Akram Nasser Juaim, Jiao Sun, Ran Nie, Wen Li, Lina Ding, Kun Wang, Jing Zhou, Meiqi Li, Minghan Chi, Biao Dong, Manlin Qi, Lin Wang
Nanozymes with peroxidase (POD)-like activity hold significant potential for addressing antibiotic-resistant bacterial infections. However, their catalytic efficiency and therapeutic efficacy need further improvement to broaden their clinical applications. A key challenge is achieving efficient energy transfer from photosensitizing molecules to nanozymes, which is critical for enhancing catalytic performance. In this study, a universal strategy is developed to bridge nanozymes and photosensitizing molecules, designing photoactivated nanozymes called IR820/PDA@mCeO2 (IR/P@Ce). By integrating IR820, a photosensitizer, with mesoporous ceria (mCeO2), it facilitates efficient electron transfer through polydopamine (PDA) bridge molecules, resulting in enhanced POD-like catalytic performance and reactive oxygen species production. Additionally, PDA stabilized the nanozyme, improved photothermal therapy, and enhanced photodynamic therapy under near-infrared light exposure, further amplifying bacterial destruction. This multifunctional nanozyme demonstrated strong antibacterial efficacy against both Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria. Moreover, its synergistic approach not only facilitated bacterial eradication but also accelerated wound healing in vivo, making it a promising therapeutic alternative for managing bacterial infections and promoting tissue regeneration.
{"title":"IR820 Sensitized Ceria Nanozyme via PDA Bridging for Multifaceted Antibacterial Wound Healing Therapy","authors":"Akram Nasser Juaim, Jiao Sun, Ran Nie, Wen Li, Lina Ding, Kun Wang, Jing Zhou, Meiqi Li, Minghan Chi, Biao Dong, Manlin Qi, Lin Wang","doi":"10.1002/smll.202500382","DOIUrl":"https://doi.org/10.1002/smll.202500382","url":null,"abstract":"Nanozymes with peroxidase (POD)-like activity hold significant potential for addressing antibiotic-resistant bacterial infections. However, their catalytic efficiency and therapeutic efficacy need further improvement to broaden their clinical applications. A key challenge is achieving efficient energy transfer from photosensitizing molecules to nanozymes, which is critical for enhancing catalytic performance. In this study, a universal strategy is developed to bridge nanozymes and photosensitizing molecules, designing photoactivated nanozymes called IR820/PDA@mCeO<sub>2</sub> (IR/P@Ce). By integrating IR820, a photosensitizer, with mesoporous ceria (mCeO<sub>2</sub>), it facilitates efficient electron transfer through polydopamine (PDA) bridge molecules, resulting in enhanced POD-like catalytic performance and reactive oxygen species production. Additionally, PDA stabilized the nanozyme, improved photothermal therapy, and enhanced photodynamic therapy under near-infrared light exposure, further amplifying bacterial destruction. This multifunctional nanozyme demonstrated strong antibacterial efficacy against both Gram-positive (<i>Staphylococcus aureus</i>) and Gram-negative (<i>Escherichia coli</i>) bacteria. Moreover, its synergistic approach not only facilitated bacterial eradication but also accelerated wound healing in vivo, making it a promising therapeutic alternative for managing bacterial infections and promoting tissue regeneration.","PeriodicalId":228,"journal":{"name":"Small","volume":"88 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737115","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}
Yiwan Huang, Qin Teng, Sanyu Qian, Tao Liu, Shijun Long, Zhen Li, Jin Tao, Xuefeng Li
Polyampholyte (PA) hydrogels, composed of charged hydrophilic networks with both positive and negative groups, have attracted great attention due to the unique structure and excellent antifouling properties. Yet, the superhydrophilicity usually makes non-neutral PA (n-PA) gels highly swollen and mechanically very weak in aqueous environments, severely limiting their applications. Herein metal-coordination bonds are designed to introduce to synergistically toughen n-PA hydrogels with ionic bonds via a secondary equilibrium strategy. In the design, as-prepared n-PA gels are dialyzed in metal-ion solutions and deionized water in sequence to achieve the tough gels. Through this strategy, the weak n-PA gels can be significantly toughened by the synergy of ionic and metal-coordination bonds. A systematic study indicates that both the molar ratio of oppositely charged monomers and the metal-ion concentration affect the mechanical enhancements clearly. The universality of the proposed strategy is further proved by selecting different gel systems and multivalent metal ions. Notably, low metal-ion concentrations (≤0.1 m) of dialysis solutions can enable synergistic toughening. Theoretical models are also adopted to disclose the toughening mechanism. This work not only expands the understanding on the fabrication of strong and tough PA hydrogels but also provides some insights for PA gels in electrolyte solutions.
