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Advanced Materials
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Advanced Materials

VCH Publishers

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0935-9648

Advanced Materials/Journal Advanced MaterialsSCIISTPEIAHCI
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    Schottky-Barrier-Free Plasmonic WO_3-Based Photocatalysts for Simultaneous N_2 Fixation and H_2O_2 Generation

    Ke AnBoyuan WuJingtian HuXiaopeng Bai...
    e15476.1-e15476.13页
    查看更多>>摘要:Plasmonic photocatalysis has recently received much attention in generating high-value-added products. Schottky-barrier-free plasmonic photocatalysts are frontier materials that can effectively employ localized surface plasmon resonance to generate and utilize hot charge carriers. Herein, the development of a new type of Schottky-barrier-free plasmonic WO_3-based photocatalyst through hydrogen doping, oxygen vacancy (OV) introduction, and metal doping is reported. Hydrogen doping and OV introduction broaden the light absorption range of the WO_3-based photocatalyst, thereby enabling the generation of more hot charge carriers. Metal doping provides more catalytically active sites. More interestingly, both hot electrons and holes can be used to generate high-value-added products, i.e., ammonia and hydrogen peroxide. The optimal Mo-H_(0.23)WO_(3-x) photocatalyst exhibits excellent ammonia and hydrogen peroxide production rates of 187.53 and 196.25 μmol g~(-1) h~(-1), respectively. Furthermore, a biphasic photocatalytic system is designed to suppress light absorption by water and maximize sunlight utilization. This work expands the scope of plasmonic photocatalysts towards degenerately doped plasmonic metal oxide semiconductors and provides a new paradigm for the solar-driven generation of high-value-added products.

    Stopping Phase Separation Enables Durable Wide-Bandgap Photovoltaic Perovskites

    Xiao-Ying HeBin SongKai-Li WangNan Li...
    e18492.1-e18492.11页
    查看更多>>摘要:Light-induced halide segregation presents a fundamental barrier to the longevity of wide-bandgap (WBG) mixed-halide perovskites. Herein, a multifunctional ionic polymer, polyquaternium-37, is reported as an effective grain boundary passivator to inhibit the degradation pathway. This dual-interaction mechanism concertedly arrests halide migration at grain boundaries, thereby suppressing local electric-field and ultimately curbing light-induced phase separation. Consequently, the modified WBG perovskites demonstrate robust photostability under light stress. The champion inverted perovskite photovoltaic device delivers a power conversion efficiency (PCE) of 22.86% under AM 1.5G illumination and an outstanding indoor PCE of 43.19% under 1000 lux. Remarkably, the modified device exhibits a projected T_(90) lifetime exceeding 10 000 h under continuous indoor light cycling. This work pioneers a facile solution to halide segregation via grain boundary engineering, paving the way for operationally stable WBG perovskite photovoltaics.

    Integrated TRNG and PUF Based on Room-Temperature Phosphorescent Polymer Dielectric Gated Phototransistors

    Ruiduan JiWei HuangBaoshuai LiangXiaosong Wu...
    e09239.1-e09239.13页
    查看更多>>摘要:Harnessing the entropy of multiple transitions between different electronic states in room-temperature phosphorescence (RTP) not only overcomes the drawbacks of authentication via afterglow but also holds significant potential for cryptographic protocols that are immune to attacks from future quantum computers. However, such an objective has yet to be realized. Here, RTP films are incorporated as a dielectric layer in phototransistors, which give two distinct outputs, i.e., phosphorescence (I_p) from the dielectric layer and photocurrent (I_d) across the source-drain electrode. The susceptible thermodynamics of electron transitions and the triplet-to-singlet energy transfer at the dielectric-semiconductor interface causing I_p to vary with each readout, thereby enabling true random number generator (TRNG) functionality. Whereas I_d is mainly governed by film quality and interfacial defects, which vary among different batches due to inherent randomness introduced during fabrication, making it suitable as a physical unclonable function (PUF). Detailed studies reveal that the two outputs demonstrate excellent uniqueness and independence, with a Hamming weight of 0.50, an inter-Hamming distance of 50.27%, a Pearson correlation coefficient of −0.0054, and an encoding capacity of 2~(25) within a 5 × 5 transistor array. This work represents a breakthrough of integrated optoelectronic devices for highly secure authentication while also inspiring new applications for RTP materials.

