Yuqin Su, Qunqing Lin, Xinyi Lv, Yan Li, Kun Zhang, Xiuting Wu, Ying Zhou, Yashuang Guo, Maria A. Sandzhieva, Sergey V. Makarov, Hengyang Xiang, Haibo Zeng
Mixed-halide perovskite plays important role in wide-color gamut displays as a vital material for three primary colors. However, halide segregation and caused unstable spectra are the intrinsic problem in mixed-halide perovskite light-emitting diodes (PeLEDs) originating from the lattice strain and the resulting defects in perovskite quantum dots (PQDs). Here, smaller transition metal cations are applied to replace Pb2+ and release lattice strain, which avoids halogen escaping/halide vacancies forming to ensure high photoluminescence quantum yield (PLQY) and stable spectra. However, the actual doping amount is limited by ionic size and chemical environment, which will affect the improvement of optoelectronic performance. Thus, this study proposes a strategy by introducing tri-n-octylphosphine to coordinate strongly with metal cations and catch them to participate the nucleation-growth process. Through doping transition metal cations effectively, the CsPb(BrI)3 PQDs show high PLQY (92%) and long lifetime (107.83 ns). Further, highly efficient pure-red PeLEDs with highest external quantum efficiency of 16.86% is fabricated and the spectrum can be stabilized at 630 nm with only 1 nm red-shift under bias, showing the promising potential of PQDs for next-generation display.
{"title":"Controllable Transition Metal Cations Doping Enable Efficient and Spectral Stable Pure-Red Perovskite QLED","authors":"Yuqin Su, Qunqing Lin, Xinyi Lv, Yan Li, Kun Zhang, Xiuting Wu, Ying Zhou, Yashuang Guo, Maria A. Sandzhieva, Sergey V. Makarov, Hengyang Xiang, Haibo Zeng","doi":"10.1002/smll.202412227","DOIUrl":"https://doi.org/10.1002/smll.202412227","url":null,"abstract":"Mixed-halide perovskite plays important role in wide-color gamut displays as a vital material for three primary colors. However, halide segregation and caused unstable spectra are the intrinsic problem in mixed-halide perovskite light-emitting diodes (PeLEDs) originating from the lattice strain and the resulting defects in perovskite quantum dots (PQDs). Here, smaller transition metal cations are applied to replace Pb<sup>2+</sup> and release lattice strain, which avoids halogen escaping/halide vacancies forming to ensure high photoluminescence quantum yield (PLQY) and stable spectra. However, the actual doping amount is limited by ionic size and chemical environment, which will affect the improvement of optoelectronic performance. Thus, this study proposes a strategy by introducing tri-n-octylphosphine to coordinate strongly with metal cations and catch them to participate the nucleation-growth process. Through doping transition metal cations effectively, the CsPb(BrI)<sub>3</sub> PQDs show high PLQY (92%) and long lifetime (107.83 ns). Further, highly efficient pure-red PeLEDs with highest external quantum efficiency of 16.86% is fabricated and the spectrum can be stabilized at 630 nm with only 1 nm red-shift under bias, showing the promising potential of PQDs for next-generation display.","PeriodicalId":228,"journal":{"name":"Small","volume":"166 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418334","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}
Yu Jin, Zhaoyou Chu, Pengfei Zhu, Yechun Jiang, Hui Shen, Yujie Wang, Silong Wu, Miaomiao Yang, Haisheng Qian, Yan Ma
The management of abscess wounds induced by antibiotic-resistant bacterial infections has become increasingly formidable due to the widespread overutilization and misuse of antimicrobial agents. This study presents an innovative dissolvable microneedle (MN) patch incorporating Au@ZnO/Ce nanocomposites and vancomycin (AZC/Van@MN), exhibiting robust antimicrobial and anti-inflammatory properties, meticulously engineered for the therapeutic intervention of abscess wounds. The developed AZC/Van@MN patch demonstrates exceptional biocompatibility as evidenced by comprehensive histopathological and hematological assessments. It effectively eradicates bacterial colonies through the synergistic action of Van and mild photothermal therapy (PTT, ≤42 °C). Transcriptomic analysis elucidates that the antibacterial mechanism involves the upregulation of riboflavin biosynthesis and the suppression of arginine biosynthesis pathways. Furthermore, AZC/Van@MN significantly reduces abscess dimensions, bacterial load, and inflammatory response, while simultaneously enhancing wound healing via accelerated re-epithelialization and angiogenesis. This double-edged MN patch represents a promising strategy for combating skin abscesses instigated by antibiotic-resistant bacteria.
