Sihwan Lee, Yong Eun Cho, Ho-Young Kim, Jeong-Yun Sun
Modulating the mechanical properties of soft materials with light is essential for achieving customizable functionalities. However, existing photo-responsive materials suffer from limited mechanical performance and a restricted tunable range. Here, a photo-tunable elastomer is developed by incorporating a urethane acrylate network with selenosulfide-based dynamic covalent crosslinkers, achieving high tensile strength exceeding 1.2 MPa in their stiff state and variable Young's modulus within a 0.8 MPa range. These crosslinkers undergo selenosulfide photo-metathesis, gradually breaking under ultraviolet light and reforming under visible light, enabling fine control over the modulus, strength, and stretchability of the elastomer. In terms of controllability, the design supports multiple tunable states, which allow for the use of intermediate mechanical properties. Moreover, by modeling the crosslinking density changes with reaction kinetics, modulus variation is predicted as a function of light exposure time. The light-induced modulation facilitates localized mechanical property adjustments, generating transformable multi-material structures and enhancing fracture resistance. Integrating these crosslinkers into different polymer networks provides a strategy for creating various photo-tunable elastomers and gels.
{"title":"Photo-Tunable Elastomers Enabling Reversible, Broad-Range Modulation of Mechanical Properties Via Dynamic Covalent Crosslinkers","authors":"Sihwan Lee, Yong Eun Cho, Ho-Young Kim, Jeong-Yun Sun","doi":"10.1002/smll.202412657","DOIUrl":"https://doi.org/10.1002/smll.202412657","url":null,"abstract":"Modulating the mechanical properties of soft materials with light is essential for achieving customizable functionalities. However, existing photo-responsive materials suffer from limited mechanical performance and a restricted tunable range. Here, a photo-tunable elastomer is developed by incorporating a urethane acrylate network with selenosulfide-based dynamic covalent crosslinkers, achieving high tensile strength exceeding 1.2 MPa in their stiff state and variable Young's modulus within a 0.8 MPa range. These crosslinkers undergo selenosulfide photo-metathesis, gradually breaking under ultraviolet light and reforming under visible light, enabling fine control over the modulus, strength, and stretchability of the elastomer. In terms of controllability, the design supports multiple tunable states, which allow for the use of intermediate mechanical properties. Moreover, by modeling the crosslinking density changes with reaction kinetics, modulus variation is predicted as a function of light exposure time. The light-induced modulation facilitates localized mechanical property adjustments, generating transformable multi-material structures and enhancing fracture resistance. Integrating these crosslinkers into different polymer networks provides a strategy for creating various photo-tunable elastomers and gels.","PeriodicalId":228,"journal":{"name":"Small","volume":"7 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867241","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}
Lithium argyrodite sulfide electrolytes show great potential in all‐solid‐state lithium metal batteries (ASSLMBs) due to their high ionic conductivity and ductile feature, among which Li6PS5I presents the most promising stability with Li metals but a low ionic conductivity (≈10−6 S cm−1). It is because of the absence of S2−/I− disorder and thus the forbidden Li+ ion intercage migrations. Herein, argyrodite particles with iodine‐gradient‐disordered interphase were designed that opened up the proscribed Li+ ion intercage jumps and synergistically blocked the interfacial electron leakage for ultrastable ASSLMBs. Density functional theory calculations and 7Li spin‐lattice relaxation NMR experiments prove the activated and even accelerated intercage Li+ conduction with reduced migration barrier. Electrostatic potential profiles also certify the electron transition‐shielding interphase as the origin of parasitic‐reaction‐free Li interface. Gathered evidence of, other characterizations demonstrated the combination of high ionic conductivities (cold press 5.7 mS cm−1), low electron conductivity (1.5×10−8 S cm−1), improved critical current density (1.65 mA cm−2), excellent stability with Li metal (over 1,500 h) and prominent cycling and rate performance. This study provides insights on novel interphase design to fulfill the cooperatively high ionic conductivity and high Li metal‐compatibility for high‐performance ASSLMBs.