    Topological Structure-Induced Piezoelectricity from the α-Phase Poly(Vinylidene Fluoride)

    Tao YangWeili DengXin ChenQungui Wang...
    e18326.1-e18326.8页
    查看更多>>摘要:Topologically polar structures offer a rich landscape for uncovering emergent phenomena inaccessible in traditional ferroelectric materials. In contrast to the numerous examples found in ferroelectric oxides, topological structures identified in ferroelectric polymers are extremely rare. Here, the creation of a meron-like topological polar structure is demonstrated in the non-polar α-phase poly(vinylidene fluoride) (PVDF). The formation of the twisted lamellae within ring-banded polymer spherulites and the resulting topological structure are revealed using combined experimental and computational methods. Non-zero polarization is demonstrated using Kelvin probe force microscopy, second harmonic generation measurement, and dielectric spectroscopy, and verify the facilitation of polarization orientation by strain in the topological α-phase PVDF. Accordingly, piezoelectricity in the topological α-phase PVDF is demonstrated through both direct and converse measurements and reveals a strong correlation between polarization, the piezoelectric coefficient, and the topological structure. This result offers a new perspective on creating polar topological structures and inducing formerly symmetry-forbidden properties like piezoelectricity in the non-polar phase of ferroelectric polymers.

    A Spin-Engineered Nanozyme Overcomes the Activity-Selectivity Trade-Off for Sustainable Adhesive Production From Lignin Biomass Conversion

    Yixin YuRan XuXuetong WuBilian Wang...
    e17928.1-e17928.19页
    查看更多>>摘要:Lignin, a major component of plant cell walls, is the most abundant source of natural aromatic polymers. Efficient production of its valuable degradation products requires highly selective catalysts. This study introduces a spin-statemodulated nanozyme system for precise lignin depolymerization into targeted biobased chemicals. Precise copper spin state control in two-dimensional (2D) copper-based metal organic framework (MOF) nanozymes, achieved via redox treatment and ligand exchange modulation, replicates natural laccase multicopper center spin synergy. Integrated experiments and theory reveal a volcano-shaped spin state-activity correlation, enabling synthesis of optimized nanozyme Cu(OH)_2BDC-LA-OAc (COHBLO). This material demonstrates exceptional laccase-mimicking activity, with a peak reaction rate 70 times higher than natural laccase and a 5.14-fold specific activity increase. Through laccase-like catalysis, it selectively cleaves lignin β-O-4 linkages, directionally yielding fragments rich in phenolic hydroxyl groups. Their efficient reaction with epoxy groups produces a nanolignin-based epoxy adhesive. Featuring a three-dimensional cross-linked network, this adhesive delivers superior bonding under varied conditions. Its shear strength significantly surpasses commercial phenolic resins while eliminating conventional adhesive formaldehyde emissions. This study advances 2D MOF nanozyme design and establishes an integrated pathway from controlled lignin depolymerization to high-performance adhesive production, providing key theoretical and practical foundations for biomass valorization and sustainable adhesive development.

    Ferroelectrics Hybrids: Harnessing Multifunctionality of 2D Semiconductors in the Post-Moore Era

    Haixin QiuXiaoshi QianDahong QianPaolo Samori...
    e17269.1-e17269.31页
    查看更多>>摘要:The rise of big data in today’s computing has highlighted the significant limitations of von Neumann architectures for data storage and processing. Concurrently, the downscaling of silicon-based transistors while retaining low power efficiency and high system reliability has become increasingly challenging. By adopting a post-Moore approach, this Review proposes the use of hybrid systems comprising ferroelectric materials, 2D semiconductors, and functional molecular switches to respond to current demands for simultaneous high integration density and multifunctional performance. The representative applications of 2D ferroelectric field-effect transistors (FeFETs) are reviewed and advances in shrinking ferroelectric domain walls at the (sub)nanometer scale are highlighted. The incorporation of molecular switches to enable multimodal device programmability is explored and the implementation of monolithic 3D (M3D) integration to boost chip-level density and system functionality is discussed. Finally, a forward-looking vision is presented for future transistors built upon novel ferroelectric platforms. Taken together, this triple-hybrid paradigm offers a compelling path to transcend Moore’s law, paving the way for next-generation electronics with unprecedented functions and performance.

    The Space Within: How Architected Voids Promote Tissue Formation

    Anna Puiggali-JouIsabel B. HuiCarla Fernandez-RicoMarcy Zenobi-Wong...
    e07385.1-e07385.36页
    查看更多>>摘要:Physiological void spaces exist at every scale of the human body, from organs to molecules, facilitating transport, signal propagation, and localized biochemical activity. Constriction of these spaces (e.g., arterial occlusion, fibrosis) highlights their importance, making their mimicry essential in tissue engineering (TE). This review examines four key strategies for introducing porosity into hydrogels across multiple length scales: templating, microgels, phase separation, and 3D printing. The first three methods enable the engineering of physiological environments at the nano- to micro-scale, mimicking tissue- and extracellular matrix (ECM)-level spaces. Templating involves embedding and removal of gas, liquid, or solid phases, leaving behind pores. Microgel annealing generates inherent interstitial voids. Liquid–liquid phase separation (LLPS) creates biphasic networks reminiscent of native ECM. The fourth approach, extrusion- and light-based 3D printing techniques, enables the fabrication of larger-scale spaces, such as luminal structures (e.g., vasculature, airways, and ducts). Combining these methods enables the creation of hierarchical architectures from the nano- to centimeter scale. The review also highlights Filamented Light (FLight) technology, which creates internal microstructural voids relevant to anisotropic tissues. This review offers insights into current methods and their convergence for generating biomimetic void spaces to meet the physiological demands of cells, tissues, and organs.

