Black phosphorus nanosheets (BPNSs) have recently emerged as a valuable addition to the diverse family of 2D materials, holding promises for a wide range of applications. However, their practical use is limited by poor stability under ambient conditions, as they degrade quickly when exposed to light, air, or moisture. Noncovalent functionalization offers a promising approach to address these challenges. Herein, viologen derivatives are incorporated into a BPNS suspension in acetonitrile, resulting in the formation of two hybrid materials. These hybrids are subsequently stored under ambient conditions to track their degradation over time. The degradation behavior of these functionalized BPNSs is analyzed and compared to that of pristine BPNSs stored in both nitrogen and ambient environments, using X-ray photoelectron spectroscopy. Interestingly, the two viologen-based hybrid systems exhibited varying degrees of ambient protection efficiency, attributed to differences in their average adsorption energies and aggregation kinetics with BPNSs. Methyl viologen-functionalized BPNSs showed markedly reduced degradation in ambient conditions, with less pronounced differences for samples stored in a protected environment. This study introduces a promising strategy for enhancing the stability of BPNSs, making them more resistant to decomposition and potentially suitable for energy storage applications and optoelectronic devices.
{"title":"Boosting 2D Black Phosphorus Ambient Stability: Noncovalent Functionalization Using Viologen Molecules","authors":"Ishan Sarkar, Cong Guo, Cheng Peng, Yu Wang, Yafei Li, Xiaoyan Zhang","doi":"10.1002/smll.202410300","DOIUrl":"https://doi.org/10.1002/smll.202410300","url":null,"abstract":"Black phosphorus nanosheets (BPNSs) have recently emerged as a valuable addition to the diverse family of 2D materials, holding promises for a wide range of applications. However, their practical use is limited by poor stability under ambient conditions, as they degrade quickly when exposed to light, air, or moisture. Noncovalent functionalization offers a promising approach to address these challenges. Herein, viologen derivatives are incorporated into a BPNS suspension in acetonitrile, resulting in the formation of two hybrid materials. These hybrids are subsequently stored under ambient conditions to track their degradation over time. The degradation behavior of these functionalized BPNSs is analyzed and compared to that of pristine BPNSs stored in both nitrogen and ambient environments, using X-ray photoelectron spectroscopy. Interestingly, the two viologen-based hybrid systems exhibited varying degrees of ambient protection efficiency, attributed to differences in their average adsorption energies and aggregation kinetics with BPNSs. Methyl viologen-functionalized BPNSs showed markedly reduced degradation in ambient conditions, with less pronounced differences for samples stored in a protected environment. This study introduces a promising strategy for enhancing the stability of BPNSs, making them more resistant to decomposition and potentially suitable for energy storage applications and optoelectronic devices.","PeriodicalId":228,"journal":{"name":"Small","volume":"37 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666600","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}
Jingyu Yan, Mengjia Zhang, Yongning Yi, Ran Ran, Bote Zhao, Wei Zhou, Wei Wang
Solid oxide cells (SOCs) are promising electrochemical energy conversion/storage devices for the generation of electricity and/or valuable chemical products due to the high efficiency, superior reversibility and low emissions. However, the large-scale applications of SOCs are strongly limited by the inferior stability and high costs due to the high operational temperatures (≈800 °C). Extensive researches are reported on reducing the operating temperatures of SOCs to suppress the costs and improve the long-term stability. Nevertheless, as a key component in SOCs, the electrolytes suffer from inferior ionic conductivities at reduced temperatures. Nanotechnology and relevant nanomaterials display great potential to improve the ionic conductivities and durability of electrolytes for low-temperature (LT)-SOCs due to the advantageous functionalities including distinct surface/interface properties and the creation of nanoeffect. Herein, a timely review about the utilization of nanotechnology for the design and fabrication of high-performance electrolytes for LT-SOCs is presented from the aspects of nanostructuring methodology and nanomaterial design strategies. The current limitations, remaining challenges, and future research directions related to the use of nanotechnology and nanomaterials in the development of electrolytes for LT-SOCs are also presented and discussed. Here valuable guidelines are provided for the further advancement of nanotechnology-based energy conversion/storage technologies.
