ABSTRACT Aqueous zinc‐based batteries (ZBs) are widely regarded as highly promising candidates for next‐generation energy storage, primarily owing to their intrinsic safety, cost‐effectiveness, and impressive energy density. Nevertheless, their practical commercialization is severely bottlenecked by chronic interfacial instabilities, including uncontrollable zinc dendrite proliferation and severe water‐induced parasitic reactions. To fundamentally address these common challenges, transitioning from liquid electrolytes to quasi‐solid‐state electrolytes (QSSEs) is a highly promising approach. Among the various QSSEs matrixes, natural biomass materials such as cellulose, alginate, chitosan, and lignin have emerged as excellent candidates for framework materials due to their abundant availability, natural sustainability, and unique physicochemical properties. This review comprehensively examines the recent advancements in biomass‐derived QSSEs for ZBs. We systematically elucidate the core energy storage mechanisms and the indispensable role of biomass functional moieties in regulating the Zn2+ solvation sheath to suppress side reactions. Furthermore, we critically analyze performance‐oriented structural engineering strategies aimed at decoupling ionic conductivity from mechanical robustness, broadening thermal adaptability, and optimizing electrode–electrolyte interfacial compatibility. Finally, we highlight the current progress of these materials across diverse solvent systems and outline the persisting bottlenecks, providing a strategic roadmap for the future design of highly reversible, environmentally benign ZBs.
ABSTRACT Covalent organic frameworks (COFs) offer a tunable platform for optoelectronic memristors by coupling light absorption with history‐dependent conductance, yet their potential remains underexplored. This review systematically examines how structural features, including linkage chemistry, donor–acceptor organisation, dimensionality, layer stacking, photochromic groups, redox centres and pore environments, govern the generation and stabilisation of excited, charged, isomeric and ionic states. It then traces the translation of these states into device‐level conductance modulation via molecular switching, photoredox reactions, charge trapping, interfacial photogating and ion or filament motion, with special emphasis on film quality, electrode contacts and semiconductor heterointerfaces. Functional capabilities such as temporal plasticity, bidirectional programming, spectral encoding, adaptive vision, denoising, motion recognition and task‐specific sensing are critically assessed, distinguishing genuine device responses from software simulations and physically integrated arrays. From this analysis, three design rules emerge: charge separation must operate within a reversible kinetic window, the stored state should be identifiable independently of conductance, and framework architecture must align with the device current path. The primary opportunity lies in linking chemically defined state variables to optically addressable conductance, whereas major challenges include incomplete mechanistic validation, limited device statistics, environmental instability and the lack of fully integrated addressable COF arrays. The review concludes with priorities for mechanism‐resolved characterisation, scalable processing and circuit integration.
ABSTRACT Multicolor luminescent solids that undergo sequential switching in response to a single stimulus are highly desirable yet seldom realized. Here, we report a single cocrystal system of 9,10‐bis(phenylethynyl)anthracene (BPEA) and octafluoronaphthalene (OFN) that exhibits three‐stage vapofluorochromism upon solvent vapor exposure, with the emission color evolving from green to orange and finally to yellow. This sequential transition arises from programmed, affinity‐governed OFN sublimation. The 1:1 phase (B1O1) emits green, partial OFN loss generates a metastable 2:1 phase (B2O1) emitting orange, and complete removal restores pure BPEA with yellow fluorescence. The disassembly process is effective across various solvent vapors, highlighting its general applicability. Our findings unveil the dynamic potential of arene‐perfluoroarene interactions beyond static assembly and provide a new pathway to programmable multi‐state luminescence switching in a single material with a single stimulus.
ABSTRACT Photocatalytic CO 2 conversion is a promising strategy to mitigate CO 2 emissions and address energy sustainability challenges simultaneously. Herein, a covalent organic framework (COF)‐decorated tetragonal bismuth vanadate (t‐BiVO 4 ) heterostructure was fabricated via a facile in situ growth strategy for efficient photocatalytic CO 2 reduction. t‐BiVO 4 (BV) was formed from monoclinic BiVO 4 (m‐BiVO 4 ) by phase transformation, triggered by the presence of tris(2‐pyridylmethyl) amine (TpMA)‐COF. Hybrid catalysts TpMA‐BV with different TpMA concentrations (0‒20 wt%) were evaluated for CO 2 photoreduction. The catalyst containing 10 wt% TpMA exhibited a remarkable CO production rate of 4.73 mmol g cat −1 h −1 , greatly surpassing that of pristine m‐BiVO 4 . The enhanced photocatalytic performance could be attributed to the synergistic effect arising from the intimate interfacial contact between TpMA and t‐BiVO 4 . The intrinsic microporosity of TpMA‐COF facilitates CO 2 enrichment on the surface, and t‐BiVO 4 acts as a visible‐light‐driven electron donor. The well‐defined π‐conjugated framework of TpMA‐COF serves as an electron‐accepting platform, enabling rapid interfacial charge transfer and suppressing charge recombination. Time‐resolved in situ diffuse reflectance Fourier‐transform infrared spectroscopy (in situ DRIFTS) unraveled the reaction pathway, revealing high selectivity toward CO 2 reduction via *COOH intermediate. The work demonstrates that integrating inorganic semiconductors with reticular COFs provides an effective heterojunction design strategy for sustainable solar‐driven CO 2 conversion.
ABSTRACT Organic room‐temperature phosphorescence (RTP) represents a distinctive photophysical phenomenon intrinsically linked to the interplay between intersystem crossing (ISC) efficiency and spin‐orbit coupling (SOC). Consequently, precise modulation of these fundamental properties is essential for achieving desirable RTP characteristics. Molecular geometry can influence the electronic factors associated with ISC and SOC. Nevertheless, systematic investigations aimed at elucidating and strategically manipulating molecular configurations to tailor RTP properties remain insufficiently explored. Herein, we present a rigid‐flexible regulation strategy: two pairs of novel annulene derivatives (C6‐BNH and C6‐BNPM, C8‐BNH and C8‐BNPM) with distinct molecular configurations were designed and synthesized. Interestingly, the non‐coplanar flexible structures of C8‐BNH and C8‐BNPM exhibited desirable phosphorescence properties, whereas their rigid planar counterparts (C6‐BNH and C6‐BNPM) displayed only very weak RTP that was barely perceptible to the naked eye. Structure–photophysics relationships were examined using photoluminescence measurements, crystal structures, and theoretical calculations. The results suggest that the C8 compounds undergo changes in molecular geometry, intermolecular contacts, and aromaticity‐related descriptors between the ground and excited states. These observations, together with the calculated SOC matrix elements, are consistent with a greater ISC propensity in the C8 series and may contribute to its RTP behavior. This work presents an effective molecular configuration modulation approach for RTP material development, advancing research in the exciting yet underexplored field of organic RTP.