{"title":"Activating Forbidden Intercage‐Ionic‐Diffusivity by Anion‐Gradient‐Disordered Interphase for Ultrastable Argyrodite‐Based All‐Solid‐State Lithium Metal Batteries","authors":"Ruiqi Guo, Yuxi Zhong, Peng Yu, Kaidi Kang, Songjie Li, Zhifan Hu, Xinran Wang, Chuan Wu, Ying Bai","doi":"10.1002/smll.202500764","DOIUrl":"https://doi.org/10.1002/smll.202500764","url":null,"abstract":"Lithium argyrodite sulfide electrolytes show great potential in all‐solid‐state lithium metal batteries (ASSLMBs) due to their high ionic conductivity and ductile feature, among which Li<jats:sub>6</jats:sub>PS<jats:sub>5</jats:sub>I presents the most promising stability with Li metals but a low ionic conductivity (≈10<jats:sup>−6</jats:sup> S cm<jats:sup>−1</jats:sup>). It is because of the absence of S<jats:sup>2−</jats:sup>/I<jats:sup>−</jats:sup> disorder and thus the forbidden Li<jats:sup>+</jats:sup> ion intercage migrations. Herein, argyrodite particles with iodine‐gradient‐disordered interphase were designed that opened up the proscribed Li<jats:sup>+</jats:sup> ion intercage jumps and synergistically blocked the interfacial electron leakage for ultrastable ASSLMBs. Density functional theory calculations and <jats:sup>7</jats:sup>Li spin‐lattice relaxation NMR experiments prove the activated and even accelerated intercage Li<jats:sup>+</jats:sup> conduction with reduced migration barrier. Electrostatic potential profiles also certify the electron transition‐shielding interphase as the origin of parasitic‐reaction‐free Li interface. Gathered evidence of, other characterizations demonstrated the combination of high ionic conductivities (cold press 5.7 mS cm<jats:sup>−1</jats:sup>), low electron conductivity (1.5×10<jats:sup>−8</jats:sup> S cm<jats:sup>−1</jats:sup>), improved critical current density (1.65 mA cm<jats:sup>−2</jats:sup>), excellent stability with Li metal (over 1,500 h) and prominent cycling and rate performance. This study provides insights on novel interphase design to fulfill the cooperatively high ionic conductivity and high Li metal‐compatibility for high‐performance ASSLMBs.","PeriodicalId":228,"journal":{"name":"Small","volume":"71 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866655","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}
Zutian Chen, Juan Yang, Ruotong Li, Bin Yan, Pei Chen, Jieshan Qiu
Single-atom catalysts (SACs) offer an efficient solution of a well-defined structure-activity relationship for boosting iodine redox kinetics and suppressing the shuttle effect in zinc-iodine (Zn-I2) batteries, but the further upgradation of their electrocatalytic activity is still constrained to date. Herein, atomically dispersed transition-metal electrocatalysts comprised of heteronuclear nickel-cobalt diatomic sites anchored on porous carbon nanosheets (Ni-Co-DA/PCNs) are proposed by a novel interlayer-confinement pyrolysis strategy. Thereinto, the NiCoAl-layered double hydroxides are employed as the 2D topological structure to induce the confined polycondensation of aromatic hydrocarbon precursors, and the transition-metal ions are simultaneously trapped in hierarchical carbon frameworks by the oxygen-containing species. The detailed experimental investigations combined with the in situ Raman spectroscopy reveal that the Ni-Co-DA/PCNs electrocatalyst with well-defined M-O4 pair and high specific surface area is capable of facilitating the adsorption and fast conversion of polyiodides, thereby accelerating the redox kinetics of I2/I‒ and protecting zinc anode. Consequently, the assembled Zn-I2 batteries with the Ni-Co-DA/PCNs/I2 cathode exhibit a high discharge capacity of 216.7 mAh g‒1 at 0.2 A g‒1 with excellent rate capability and ultralong cycling lifespan over 9000 cycles with a capacity decay of only 0.0018% per cycle, which is far superior to those of Ni/Co SACs. This work provides a new insight into the design of dual-atom catalysts for Zn-halogens batteries.