{"title":"Synergistically Toughening Non-Neutral Polyampholyte Hydrogels by Ionic and Coordination Bonds at Low Metal-Ion Contents","authors":"Yiwan Huang, Qin Teng, Sanyu Qian, Tao Liu, Shijun Long, Zhen Li, Jin Tao, Xuefeng Li","doi":"10.1002/smll.202500258","DOIUrl":"https://doi.org/10.1002/smll.202500258","url":null,"abstract":"Polyampholyte (PA) hydrogels, composed of charged hydrophilic networks with both positive and negative groups, have attracted great attention due to the unique structure and excellent antifouling properties. Yet, the superhydrophilicity usually makes non-neutral PA (<i>n</i>-PA) gels highly swollen and mechanically very weak in aqueous environments, severely limiting their applications. Herein metal-coordination bonds are designed to introduce to synergistically toughen <i>n</i>-PA hydrogels with ionic bonds via a secondary equilibrium strategy. In the design, as-prepared <i>n</i>-PA gels are dialyzed in metal-ion solutions and deionized water in sequence to achieve the tough gels. Through this strategy, the weak <i>n</i>-PA gels can be significantly toughened by the synergy of ionic and metal-coordination bonds. A systematic study indicates that both the molar ratio of oppositely charged monomers and the metal-ion concentration affect the mechanical enhancements clearly. The universality of the proposed strategy is further proved by selecting different gel systems and multivalent metal ions. Notably, low metal-ion concentrations (≤0.1 <span>m</span>) of dialysis solutions can enable synergistic toughening. Theoretical models are also adopted to disclose the toughening mechanism. This work not only expands the understanding on the fabrication of strong and tough PA hydrogels but also provides some insights for PA gels in electrolyte solutions.","PeriodicalId":228,"journal":{"name":"Small","volume":"40 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737116","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}
Ashok Kumar, Atul G. Chakkar, Chayan Das, Pradeep Kumar, Satyajit Sahu, Michael Saliba, Mahesh Kumar
Self-powered broadband photodetectors utilizing 2D transition metal dichalcogenides (TMDs) are highly promising due to their remarkable light absorption capabilities and high sensitivity, making them suitable for applications such as military surveillance and wireless light detection systems. However, their performance is constrained by inadequate absorption, suboptimal charge carrier separation, and slow response times. In response to these limitations, the study fabricates a self-powered photodetector employing a heterostructure composed of WS2 nanoparticles anchored to CVD-synthesized MoS2, operating within the visible to near-infrared spectrum. The device demonstrates a responsivity of 283 mA W−1 and a detectivity 6.44 × 1012 Jones, alongside an external quantum efficiency of 61% under exposure of 580 nm. In comparison to pristine MoS2, the MoS2-WS2 photodetector exhibited approximately 12-fold and 11-fold enhancements in responsivity and detectivity, respectively, in addition to fast response time of ≈375 µs and 6 ms. Additionally, density functional theory (DFT) calculations are used to analyze the increase in dark current that is observed following WS₂ nanoparticle anchored on MoS₂. This investigation highlights the potential of 2D heterostructures in the development of high-performance broadband photodetectors, which offer improved responsivity, stability, and self-powered operation for advanced optoelectronic applications.