{"title":"Double-Edged Dissolving Microneedle Patches Loaded with Zn/Ce Composites and Vancomycin for Treatment of Drug-Resistant Bacterial Infected Skin Abscess","authors":"Yu Jin, Zhaoyou Chu, Pengfei Zhu, Yechun Jiang, Hui Shen, Yujie Wang, Silong Wu, Miaomiao Yang, Haisheng Qian, Yan Ma","doi":"10.1002/smll.202412165","DOIUrl":"https://doi.org/10.1002/smll.202412165","url":null,"abstract":"The management of abscess wounds induced by antibiotic-resistant bacterial infections has become increasingly formidable due to the widespread overutilization and misuse of antimicrobial agents. This study presents an innovative dissolvable microneedle (MN) patch incorporating Au@ZnO/Ce nanocomposites and vancomycin (AZC/Van@MN), exhibiting robust antimicrobial and anti-inflammatory properties, meticulously engineered for the therapeutic intervention of abscess wounds. The developed AZC/Van@MN patch demonstrates exceptional biocompatibility as evidenced by comprehensive histopathological and hematological assessments. It effectively eradicates bacterial colonies through the synergistic action of Van and mild photothermal therapy (PTT, ≤42 °C). Transcriptomic analysis elucidates that the antibacterial mechanism involves the upregulation of riboflavin biosynthesis and the suppression of arginine biosynthesis pathways. Furthermore, AZC/Van@MN significantly reduces abscess dimensions, bacterial load, and inflammatory response, while simultaneously enhancing wound healing via accelerated re-epithelialization and angiogenesis. This double-edged MN patch represents a promising strategy for combating skin abscesses instigated by antibiotic-resistant bacteria.","PeriodicalId":228,"journal":{"name":"Small","volume":"129 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418337","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}
Luoyingzi Xie, Jie Gong, Zhiqiang He, Weinan Zhang, Haoyu Wang, Shitao Wu, Xianxing Wang, Pijiang Sun, Lei Cai, Zhongjun Wu, Huaizhi Wang
Cancer is one of the most important challenges worldwide with an increasing incidence. However, most of patients with malignant cancer receiving traditional therapies have tumor recurrence and short-term 5-year survival. Herein, a novel Cu2O-MnO@PEG (CMP) nanomaterial is developed to treat tumors. CMP directly mediates cuproptosis in tumor cells. Meanwhile, CMP potentiates anti-tumor immune responses in the tumor microenvironment (TME) to induce tumor regression. CMP improves the tumor antigen processing and presentation of dendritic cells and tumor-associated macrophages, and further promotes CD8+ T cell responses, especially for cytotoxic CD8+ T cells and transitory exhausted CD8+ T cells. Additionally, CMP downregulates the proportion of Treg cells and CTLA-4 expression on Treg cells. Notably, CMP induces systemic immune responses against distant tumors and long-term immune memory. Furthermore, CMP synergized with PD-L1 mAb promotes tumor inhibition and sustains the anti-tumor efficacy post PD-L1 mAb treatment. Collectively, this strategy has the clinically therapeutic potential for tumors by facilitating cuproptosis in tumor cells and anti-tumor immune responses.
