The YAB:Cr³⁺ phosphor has an intense broadband absorption to the blue light, simultaneously exhibiting the sharp-line ²E emission and the broadband ⁴ T₂ emission of Cr³⁺ with a QY of ~86.7%. The far-red broadband emissions of YAB:Cr³⁺ centered at ~735 nm show a high resemblance to the active-state (P_FR) absorption of plant phytochrome. Moreover, the YAB:Cr³⁺ phosphor shows the thermally enhanced luminescence at temperatures of 303−393 K and the near-zero thermal quenching up to 423 K. The anomalous thermal enhancement is attributed to the temperature-dependent repopulation between ²E and ⁴ T₂ states. Finally, a pc-LED device was fabricated with the YAB:Cr³⁺ phosphor and blue chip, exhibiting the light out power of ~50.6 mW and energy conversion efficiency of ~17.4% at 100 mA drive current, respectively. The exceptional PL features including suitable excitation/emission wavelengths, suppressed thermal quenching and high QY make YAB:Cr³⁺ phosphors very promising for applications in plant growth pc-LEDs.     

致密砂岩油藏能量补充方式评价及优化

针对致密砂岩油藏大规模体积压裂开发后能量补充困难的问题,利用自主设计制作的大型人造三维岩心物理模型和物理模拟实验舱,开展致密砂岩油藏能量补充方式优化研究。实验结果表明:致密砂岩油藏压裂开发过程中,地层能量损耗严重,采取注水或注气的方式可有效进行能量补充;地层中裂缝规模越大,越有利于原油渗流,后续补充能量的传播范围越广,有助于进一步提高原油采收率;从提高驱油效率和扩大波及系数方面优选吞吐渗吸介质,CO₂均优于活性水,CO₂吞吐开发在矿场试验中取得了显著的增油效果,因此,CO₂吞吐作为一种有效的能量补充方式在致密油开发中展现了良好的应用前景。该文分析了致密砂岩储层水平井压裂开发的渗流规律,优选出致密砂岩储层大规模压裂开发后最佳渗吸介质,可为致密砂岩油藏开发设计提供重要的理论依据。     

天然气水合物储层泥质细粉砂挡砂介质堵塞规律与微观挡砂机制

中国南海海域部分天然气水合物储层中地层砂为高泥质含量细粉砂，开采防控砂难度较大。针对高泥质细粉砂挡砂机制问题，使用粒度中值为10.13 μm的泥质细粉砂样品，模拟单向气液携砂流动条件，使用绕丝筛板、金属烧结网、金属纤维、预充填陶粒4类挡砂介质在20~80 μm挡砂精度下进行挡砂模拟实验，采用显微成像系统观察挡砂介质内部及表面砂粒沉积与堵塞动态，分析介质流通性能和挡砂性能变化，总结堵塞规律、微观挡砂机制与形态及其控制因素。研究结果表明，不同类型和精度的挡砂介质对泥质细粉砂的堵塞总体呈现堵塞开始、堵塞加剧和堵塞平衡3个阶段。随着驱替进行，挡砂介质渗透率逐渐降低，幅度会高达90%以上；同时过砂速度减缓，最终过砂率为5%~10%。根据堵塞规律和微观图像分析，提出了粗组分分选桥架、局部砂团适度挡砂、整体砂桥阻挡等挡砂介质对泥质细粉砂的3种微观挡砂机制。以粗组分分选桥架挡砂机制为主的挡砂工况下，挡砂介质堵塞渗透率较高，但过砂率超过15%，挡砂效果较差；以整体砂桥挡砂机制为主时，过砂率在10%以下，挡砂性能较好，但各类挡砂介质的堵塞渗透率不足1 D，流通性能较差。局部砂团适度挡砂机制为主时介质挡砂性能及流通性能介于两者之间。挡砂介质对天然气水合物储层泥质细粉砂的微观挡砂机制和形态受挡砂介质类型、精度、地层砂特征以及流动条件等因素控制，其规律对于水合物泥质细粉砂防控砂优化有指导意义。     

Progressive NO2 Sensors with Rapid Alarm and Persistent Memory-Type Responses for Wide-Range Sensing Using Antimony Triselenide Nanoflakes

Antimony triselenide (Sb₂Se₃) nanoflake-based nitrogen dioxide (NO₂) sensors exhibit a progressive bifunctional gas-sensing performance, with a rapid alarm for hazardous highly concentrated gases, and an advanced memory-type function for low-concentration (<1 ppm) monitoring repeated under potentially fatal exposure. Rectangular and cuboid shaped Sb₂Se₃ nanoflakes, comprising van der Waals planes with large surface areas and covalent bond planes with small areas, can rapidly detect a wide range of NO₂ gas concentrations from 0.1 to 100 ppm. These Sb₂Se₃ nanoflakes are found to be suitable for physisorption-based gas sensing owing to their anisotropic quasi-2D crystal structure with extremely enlarged van der Waals planes, where they are humidity-insensitive and consequently exhibit an extremely stable baseline current. The Sb₂Se₃ nanoflake sensor exhibits a room-temperature/low-voltage operation, which is noticeable owing to its low energy consumption and rapid response even under a NO₂ gas flow of only 1 ppm. As a result, the Sb₂Se₃ nanoflake sensor is suitable for the development of a rapid alarm system. Furthermore, the persistent gas-sensing conductivity of the sensor with a slow decaying current can enable the development of a progressive memory-type sensor that retains the previous signal under irregular gas injection at low concentrations.     

Bioinspired Supramolecular Slippery Organogels for Controlling Pathogen Spread by Respiratory Droplets

Surface-deposited pathogens are sources for the spread of infectious diseases. Protecting public facilities with a replaceable or recyclable antifouling coating is a promising approach to control pathogen transmission. However, most antifouling coatings are less effective in preventing pathogen-contained respiratory droplets because these tiny droplets are difficult to repel, and the deposited pathogens can remain viable from hours to days. Inspired by mucus, an antimicrobial supramolecular organogel for the control of microdroplet-mediated pathogen spread is developed. The developed organogel coating harvests a couple of unique features including localized molecular control-release, readily damage healing, and persistent fouling-release properties, which are preferential for antifouling coating. Microdroplets deposited on the organogel surfaces will be spontaneously wrapped with a thin liquid layer, and will therefore be disinfected rapidly due to a mechanism of spatially enhanced release of bactericidal molecules. Furthermore, the persistent fouling-release and damage-healing properties will significantly extend the life-span of the coating, making it promising for diverse applications.