{"title":"Self-Powered Broadband Photodetectors Based on WS2-Anchored MoS2 with Enhanced Responsivity and Detectivity","authors":"Ashok Kumar, Atul G. Chakkar, Chayan Das, Pradeep Kumar, Satyajit Sahu, Michael Saliba, Mahesh Kumar","doi":"10.1002/smll.202502900","DOIUrl":"https://doi.org/10.1002/smll.202502900","url":null,"abstract":"Self-powered broadband photodetectors utilizing 2D transition metal dichalcogenides (TMDs) are highly promising due to their remarkable light absorption capabilities and high sensitivity, making them suitable for applications such as military surveillance and wireless light detection systems. However, their performance is constrained by inadequate absorption, suboptimal charge carrier separation, and slow response times. In response to these limitations, the study fabricates a self-powered photodetector employing a heterostructure composed of WS<sub>2</sub> nanoparticles anchored to CVD-synthesized MoS<sub>2</sub>, operating within the visible to near-infrared spectrum. The device demonstrates a responsivity of 283 mA W<sup>−1</sup> and a detectivity 6.44 × 10<sup>12</sup> Jones, alongside an external quantum efficiency of 61% under exposure of 580 nm. In comparison to pristine MoS<sub>2</sub>, the MoS<sub>2</sub>-WS<sub>2</sub> photodetector exhibited approximately 12-fold and 11-fold enhancements in responsivity and detectivity, respectively, in addition to fast response time of ≈375 µs and 6 ms. Additionally, density functional theory (DFT) calculations are used to analyze the increase in dark current that is observed following WS₂ nanoparticle anchored on MoS₂. This investigation highlights the potential of 2D heterostructures in the development of high-performance broadband photodetectors, which offer improved responsivity, stability, and self-powered operation for advanced optoelectronic applications.","PeriodicalId":228,"journal":{"name":"Small","volume":"72 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737120","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}
Bacteria-infected diabetic wounds seriously threaten the lives of patients because diabetic ulcer tissues are quite difficult to repair while the bacteria infections deteriorate this course. Clinically used antibiotics cannot fulfil this mission but introduce the risk of bacterial resistance simultaneously. Herein, a near-infrared (NIR) light-responsive composite hydrogel is developed for rapid bacterial eradication and healing of Staphylococcus aureus (S. aureus)-infected diabetic wounds. The hydrogel incorporates copper (Cu)-doped graphitic carbon nitride (g-C3N4) nanosheets combined with black phosphorus (BP) nanosheets through electrostatic bonding and π–π stacking interactions, uniformly dispersed within a chitosan (CS) matrix crosslinked with polyvinyl alcohol (PVA) (Cu-CN/BP@Gel). Under NIR light irradiation, Cu-doping accelerated hot electron flow and improved the photothermal effect. Additionally, the built-in electric field formed by Cu-CN/BP accelerated interfacial electron flow and inhibited the recombination of electron-hole pairs, enhancing reactive oxygen species (ROS) generation. Then, Cu-CN/BP@Gel hydrogel can reach the antibacterial rate of 99.18% against S. aureus. The successful application of the Cu-CN/BP@Gel hydrogel in diabetic wound infection presents a new method for wound healing in a high blood sugar and ROS environment.
