Studies of Functional Defects for Fast Na‐Ion Conduction in Na3−yPS4−xClx with a Combined Experimental and Computational Approach

All‐solid‐state rechargeable sodium (Na)‐ion batteries are promising for inexpensive and high‐energy‐density large‐scale energy storage. In this contribution, new Na solid electrolytes, Na_3?yPS_4?xCl_x, are synthesized with a strategic approach, which allows maximum substitution of Cl for S (x = 0.2) without significant compromise of structural integrity or Na deficiency. A maximum conductivity of 1.96 mS cm^?1 at 25 °C is achieved for Na_3.0PS_3.8Cl_0.2, which is two orders of magnitude higher compared with that of tetragonal Na₃PS₄ (t‐Na₃PS₄). The activation energy (E_a) is determined to be 0.19 eV. Ab initio molecular dynamics simulations shed light on the merit of maximizing Cl‐doping while maintaining low Na deficiency in enhanced Na‐ion conduction. Solid‐state nuclear magnetic resonance (NMR) characterizations confirm the successful substitution of Cl for S and the resulting change of P oxidation state from 5+ to 4+, which is also verified by spin moment analysis. Ion transport pathways are determined with a tracer‐exchange NMR method. The functional detects that promote Na ‐ion transport are maximized for further improvement in ionic conductivity. Full‐cell performance is demonstrated using Na/Na_3.0PS_3.8Cl_0.2/Na₃V₂(PO₄)₃ with a reversible capacity of ≈100 mAh g^‐1 at room temperature.     

Flexible and Transparent Electrochromic Displays with Simultaneously Implementable Subpixelated Ion Gel‐Based Viologens by Multiple Patterning

Electrochromic materials reversibly change colors by redox reactions depending on the oxidation states. To utilize electrochromic materials for active‐matrix display applications, an electrochromic display (ECD) requires simultaneous implementation of various colors and a fine‐pixelation process. Herein, flexible and transparent ECDs with simultaneously implementable subpixelated EC gels by sequential multiple patterning are successfully demonstrated. Ionic liquid‐based EC gels of monoheptyl‐viologen, diheptyl‐viologen (DHV), and diphenyl‐viologen (DPV) are used to create the colors of ECDs: magenta, blue, and green, respectively. Especially, to realize an improved green color, DHV–DPV composite gels are synthesized. Three EC gels exhibit stable properties without degradation during repetitive operation. Moreover, a transmittance greater than 90% is maintained in a bleached state, which is sufficient for application as a transparent display. The subpixelation process for multicolored‐flexible ECDs is designed to facilitate both easy fabrication and rapid operation with various patterns at low cost. The subpixelated EC gels using a film mask can be implemented to a minimum size of 200 µm. Furthermore, the subpixelated flexible ECDs exhibit high durability even after 1000 cycles of mechanical bending tests at a bending radius of 10 mm. Therefore, these EC materials can be used directly for flexible and transparent active‐matrix displays.     

Anti‐Oxygen Leaking LiCoO2

LiCoO₂ is a prime example of widely used cathodes that suffer from the structural/thermal instability issues that lead to the release of their lattice oxygen under nonequilibrium conditions and safety concerns in Li‐ion batteries. Here, it is shown that an atomically thin layer of reduced graphene oxide can suppress oxygen release from Li_xCoO₂ particles and improve their structural stability. Electrochemical cycling, differential electrochemical mass spectroscopy, differential scanning calorimetry, and in situ heating transmission electron microscopy are performed to characterize the effectiveness of the graphene‐coating on the abusive tolerance of Li_xCoO₂. Electrochemical cycling mass spectroscopy results suggest that oxygen release is hindered at high cutoff voltage cycling when the cathode is coated with reduced graphene oxide. Thermal analysis, in situ heating transmission electron microscopy, and electron energy loss spectroscopy results show that the reduction of Co species from the graphene‐coated samples is delayed when compared with bare cathodes. Finally, density functional theory and ab initio molecular dynamics calculations show that the rGO layers could suppress O₂ formation more effectively due to the strong C? O_cathode bond formation at the interface of rGO/LCO where low coordination oxygens exist. This investigation uncovers a reliable approach for hindering the oxygen release reaction and improving the thermal stability of battery cathodes.     

