Progress of Phosphate-based Polyanion Cathodes for Aqueous Rechargeable Zinc Batteries

Aqueous rechargeable zinc batteries (ARZBs) are recently prevailing devices that utilize the abundant Zn resources and the merits of aqueous electrolytes to become a competitive alternative for large-scale energy storage. Benefiting from the unique inductive effect and flexible structure, the past five years have experienced a diversiform of phosphate-based polyanion materials that are used as cathodes in ARZBs. In this review, the most recent advances in the Zn²⁺ storage mechanisms and electrolyte optimization of the phosphate-based cathodes of ARZBs, which mainly focus on vanadium/iron-based phosphates and their derivatives are presented. Furthermore, in addition to significant progress on polyanion phosphate-based cathode materials, the design strategies both for electrode materials and compatible electrolytes are also elaborated to improve the energy density and extend the cycling life of aqueous Zn/polyanion batteries.     

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.     

Boosting Piezo-Catalytic Activity of KNN-Based Materials with Phase Boundary and Defect Engineering

Although the piezo-catalysis is promising for the environmental remediation and biomedicine, the piezo-catalytic properties of various piezoelectric materials are limited by low carrier concentrations and mobility, and rapid electron-hole pair recombination, and reported regulating strategies are quite complex and difficult. Herein, a new and simple strategy, integrating phase boundary engineering and defect engineering, to boost the piezo-catalytic activity of potassium sodium niobate ((K, Na)NbO₃, KNN) based materials is innovatively proposed. Tur strategy is validated by exampling 0.96(K_0.48Na_0.52)Nb_0.955Sb_0.045O₃-0.04(Bi_xNa_4-3x)_0.5ZrO₃-0.3%Fe₂O₃ material having phase boundary engineering and conducted the defect engineering via the high-energy sand-grinding. A high reaction rate constant k of 92.49 × 10⁻³ min⁻¹ in the sand-grinding sample is obtained, which is 2.40 times than that of non-sand-grinding one and superior to those of other representative lead-free perovskite piezoelectric materials. Meanwhile, the sand-grinding sample has remarkable bactericidal properties against Escherichia coli and Staphylococcus aureus. Superior piezo-catalytic activities originate from the enhanced electron-hole pair separation and the increased carrier concentration. This study provides a novel method for improving the piezo-catalytic activities of lead-free piezoelectric materials and holds great promise for harnessing natural energy and disease treatment.     

New Polymerized Small Molecular Acceptors with Non-Aromatic π-Conjugated Linkers for Efficient All-Polymer Solar Cells

Developing new polymerized small molecular acceptor (PSMA) is pivotal for improving the performance of all-polymer solar cells. On the basis of this newly developed CH-series small molecule acceptors, two PSMAs are reported herein (namely PZC16 and PZC17, respectively). To reduce the molecular torsion caused by the traditional aromatic π-bridges, non-aromatic conjugated units (ethynyl for PZC16 and vinylene for PZC17) are adopted as the linkers and their effect on the photo-physical properties as well as the device performance are systematically investigated. Both polymer acceptors exhibit co-planar molecular conformation, along with broad absorption ranges and suitable energy levels. In comparison with the PM6:PZC16 film, the PM6:PZC17 film exhibits more uniform phase separation in morphology with a distinct bi-continuous network and better crystallinity. The PM6:PZC17-binary-based devices exhibit a satisfactory PCE of 16.33%, significantly higher than 9.22% of the PZC16-based devices. Impressively, PM6:PZC17-based large area device (ca. 1 cm²) achieves an excellent PCE of 15.14%, which is among the top performance for reported all-polymer solar cells (all-PSCs).     

A Polymer Defect Passivator for Efficient Hole-Conductor-Free Printable Mesoscopic Perovskite Solar Cells

Due to the low cost and excellent potential for mass production, printable mesoscopic perovskite solar cells (p-MPSCs) have drawn a lot of attention among other device structures. However, the low open-circuit voltage (V_OC) of such devices restricts their power conversion efficiency (PCE). This limitation is brought by the high defect density at perovskite grain boundaries in the mesoporous scaffold, which results in severe nonradiative recombination and is detrimental to the V_OC. To improve the perovskite crystallization process, passivate the perovskite defects, and enhance the PCE, additive engineering is an effective way. Herein, a polymeric Lewis base polysuccinimide (PSI) is added to the perovskite precursor solution as an additive. It improves the perovskite crystallinity and its carbonyl groups strongly coordinate with Pb²⁺, which can effectively passivate defects. Additionally, compared with its monomer, succinimide (SI), PSI serves as a better defect passivator because the long-chained macromolecule can be firmly anchored on those defect sites and form a stronger interaction with perovskite grains. As a result, the champion device has a PCE of 18.84%, and the V_OC rises from 973 to 1030 mV. This study offers a new strategy for fabricating efficient p-MPSCs.     