{"title":"Accelerating Interface NIR-Induced Charge Transfer Through Cu and Black Phosphorus Modifying G-C3N4 for Rapid Healing of Staphylococcus aureus Infected Diabetic Ulcer Wounds","authors":"Hongbo Wang, Chaofeng Wang, Shuilin Wu, Danning Yan, Caihui Huang, Congyang Mao, Yufeng Zheng, Hanpeng Liu, Liguo Jin, Shengli Zhu, Zhaoyang Li, Hui Jiang, Xiangmei Liu","doi":"10.1002/smll.202500378","DOIUrl":"https://doi.org/10.1002/smll.202500378","url":null,"abstract":"Bacteria-infected diabetic wounds seriously threaten the lives of patients because diabetic ulcer tissues are quite difficult to repair while the bacteria infections deteriorate this course. Clinically used antibiotics cannot fulfil this mission but introduce the risk of bacterial resistance simultaneously. Herein, a near-infrared (NIR) light-responsive composite hydrogel is developed for rapid bacterial eradication and healing of <i>Staphylococcus aureus</i> (<i>S. aureus</i>)-infected diabetic wounds. The hydrogel incorporates copper (Cu)-doped graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) nanosheets combined with black phosphorus (BP) nanosheets through electrostatic bonding and π–π stacking interactions, uniformly dispersed within a chitosan (CS) matrix crosslinked with polyvinyl alcohol (PVA) (Cu-CN/BP@Gel). Under NIR light irradiation, Cu-doping accelerated hot electron flow and improved the photothermal effect. Additionally, the built-in electric field formed by Cu-CN/BP accelerated interfacial electron flow and inhibited the recombination of electron-hole pairs, enhancing reactive oxygen species (ROS) generation. Then, Cu-CN/BP@Gel hydrogel can reach the antibacterial rate of 99.18% against <i>S. aureus</i>. The successful application of the Cu-CN/BP@Gel hydrogel in diabetic wound infection presents a new method for wound healing in a high blood sugar and ROS environment.","PeriodicalId":228,"journal":{"name":"Small","volume":"58 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736860","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}
Nanocatalytic platforms are promising in cancer therapeutics via combining multiple treatments, which can be leveraged through the metabolic dysfunction in cancer progression. However, the lack of effective tumor delivery platforms hampers this approach. Here, a gelatin-based platform is designed that is preloaded with gold nanoparticles and photothermal polypyrrole (GNPs@AuNPs-PPy) with an acid-induced doping enhancement. Benefiting from the tumor associated overexpression of H2O2, peroxidase-like Au nanoparticles induce a burst of oxidative reactive oxygen species in the local tumor microenvironment (TME). Subsequent orchestration of redox surroundings recruits immune cells, showcasing an effective antineoplastic pathway. Under near infrared light (NIR) irradiation, nanohybrids exhibit dual pH/NIR enhanced drug release within the TME, while allowing for multimodal imaging-guided theranostics. Leveraging this modality, GNPs@AuNPs-PPy delivers quercetin (a natural antitumor mediator) in TME, boosting anti-tumor therapy. The gelatin-mediated nanomedicine provides an alternative platform for combinatorial dynamic antitumor treatment.
{"title":"Enhanced Delivery of Photothermal Gelatin Nanoparticle for Redox Balanced Nanocatalytic Tumor Chemotherapy","authors":"Jiayi Hu, Xiaoyu Jia, Manlin Li, Guangxin Duan, Kwan Man, Hongliang Dai, Ling Wen, Hongya Geng","doi":"10.1002/smll.202411018","DOIUrl":"https://doi.org/10.1002/smll.202411018","url":null,"abstract":"Nanocatalytic platforms are promising in cancer therapeutics via combining multiple treatments, which can be leveraged through the metabolic dysfunction in cancer progression. However, the lack of effective tumor delivery platforms hampers this approach. Here, a gelatin-based platform is designed that is preloaded with gold nanoparticles and photothermal polypyrrole (GNPs@AuNPs-PPy) with an acid-induced doping enhancement. Benefiting from the tumor associated overexpression of H<sub>2</sub>O<sub>2</sub>, peroxidase-like Au nanoparticles induce a burst of oxidative reactive oxygen species in the local tumor microenvironment (TME). Subsequent orchestration of redox surroundings recruits immune cells, showcasing an effective antineoplastic pathway. Under near infrared light (NIR) irradiation, nanohybrids exhibit dual pH/NIR enhanced drug release within the TME, while allowing for multimodal imaging-guided theranostics. Leveraging this modality, GNPs@AuNPs-PPy delivers quercetin (a natural antitumor mediator) in TME, boosting anti-tumor therapy. The gelatin-mediated nanomedicine provides an alternative platform for combinatorial dynamic antitumor treatment.","PeriodicalId":228,"journal":{"name":"Small","volume":"36 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737188","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}