Precise Molecular Engineering of Photosensitizers with Aggregation‐Induced Emission over 800 nm for Photodynamic Therapy

Owing to efficient singlet oxygen (¹O₂) generation in aggregate state, photosensitizers (PSs) with aggregation‐induced emission (AIE) have attracted much research interests in photodynamic therapy (PDT). In addition to high ¹O₂ generation efficiency, strong molar absorption in long‐wavelength range and near‐infrared (NIR) emission are also highly desirable, but difficult to achieve for AIE PSs since the twisted structures in AIE moieties usually lead to absorption and emission in short‐wavelength range. In this contribution, through acceptor engineering, a new AIE PS of TBT is designed to show aggregation‐induced NIR emission centered at 810 nm, broad absorption in the range between 300 and 700 nm with a large molar absorption coefficient and a high ¹O₂ generation efficiency under white light irradiation. Further, donor engineering by attaching two branched flexible chains to TBT yielded TBTC8 , which circumvented the strong intermolecular interactions of TBT in nanoparticles (NPs), yielding TBTC8 NPs with optimized overall performance in ¹O₂ generation, absorption, and emission. Subsequent PDT results in both in vitro and in vivo studies indicate that TBTC8 NPs are promising candidates in practical application.     

Mimicking Neuroplasticity in a Hybrid Biopolymer Transistor by Dual Modes Modulation

Neuromorphic computing systems that are capable of parallel information storage and processing with high area and energy efficiencies, offer important opportunities for future storage systems and in‐memory computing. Here, it is shown that a carbon dots/silk protein (CDs/silk) blend can be used as a light‐tunable charge trapping medium to fabricate an electro‐photoactive transistor synapse. The synaptic device can be optically operated in volatile or nonvolatile modes, ensuring concomitant short‐term and long‐term neuroplasticity. The synaptic‐like behaviors are attributed to the photogating effect induced by trapped photogenerated electrons in the hybrid CDs/silk film which is confirmed with atomic force microscopy based electrical techniques. In addition, system‐level pattern recognition capability of the synaptic device is evaluated by a single‐layer perceptron model. The remote optical operation of neuromorphic architecture provides promising building blocks to complete bioinspired photonic computing paradigms.     

Robust Design of Dual‐Phasic Carbon Cathode for Lithium–Oxygen Batteries

Given that the performance of a lithium–oxygen battery (LOB) is determined by the electrochemical reactions occurring on the cathode, the development of advanced cathode nanoarchitectures is of great importance for the realization of high‐energy‐density, reversible LOBs. Herein, a robust cathode design is proposed for LOBs based on a dual‐phasic carbon nanoarchitecture. The cathode is composed of an interwoven network of porous metal–organic framework (MOF) derived carbon (MOF‐C) and conductive carbon nanotubes (CNTs). The dual‐phasic nanoarchitecture incorporates the advantages of both components: MOF‐C provides a large surface area for the oxygen reactions and a large pore volume for Li₂O₂ storage, and CNTs provide facile pathways for electron and O₂ transport as well as additional void spaces for Li₂O₂ accommodation. It is demonstrated that the synergistic nanoarchitecturing of the dual‐phasic MOF‐C/CNT material results in promising electrochemical performance of LOBs, as evidenced by a high discharge capacity of ≈10 050 mAh g^?1 and a stable cycling performance over 75 cycles.     

Rational Engineering of Multilayered Co3O4/ZnO Nanocatalysts through Chemical Transformations from Matryoshka‐Type ZIFs

Hybrid metal oxides with multilayered structures exhibit unique physical and chemical properties, particularly important to heterogeneous catalysis. However, regulations of morphology, spatial location, and shell numbers of the hybrid metal oxides still remain a challenge. Herein, binary Co₃O₄/ZnO nanocages with multilayered structures (up to eight layers) are prepared via chemical transformation from diverse Matryoshka‐type zeolitic imidazolate frameworks (ZIFs) via a straightforward and scalable calcination method. More importantly, the obtained ZIF‐derived metal oxides (ZDMOs) with versatile layer numbers exhibit remarkable catalytic activity for both gas‐phase CO oxidation and CO₂ hydrogenation reactions, which are directly related to the sophisticated shell numbers (i.e., Co₃O₄‐terminated layers or ZnO‐terminated layers). Particularly, in situ reflectance infrared Fourier transform spectroscopy (DRIFTS) results indicate that the promotional effects of the multilayered structures indeed exist in CO₂ hydrogenation, wherein the key reaction intermediates are quite different for five‐layer and six‐layer ZDMOs. For instance, *HCOO is the predominant intermediate over the six‐layer ZDMO; on the contrary, *H₃CO is the crucial species over the five‐layer ZDMO. The ZnO/Co₃O₄ interface should be the active sites for CO₂ hydrogenation to *HCOO and *H₃CO species, which are ultimately converted to the products (CH₄ or methanol). Accordingly, the work here provides a convenient way to facilely engineer multilayered Co₃O₄/ZnO nanocomposites with precisely controlled shell numbers for heterogeneous catalysis applications.     