{"title":"A Copper-Manganese Based Nanocomposite Induces Cuproptosis and Potentiates Anti-Tumor Immune Responses","authors":"Luoyingzi Xie, Jie Gong, Zhiqiang He, Weinan Zhang, Haoyu Wang, Shitao Wu, Xianxing Wang, Pijiang Sun, Lei Cai, Zhongjun Wu, Huaizhi Wang","doi":"10.1002/smll.202412174","DOIUrl":"https://doi.org/10.1002/smll.202412174","url":null,"abstract":"Cancer is one of the most important challenges worldwide with an increasing incidence. However, most of patients with malignant cancer receiving traditional therapies have tumor recurrence and short-term 5-year survival. Herein, a novel Cu<sub>2</sub>O-MnO@PEG (CMP) nanomaterial is developed to treat tumors. CMP directly mediates cuproptosis in tumor cells. Meanwhile, CMP potentiates anti-tumor immune responses in the tumor microenvironment (TME) to induce tumor regression. CMP improves the tumor antigen processing and presentation of dendritic cells and tumor-associated macrophages, and further promotes CD8<sup>+</sup> T cell responses, especially for cytotoxic CD8<sup>+</sup> T cells and transitory exhausted CD8<sup>+</sup> T cells. Additionally, CMP downregulates the proportion of Treg cells and CTLA-4 expression on Treg cells. Notably, CMP induces systemic immune responses against distant tumors and long-term immune memory. Furthermore, CMP synergized with PD-L1 mAb promotes tumor inhibition and sustains the anti-tumor efficacy post PD-L1 mAb treatment. Collectively, this strategy has the clinically therapeutic potential for tumors by facilitating cuproptosis in tumor cells and anti-tumor immune responses.","PeriodicalId":228,"journal":{"name":"Small","volume":"1 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418065","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}
Nonradical-driven degradation pathways have emerged as a promising solution for the removal of emerging organic pollutants in complex water matrices. How to construct nonradical systems remains a challenge. In this study, a novel silicon carbide (SiC)-supported cobalt single-atom catalyst (Co/SiC) is developed to induce nonradicals activation of peroxymonosulfate toward the degradation of sulfamethoxazole (SMX). The normalized degradation rate of SMX reaches 16.425 L·min−1·g−1·mm−1, significantly outperforming most reported single-atom catalysts. Surface-bound reactive species dominate the SMX degradation process, followed by high-valent cobalt oxo. Experimental and characterization results demonstrate that the unique Co-Si coordination structure facilitated electron transfer, and lowered the energy barrier for the formation of surface-bound reactive species, thereby exhibiting superior resistance to inorganic ions. In a seven-day continuous column experiment, SMX, atrazine, and bisphenol A are completely removed from actual secondary effluent, confirming the stability and effectiveness of the catalyst in real wastewater systems. Moreover, the acute toxicity of treated secondary effluent almost disappears. These results highlight the potential of Co-Si coordination in driving electron transfer for the generation of nonradicals, offering a promising approach to addressing the challenges of the removal of emerging organic pollutants from the complex wastewater.
{"title":"Cobalt-Silicon Coordination-Induced Nonradical Activation of Peroxymonosulfate for Enhancing the Degradation of Organic Pollutants in Real Wastewater","authors":"Shizong Wang, Jianlong Wang","doi":"10.1002/smll.202500434","DOIUrl":"https://doi.org/10.1002/smll.202500434","url":null,"abstract":"Nonradical-driven degradation pathways have emerged as a promising solution for the removal of emerging organic pollutants in complex water matrices. How to construct nonradical systems remains a challenge. In this study, a novel silicon carbide (SiC)-supported cobalt single-atom catalyst (Co/SiC) is developed to induce nonradicals activation of peroxymonosulfate toward the degradation of sulfamethoxazole (SMX). The normalized degradation rate of SMX reaches 16.425 L·min<sup>−1</sup>·g<sup>−1</sup>·m<span>m</span><sup>−1</sup>, significantly outperforming most reported single-atom catalysts. Surface-bound reactive species dominate the SMX degradation process, followed by high-valent cobalt oxo. Experimental and characterization results demonstrate that the unique Co-Si coordination structure facilitated electron transfer, and lowered the energy barrier for the formation of surface-bound reactive species, thereby exhibiting superior resistance to inorganic ions. In a seven-day continuous column experiment, SMX, atrazine, and bisphenol A are completely removed from actual secondary effluent, confirming the stability and effectiveness of the catalyst in real wastewater systems. Moreover, the acute toxicity of treated secondary effluent almost disappears. These results highlight the potential of Co-Si coordination in driving electron transfer for the generation of nonradicals, offering a promising approach to addressing the challenges of the removal of emerging organic pollutants from the complex wastewater.","PeriodicalId":228,"journal":{"name":"Small","volume":"1 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418147","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}
Wan Jae Dong, Jan Paul Menzel, Zhengwei Ye, Zhuoran Long, Ishtiaque Ahmed Navid, Victor S. Batista, Zetian Mi
Metal-support interactions are crucial in the electrochemical synthesis of ammonia (NH3) from nitrate (NO3−) reduction reaction, enabling efficient NH3 production under mild conditions. However, the complexity of the reaction pathways often limits efficiency. Here, a photoelectrochemical system composed of gold (Au) nanoclusters supported on gallium nitride (GaN) nanowires is introduced, grown on a n+-p Si wafer, for selective reduction of NO3− to NH3 under solar illumination. NO3− ions are preferentially adsorbed and reduced to nitrite (NO2−) on the GaN nanowires, which then transfer to adjacent Au nanoclusters to complete the NH3 synthesis. This mechanism is confirmed by both experimental data and theoretical calculations. Optimizing the surface coverage and size of Au nanoclusters on the GaN nanowires significantly enhanced catalytic activity compared to that on planar n+-p Si photoelectrodes, achieving a faradaic efficiency of 91.8% at −0.4 VRHE and a high NH3 production rate of 131.1 µmol cm−2 h−1 at −0.8 VRHE. These findings highlight the synergetic effect between metal co-catalysts and semiconductor supports in designing photoelectrodes for multi-step NO3− reduction.