{"title":"Boosting Iodine Redox Kinetics by Nickel-Cobalt Diatomic Electrocatalyst for Zinc-Iodine Batteries","authors":"Zutian Chen, Juan Yang, Ruotong Li, Bin Yan, Pei Chen, Jieshan Qiu","doi":"10.1002/smll.202500936","DOIUrl":"https://doi.org/10.1002/smll.202500936","url":null,"abstract":"Single-atom catalysts (SACs) offer an efficient solution of a well-defined structure-activity relationship for boosting iodine redox kinetics and suppressing the shuttle effect in zinc-iodine (Zn-I<sub>2</sub>) batteries, but the further upgradation of their electrocatalytic activity is still constrained to date. Herein, atomically dispersed transition-metal electrocatalysts comprised of heteronuclear nickel-cobalt diatomic sites anchored on porous carbon nanosheets (Ni-Co-DA/PCNs) are proposed by a novel interlayer-confinement pyrolysis strategy. Thereinto, the NiCoAl-layered double hydroxides are employed as the 2D topological structure to induce the confined polycondensation of aromatic hydrocarbon precursors, and the transition-metal ions are simultaneously trapped in hierarchical carbon frameworks by the oxygen-containing species. The detailed experimental investigations combined with the in situ Raman spectroscopy reveal that the Ni-Co-DA/PCNs electrocatalyst with well-defined M-O<sub>4</sub> pair and high specific surface area is capable of facilitating the adsorption and fast conversion of polyiodides, thereby accelerating the redox kinetics of I<sub>2</sub>/I<sup>‒</sup> and protecting zinc anode. Consequently, the assembled Zn-I<sub>2</sub> batteries with the Ni-Co-DA/PCNs/I<sub>2</sub> cathode exhibit a high discharge capacity of 216.7 mAh g<sup>‒1</sup> at 0.2 A g<sup>‒1</sup> with excellent rate capability and ultralong cycling lifespan over 9000 cycles with a capacity decay of only 0.0018% per cycle, which is far superior to those of Ni/Co SACs. This work provides a new insight into the design of dual-atom catalysts for Zn-halogens batteries.","PeriodicalId":228,"journal":{"name":"Small","volume":"138 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867223","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}
Changsheng Du, Wenjing Na, Haojie Huang, Yunqi Liu, Jianyi Chen
The development of efficient solid-state luminescent covalent organic frameworks (COFs) is crucial for advancing applications in sensing, imaging, and optoelectronics. However, achieving high photoluminescent quantum yields (PLQY) in imine-linked COFs remains challenging due to the presence of complex nonradiative quenching pathways. Here, the design and synthesis of a novel series of solid-state photoluminescent imine-linked 2D covalent organic frameworks (2D COFs) are reported through condensation of rigid building blocks. These COFs display high crystallinity and porosity, and with a remarkable PLQY of up to 39% in the solid state. The high luminescent efficiency is attributed to the donor–acceptor–donor structure within the aldehyde moieties, which facilitates selective charge transfer excitation between the donor moiety, triphenylamine, and the acceptor moiety, benzothiadiazole, bypassing the imine bonds, suppressing nonradiative quenching pathways associated with imine bond rotation in the excited states. Furthermore, the obtained COF shows potential for bioimaging applications.