A 2.20 eV Bandgap Polymer Donor for Efficient Colorful Semitransparent Organic Solar Cells

Semitransparent organic solar cells (ST-OSCs) have attracted increasing attention due to their promising prospect in building-integrated photovoltaics. Generally, efficient ST-OSCs with good average visible transmittance (AVT) can be realized by developing active layer materials with light absorption far from the visible light range. Herein, the development of ultrawide bandgap polymer donors with near-ultraviolet absorption, paired with near-infrared acceptors, is proposed to achieve high-performance ST-OSCs. The key points for the design of ultrawide bandgap polymers include constructing donor–donor type conjugated skeleton, suppressing the quinoidal resonance effect, and minimizing the twist of conjugated skeleton via noncovalent conformational locks. As a proof of concept, a polymer named PBOF with an optical bandgap of 2.20 eV is synthesized, which exhibited largely reduced overlap with the human eye photopic response spectrum and afforded a power conversion efficiency (PCE) of 16.40% in opaque device. As a result, ST-OSCs with a PCE over 10% and an AVT over 30% are achieved without optical modulation. Moreover, colorful ST-OSCs with visual aesthetics can be achieved by tuning the donor/acceptor weight ratio in active layer benefiting from the ultrawide bandgap nature of PBOF. This study demonstrates the great potential of ultrawide bandgap polymers for efficient colorful ST-OSCs.     

Macrophage Membrane-Coated Nanoparticles Sensitize Glioblastoma to Radiation by Suppressing Proneural–Mesenchymal Transformation in Glioma Stem Cells

Radiotherapy is identified as a crucial treatment for patients with glioblastoma, but recurrence is inevitable. The efficacy of radiotherapy is severely hampered partially due to the tumor evolution. Growing evidence suggests that proneural glioma stem cells can acquire mesenchymal features coupled with increased radioresistance. Thus, a better understanding of mechanisms underlying tumor subclonal evolution may develop new strategies. Herein, data highlighting a positive correlation between the accumulation of macrophage in the glioblastoma microenvironment after irradiation and mesenchymal transdifferentiation in glioblastoma are presented. Mechanistically, elevated production of inflammatory cytokines released by macrophages promotes mesenchymal transition in an NF-κB-dependent manner. Hence, rationally designed macrophage membrane-coated porous mesoporous silica nanoparticles (MMNs) in which therapeutic anti-NF-κB peptides are loaded for enhancing radiotherapy of glioblastoma are constructed. The combination of MMNs and fractionated irradiation results in the blockage of tumor evolution and therapy resistance in glioblastoma-bearing mice. Intriguingly, the macrophage invasion across the blood-brain barrier is inhibited competitively by MMNs, suggesting that these nanoparticles can fundamentally halt the evolution of radioresistant clones. Taken together, the biomimetic MMNs represent a promising strategy that prevents mesenchymal transition and improves therapeutic response to irradiation as well as overall survival in patients with glioblastoma.     

Ultra-Stable and Sensitive Ultraviolet Photodetectors Based on Monocrystalline Perovskite Thin Films

The detection of ultraviolet (UV) radiation with effective performance and robust stability is essential to practical applications. Metal halide single-crystal perovskites (ABX₃) are promising next-generation materials for UV detection. The device performance of all-inorganic CsPbCl₃ photodetectors (PDs) is still limited by inner imperfection of crystals grown in solution. Here wafer-scale single-crystal CsPbCl₃ thin films are successfully grown by vapor-phase epitaxy method, and the as-constructed PDs under UV light illumination exhibit an ultralow dark current of 7.18 pA, ultrahigh ON/OFF ratio of ≈5.22 × 10⁵, competitive responsivity of 32.8 A W⁻¹, external quantum efficiency of 10867% and specific detectivity of 4.22 × 10¹² Jones. More importantly, they feature superb long-term stability toward moisture and oxygen within twenty-one months, good temperature tolerances at low and high temperatures. The ability of the photodetector arrays for excellent UV light imaging is further demonstrated.     

C-Shaped Cartilage Development Using Wharton's Jelly-Derived Hydrogels to Assemble a Highly Biomimetic Neotrachea for use in Circumferential Tracheal Reconstruction

A highly biomimetic neotrachea with C-shaped cartilage rings has promising clinical applications in the treatment of circumferential tracheal defects (CTDs) owing to its structure and physiological function. However, to date, most fabricated tracheal cartilages are O-shaped. In this study, finite element analysis demonstrates C-shaped cartilage rings that exhibit better compliance than O-shaped. Hydrogel is developed using methacryloyl-modified decellularized Wharton's jelly matrix (DWJMA) for the regeneration of C-shaped cartilage rings. This novel hydrogel possesses adjustable physicochemical properties and favorable cytocompatibility. When loaded with chondrocytes, DWJMA hydrogels support the optimal cartilage regeneration both in vitro and in vivo. More importantly, a highly biomimetic neotrachea simultaneously simulating the structural and physiological properties of the normal trachea is regenerated via modular assembly of several individual C-shaped cartilage rings. The results demonstrate the highly biomimetic neotrachea have better patency (88.6 ± 6.1% vs 74.4 ± 9.4%, p < 0.05), improve the survival rate, alleviate weight loss and mucoid impaction, than its O-shaped counterpart when used for the treatment of CTDs in a rabbit model. Therefore, this study proposes a novel hydrogel for the regeneration of C-shaped cartilage and provides new insights into the treatment of CTDs using a highly biomimetic neotrachea with C-shaped cartilage rings.