{"title":"Synergistic Metal-Support Interactions in Au/GaN Catalysts for Photoelectrochemical Nitrate Reduction to Ammonia","authors":"Wan Jae Dong, Jan Paul Menzel, Zhengwei Ye, Zhuoran Long, Ishtiaque Ahmed Navid, Victor S. Batista, Zetian Mi","doi":"10.1002/smll.202412089","DOIUrl":"https://doi.org/10.1002/smll.202412089","url":null,"abstract":"Metal-support interactions are crucial in the electrochemical synthesis of ammonia (NH<sub>3</sub>) from nitrate (NO<sub>3</sub><sup>−</sup>) reduction reaction, enabling efficient NH<sub>3</sub> production under mild conditions. However, the complexity of the reaction pathways often limits efficiency. Here, a photoelectrochemical system composed of gold (Au) nanoclusters supported on gallium nitride (GaN) nanowires is introduced, grown on a n<sup>+</sup>-p Si wafer, for selective reduction of NO<sub>3</sub><sup>−</sup> to NH<sub>3</sub> under solar illumination. NO<sub>3</sub><sup>−</sup> ions are preferentially adsorbed and reduced to nitrite (NO<sub>2</sub><sup>−</sup>) on the GaN nanowires, which then transfer to adjacent Au nanoclusters to complete the NH<sub>3</sub> synthesis. This mechanism is confirmed by both experimental data and theoretical calculations. Optimizing the surface coverage and size of Au nanoclusters on the GaN nanowires significantly enhanced catalytic activity compared to that on planar n<sup>+</sup>-p Si photoelectrodes, achieving a faradaic efficiency of 91.8% at −0.4 V<sub>RHE</sub> and a high NH<sub>3</sub> production rate of 131.1 µmol cm<sup>−2</sup> h<sup>−1</sup> at −0.8 V<sub>RHE</sub>. These findings highlight the synergetic effect between metal co-catalysts and semiconductor supports in designing photoelectrodes for multi-step NO<sub>3</sub><sup>−</sup> reduction.","PeriodicalId":228,"journal":{"name":"Small","volume":"48 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418064","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}
Eider Berganza, Felipe Tejo, Guilherme H. R. Bittencourt, Vagson L. Carvalho-Santos, Oksana Chubykalo-Fesenko, Agustina Asenjo
Curvature and geometry have significant implications in fundamental physics, leading to the appearance of intriguing novel phenomena. In the field of nanomagnetism, geometrical-induced effects yield important consequences, which, despite their relevance for domain wall (DW) motion-based applications, still await experimental validation. In this letter, a spiral-shaped magnetic nanostructure is used to demonstrate experimentally that curvature gradients determine DW motion. A saturating magnetic field is applied to the spirals to induce the magnetic onion state, generating head-to-head (HtH) and tail-to-tail (TtT) DW. Curvature gradient promotes domain wall motion through a local curvature-dependent effective force, toward regions of higher curvature. These effects have been studied by measuring depinning fields and supported by micromagnetic simulations and an analytical model. Our results show the potential of curvature engineering for the realization of low-energy spintronic devices.