{"title":"Nanotechnology-Based Design and Fabrication of Advanced Electrolytes for Solid Oxide Cells","authors":"Jingyu Yan, Mengjia Zhang, Yongning Yi, Ran Ran, Bote Zhao, Wei Zhou, Wei Wang","doi":"10.1002/smll.202409648","DOIUrl":"https://doi.org/10.1002/smll.202409648","url":null,"abstract":"Solid oxide cells (SOCs) are promising electrochemical energy conversion/storage devices for the generation of electricity and/or valuable chemical products due to the high efficiency, superior reversibility and low emissions. However, the large-scale applications of SOCs are strongly limited by the inferior stability and high costs due to the high operational temperatures (≈800 °C). Extensive researches are reported on reducing the operating temperatures of SOCs to suppress the costs and improve the long-term stability. Nevertheless, as a key component in SOCs, the electrolytes suffer from inferior ionic conductivities at reduced temperatures. Nanotechnology and relevant nanomaterials display great potential to improve the ionic conductivities and durability of electrolytes for low-temperature (LT)-SOCs due to the advantageous functionalities including distinct surface/interface properties and the creation of nanoeffect. Herein, a timely review about the utilization of nanotechnology for the design and fabrication of high-performance electrolytes for LT-SOCs is presented from the aspects of nanostructuring methodology and nanomaterial design strategies. The current limitations, remaining challenges, and future research directions related to the use of nanotechnology and nanomaterials in the development of electrolytes for LT-SOCs are also presented and discussed. Here valuable guidelines are provided for the further advancement of nanotechnology-based energy conversion/storage technologies.","PeriodicalId":228,"journal":{"name":"Small","volume":"61 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666594","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}
Feng Zhang, Lilin Song, Ruixuan Wang, Bei Zhao, Jian Huang, Luling Wu, Yufan Fan, Hong Lin, Zhengtao Jiang, Xiaodi Yang, Hairong Zeng, Xin Yang, Tony D. James, Guangbo Ge
Cytochrome P450 3A4 (CYP3A4) is a key mediator in xenobiotic metabolism and drug-drug interactions (DDI), developing orally active fluorogenic substrates for sensing and imaging of a target enzyme in biological systems remains challenging. Here, an artificial intelligence (AI)-driven strategy is used to construct a highly specific and orally active fluorogenic substrate for imaging CYP3A4 in complex biological systems. After the fusion of an AI-selected drug-like fragment with a CYP3A4-preferred fluorophore, three candidates are designed and synthesized. Among all evaluated candidates, NFa exhibits excellent isoform-specificity, ultra-high sensitivity, outstanding spatial resolution, favorable safety profiles, and acceptable oral bioavailability. Specifically, NFa excels at functional in situ imaging of CYP3A4 in living systems with exceptional endoplasmic reticulum (ER)-colocalization performance and high imaging resolution, while this agent can also replace hCYP3A4 drug-substrates for high-throughput screening of CYP3A4 inhibitors and for assessing DDI potential in vivo. With the help of NFa, a novel CYP3A4 inhibitor (D13) was discovered, and its anti-CYP3A4 effects are assessed in live cells, ex vivo and in vivo. Collectively, an AI-powered strategy is adapted for developing highly-specific and drug-like fluorogenic substrates, resulting in the first orally available tool (NFa) for sensing and imaging CYP3A4 activities, which facilitates CYP3A4-associated fundamental investigations and the drug discovery process.