The construction of freestanding carbon nanofiber membrane with single-atomic metal active sites and interconnected microchannels as air electrodes is vital for boosting the performance of zinc–air batteries (ZABs). Herein, single-atomic Fe sites is prepared on freestanding hierarchical nitrogen/phosphorus co-doped carbon nanofibers (Fe SACs@PNCNFs) by loading Fe-doped zeolitic imidazolate framework-8 with leaf-like structures on electrospun polyacrylonitrile (PAN) nanofibers with subsequent multi-step pyrolysis in the presence of sodium monophosphate, which are confirmed to be in the form of Fe-N3P1 by X-ray adsorption spectra. The asymmetric N/P coordinated Fe sites is theoretically demonstrated to boost the ORR performance with a half-wave potential of 0.89 V due to the weakened *O adsorption while stabilizing *OOH adsorption arising from the increased charge density of Fe sites compared to symmetric N coordinated Fe sites with Fe-N4. Moreover, when liquid and quasi-solid ZABs are assembled, excellent battery performance is also achieved with peak power density of 163 and 72 mW cm−2 as well as good stability for more than 190 and 65 h, respectively.
{"title":"Construction of Asymmetric Fe-N3P1 Sites on Freestanding Nitrogen/Phosphorus Co-Doped Carbon Nanofibers for Boosting Oxygen Electrocatalysis and Zinc–Air Batteries","authors":"Yuanjian Liu, Haocheng Liu, Lina Li, Yan Tang, Yanyan Sun, Jiang Zhou","doi":"10.1002/smll.202501495","DOIUrl":"https://doi.org/10.1002/smll.202501495","url":null,"abstract":"The construction of freestanding carbon nanofiber membrane with single-atomic metal active sites and interconnected microchannels as air electrodes is vital for boosting the performance of zinc–air batteries (ZABs). Herein, single-atomic Fe sites is prepared on freestanding hierarchical nitrogen/phosphorus co-doped carbon nanofibers (Fe SACs@PNCNFs) by loading Fe-doped zeolitic imidazolate framework-8 with leaf-like structures on electrospun polyacrylonitrile (PAN) nanofibers with subsequent multi-step pyrolysis in the presence of sodium monophosphate, which are confirmed to be in the form of Fe-N<sub>3</sub>P<sub>1</sub> by X-ray adsorption spectra. The asymmetric N/P coordinated Fe sites is theoretically demonstrated to boost the ORR performance with a half-wave potential of 0.89 V due to the weakened <sup>*</sup>O adsorption while stabilizing <sup>*</sup>OOH adsorption arising from the increased charge density of Fe sites compared to symmetric N coordinated Fe sites with Fe-N<sub>4</sub>. Moreover, when liquid and quasi-solid ZABs are assembled, excellent battery performance is also achieved with peak power density of 163 and 72 mW cm<sup>−2</sup> as well as good stability for more than 190 and 65 h, respectively.","PeriodicalId":228,"journal":{"name":"Small","volume":"58 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736859","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}
Yufei You, Ziwei He, Jianwei Zhou, Yuhang Qi, Chong Luo
As the feature sizes of integrated circuits continue to shrink, the phenomenon of electrical migration in Cu interconnects becomes more severe. Due to the excellent properties of Ru such as short electron mean free path and good resistance to electrical migration, it has the potential to become the next-generation interconnect material. Ru chemical mechanical polishing (CMP) is a crucial step in the fabrication of integrated circuits, with oxidation being the step limiting the Ru removal rate, which affects the efficiency of semiconductor manufacturing. In this study, using the H2O2/PDS/FeIII-NTA system, the removal rate of Ru is improved to 1202 Å min−1 via abrasive-free CMP at pH = 7; the surface roughness is only 0.94 nm, demonstrating superior surface quality at the atomic level. This system features a synergistic catalytic mechanism, producing the active oxidants HO•, SO4•−, and FeIV = O. These active oxidants have strong oxidation capacity and lead to the oxidation of Ru into RuO2 and RuO3 and their subsequent oxidation into soluble RuO4− and RuO42−, which results in the formation of a porous oxide layer on the surface of Ru. The oxidation and mechanical effects reach an equilibrium state and accelerate the removal of Ru.