{"title":"Experimental Evidence of Curvature Gradient Driven Domain Wall Automotion","authors":"Eider Berganza, Felipe Tejo, Guilherme H. R. Bittencourt, Vagson L. Carvalho-Santos, Oksana Chubykalo-Fesenko, Agustina Asenjo","doi":"10.1002/smll.202407084","DOIUrl":"https://doi.org/10.1002/smll.202407084","url":null,"abstract":"Curvature and geometry have significant implications in fundamental physics, leading to the appearance of intriguing novel phenomena. In the field of nanomagnetism, geometrical-induced effects yield important consequences, which, despite their relevance for domain wall (DW) motion-based applications, still await experimental validation. In this letter, a spiral-shaped magnetic nanostructure is used to demonstrate experimentally that curvature gradients determine DW motion. A saturating magnetic field is applied to the spirals to induce the magnetic onion state, generating head-to-head (HtH) and tail-to-tail (TtT) DW. Curvature gradient promotes domain wall motion through a local curvature-dependent effective force, toward regions of higher curvature. These effects have been studied by measuring depinning fields and supported by micromagnetic simulations and an analytical model. Our results show the potential of curvature engineering for the realization of low-energy spintronic devices.","PeriodicalId":228,"journal":{"name":"Small","volume":"22 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418335","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}
Xia Chen, Ping Feng, Yong Zheng, Hui Li, Youfang Zhang, Yi Shen, Yan Yan, Mingkai Liu, Liqun Ye
The growing global energy demands, coupled with the imperative for sustainable environmental challenges, have sparked significant interest in electrochemical energy storage and conversion (EESC) technologies. Metal-free heteroatom-doped carbon materials, especially those codoped with nitrogen (N) and sulfur (S), have gained prominence due to their exceptional conductivity, large specific surface area, remarkable chemical stability, and enhanced electrochemical performance. The strategic incorporation of N and S atoms into the carbon framework plays a pivotal role in modulating electron distribution and creating catalytically active sites, thereby significantly enhancing the EESC performance. This review examines the key synthetic strategies for fabricating N, S codoped carbon materials (NSDCMs) and provides a comprehensive overview of recent advancements in NSDCMs for EESC applications. These encompass various electrochemical energy storage systems such as supercapacitors, alkali-ion batteries, and lithium–sulfur batteries. Energy conversion processes, including hydrogen evolution, oxygen reduction/evolution, and carbon dioxide reduction are also covered. Finally, future research directions for NSDCMs are discussed in the EESC field, aiming to highlight their promising potential and multifunctional capabilities in driving further advancements in electrochemical energy systems.
{"title":"Emerging Nitrogen and Sulfur Co-doped Carbon Materials for Electrochemical Energy Storage and Conversion","authors":"Xia Chen, Ping Feng, Yong Zheng, Hui Li, Youfang Zhang, Yi Shen, Yan Yan, Mingkai Liu, Liqun Ye","doi":"10.1002/smll.202412191","DOIUrl":"https://doi.org/10.1002/smll.202412191","url":null,"abstract":"The growing global energy demands, coupled with the imperative for sustainable environmental challenges, have sparked significant interest in electrochemical energy storage and conversion (EESC) technologies. Metal-free heteroatom-doped carbon materials, especially those codoped with nitrogen (N) and sulfur (S), have gained prominence due to their exceptional conductivity, large specific surface area, remarkable chemical stability, and enhanced electrochemical performance. The strategic incorporation of N and S atoms into the carbon framework plays a pivotal role in modulating electron distribution and creating catalytically active sites, thereby significantly enhancing the EESC performance. This review examines the key synthetic strategies for fabricating N, S codoped carbon materials (NSDCMs) and provides a comprehensive overview of recent advancements in NSDCMs for EESC applications. These encompass various electrochemical energy storage systems such as supercapacitors, alkali-ion batteries, and lithium–sulfur batteries. Energy conversion processes, including hydrogen evolution, oxygen reduction/evolution, and carbon dioxide reduction are also covered. Finally, future research directions for NSDCMs are discussed in the EESC field, aiming to highlight their promising potential and multifunctional capabilities in driving further advancements in electrochemical energy systems.","PeriodicalId":228,"journal":{"name":"Small","volume":"13 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418100","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}
Rational design of molecular architectures is crucial for developing advanced materials such as covalent-organic frameworks (COFs) with excellent sensing performance. In this work, two isostructural COFs (β-keto-AnCOF and imine-AnCOF) with the same conjugated linkers but distinct linkages are constructed. Although both COFs have porous structure and semiconductor behavior conferred by the identical conjugated backbones, β-keto-AnCOF with ─C═O side groups exhibits superior room-temperature ammonia (NH3) sensing performance than imine-AnCOF and even the state-of-the-art dynamic and commercial NH3 sensors, i.e., high sensitivity up to 18.94% ppm−1, ultralow experimental detection limit of 1 ppb, outstanding selectivity, and remarkable response stability and reproducibility after 180 days. In situ spectroscopy and theoretical calculation reveal that the additional charge transfer between NH3 and ─C═O sites in β-keto-AnCOF effectively increases the distance between Fermi level and the valence band, enabling highly-sensitive NH3 detection at ppb levels. This work provides novel molecular architectures for next-generation high-performance sensors.