{"title":"Functional Imaging of CYP3A4 at Multiple Dimensions Using an AI-Driven High Performance Fluorogenic Substrate","authors":"Feng Zhang, Lilin Song, Ruixuan Wang, Bei Zhao, Jian Huang, Luling Wu, Yufan Fan, Hong Lin, Zhengtao Jiang, Xiaodi Yang, Hairong Zeng, Xin Yang, Tony D. James, Guangbo Ge","doi":"10.1002/smll.202412178","DOIUrl":"https://doi.org/10.1002/smll.202412178","url":null,"abstract":"Cytochrome P450 3A4 (CYP3A4) is a key mediator in xenobiotic metabolism and drug-drug interactions (DDI), developing orally active fluorogenic substrates for sensing and imaging of a target enzyme in biological systems remains challenging. Here, an artificial intelligence (AI)-driven strategy is used to construct a highly specific and orally active fluorogenic substrate for imaging CYP3A4 in complex biological systems. After the fusion of an AI-selected drug-like fragment with a CYP3A4-preferred fluorophore, three candidates are designed and synthesized. Among all evaluated candidates, NFa exhibits excellent isoform-specificity, ultra-high sensitivity, outstanding spatial resolution, favorable safety profiles, and acceptable oral bioavailability. Specifically, NFa excels at functional in situ imaging of CYP3A4 in living systems with exceptional endoplasmic reticulum (ER)-colocalization performance and high imaging resolution, while this agent can also replace hCYP3A4 drug-substrates for high-throughput screening of CYP3A4 inhibitors and for assessing DDI potential in vivo. With the help of NFa, a novel CYP3A4 inhibitor (D13) was discovered, and its anti-CYP3A4 effects are assessed in live cells, ex vivo and in vivo. Collectively, an AI-powered strategy is adapted for developing highly-specific and drug-like fluorogenic substrates, resulting in the first orally available tool (NFa) for sensing and imaging CYP3A4 activities, which facilitates CYP3A4-associated fundamental investigations and the drug discovery process.","PeriodicalId":228,"journal":{"name":"Small","volume":"24 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666597","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}
Aqueous zinc ion batteries (AZIBs) are promising candidates for large-scale energy storage systems due to their high safety and low cost. Among diverse cathodes, spinel ZnV2O4 (ZVO) becomes more prominent thanks to its high storage capacity and long cycling life. However, the slow diffusion kinetics, vanadium dissolution, and ambiguous zinc-storage mechanism restrict its prospective applications. For this, herein, unique ZVO flower-shaped nano/micro-architectures with carbon coating (ZVO@C) are designed to enhance active electrode-electrolyte sur-/interfaces and reduce ion diffusion distance, while the nano-carbon shell improves electrical conductivity of cathodes and inhibits the active vanadium dissolution. Furthermore, the essential zinc-storage mechanism of ZVO@C is first clarified that the irreversible electrochemically-induced phase formation of ZnV3O8 and Zn3(OH)2V2O7·2H2O during the first cycle, rather than ZVO itself, which are the genuine electroactive phases for following zinc storage. Theoretical calculations reveal that the two newly-formed phases are intrinsically endowed with good conductivity and boosted diffusion kinetics for reversible co-(de)intercalation of Zn2+ and H+. The optimized ZVO@C shows superior cycling stability with 208.7 mAh g−1 after 5000 cycles even at 10 A g−1. Essentially, the contribution provides in-depth insights for intriguing phase transition involved zinc-storage mechanism and promotes commercial applications of vanadium-based cathodes for long-lifespan AZIBs.
{"title":"Unveiling Electrochemically Induced Phase Transition of Hierarchical ZnV2O4@C Superstructures Toward Advanced Aqueous Zinc Ion Batteries","authors":"Shujia Zhang, Xiaolong Jia, Fulu Chu, Linrui Hou, Changzhou Yuan","doi":"10.1002/smll.202500321","DOIUrl":"https://doi.org/10.1002/smll.202500321","url":null,"abstract":"Aqueous zinc ion batteries (AZIBs) are promising candidates for large-scale energy storage systems due to their high safety and low cost. Among diverse cathodes, spinel ZnV<sub>2</sub>O<sub>4</sub> (ZVO) becomes more prominent thanks to its high storage capacity and long cycling life. However, the slow diffusion kinetics, vanadium dissolution, and ambiguous zinc-storage mechanism restrict its prospective applications. For this, herein, unique ZVO flower-shaped nano/micro-architectures with carbon coating (ZVO@C) are designed to enhance active electrode-electrolyte sur-/interfaces and reduce ion diffusion distance, while the nano-carbon shell improves electrical conductivity