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{"title":"Designing Polar Covalent Hybrid Cadmium-Based Chalcohalides Ultraviolet Nonlinear Optical Crystal with Strong Optical Anisotropy via Double-Site Dual FBUs Tailoring","authors":"Yi-Fan Fu, Wen-Dong Yao, Jiajing Wu, Qiao-Feng Huang, Yu-Mei Zhang, Wenfeng Zhou, Wenlong Liu, Sheng-Ping Guo","doi":"10.1002/smll.202412173","DOIUrl":"https://doi.org/10.1002/smll.202412173","url":null,"abstract":"The pressing demand for both established and innovative technologies to expand laser wavelengths has rendered high-performance nonlinear optical (NLO) crystals with large optical anisotropy indispensable. Here, centrosymmetric [SHC(NH₂)₂]₂CdBr₄ (<b>1</b>) and <i>pseudo</i>-2D layered [SC(NH₂)₂]₂CdBr₂ (<b>2</b>), as well as <i>pseudo</i>-3D noncentrosymmetric [SC(NH₂)₂]₂CdCl₂ <b>(3)</b> are successfully synthesized through the introduction of <i>π</i>-conjugated SC(NH₂)₂ groups. Compared to ionic compound <b>1</b> containing full-halogen coordination tetrahedra, covalent compounds <b>2</b> and <b>3</b> featuring novel polar [SC(NH₂)₂]₂CdX₂ (X = Br, Cl) tetrahedral units demonstrate enhanced bandgaps (&gt;4 eV) and birefringences (&gt;0.3@546 nm) due to the unique coordination environment. Remarkably, <b>3</b> exhibits a strong second-harmonic generation (SHG) response (2.1 × KH₂PO₄(KDP)), high laser-induced damage thresholds (30 × AgGaS₂(AGS), and excellent water stability. The birefringence of <b>3</b> is the largest among the hybrid halides NLO crystals containing d¹⁰ metal cations. Detailed theoretical calculations confirm that such a modified double-site dual functional building units (FBUs) substitution is an effective strategy for designing superior optical materials with large birefringence and strong SHG response, paving the way for the development of high-performance devices in related fields.","PeriodicalId":228,"journal":{"name":"Small","volume":"10 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044735","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effects of Unit Cell Size on Thermal Conductivity in Two Different Polymorphs of Niobium Diselenide","authors":"Sungjin Park, Kyomin Kim, Kwangrae Kim, Wooyoung Lee, Aloysius Soon, Jong-wook Roh, Woochul Kim","doi":"10.1002/smll.202408948","DOIUrl":"https://doi.org/10.1002/smll.202408948","url":null,"abstract":"2D materials possess weak inter-layer van der Waals bonding, allowing them to exist as different polymorphs depending on the stacking sequence of the layers. Herein, the thermal conductivities of the 2H-NbSe₂ and 2H-3R-NbSe₂ polymorphs by conducting experimental measurements and theoretical analysis are comparatively studied. Owing to its 1.8 times larger unit cell, 2H-3R-NbSe₂ has a considerably greater number of optical phonon branches than does 2H-NbSe₂, suggesting that 2H-3R-NbSe₂ absorbs thermal energy rather than transporting it. In addition, scattering is more likely to occur in 2H-3R-NbSe₂ because a far greater number of states satisfy the selection rule. As a result of these, the 2H-3R-NbSe₂ has considerably lower thermal conductivity than that of the 2H-NbSe₂. The results highlight how the size of the unit cell affects the thermal conductivities of polymorphs.","PeriodicalId":228,"journal":{"name":"Small","volume":"59 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044756","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Achieving Near Infrared Photodegradation by the Synergistic Effect of Z-Scheme Heterojunction and Antenna of Rare Earth Single Atoms","authors":"Jianzhe Sun, Guofeng Wang","doi":"10.1002/smll.202412148","DOIUrl":"https://doi.org/10.1002/smll.202412148","url":null,"abstract":"Near-infrared light response catalysts have received great attention in renewable solar energy conversion, energy production, and environmental purification. Here, near-infrared photodegradation is successfully achieved in rare earth single atom anchored NaYF₄@g-C₃N₄ heterojunctions by the synergistic effect of Z-scheme heterojunction and antenna of rare earth single atoms. The UV–vis light emitted by Tm³⁺ can not only be directly absorbed by g-C₃N₄ to generate electron–hole pairs, realizing efficient energy transfer, but also be absorbed by NaYF₄ substrate, and generating photo-generated electrons at its impurity level, transferring the active charge to the valence band of g-C₃N₄, forming a Z-scheme heterojunction and further improving the photocatalytic efficiency. Importantly, Tm single atoms has multiple functions such as acting as