    Trace Chlorine-Induced Lattice Oxygen Activation for Enhanced High-Temperature CO_2 Electrolysis

    Shaowei ZhangXueyu HuTianfu LiuHewei Liu...
    e18116.1-e18116.11页
    查看更多>>摘要:Tuning lattice oxygen activity in perovskite oxides (ABO_3) offers a promising approach to overcome the intrinsic trade-off between catalytic activity and stability in redox reactions. However, precise modulation and mechanistic understanding of lattice oxygen activation remain elusive under high-temperature CO_2 electrolysis conditions. Herein, a novel anion activation strategy is proposed by incorporating trace chloride ions (Cl~-) into the O-sites of Sr_2_Fe_(1.5)Mo_(0.5)O_(6-δ) perovskite forming an oxychloride cathode. This Cl~- substitution activates lattice oxygen reactivity by weakening Mo-O/Fe-O covalency, thereby facilitating the formation and redistribution of oxygen vacancies, accelerating bulk oxygen ion transport, enhancing CO_2 adsorption and carbonate intermediate formation, and ultimately promoting CO_2 reduction kinetics. As a result, the oxychloride cathode achieves a 60.2–80.8% enhancement in CO_2-to-CO electrolysis, reaching 2.02 A cm~(-2) at 800 ℃ and 1.5 V with ≈100% Faradaic efficiency, while maintaining exceptional stability of 500 h. This work establishes a new paradigm of O-site anion engineering to unlock lattice oxygen activity for electrocatalytic reactions.

    Thermoplastic Molding of Chitosan to Form Living Plastic Materials

    Reddhy MahlePeggy CebeNilotpal MajumderOnur Hasturk...
    e11623.1-e11623.14页
    查看更多>>摘要:Numerous approaches for the solution-based fabrication of chitosan-based materials are reported, but most often result in materials with limitations in terms of stability in aqueous systems and mechanics unless chemical cross-linking is utilized. In the present study, a thermomechanical compression method is presented for solid-state processing of chitosan powders into dense bulk plastic-like materials where the mechanical and physical properties can be tailored. To achieve this outcome, chitosan-citrate complexes, formed through ionic cross-linking and amidation, undergo thermal fusion at high temperature and pressure to generate robust materials with retention of the inherent properties of chitosan, including biodegradability and cytocompatibility. The chitosan-based plastics can be doped with enzymes and antibiotics with retention of bioactivity and are also explored as living materials when microbial cells (e.g., Pseudomonas putida) are included in the process and subsequently shown to maintain metabolic functions to degrade organic pollutants. This thermoplastic approach for solid-state processing of chitosan enables the development of a variety of new materials and composites with embedded biomolecules for enhanced functions. This solid-state fabrication of chitosan bulk materials approach eliminates the need for conventional solution-based processing, enabling rapid material production via compression molding while reducing costs, minimizing waste, and improving overall manufacturing efficiency.

    Light-Up Nanostructures with Allosterically Controlled Fluorogenic DNA Aptamers

    Tianqing ZhangXinmin QianJiayi ZhangHuangchen Cui...
    e14306.1-e14306.13页
    查看更多>>摘要:In this study, a systematic approach is presented for the rational design of synthetic allosteric DNA aptamers. This methodology enables precise control over the allosteric ON–OFF transition in fluorescent DNA aptamers, allowing for the engineering of aptamers with highly tunable fluorescent properties. When combined with toehold-mediated strand displacement, a series of allosteric aptamers is developed in which the target sequence functions as a specific allosteric modulator. Furthermore, these aptamers are applied in synthetic DNA computing and in the construction of responsive nanostructures that light up upon activation. In this study, a systematic approach is presented for the rational design of synthetic allosteric DNA aptamers. This methodology enables precise control over the allosteric ON–OFF transition in fluorescent DNA aptamers, allowing for the engineering of aptamers with highly tunable fluorescent properties. When combined with toehold-mediated strand displacement, a series of allosteric aptamers is developed in which the target sequence functions as a specific allosteric modulator. Furthermore, these aptamers are applied in synthetic DNA computing and in the construction of responsive nanostructures that light up upon activation.