of cathodes and inhibits the active vanadium dissolution. Furthermore, the essential zinc-storage mechanism of ZVO@C is first clarified that the irreversible electrochemically-induced phase formation of ZnV<sub>3</sub>O<sub>8</sub> and Zn<sub>3</sub>(OH)<sub>2</sub>V<sub>2</sub>O<sub>7</sub>·2H<sub>2</sub>O during the first cycle, rather than ZVO itself, which are the genuine electroactive phases for following zinc storage. Theoretical calculations reveal that the two newly-formed phases are intrinsically endowed with good conductivity and boosted diffusion kinetics for reversible co-(de)intercalation of Zn<sup>2+</sup> and H<sup>+</sup>. The optimized ZVO@C shows superior cycling stability with 208.7 mAh g<sup>−1</sup> after 5000 cycles even at 10 A g<sup>−1</sup>. Essentially, the contribution provides in-depth insights for intriguing phase transition involved zinc-storage mechanism and promotes commercial applications of vanadium-based cathodes for long-lifespan AZIBs.","PeriodicalId":228,"journal":{"name":"Small","volume":"214 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666512","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}
At atmospheric pressure, the main challenge in the photocatalytic oxidation of CH4 to CH3OH is to absorb and activate the inert C─H bond while preventing excessive oxidation of CH3OH. In this study, metal-supported ZnO nanoflowers (Ag-ZnO) are designed to produce abundant active interfacial oxygen sites for CH4 oxidation at atmospheric pressure, with a CH3OH yield reaching 1300 µmol gcat−1 h−1 and the selectivity is 94%. DFT calculation and in situ analysis show that the addition of Ag regulates the electron state density and band center of O, which is beneficial to the adsorption of CH4, and decreases the dissociation energy barrier of C─H bond at OL(Lattice oxygen) site. The further selective conversion of ·CH3 to CH3OH involves two different pathways: one pathway consists of the oxidation of ·CH3 by OL, and the other pathway is the combination of ·CH3 and ·OH generated from dissolved O2 (0.28 mm) in water. Notably, in the photochemical flow device, the yield of CH3OH is increased to 5200 µmol gcat−1 h−1 and the selectivity is close to 100%. This work offers valuable insights into reactive interfaces, morphological engineering, and the control of intermediate evolution toward selective conversion of CH4 to oxygenates at atmospheric pressure.
{"title":"Ag-ZnO Nanoflowers Enable Highly Selective Photocatalytic Conversion of CH4 to CH3OH at Atmospheric Pressure: Unraveling Reactive Interfaces and Intermediate Control","authors":"Boshi Zheng, Yi Wan, Qi Hua, Wenbin Wang, Shuai Wang, Zhengchao Wang, Yajun Zhang, Shuxu Zhu, Haonan Zhang, Minjun Zhou, Mingbo Wu, Wenting Wu","doi":"10.1002/smll.202501237","DOIUrl":"https://doi.org/10.1002/smll.202501237","url":null,"abstract":"At atmospheric pressure, the main challenge in the photocatalytic oxidation of CH<sub>4</sub> to CH<sub>3</sub>OH is to absorb and activate the inert C─H bond while preventing excessive oxidation of CH<sub>3</sub>OH. In this study, metal-supported ZnO nanoflowers (Ag-ZnO) are designed to produce abundant active interfacial oxygen sites for CH<sub>4</sub> oxidation at atmospheric pressure, with a CH<sub>3</sub>OH yield reaching 1300 µmol g<sub>cat</sub>\u0000<sup>−1</sup> h<sup>−1</sup> and the selectivity is 94%. DFT calculation and in situ analysis show that the addition of Ag regulates the electron state density and band center of O, which is beneficial to the adsorption of CH<sub>4</sub>, and decreases the dissociation energy barrier of C─H bond at O<sub>L</sub>(Lattice oxygen) site. The further selective conversion of ·CH<sub>3</sub> to CH<sub>3</sub>OH involves two different pathways: one pathway consists of the oxidation of ·CH<sub>3</sub> by O<sub>L</sub>, and the other pathway is the combination of ·CH<sub>3</sub> and ·OH generated from dissolved O<sub>2</sub> (0.28 m<span>m</span>) in water. Notably, in the photochemical flow device, the yield of CH<sub>3</sub>OH is increased to 5200 µmol g<sub>cat</sub>\u0000<sup>−1</sup> h<sup>−1</sup> and the selectivity is close to 100%. This work offers valuable insights into reactive interfaces, morphological engineering, and the control of intermediate evolution toward selective conversion of CH<sub>4</sub> to oxygenates at atmospheric pressure.","PeriodicalId":228,"journal":{"name":"Small","volume":"214 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666599","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}