charge transfer channels to facilitate charge transfer, regulating the critical distance of energy transfer, and prolonging electron–hole pair lifetime. Under NIR light, it exhibited remarkable performance in degrading antibiotics (the removal rate of TC reached 91% for 6 h) while maintaining excellent stability. The LC-MS/MS technology is used to reveal the reaction intermediates, active species, and reaction pathways, and the complex mechanism of photodegradation is further proposed. This study provides experimental and theoretical support for designing and synthesizing catalysts with near-infrared light response characteristics.","PeriodicalId":228,"journal":{"name":"Small","volume":"114 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044638","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Supercritical CO2-Induced Chemical Pressure on BaZrO3 for Room-Temperature Ferromagnetism","authors":"Duo Fu, Mingzhu Tan, Yuning Liang, Qun Xu","doi":"10.1002/smll.202411243","DOIUrl":"https://doi.org/10.1002/smll.202411243","url":null,"abstract":"The modulation of intrinsic magnetic properties of materials is of great importance for the exploration of new materials in the fields of information storage and spintronics. Herein, room-temperature ferromagnetic properties in BaZrO₃ are successfully induced using supercritical CO₂. The highest saturation magnetization intensity of BaZrO₃ is observed at 16 MPa, with a value of 0.08189 emu g⁻¹. It is noteworthy that this technique is observed to modulate the ferromagnetic properties of the material by converting the external physical pressure into the chemical pressure within the material through the intercalation and de-intercalation of CO₂ molecules. This result gives us a new understanding of the modification mechanism of SC-CO₂, which is important for material modification.","PeriodicalId":228,"journal":{"name":"Small","volume":"59 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044640","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhancement Mechanism of Photo-Induced Artificial Boundary on Ultrastable Hybrid Solid-electrolyte Interphase of Si Anodes","authors":"Zeyu Xu, Zhenzhuo Liu, Haibo Shao, Yingchun Liu, Jianming Wang","doi":"10.1002/smll.202410930","DOIUrl":"https://doi.org/10.1002/smll.202410930","url":null,"abstract":"Unstable solid-electrolyte interphase (SEI) film resulting from chemically active surface state and huge volume fluctuation limits the development of Si-based anode materials in lithium-ion batteries. Herein, a photo-initiated polypyrrole (PPy) coating is manufactured on Si nanoparticles to guide the in situ generation of PPy-integrated hybrid SEI film (hSEI). The hSEI film shows excellent structure stability and optimized component composition for lithium storage. More promisingly, the photo-initiated hSEI precursor with more uniform thickness, stronger interaction with inner particles, and higher mechanical strength further enables the structural integrity of the hSEI film. The highly ordered interchain structure of photo-initiated hSEI precursor can maintain effective Li⁺ transport during the electrochemical cycling. Consequently, SiNPs@hSEI-L anode maintains a reversible capacity of 1044.7 mAh g⁻¹ after 500 cycles at 2 A g⁻¹, manifesting superior electrochemical lithium storage. This work proposes a novel polymer-integrated hSEI formation and provides an effective reference for the optimization of semiconductor materials.","PeriodicalId":228,"journal":{"name":"Small","volume":"2 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044742","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dehydroxylated Polyvinyl Alcohol Separator Enables Fast Kinetics in Zinc-Metal Batteries","authors":"Yao Qin, Fuhua Yang, Jodie A. Yuwono, Alberto Varzi","doi":"10.1002/smll.202410758","DOIUrl":"https://doi.org/10.1002/smll.202410758","url":null,"abstract":"Separators are critical components of zinc-metal batteries (ZMBs). Despite their high ionic conductivity and excellent electrolyte retention, the widely used glass fiber (GF) membranes suffer from poor mechanical stability and cannot suppress dendrite growth, leading to rapid battery failure. Contrarily, polymer-based separators offer superior mechanical strength and facilitate more homogeneous zinc (Zn) deposition. However, they typically suffer from sluggish ion transport kinetics and poor wettability by aqueous electrolytes, resulting in unsatisfactory electrochemical performance. Here a dehydroxylation strategy is proposed to overcome the