{"title":"Solid-State Photoluminescent Imine-Linked Two-Dimensional Covalent Organic Frameworks","authors":"Changsheng Du, Wenjing Na, Haojie Huang, Yunqi Liu, Jianyi Chen","doi":"10.1002/smll.202501607","DOIUrl":"https://doi.org/10.1002/smll.202501607","url":null,"abstract":"The development of efficient solid-state luminescent covalent organic frameworks (COFs) is crucial for advancing applications in sensing, imaging, and optoelectronics. However, achieving high photoluminescent quantum yields (PLQY) in imine-linked COFs remains challenging due to the presence of complex nonradiative quenching pathways. Here, the design and synthesis of a novel series of solid-state photoluminescent imine-linked 2D covalent organic frameworks (2D COFs) are reported through condensation of rigid building blocks. These COFs display high crystallinity and porosity, and with a remarkable PLQY of up to 39% in the solid state. The high luminescent efficiency is attributed to the donor–acceptor–donor structure within the aldehyde moieties, which facilitates selective charge transfer excitation between the donor moiety, triphenylamine, and the acceptor moiety, benzothiadiazole, bypassing the imine bonds, suppressing nonradiative quenching pathways associated with imine bond rotation in the excited states. Furthermore, the obtained COF shows potential for bioimaging applications.","PeriodicalId":228,"journal":{"name":"Small","volume":"7 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867225","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}
Yifan Hu, Luchan Lin, Junde Ji, Weiqing Wu, Xinde Zuo, Zhengjie Cai, Hao Li, Huan Shang, Zhuguo Li
Large-differential semiconductor and oxide interconnect are widely used in high-performance multi-function integrated microsystems. In this work, spatial-confined plasma-assisted ultrafast laser microwelding has been developed to activate the inert surface and improve mass transportation for robust semiconductor-oxide integration. The inherent stress concentration within the weld of semiconductor (Si) and oxide (Sapphire) can be compensated by inserting hundreds-of-nanometer-thick intermediate oxide layer (SiO2). Amorphous silicate with embedded Si nanocrystals is generated to facilitate the bond between Si and Sapphire. While, SiO2 jet with extremely high energy can expand into the interior of Sapphire, bringing in numerous bonding sites. The shear strength of welded Si and Sapphire structures can be up to 10.7 ± 0.8 MPa. As-received heterostructures also show high chemical resistance to acid (pH 2) and alkaline (pH 12) solutions, where the corrosive liquid is well preserved in the welded cavity after a long time. Developed Si-based SERS optofluidic sensor by ultrafast laser microwleding of Si substrate and Sapphire window shows the reliable ability for high-sensitive detection of low-concentration chemicals (down to 10−12 mol L−1). This method can be also applicable for large-differential materials integration with broad combinations (e.g., Si/Ga2O3 and SiC/Sapphire), which is promising for high-performance multi-function micro devices development.
{"title":"Chemical-Resistant, Highly-Impermeable Integration of Large Differential Semiconductor and Oxide by Spatial-Confined Plasma Assisted Ultrafast Laser Microwelding for Optofluidic Microsystem","authors":"Yifan Hu, Luchan Lin, Junde Ji, Weiqing Wu, Xinde Zuo, Zhengjie Cai, Hao Li, Huan Shang, Zhuguo Li","doi":"10.1002/smll.202500881","DOIUrl":"https://doi.org/10.1002/smll.202500881","url":null,"abstract":"Large-differential semiconductor and oxide interconnect are widely used in high-performance multi-function integrated microsystems. In this work, spatial-confined plasma-assisted ultrafast laser microwelding has been developed to activate the inert surface and improve mass transportation for robust semiconductor-oxide integration. The inherent stress concentration within the weld of semiconductor (Si) and oxide (Sapphire) can be compensated by inserting hundreds-of-nanometer-thick intermediate oxide layer (SiO<sub>2</sub>). Amorphous silicate with embedded Si nanocrystals is generated to facilitate the bond between Si and Sapphire. While, SiO<sub>2</sub> jet with extremely high energy can expand into the interior of Sapphire, bringing in numerous bonding sites. The shear strength of welded Si and Sapphire structures can be up to 10.7 ± 0.8 MPa. As-received heterostructures also show high chemical resistance to acid (pH 2) and alkaline (pH 12) solutions, where the corrosive liquid is well preserved in the welded cavity after a long time. Developed Si-based SERS optofluidic sensor by ultrafast laser microwleding of Si substrate and Sapphire window shows the reliable ability for high-sensitive detection of low-concentration chemicals (down to 10<sup>−12</sup> mol L<sup>−1</sup>). This method can be also applicable for large-differential materials integration with broad combinations (e.g., Si/Ga<sub>2</sub>O<sub>3</sub> and SiC/Sapphire), which is promising for high-performance multi-function micro devices development.","PeriodicalId":228,"journal":{"name":"Small","volume":"7 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867237","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}
Polyborate anion is a tunable and versatile framework that offers a long-term structural stability, providing the active sites to tolerate various coordination ions to induce functionalities. However, their random arrangement typiaclly weakens the optical anisotropy despite high bandgaps. Converting these flexible frameworks into optical-active states remains challenging. Herein, a full optical-active model is proposed where all coordination groups are optimally arranged and fully contribute to the total optical anisotropy in the lattice. A new polyborate is reported with a high optical anisotropy quality factor (F = 0.984), based on a terminal stretch strategy using nucleophilic groups. This renders its framework almost entirely optically active and thus leads to a strong deep-ultraviolet (deep-UV) optical anisotropy of Δnexp = 0.148 in borate system. Theoretical and structural evidence supports the role of nucleophilic groups and orbital hybridization in inducing a preferred configuration of the optical-active module. These findings not only validate the viability of using the full optical-active model to break the intrinsic defect of small optical anisotropy of polyanionic materials, but also expand the alternative system of promising deep-UV optical crystals with new polyanion system that has been neglected for a long time.