Hydrogen, as an environmentally sustainable energy carrier, offers substantial potential for addressing the global energy crisis. The development of highly efficient catalysts to accelerate the hydrogen evolution reaction (HER) is critical for the realization of electrochemical hydrogen production via water splitting. Herein, a novel heterogeneous catalyst consisting of PtNi nanoalloys with Pt-enriched surfaces is obtained, which are uniformly distributed within nitrogen-doped hollow carbon nanoshells derived from a complex of Ni-EDTA (ethylene diamine tetraacetate). Remarkably, the fabricated NE-PtNiNC catalyst demonstrates exceptional HER performance, exhibiting an ultra-low overpotential of 3 mV at 10 mA cm−2 and 6.8-fold higher mass activity compared to the commercial Pt/C catalyst, positioning it as one of the most advanced catalysts to date. Additionally, it shows outstanding stability over 200 h and exhibits promising potential for practical deployment in two-electrode water electrolysis systems. Theoretical analyses further reveal that the Pt-skin@PtNi structure, with its lowest d-band center, fosters a more pronounced overlap of the 5d electron cloud at the surface Pt sites. This interaction results in increased electron density on the Pt skin, facilitating water dissociation and significantly enhancing the intrinsic HER activity and durability.
{"title":"Pt-Skin Coated PtNi Alloy in Carbon Nanoshells for Enhanced Hydrogen Evolution Activity and Durability","authors":"Yuandong Yang, Jie Liu, Chen Sun, Yuting Fu, Qipeng Li, Jinjie Qian","doi":"10.1002/smll.202503294","DOIUrl":"https://doi.org/10.1002/smll.202503294","url":null,"abstract":"Hydrogen, as an environmentally sustainable energy carrier, offers substantial potential for addressing the global energy crisis. The development of highly efficient catalysts to accelerate the hydrogen evolution reaction (HER) is critical for the realization of electrochemical hydrogen production via water splitting. Herein, a novel heterogeneous catalyst consisting of PtNi nanoalloys with Pt-enriched surfaces is obtained, which are uniformly distributed within nitrogen-doped hollow carbon nanoshells derived from a complex of Ni-EDTA (ethylene diamine tetraacetate). Remarkably, the fabricated NE-PtNiNC catalyst demonstrates exceptional HER performance, exhibiting an ultra-low overpotential of 3 mV at 10 mA cm<sup>−2</sup> and 6.8-fold higher mass activity compared to the commercial Pt/C catalyst, positioning it as one of the most advanced catalysts to date. Additionally, it shows outstanding stability over 200 h and exhibits promising potential for practical deployment in two-electrode water electrolysis systems. Theoretical analyses further reveal that the Pt-skin@PtNi structure, with its lowest d-band center, fosters a more pronounced overlap of the 5d electron cloud at the surface Pt sites. This interaction results in increased electron density on the Pt skin, facilitating water dissociation and significantly enhancing the intrinsic HER activity and durability.","PeriodicalId":228,"journal":{"name":"Small","volume":"22 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666513","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}
Xuyang Lu, Siling Liu, Lei Zhang, Shaobo Ye, Chenchen Yue, Yufei Feng, Yu Zhou, Zhao Liang, Ying Wang, Weiyou Yang, Qing Shi
Dendrite growth, corrosion, and hydrogen evolution are major issues for Zn anodes, which seriously hinder the further practical application of aqueous zinc-ion batteries. To address these issues, Zirconium Nitride (ZrN) layer with a thickness of 110 nm is uniformly deposited on the surface of Zn anode using plasma-enhanced atomic layer deposition (PE-ALD). In/ex situ characterizations verify that the as-introduced ZrN layer has excellent anticorrosive and zincophilic ability, which can suppress corrosion and hydrogen evolution, lower the nucleation energy barrier for Zn2+ deposition, and effectively inhibit dendrite growth. Theoretical calculations also reveal that ZrN exhibits significantly higher adsorption capacity for Zn2+ compared to bare Zn, which is conducive to regulating the Zn deposition behavior. This innovative interface significantly extends battery cycle life and enhances coulombic efficiency. Encouragingly, under a current density of 5 mA cm−2 and areal capacity of 1 mAh cm−2, the Zn@ZrN symmetrical cells demonstrate an extraordinary cycling life of up to 5000 h, significantly surpassing other reported Zn anodes modified by films/coatings. In addition, it also exhibits an impressive cycling life of 1200 h at 1 mA cm−2 and 1 mAh cm−2. The full cells of Zn@ZrN||MnO2 retain high capacity after 1000 cycles, markedly outperforming conventional Zn||MnO2 batteries.