above-mentioned limitations for polyvinyl alcohol (PVA) separators. A dehydroxylated PVA-based membrane (DHPVA) is synthesized at a relatively low temperature in a highly concentrated alkaline solution. Part of the hydroxyl groups are removed and, as a result, the hydrogen bonding between PVA chains, which is deemed responsible for the sluggish ion transport kinetics, is minimized. At 20 °C, the ionic conductivity of DHPVA reaches 12.5 mS cm⁻¹, which is almost 4 times higher than that of PVA. Additionally, DHPVA effectively promotes uniform Zn deposition, leading to a significantly extended cycle life and reduced polarization, both in a/symmetric (Cu/Zn and Zn/Zn) and full cells (Zn/NaV₃O₈). This study provides a new, effective, yet simple approach to improve the performance of ZMBs.","PeriodicalId":228,"journal":{"name":"Small","volume":"48 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044731","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhanced Photocatalytic Degradation of Chlorsulfuron by MoS2/MIL101(Fe) S-Scheme Heterojunction: A Conversion Mechanism Dominated by Electrons and Long-Lifetime Reactive Species","authors":"Bingkun Liu, Weijun Tian, Zhiyang Lu, Bingjie Huo, Jing Zhao, Mengyuan Zou, Meile Chu","doi":"10.1002/smll.202412019","DOIUrl":"https://doi.org/10.1002/smll.202412019","url":null,"abstract":"Altering the generation route of reactive species is a potent means to augment the photocatalytic activity. In this study, MoS₂/MIL-101(Fe) S-scheme heterojunction (MF2) is prepared using a water/solvent thermal method for photocatalytic degradation of chlorsulfuron. Driven by the internal electric field, the local electron density of MF2 is redistributed, thus enhancing the adsorption of O₂. This promoted charge transfer to generate e⁻, •<span data-altimg=\"/cms/asset/adc8d5d1-a2b0-46eb-b775-bfe23c11a0e4/smll202412019-math-0001.png\"></span><math altimg=\"urn:x-wiley:16136810:media:smll202412019:smll202412019-math-0001\" display=\"inline\" location=\"graphic/smll202412019-math-0001.png\">\u0000<semantics>\u0000<msubsup>\u0000<mi mathvariant=\"normal\">O</mi>\u0000<mn>2</mn>\u0000<mo>−</mo>\u0000</msubsup>\u0000${mathrm{O}}_{mathrm{2}}^ - $</annotation>\u0000</semantics></math>, and H₂O₂ for efficient oxidation of chlorsulfuron. It is confirmed that photogenerated electrons and long-lifetime reactive species (•<span data-altimg=\"/cms/asset/96f48833-431d-40a5-b166-1862b1de7f29/smll202412019-math-0002.png\"></span><math altimg=\"urn:x-wiley:16136810:media:smll202412019:smll202412019-math-0002\" display=\"inline\" location=\"graphic/smll202412019-math-0002.png\">\u0000<semantics>\u0000<msubsup>\u0000<mi mathvariant=\"normal\">O</mi>\u0000<mn>2</mn>\u0000<mo>−</mo>\u0000</msubsup>\u0000${mathrm{O}}_{mathrm{2}}^ - $</annotation>\u0000</semantics></math> and H₂O₂) played a major role. The degradation activity of MF2 for chlorsulfuron is much higher than MoS₂ (42.21 times) and MIL-101(Fe) (4.06 times). The charge transfer mechanism of the MF2 S-scheme heterojunction is verified by experimental studies and Density Functional Theory simulation calculations. In addition, MF2 exhibited great potential for practical applications. This work provided new insights into the construction of S-scheme heterojunctions and long-lifetime reactive species-dominated conversion mechanisms.","PeriodicalId":228,"journal":{"name":"Small","volume":"49 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044788","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photoresponsive Bio-Heterojunctions Eliciting Immunogenicity to Prevent Infection Recurrence and Accelerating Chronic Wound Regeneration","authors":"Yingming Yang, Kunneng Liang, Zilin Zhou, Yuanyuan Tu, Meng Li, Ziyou Wang, Yi Deng, Jiyao Li","doi":"10.1002/smll.202410522","DOIUrl":"https://doi.org/10.1002/smll.202410522","url":null,"abstract":"Dynamic therapy utilizes reactive oxygen species (ROS) to antibacterial and enhance the innate immune system to treat bacterial infections. If ROS levels are too low, the elimination of pathogens and the enhancement of innate immunity cannot be achieved. However, excess accumulation of ROS may impact intracellular glutathione (GSH) levels, hindering T cell maturation and the establishment of immune memory. Herein, a multifunctional nanofiber membrane is designed, consisting of a polymer scaffold, MXene/CeO₂ bio-heterojunctions (MX@Ce bio-HJs), and lactate oxidase (Lox) to balance the production of ROS, for the treatment of recurrent bacterial infections. In this system, MX@Ce