{"title":"Enhanced Ruthenium Removal and Superior Surface Quality via Abrasive-Free Chemical Mechanical Polishing Using Synergistic Catalysis with the H2O2/PDS/FeIII-NTA System","authors":"Yufei You, Ziwei He, Jianwei Zhou, Yuhang Qi, Chong Luo","doi":"10.1002/smll.202410586","DOIUrl":"https://doi.org/10.1002/smll.202410586","url":null,"abstract":"As the feature sizes of integrated circuits continue to shrink, the phenomenon of electrical migration in Cu interconnects becomes more severe. Due to the excellent properties of Ru such as short electron mean free path and good resistance to electrical migration, it has the potential to become the next-generation interconnect material. Ru chemical mechanical polishing (CMP) is a crucial step in the fabrication of integrated circuits, with oxidation being the step limiting the Ru removal rate, which affects the efficiency of semiconductor manufacturing. In this study, using the H<sub>2</sub>O<sub>2</sub>/PDS/Fe<sup>III</sup>-NTA system, the removal rate of Ru is improved to 1202 Å min<sup>−1</sup> via abrasive-free CMP at pH = 7; the surface roughness is only 0.94 nm, demonstrating superior surface quality at the atomic level. This system features a synergistic catalytic mechanism, producing the active oxidants HO<sup>•</sup>, SO<sub>4</sub><sup>•−</sup>, and Fe<sup>IV</sup> = O. These active oxidants have strong oxidation capacity and lead to the oxidation of Ru into RuO<sub>2</sub> and RuO<sub>3</sub> and their subsequent oxidation into soluble RuO<sub>4</sub><sup>−</sup> and RuO<sub>4</sub><sup>2−</sup>, which results in the formation of a porous oxide layer on the surface of Ru. The oxidation and mechanical effects reach an equilibrium state and accelerate the removal of Ru.","PeriodicalId":228,"journal":{"name":"Small","volume":"73 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737184","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}
Markus Ostermann, Marko Piljević, Elahe Akbari, Prathamesh Patil, Veronika Zahorodna, Ivan Baginskiy, Oleksiy Gogotsi, Carsten Gachot, Manel Rodríguez Ripoll, Markus Valtiner, Pierluigi Bilotto
MXenes are a 2D materials (2DM) class with high industrialization potential, owing to their superb properties and compositional variety. However, ensuring high etching efficiency in the synthesis process without involving toxic, hazardous or non-sustainable chemicals are challenging. In this work, an upscalable electrochemical MXene synthesis is presented. This novel protocol uses a non-toxic and sustainable sodium tetrafluoroborate/hydrochloric acid (NaBF4/HCl) electrolyte and increases etching efficiency by applying cathodic pulsing via pulse voltammetry. Hydrogen bubble formation restores electrochemical activity, and effectively supports 2D-sheet removal, allowing continuous etching at higher yields in situ. In detail, yields of up to 60% electrochemical MXene (EC-MXene) with no byproducts from a single exfoliation cycle are achieved. EC-MXene had an excellent quality with high purity as assessed using chemical mapping by scanning electron microscopy with energy dispersive electron spectroscopy (SEM/EDX) and surface termination analysis performed with X-ray photoelectron spectroscopy (XPS) and, for the first time, with low energy ion scattering (LEIS). Further properties of EC-MXenes such as dimensions and adhesion energy of single flakes, vibrational peaks, and interlayer spacing are provided by atomic force microscopy (AFM), X-ray diffraction (XRD), Raman spectroscopy (Raman), and transmission electron microscopy (TEM) respectively. Pulsed electrochemical synthesis is key to surface reactivation at the electrodes' interface, which results in improved exfoliation and quality of EC-MXenes. This paves the way for scaling up and green industrialization of MXenes.