{"title":"Nano-Scale ZrN Film Modified Zn Anode with Ultra-Long Cycle Life Over 5000 H","authors":"Xuyang Lu, Siling Liu, Lei Zhang, Shaobo Ye, Chenchen Yue, Yufei Feng, Yu Zhou, Zhao Liang, Ying Wang, Weiyou Yang, Qing Shi","doi":"10.1002/smll.202502480","DOIUrl":"https://doi.org/10.1002/smll.202502480","url":null,"abstract":"Dendrite growth, corrosion, and hydrogen evolution are major issues for Zn anodes, which seriously hinder the further practical application of aqueous zinc-ion batteries. To address these issues, Zirconium Nitride (ZrN) layer with a thickness of 110 nm is uniformly deposited on the surface of Zn anode using plasma-enhanced atomic layer deposition (PE-ALD). In/ex situ characterizations verify that the as-introduced ZrN layer has excellent anticorrosive and zincophilic ability, which can suppress corrosion and hydrogen evolution, lower the nucleation energy barrier for Zn<sup>2+</sup> deposition, and effectively inhibit dendrite growth. Theoretical calculations also reveal that ZrN exhibits significantly higher adsorption capacity for Zn<sup>2+</sup> compared to bare Zn, which is conducive to regulating the Zn deposition behavior. This innovative interface significantly extends battery cycle life and enhances coulombic efficiency. Encouragingly, under a current density of 5 mA cm<sup>−2</sup> and areal capacity of 1 mAh cm<sup>−2</sup>, the Zn@ZrN symmetrical cells demonstrate an extraordinary cycling life of up to 5000 h, significantly surpassing other reported Zn anodes modified by films/coatings. In addition, it also exhibits an impressive cycling life of 1200 h at 1 mA cm<sup>−2</sup> and 1 mAh cm<sup>−2</sup>. The full cells of Zn@ZrN||MnO<sub>2</sub> retain high capacity after 1000 cycles, markedly outperforming conventional Zn||MnO<sub>2</sub> batteries.","PeriodicalId":228,"journal":{"name":"Small","volume":"3 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666505","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}
Strategic alteration of the chelating atoms around the metal center can modify the electronic band structure of the electrocatalyst, improving its performance in oxygen evolution and reduction reactions (OER/ORR). Advancements in the development of catalysts with heteroatoms and axial modifications in the coordination sphere are mostly limited to single-molecule electrocatalysts or elevated temperature-mediated pyrolysis approaches for oxygen electrocatalysis. Inspired by biological catalytic systems with axial coordination, a pyrolysis-free strategic methodology is adopted for the synthesis of an iron-metaled covalent organic polymer matrix axially laminated over cobalt-based metal-organic framework through an imidazole moiety. Precise engineering of coordination atoms in synthesized core-shell material, featuring dual metal sites with distinct neighboring atom exhibits mutual synergy due to the presence of bridging imidazole moiety between two metal sites. Modulated synergism navigates the electronic structure such that it favors specific reactant adsorption on specific metal sites during bifunctional O2 electrocatalysis as confirmed through in situ Raman spectroscopy and in situ attenuated total reflection infrared (ATR-IR) spectroscopy. Through dynamic correlation between the in-situ studies and modified d-band center obtained theoretically, the pivotal role of axial coordination linkage mediated synergism favoring ORR/OER process via target-specific reactant adsorption is demonstrated.