bio-HJs upon near-infrared ray (NIR) generate photodynamic therapy, while Lox responds to the wound microenvironment exert chemodynamic therapy, synergistically produce ROS to rapidly eradicate bacteria, amplify the ability of dendritic cells to recognize and present antigens of bacterial fragments, and enhance innate immunity. Without NIR, MX@Ce bio-HJs showcase catalase-like and superoxide dismutase-like activities, scavenging subsequent ROS accumulation, promoting T cell maturation to form acquired immune memory, and combating recurrent bacterial infection. Such work highlights the potential to combat in situ bacterial infections and recurrent bacterial infections and inspires the development of future antibacterial therapies.","PeriodicalId":228,"journal":{"name":"Small","volume":"38 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044730","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Systematic Study of the Synthesis of Monodisperse CsPbI3 Perovskite Nanoplatelets for Efficient Color-Pure Light Emitting Diodes","authors":"Aleksandr P. Litvin, Jie Guo, Jianxun Wang, Xiaoyu Zhang, Weitao Zheng, Andrey L. Rogach","doi":"10.1002/smll.202408422","DOIUrl":"https://doi.org/10.1002/smll.202408422","url":null,"abstract":"Metal halide perovskite nanoplatelets (NPls) possess ultra-narrow photoluminescence (PL) bands tunable over the entire visible spectral range, which makes them promising for utilization in light-emitting diodes (LEDs) with spectrally pure emission colors. This calls for development of synthetic methods toward perovskite NPls with a high degree of control over both their thickness and lateral dimensions. A general strategy is developed to obtain such monodisperse CsPbI₃ NPls through the control over the halide-to-lead ratio during heating-up reaction. The excess of iodine precursor changes the chemical equilibrium, thus yielding monodisperse (3 monolayers in thickness) CsPbI₃ NPls whose PL width constitutes ≈22 nm, while the lateral dimensions of NPls are determined by choice of precursor and by the reaction temperature. Postsynthetic cation exchange on the A-site of the perovskite lattice allows for the tuning of the PL peak position, while simultaneous removal of the excess ligands and the surface passivation allows for improvement of the PL quantum yield to 96% and ensures superior stability of optical properties upon storage. Electroluminescent LEDs with the peak values are fabricated for the external quantum efficiency and luminance being 9.45% and 29800 cd m⁻², respectively, and a narrow (≈26 nm) electroluminescence peak at 601 nm.","PeriodicalId":228,"journal":{"name":"Small","volume":"11 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143026459","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Insights on Fabrication Strategies and Energy Storage Mechanisms of Transition Metal Dichalcogenides Cathodes for Aqueous Zn‐Based Batteries","authors":"Shengwei Li, Pratteek Das, Xiao Wang, Chenyang Li, Zhong‐Shuai Wu, Hui‐Ming Cheng","doi":"10.1002/smll.202410036","DOIUrl":"https://doi.org/10.1002/smll.202410036","url":null,"abstract":"Aqueous zinc‐based batteries (AZBs) are gaining widespread attention owing to their intrinsic safety, relatively low electrode potential, and high theoretical capacity. Transition metal dichalcogenides (TMDs) have convenient 2D ion diffusion channels, so they have been identified as promising host materials for AZBs, but face several key challenges such as the narrow interlayer spacing and the lack of in‐deep understanding energy storage mechanisms. This review presents a comprehensive summary and discussion of the intrinsic structure, charge storage mechanisms, and key fabrication strategies of TMD‐based cathodes for AZBs. Firstly, the structural features including phase types and electrical properties of TMDs are underscored. Then, the charge storage mechanisms and activation principles in TMDs are elaborated along with the discussions about their influence on electrochemical performance. Afterward, specific attention is focused on the fabrication strategies of high‐performance TMD cathodes, including interlayer expansion, defect creation, phase transition, and heteroatom doping. Finally, the key challenges are considered and potential effective strategies are proposed to design high‐performance aqueous Zn‐TMDs batteries.","PeriodicalId":228,"journal":{"name":"Small","volume":"74 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143026579","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}