{"title":"Linkage Engineering of Semiconductive Covalent-Organic Frameworks toward Room-Temperature Ppb-Level Selective Ammonia Sensing","authors":"Zhuang Yan, Munan Fang, Longfei Wang, Huiwen Gao, Yue Ying, Jinlei Yang, Jiahua Wang, Yaling Liu, Zhiyong Tang","doi":"10.1002/smll.202407436","DOIUrl":"https://doi.org/10.1002/smll.202407436","url":null,"abstract":"Rational design of molecular architectures is crucial for developing advanced materials such as covalent-organic frameworks (COFs) with excellent sensing performance. In this work, two isostructural COFs (β-keto-AnCOF and imine-AnCOF) with the same conjugated linkers but distinct linkages are constructed. Although both COFs have porous structure and semiconductor behavior conferred by the identical conjugated backbones, β-keto-AnCOF with ─C═O side groups exhibits superior room-temperature ammonia (NH<sub>3</sub>) sensing performance than imine-AnCOF and even the state-of-the-art dynamic and commercial NH<sub>3</sub> sensors, i.e., high sensitivity up to 18.94% ppm<sup>−1</sup>, ultralow experimental detection limit of 1 ppb, outstanding selectivity, and remarkable response stability and reproducibility after 180 days. In situ spectroscopy and theoretical calculation reveal that the additional charge transfer between NH<sub>3</sub> and ─C═O sites in β-keto-AnCOF effectively increases the distance between Fermi level and the valence band, enabling highly-sensitive NH<sub>3</sub> detection at ppb levels. This work provides novel molecular architectures for next-generation high-performance sensors.","PeriodicalId":228,"journal":{"name":"Small","volume":"21 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418066","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}
2D metal carbides/nitrides (MXenes) have attracted considerable interests in NH3 sensing due to their high electrical conductivity and abundant terminal groups. However, the strong interlayer interactions between MXene nanosheets result in challenges related to sensor recovery and rapid response decay in MXene-based sensors. Here, A one-step hydrothermal strategy is developed that anchors Zn atoms and grows ZnO polycrystals on the Ti vacancies of Ti3C2Tx layers, forming a sandwich-structured ZnO/Ti3C2Tx heterojunction. At room temperature, the NH3 sensitivity of ZnO/Ti3C2Tx is a remarkable 45-fold higher than that of Ti3C2Tx, with a low detection limit of 138 ppb and a rapid recovery time of 39 s. Furthermore, the heterojunction exhibits exceptional long-term stability, maintaining a consistent response over 21 days. The results confirm that in situ intercalation of the ZnO polycrystals effectively solves the recovery problem in MXene substrates by completely exfoliating the Ti3C2Tx nanosheets. Meanwhile, the room-temperature sensing performance and recovery speed of the sandwich-structured ZnO/Ti3C2Tx is enhanced by rapid electron conduction. This straightforward and effective route for in situ exfoliation and intercalation of MXene layers promises the broader use of 2Dmaterial heterojunctions in sensing applications.