{"title":"Harnessing Bio-Inspired Axial Coordination to Boost Synergistic Effects for Enhanced Bifunctional Oxygen Electrocatalysis","authors":"Surajit Samui, Asif Iqbal, Ranjit Thapa, Ramendra Sundar Dey","doi":"10.1002/smll.202500911","DOIUrl":"https://doi.org/10.1002/smll.202500911","url":null,"abstract":"Strategic alteration of the chelating atoms around the metal center can modify the electronic band structure of the electrocatalyst, improving its performance in oxygen evolution and reduction reactions (OER/ORR). Advancements in the development of catalysts with heteroatoms and axial modifications in the coordination sphere are mostly limited to single-molecule electrocatalysts or elevated temperature-mediated pyrolysis approaches for oxygen electrocatalysis. Inspired by biological catalytic systems with axial coordination, a pyrolysis-free strategic methodology is adopted for the synthesis of an iron-metaled covalent organic polymer matrix axially laminated over cobalt-based metal-organic framework through an imidazole moiety. Precise engineering of coordination atoms in synthesized core-shell material, featuring dual metal sites with distinct neighboring atom exhibits mutual synergy due to the presence of bridging imidazole moiety between two metal sites. Modulated synergism navigates the electronic structure such that it favors specific reactant adsorption on specific metal sites during bifunctional O<sub>2</sub> electrocatalysis as confirmed through in situ Raman spectroscopy and in situ attenuated total reflection infrared (ATR-IR) spectroscopy. Through dynamic correlation between the in-situ studies and modified d-band center obtained theoretically, the pivotal role of axial coordination linkage mediated synergism favoring ORR/OER process via target-specific reactant adsorption is demonstrated.","PeriodicalId":228,"journal":{"name":"Small","volume":"28 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143666598","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}
Yue Li, Md Rafique Un Nabi, Hyowon Park, Yuzi Liu, Stephan Rosenkranz, Amanda K. Petford-Long, Jin Hu, Suzanne G.E. te Velthuis, Charudatta Phatak
Ferrimagnets, which have both ferromagnetic and antiferromagnetic coupling, are attracting increased attention in the realm of spintronic devices due to advantages such as ultrafast dynamics and a suppressed skyrmion Hall effect. Thus, understanding the behavior of nontrivial spin textures in ferrimagnets is crucial; however, comprehensive reports on this topic remain limited. Here, the magnetic spin textures of ferrimagnetic Mn2 − xZnxSb (x = 0.85) is explored as a function of temperature and applied magnetic field. The spin textures can be tuned to a variety of states, including stripes, skyrmion bags, and a skyrmion lattice. Chiral Néel-type magnetic structures are visualized using Lorentz transmission electron microscopy. Mn(I) ions are slightly shifted toward the Sb sites, which may be due to a strong electrostatic interaction between Mn and Sb ions. This local structural distortion breaks the inversion symmetry and introduces an effective Dzyaloshinkii–Moriya interaction. This work thus provides a pathway to use doping and heterogeneity in a ferrimagnet to control and generate chiral nontrivial spin textures.