3D Macroscopic Architectures from Self‐Assembled MXene Hydrogels

Assembly of 2D MXene sheets into a 3D macroscopic architecture is highly desirable to overcome the severe restacking problem of 2D MXene sheets and develop MXene‐based functional materials. However, unlike graphene, 3D MXene macroassembly directly from the individual 2D sheets is hard to achieve for the intrinsic property of MXene. Here a new gelation method is reported to prepare a 3D structured hydrogel from 2D MXene sheets that is assisted by graphene oxide and a suitable reductant. As a supercapacitor electrode, the hydrogel delivers a superb capacitance up to 370 F g^?1 at 5 A g^?1, and more promisingly, demonstrates an exceptionally high rate performance with the capacitance of 165 F g^?1 even at 1000 A g^?1. Moreover, using controllable drying processes, MXene hydrogels are transformed into different monoliths with structures ranging from a loosely organized porous aerogel to a dense solid. As a result, a 3D porous MXene aerogel shows excellent adsorption capacity to simultaneously remove various classes of organic liquids and heavy metal ions while the dense solid has excellent mechanical performance with a high Young's modulus and hardness.     

Engineering a Nanoscale Al‐MOF‐Armored Antigen Carried by a “Trojan Horse”‐Like Platform for Oral Vaccination to Induce Potent and Long‐Lasting Immunity

Vaccination via the oral administration of an antigen faces many challenges, including gastrointestinal (GI) proteolysis and mucosal barriers. To limit GI proteolysis, a biomimetically mineralized aluminum‐based metal–organic framework (Al‐MOF) system that is resistant to ambient temperature and pH and can act synergistically as a delivery vehicle and an adjuvant is synthesized over a model antigen ovalbumin (OVA) to act as armor. To overcome mucosal barriers, a yeast‐derived capsule is used to carry the Al‐MOF‐armored OVA as a “Trojan Horse”‐like transport platform. In vitro experiments reveal that the mineralization of Al‐MOFs forms an armor on OVA that protects against highly acidic and degradative GI conditions. However, the mineralized Al‐MOFs can gradually disintegrate in a phosphate ion‐containing simulated intracellular fluid, slowly releasing their encapsulated OVA. In vivo studies reveal that the “Trojan Horse”‐like transport platform specifically targets intestinal M cells, favoring the transepithelial transport of the Al‐MOF‐armored OVA, followed by subsequent endocytosis in local macrophages, ultimately accumulating in mesenteric lymph nodes, yielding long‐lasting, high‐levels of mucosal S‐IgA and serum IgG antibodies. Such an engineered delivery platform may represent a promising strategy for the oral administration of prophylactic or therapeutic antigens for vaccination.     

Rear‐Passivated Ultrathin Cu(In,Ga)Se2 Films by Al2O3 Nanostructures Using Glancing Angle Deposition Toward Photovoltaic Devices with Enhanced Efficiency

In this work, for the first time, the addition of aluminum oxide nanostructures (Al₂O₃ NSs) grown by glancing angle deposition (GLAD) is investigated on an ultrathin Cu(In,Ga)Se₂ device (400 nm) fabricated using a sequential process, i.e., post‐selenization of the metallic precursor layer. The most striking observation to emerge from this study is the alleviation of phase separation after adding the Al₂O₃ NSs with improved Se diffusion into the non‐uniformed metallic precursor due to the surface roughness resulting from the Al₂O₃ NSs. In addition, the raised Na concentration at the rear surface can be attributed to the increased diffusion of Na ion facilitated by Al₂O₃ NSs. The coverage and thickness of the Al₂O₃ NSs significantly affects the cell performance because of an increase in shunt resistance associated with the formation of Na₂Se_X and phase separation. The passivation effect attributed to the Al₂O₃ NSs is well studied using the bias‐EQE measurement and J–V characteristics under dark and illuminated conditions. With the optimization of the Al₂O₃ NSs, the remarkable enhancement in the cell performance occurs, exhibiting a power conversion efficiency increase from 2.83% to 5.33%, demonstrating a promising method for improving ultrathin Cu(In,Ga)Se₂ devices, and providing significant opportunities for further applications.