{"title":"Breaking the Natural Tendency of Deep-UV Polyborate Anion Clusters to Inducing Strong Optical Anisotropy","authors":"Ziqi Chen, Changyou Liu, Zhi Li, Juanjuan Lu, Junjie Li, Zhihua Yang, Shilie Pan, Miriding Mutailipu","doi":"10.1002/smll.202504138","DOIUrl":"https://doi.org/10.1002/smll.202504138","url":null,"abstract":"Polyborate anion is a tunable and versatile framework that offers a long-term structural stability, providing the active sites to tolerate various coordination ions to induce functionalities. However, their random arrangement typiaclly weakens the optical anisotropy despite high bandgaps. Converting these flexible frameworks into optical-active states remains challenging. Herein, a full optical-active model is proposed where all coordination groups are optimally arranged and fully contribute to the total optical anisotropy in the lattice. A new polyborate is reported with a high optical anisotropy quality factor (<i>F</i> = 0.984), based on a terminal stretch strategy using nucleophilic groups. This renders its framework almost entirely optically active and thus leads to a strong deep-ultraviolet (deep-UV) optical anisotropy of Δ<i>n<sub>exp</sub></i> = 0.148 in borate system. Theoretical and structural evidence supports the role of nucleophilic groups and orbital hybridization in inducing a preferred configuration of the optical-active module. These findings not only validate the viability of using the full optical-active model to break the intrinsic defect of small optical anisotropy of polyanionic materials, but also expand the alternative system of promising deep-UV optical crystals with new polyanion system that has been neglected for a long time.","PeriodicalId":228,"journal":{"name":"Small","volume":"33 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867238","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}
Yiqing Zhang, Zhangpeng Shi, Yimeng Shu, Muhammad Shafiq, Zhengyi Lan, Xiao Liang, Ming Ma, Hangrong Chen
Thromboangiitis obliterans (TAO) is a chronic peripheral vascular condition characterized by thrombotic and inflammatory acceleration. As a promising therapeutic modality for the TAO, mesenchymal stem cells (MSCs) transplantation is expected to circumvent the traditional drug therapy and surgical interventions. Nonetheless, the MSCs therapy is hindered owing to poor survival, retention, and engraftment of the transplanted cells. The objective of this research is to develop MSCs- and cerium oxide nanoparticles (CeNPs)-laden injectable methacrylated gelatin (GelMA)-based hydrogel microspheres by using microfluidics and discern their potential to regulate oxidative stress and inflammation in a rat model of TAO. The CeNPs-loaded photocroslinkable GelMA microspheres not only protected the transplanted MSCs against oxidative stress but also facilitated endothelial functional recovery, revascularization of the ischemic limb, and suppression of the inflammatory factors from the macrophages. The hydrogel microspheres further conferred mechanical support and prolonged the residence time of transplanted MSCs to enhance the efficacy of cell therapy. In vivo study confirmed that the combination of MSCs and CeNPs in the microsphere exhibited a positive synergistic effect on tissue recovery and angiogenesis. Taken together, this work presents a novel therapeutic approach based on the integration of stem cells and nano-micron combined hydrogel microspheres, which may have implications for TAO therapy.