{"title":"Observation of Topological Spin Textures in Ferrimagnetic Mn2 − xZnxSb","authors":"Yue Li, Md Rafique Un Nabi, Hyowon Park, Yuzi Liu, Stephan Rosenkranz, Amanda K. Petford-Long, Jin Hu, Suzanne G.E. te Velthuis, Charudatta Phatak","doi":"10.1002/smll.202406299","DOIUrl":"https://doi.org/10.1002/smll.202406299","url":null,"abstract":"Ferrimagnets, which have both ferromagnetic and antiferromagnetic coupling, are attracting increased attention in the realm of spintronic devices due to advantages such as ultrafast dynamics and a suppressed skyrmion Hall effect. Thus, understanding the behavior of nontrivial spin textures in ferrimagnets is crucial; however, comprehensive reports on this topic remain limited. Here, the magnetic spin textures of ferrimagnetic Mn<sub>2 − <i>x</i></sub>Zn<sub><i>x</i></sub>Sb (x = 0.85) is explored as a function of temperature and applied magnetic field. The spin textures can be tuned to a variety of states, including stripes, skyrmion bags, and a skyrmion lattice. Chiral Néel-type magnetic structures are visualized using Lorentz transmission electron microscopy. Mn(I) ions are slightly shifted toward the Sb sites, which may be due to a strong electrostatic interaction between Mn and Sb ions. This local structural distortion breaks the inversion symmetry and introduces an effective Dzyaloshinkii–Moriya interaction. This work thus provides a pathway to use doping and heterogeneity in a ferrimagnet to control and generate chiral nontrivial spin textures.","PeriodicalId":228,"journal":{"name":"Small","volume":"24 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660997","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}
Jun Liu, Lihong Wu, Jinchuan Zhao, Xiao Liu, Yundi Wu, Xilong Wu, Guizhen Wang
Anti-biofouling performance plays a critical role for marine application of microwave absorption materials (MAMs) to maintain their stable and durable absorption capacity. However, anti-biofouling properties are generally ignored by traditional MAMs that merely pursue strong microwave absorption (MA) capability. Herein, this work reports for the first time the preparation of ternary Cu1.8S/reduced graphene oxide/oleylamine (Cu1.8S/rGO/OLAM) composite integrated with outstanding anti-biofouling properties. Cu1.8S nanoparticles and OLAM films are sequentially generated on rGO by a one-pot solution-phase thermal decomposition method. The copper vacancy defects in Cu1.8S can effectively induce dipole polarization. The surface-coated OLAM layers can not only provide abundant heterogeneous interfaces to induce interfacial polarization, but also improve the hydrophobicity to reduce organism adhesion. Cu1.8S can also release copper ions that damage bacterial and algal cell membranes and induce protein denaturation, contributing to enhancement of anti-biofouling properties. rGO with high conductive loss and a sharp edge can both improve MA and anti-biofouling properties. Consequently, the Cu1.8S/rGO/OLAM composite exhibits a remarkable MA capability, with a minimum reflection loss value of −56.2 dB and an effective absorption bandwidth of 9.68 GHz. Additionally, Cu1.8S/rGO/OLAM composite also shows outstanding anti-biofouling performance with survival rates of bacteria and algae as low as 4% and 35%, respectively.
{"title":"Constructing Multi-Interfaced and Vacancy-Rich Cu1.8S/rGO/Oleylamine Composites Toward Anti-Biofouling Microwave Absorption","authors":"Jun Liu, Lihong Wu, Jinchuan Zhao, Xiao Liu, Yundi Wu, Xilong Wu, Guizhen Wang","doi":"10.1002/smll.202412835","DOIUrl":"https://doi.org/10.1002/smll.202412835","url":null,"abstract":"Anti-biofouling performance plays a critical role for marine application of microwave absorption materials (MAMs) to maintain their stable and durable absorption capacity. However, anti-biofouling properties are generally ignored by traditional MAMs that merely pursue strong microwave absorption (MA) capability. Herein, this work reports for the first time the preparation of ternary Cu<sub>1.8</sub>S/reduced graphene oxide/oleylamine (Cu<sub>1.8</sub>S/rGO/OLAM) composite integrated with outstanding anti-biofouling properties. Cu<sub>1.8</sub>S nanoparticles and OLAM films are sequentially generated on rGO by a one-pot solution-phase thermal decomposition method. The copper vacancy defects in Cu<sub>1.8</sub>S can effectively induce dipole polarization. The surface-coated OLAM layers can not only provide abundant heterogeneous interfaces to induce interfacial polarization, but also improve the hydrophobicity to reduce organism adhesion. Cu<sub>1.8</sub>S can also release copper ions that damage bacterial and algal cell membranes and induce protein denaturation, contributing to enhancement of anti-biofouling properties. rGO with high conductive loss and a sharp edge can both improve MA and anti-biofouling properties. Consequently, the Cu<sub>1.8</sub>S/rGO/OLAM composite exhibits a remarkable MA capability, with a minimum reflection loss value of −56.2 dB and an effective absorption bandwidth of 9.68 GHz. Additionally, Cu<sub>1.8</sub>S/rGO/OLAM composite also shows outstanding anti-biofouling performance with survival rates of bacteria and algae as low as 4% and 35%, respectively.","PeriodicalId":228,"journal":{"name":"Small","volume":"61 1","pages":""},"PeriodicalIF":13.3,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143661064","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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