{"title":"Pulsed Electrochemical Exfoliation for an HF-Free Sustainable MXene Synthesis","authors":"Markus Ostermann, Marko Piljević, Elahe Akbari, Prathamesh Patil, Veronika Zahorodna, Ivan Baginskiy, Oleksiy Gogotsi, Carsten Gachot, Manel Rodríguez Ripoll, Markus Valtiner, Pierluigi Bilotto","doi":"10.1002/smll.202500807","DOIUrl":"https://doi.org/10.1002/smll.202500807","url":null,"abstract":"MXenes are a 2D materials (2DM) class with high industrialization potential, owing to their superb properties and compositional variety. However, ensuring high etching efficiency in the synthesis process without involving toxic, hazardous or non-sustainable chemicals are challenging. In this work, an upscalable electrochemical MXene synthesis is presented. This novel protocol uses a non-toxic and sustainable sodium tetrafluoroborate/hydrochloric acid (NaBF<sub>4</sub>/HCl) electrolyte and increases etching efficiency by applying cathodic pulsing via pulse voltammetry. Hydrogen bubble formation restores electrochemical activity, and effectively supports 2D-sheet removal, allowing continuous etching at higher yields in situ. In detail, yields of up to 60% electrochemical MXene (EC-MXene) with no byproducts from a single exfoliation cycle are achieved. EC-MXene had an excellent quality with high purity as assessed using chemical mapping by scanning electron microscopy with energy dispersive electron spectroscopy (SEM/EDX) and surface termination analysis performed with X-ray photoelectron spectroscopy (XPS) and, for the first time, with low energy ion scattering (LEIS). Further properties of EC-MXenes such as dimensions and adhesion energy of single flakes, vibrational peaks, and interlayer spacing are provided by atomic force microscopy (AFM), X-ray diffraction (XRD), Raman spectroscopy (Raman), and transmission electron microscopy (TEM) respectively. Pulsed electrochemical synthesis is key to surface reactivation at the electrodes' interface, which results in improved exfoliation and quality of EC-MXenes. This paves the way for scaling up and green industrialization of MXenes.","PeriodicalId":228,"journal":{"name":"Small","volume":"44 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737174","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}
Mengsha Li, Shufen Han, Chun Dan, Tao Wu, Feng You, Xueliang Jiang, Yunhui Wu, Zhi-Min Dang
The escalating thermal challenges posed by increasing power densities in electronic devices emerge as a critical barrier to maintain their sustained and reliable operation. Addressing this issue requires the strategic development of materials with superior thermal conductivity properties to facilitate progress in high-power electronics development. Thermal conductive polymer composites by incorporating ceramic material renowned for their exceptional thermal conductivity adjustability, insulating properties, and moldability, are emerging as a promising solution to this urgent challenge. Hexagonal boron nitride (h-BN) nanomaterials emerge as highly promising candidates for thermal management applications, owing to their exceptional mechanical properties, superior thermal stability, remarkable thermal conductivity coefficients, minimal thermal expansion characteristics, and outstanding chemical inertness. In this work, the progress of ≈10 years on high thermal conductive boron nitride-filled polymer composites is thoroughly summarized. Moreover, strategies for h-BN and other boron nitride nanomaterials-filled polymer composites at synthesis, functionalization, and innovative structural design are discussed in detail. The main challenges and future development of boron nitride-polymer composites in thermal management are also proposed, which will provide meaningful guidance for the design and practical applications of thermal management materials.