{"title":"Cerium Nanozyme-Powered Hydrogel Microspheres Alleviate Thromboangiitis Obliterans via Enhanced Stem Cell Therapy","authors":"Yiqing Zhang, Zhangpeng Shi, Yimeng Shu, Muhammad Shafiq, Zhengyi Lan, Xiao Liang, Ming Ma, Hangrong Chen","doi":"10.1002/smll.202408748","DOIUrl":"https://doi.org/10.1002/smll.202408748","url":null,"abstract":"Thromboangiitis obliterans (TAO) is a chronic peripheral vascular condition characterized by thrombotic and inflammatory acceleration. As a promising therapeutic modality for the TAO, mesenchymal stem cells (MSCs) transplantation is expected to circumvent the traditional drug therapy and surgical interventions. Nonetheless, the MSCs therapy is hindered owing to poor survival, retention, and engraftment of the transplanted cells. The objective of this research is to develop MSCs- and cerium oxide nanoparticles (CeNPs)-laden injectable methacrylated gelatin (GelMA)-based hydrogel microspheres by using microfluidics and discern their potential to regulate oxidative stress and inflammation in a rat model of TAO. The CeNPs-loaded photocroslinkable GelMA microspheres not only protected the transplanted MSCs against oxidative stress but also facilitated endothelial functional recovery, revascularization of the ischemic limb, and suppression of the inflammatory factors from the macrophages. The hydrogel microspheres further conferred mechanical support and prolonged the residence time of transplanted MSCs to enhance the efficacy of cell therapy. In vivo study confirmed that the combination of MSCs and CeNPs in the microsphere exhibited a positive synergistic effect on tissue recovery and angiogenesis. Taken together, this work presents a novel therapeutic approach based on the integration of stem cells and nano-micron combined hydrogel microspheres, which may have implications for TAO therapy.","PeriodicalId":228,"journal":{"name":"Small","volume":"7 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867248","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}
Chi Zhang, Yongjie Wang, Ying Tao, Yuxin Shi, Jixing Wang, Zhong Ma, Huan Shang, Dieqing Zhang, Guisheng Li
Transition metal single-atom catalysts (SACs) find extensive application in peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs). Yet, the disparity in intrinsic activity is often attributed to thermodynamics, but few studies focused on the electronic structure between different metals. Herein, transition metal catalysts in the form of single-atom M-N4 moieties moored to graphitic carbon nitride (denoted MSA CN, M = Fe, Co, and Cu) are developed and used for activating PMS for the degradation of 4-chlorophenol. Remarkably, FeSA CN achieves a catalyst-dose-normalized kinetic rate constant of 34.2 L min−1 g−1, surpassing reported systems by 2–551 times ─ even at ultralow catalyst (0.06 mg L−1) and PMS (0.2 mm) concentration. The in situ formation of surface-bound PMS* complexes enabled the degradation of 4-chlorophenol to achieve unprecedented utilization efficiency (≈100%) through highly efficient non-radical pathways. Density functional theory calculations revealed that large spin polarization of Fe-N-C sites facilitated the d orbitals to overlap with the PMS on the metal active sites and promoted electron transport, thereby facilitating PMS adsorption and enhancing the oxidation capacity. This work establishes a mechanistic foundation for designing a single Fe-atom catalyst/PMS system in Fenton-like water treatment.