{"title":"Sandwich-Structured ZnO/MXene Heterojunction for Sensitive and Stable Room-Temperature Ammonia Sensing","authors":"Dongli Li, Zhan Zhang, Mingze Jiao, Yinan Dong, Shuyan Yu, Congju Li, Hongyan He, Jingkun Jiang, Kaihui Liu, Zehui Li","doi":"10.1002/smll.202409716","DOIUrl":"https://doi.org/10.1002/smll.202409716","url":null,"abstract":"2D metal carbides/nitrides (MXenes) have attracted considerable interests in NH<sub>3</sub> sensing due to their high electrical conductivity and abundant terminal groups. However, the strong interlayer interactions between MXene nanosheets result in challenges related to sensor recovery and rapid response decay in MXene-based sensors. Here, A one-step hydrothermal strategy is developed that anchors Zn atoms and grows ZnO polycrystals on the Ti vacancies of Ti<sub>3</sub>C<sub>2</sub>T<i><sub>x</sub></i> layers, forming a sandwich-structured ZnO/Ti<sub>3</sub>C<sub>2</sub>T<i><sub>x</sub></i> heterojunction. At room temperature, the NH<sub>3</sub> sensitivity of ZnO/Ti<sub>3</sub>C<sub>2</sub>T<i><sub>x</sub></i> is a remarkable 45-fold higher than that of Ti<sub>3</sub>C<sub>2</sub>T<i><sub>x</sub></i>, with a low detection limit of 138 ppb and a rapid recovery time of 39 s. Furthermore, the heterojunction exhibits exceptional long-term stability, maintaining a consistent response over 21 days. The results confirm that in situ intercalation of the ZnO polycrystals effectively solves the recovery problem in MXene substrates by completely exfoliating the Ti<sub>3</sub>C<sub>2</sub>T<i><sub>x</sub></i> nanosheets. Meanwhile, the room-temperature sensing performance and recovery speed of the sandwich-structured ZnO/Ti<sub>3</sub>C<sub>2</sub>T<i><sub>x</sub></i> is enhanced by rapid electron conduction. This straightforward and effective route for in situ exfoliation and intercalation of MXene layers promises the broader use of 2Dmaterial heterojunctions in sensing applications.","PeriodicalId":228,"journal":{"name":"Small","volume":"43 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418103","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}
Rational modulation in the transition distribution of electronic band structure is crucial for constructing phonon-induced enhancement effects for efficient charge separation and thus improving the photocatalytic activity of heterogeneous semiconductor systems. Herein, the indirect/direct transition modulation of layer-dependent MoS2 has been systematically investigated and modeled as a noble metal-free cocatalyst model to study the spatial behavior of carriers in the presence of the phonon effect by coupling it to the direct semiconductor CdS. Consequently, photocarrier separation at the heterojunction interface is greatly facilitated by the optimized band-matching mechanism, while phonon-interfered recombination achieves lifetime extension, which is further elucidated by theoretical simulations. Notably, the water reduction properties of the optimal CdS/MoS2 system exhibit a striking apparent quantum efficiency (31.33% at 380 nm), with an H2 evolution rate as high as 9.70 mmol h−1 g−1, which is 7.58 times higher than that of pristine CdS. Overall, this work demonstrates the capability of involved phonons for enhancing charge transfer dynamics, and provides great flexibility for precisely designing superior photocatalytic systems by manipulating the electronic band transformation.
{"title":"Optimization of CdS/MoS2 Photocatalysts for Phonon-Enhanced H2 Evolution via Indirect Transition Modulation in Layer-Dependent MoS2","authors":"Chao Zhang, Zizheng Ai, Xiaolong Xu, Meiling Huang, Zhiliang Xiu, Yongzhong Wu, Yongliang Shao, Xiaopeng Hao","doi":"10.1002/smll.202411128","DOIUrl":"https://doi.org/10.1002/smll.202411128","url":null,"abstract":"Rational modulation in the transition distribution of electronic band structure is crucial for constructing phonon-induced enhancement effects for efficient charge separation and thus improving the photocatalytic activity of heterogeneous semiconductor systems. Herein, the indirect/direct transition modulation of layer-dependent MoS<sub>2</sub> has been systematically investigated and modeled as a noble metal-free cocatalyst model to study the spatial behavior of carriers in the presence of the phonon effect by coupling it to the direct semiconductor CdS. Consequently, photocarrier separation at the heterojunction interface is greatly facilitated by the optimized band-matching mechanism, while phonon-interfered recombination achieves lifetime extension, which is further elucidated by theoretical simulations. Notably, the water reduction properties of the optimal CdS/MoS<sub>2</sub> system exhibit a striking apparent quantum efficiency (31.33% at 380 nm), with an H<sub>2</sub> evolution rate as high as 9.70 mmol h<sup>−1</sup> g<sup>−1</sup>, which is 7.58 times higher than that of pristine CdS. Overall, this work demonstrates the capability of involved phonons for enhancing charge transfer dynamics, and provides great flexibility for precisely designing superior photocatalytic systems by manipulating the electronic band transformation.","PeriodicalId":228,"journal":{"name":"Small","volume":"10 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418114","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：