{"title":"Boron Nitride-Polymer Composites with High Thermal Conductivity: Preparation, Functionalization Strategy and Innovative Structural Regulation","authors":"Mengsha Li, Shufen Han, Chun Dan, Tao Wu, Feng You, Xueliang Jiang, Yunhui Wu, Zhi-Min Dang","doi":"10.1002/smll.202412447","DOIUrl":"https://doi.org/10.1002/smll.202412447","url":null,"abstract":"The escalating thermal challenges posed by increasing power densities in electronic devices emerge as a critical barrier to maintain their sustained and reliable operation. Addressing this issue requires the strategic development of materials with superior thermal conductivity properties to facilitate progress in high-power electronics development. Thermal conductive polymer composites by incorporating ceramic material renowned for their exceptional thermal conductivity adjustability, insulating properties, and moldability, are emerging as a promising solution to this urgent challenge. Hexagonal boron nitride (h-BN) nanomaterials emerge as highly promising candidates for thermal management applications, owing to their exceptional mechanical properties, superior thermal stability, remarkable thermal conductivity coefficients, minimal thermal expansion characteristics, and outstanding chemical inertness. In this work, the progress of ≈10 years on high thermal conductive boron nitride-filled polymer composites is thoroughly summarized. Moreover, strategies for h-BN and other boron nitride nanomaterials-filled polymer composites at synthesis, functionalization, and innovative structural design are discussed in detail. The main challenges and future development of boron nitride-polymer composites in thermal management are also proposed, which will provide meaningful guidance for the design and practical applications of thermal management materials.","PeriodicalId":228,"journal":{"name":"Small","volume":"72 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737179","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}
Polymeric materials often face inherent trade-offs between mechanical performance and self-healing capabilities, which presents significant challenges to their development and practical application. Here, an effective strategy is reported to overcome these limitations. By introducing a highly crystalline polyol—characterized by its chain folding and storage chain length—and coordination bonds into polyurethane, an exceptional balance of high tensile strength (47.18 ± 2.35 MPa), exceptional elongation at break (5952.72 ± 254.20%), outstanding toughness (1396.39 ± 90.05 MJ m−3), and high hardness (shore D hardness 43.8 ± 0.8) is achieved, while also maintaining intrinsic self-healing properties. The material's self-healing is facilitated by the water solubility of polyol (polyethylene glycol, PEG), which enables rapid healing and welding at low temperatures (4 °C) with the aid of water. Additionally, the shape-memory recovery force further enhances crack closure and healing, contributing to the material's durability. This unique combination of mechanical performance and self-healing capabilities underscores the potential of this material for advanced applications that require both high mechanical properties and robust self-healing functionality.
{"title":"Multifunctional Polyurethane Exhibiting High Mechanical Performance and Shape-Memory-Assisted Self-Healing","authors":"Xiaoyue Wang, Song Li, Zenghui Yang, Yaoming Zhang, Qihua Wang, Tingmei Wang, Xinrui Zhang","doi":"10.1002/smll.202500847","DOIUrl":"https://doi.org/10.1002/smll.202500847","url":null,"abstract":"Polymeric materials often face inherent trade-offs between mechanical performance and self-healing capabilities, which presents significant challenges to their development and practical application. Here, an effective strategy is reported to overcome these limitations. By introducing a highly crystalline polyol—characterized by its chain folding and storage chain length—and coordination bonds into polyurethane, an exceptional balance of high tensile strength (47.18 ± 2.35 MPa), exceptional elongation at break (5952.72 ± 254.20%), outstanding toughness (1396.39 ± 90.05 MJ m<sup>−3</sup>), and high hardness (shore D hardness 43.8 ± 0.8) is achieved, while also maintaining intrinsic self-healing properties. The material's self-healing is facilitated by the water solubility of polyol (polyethylene glycol, PEG), which enables rapid healing and welding at low temperatures (4 °C) with the aid of water. Additionally, the shape-memory recovery force further enhances crack closure and healing, contributing to the material's durability. This unique combination of mechanical performance and self-healing capabilities underscores the potential of this material for advanced applications that require both high mechanical properties and robust self-healing functionality.","PeriodicalId":228,"journal":{"name":"Small","volume":"103 2 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737185","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}
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