{"title":"Ultrahigh Peroxymonosulfate Utilization Over a Single-Atom Iron-N-C Catalyst for Efficient Fenton-Like Chemistry via Surface-Bound Reactive Complexes","authors":"Chi Zhang, Yongjie Wang, Ying Tao, Yuxin Shi, Jixing Wang, Zhong Ma, Huan Shang, Dieqing Zhang, Guisheng Li","doi":"10.1002/smll.202501267","DOIUrl":"https://doi.org/10.1002/smll.202501267","url":null,"abstract":"Transition metal single-atom catalysts (SACs) find extensive application in peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs). Yet, the disparity in intrinsic activity is often attributed to thermodynamics, but few studies focused on the electronic structure between different metals. Herein, transition metal catalysts in the form of single-atom M-N<sub>4</sub> moieties moored to graphitic carbon nitride (denoted MSA CN, M = Fe, Co, and Cu) are developed and used for activating PMS for the degradation of 4-chlorophenol. Remarkably, FeSA CN achieves a catalyst-dose-normalized kinetic rate constant of 34.2 L min<sup>−1</sup> g<sup>−1</sup>, surpassing reported systems by 2–551 times ─ even at ultralow catalyst (0.06 mg L<sup>−1</sup>) and PMS (0.2 m<span>m</span>) concentration. The in situ formation of surface-bound PMS* complexes enabled the degradation of 4-chlorophenol to achieve unprecedented utilization efficiency (≈100%) through highly efficient non-radical pathways. Density functional theory calculations revealed that large spin polarization of Fe-N-C sites facilitated the d orbitals to overlap with the PMS on the metal active sites and promoted electron transport, thereby facilitating PMS adsorption and enhancing the oxidation capacity. This work establishes a mechanistic foundation for designing a single Fe-atom catalyst/PMS system in Fenton-like water treatment.","PeriodicalId":228,"journal":{"name":"Small","volume":"27 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867252","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}
Amorphous materials, which bear unique atomic arrangements, have garnered significant study on lithium-ion batteries due to inherent properties, including isotropy and defect distribution. Herein, a novel amorphous MoO2-x@V2O3-x@C double-core–shell structure is ingeniously designed by simple solvothermal and pyrolytic reactions, and the valence states of amorphous MoO2 and V2O3 are precisely characterized using X-ray absorption near-edge structure spectroscopic measurements. In situ XRD, in situ EIS and density functional theory calculations confirm that the amorphous structure enhances the electronic conductivity of MoO2-x@V2O3-x@C-2, optimizes the Li+ relocation paths and the associated energy barriers, thus improving the Li+ diffusion kinetics. Furthermore, the formation of V2O3-x layer, along with the establishment of a 3D network structure of amorphous carbon, enhanced the electronic conductivity and mitigated swelling of the electrodes, thereby improving stability during battery cycling. Benefiting from this multiscale coordinated design, the optimized MoO2-x@V2O3-x@C electrodes exhibit high discharge capacity of 477.5 mAh g−1 at 10.0 A g−1, along with exceptional cycling stability, showing minimal capacity loss even after undergoing 1000 cycles at 20.0 A g−1. Additionally, MoO2-x@V2O3-x@C||LiCoO2 full batteries maintain good capacity over 300 cycles. The proposed amorphous and core–shell structure fabrication concept offers novel insights into developing advanced high-efficiency energy storage materials.
{"title":"Rational Design of Carbon Covered V2O3-x Decorated Amorphous MoO2 Double-Core–Shell Structure Facilitates Ultra-High Stability and High-Rate Performance in Lithium-ion Batteries","authors":"Gaoyuan Liu, Wei Jia, Xinxin Yin, Biao Yang, Jing Xie, Jindou Hu, Zhenjiang Lu, Yali Cao","doi":"10.1002/smll.202500441","DOIUrl":"https://doi.org/10.1002/smll.202500441","url":null,"abstract":"Amorphous materials, which bear unique atomic arrangements, have garnered significant study on lithium-ion batteries due to inherent properties, including isotropy and defect distribution. Herein, a novel amorphous MoO<sub>2-</sub><i><sub>x</sub></i>@V<sub>2</sub>O<sub>3-</sub><i><sub>x</sub></i>@C double-core–shell structure is ingeniously designed by simple solvothermal and pyrolytic reactions, and the valence states of amorphous MoO<sub>2</sub> and V<sub>2</sub>O<sub>3</sub> are precisely characterized using X-ray absorption near-edge structure spectroscopic measurements. In situ XRD, in situ EIS and density functional theory calculations confirm that the amorphous structure enhances the electronic conductivity of MoO<sub>2-</sub><i><sub>x</sub></i>@V<sub>2</sub>O<sub>3-</sub><i><sub>x</sub></i>@C-2, optimizes the Li<sup>+</sup> relocation paths and the associated energy barriers, thus improving the Li<sup>+</sup> diffusion kinetics. Furthermore, the formation of V<sub>2</sub>O<sub>3-</sub><i><sub>x</sub></i> layer, along with the establishment of a 3D network structure of amorphous carbon, enhanced the electronic conductivity and mitigated swelling of the electrodes, thereby improving stability during battery cycling. Benefiting from this multiscale coordinated design, the optimized MoO<sub>2-</sub><i><sub>x</sub></i>@V<sub>2</sub>O<sub>3-</sub><i><sub>x</sub></i>@C electrodes exhibit high discharge capacity of 477.5 mAh g<sup>−1</sup> at 10.0 A g<sup>−1</sup>, along with exceptional cycling stability, showing minimal capacity loss even after undergoing 1000 cycles at 20.0 A g<sup>−1</sup>. Additionally, MoO<sub>2-</sub><i><sub>x</sub></i>@V<sub>2</sub>O<sub>3-</sub><i><sub>x</sub></i>@C||LiCoO<sub>2</sub> full batteries maintain good capacity over 300 cycles. The proposed amorphous and core–shell structure fabrication concept offers novel insights into developing advanced high-efficiency energy storage materials.","PeriodicalId":228,"journal":{"name":"Small","volume":"32 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867229","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}
Quinolone antibiotics, particularly moxifloxacin (MOX), are increasingly contaminating aquatic ecosystems, posing significant threats to both the environment and human health. Due to its hydrophilicity and stability, traditional water treatment methods are ineffective in degrading MOX. In this study, a novel S-type heterojunction photocatalyst, In-Ba-10, is introduced which combines barium titanate (BaTiO3) and indium sulfide (In2S3) to address this challenge. The In-Ba-10 catalyst demonstrates excellent photocatalytic performance, with a hydrogen production rate of 2050 µmol g−1 h−1 and a MOX degradation rate constant (k) of 0.049 min−1. Compared to BaTiO3 alone, the performance is enhanced by 48- and 49-fold, respectively. Comprehensive characterization, including Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron microscopy, reveals that the S-type heterojunction effectively promotes charge separation and transfer, reduces electron–hole recombination, and improves catalytic efficiency. First-principles calculations further confirm the role of In2S3 as the reduction site and BaTiO3 as the oxidation site. In addition to its high activity, In2S3-BaTiO3 shows stability over multiple cycles, making it a promising candidate for sustainable wastewater treatment. This study highlights the potential of S-type heterojunction photocatalysts for sustainable environmental remediation and energy applications.
{"title":"In2S3-BaTiO3 S-Type Heterojunction Photocatalyst for Efficient Antibiotic Degradation and Hydrogen Generation","authors":"Guilin Chen, Changle Zhang, Xintong Shi, Kaige Tian, Mingjun Chen, Zhennan Wang, Pengfei An, Jing Zhang, Youyong Li, Shengzhong (Frank) Liu, Shuit-Tong Lee, Junqing Yan","doi":"10.1002/smll.202412631","DOIUrl":"https://doi.org/10.1002/smll.202412631","url":null,"abstract":"Quinolone antibiotics, particularly moxifloxacin (MOX), are increasingly contaminating aquatic ecosystems, posing significant threats to both the environment and human health. Due to its hydrophilicity and stability, traditional water treatment methods are ineffective in degrading MOX. In this study, a novel S-type heterojunction photocatalyst, In-Ba-10, is introduced which combines barium titanate (BaTiO<sub>3</sub>) and indium sulfide (In<sub>2</sub>S<sub>3</sub>) to address this challenge. The In-Ba-10 catalyst demonstrates excellent photocatalytic performance, with a hydrogen production rate of 2050 µmol g<sup>−1</sup> h<sup>−1</sup> and a MOX degradation rate constant (k) of 0.049 min<sup>−1</sup>. Compared to BaTiO<sub>3</sub> alone, the performance is enhanced by 48- and 49-fold, respectively. Comprehensive characterization, including Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and electron microscopy, reveals that the S-type heterojunction effectively promotes charge separation and transfer, reduces electron–hole recombination, and improves catalytic efficiency. First-principles calculations further confirm the role of In<sub>2</sub>S<sub>3</sub> as the reduction site and BaTiO<sub>3</sub> as the oxidation site. In addition to its high activity, In<sub>2</sub>S<sub>3</sub>-BaTiO<sub>3</sub> shows stability over multiple cycles, making it a promising candidate for sustainable wastewater treatment. This study highlights the potential of S-type heterojunction photocatalysts for sustainable environmental remediation and energy applications.","PeriodicalId":228,"journal":{"name":"Small","volume":"14 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867231","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：