ABSTRACT Appropriate configuration combined with strong interface bonding is the essential requirement for developing high wear‐resistant coatings. Herein, based on the powder‐pack boriding process, the properties of Ti6Al4V alloy are effectively improved by constructing a serrate tribological boride composite layer. Scanning electron microscope (SEM) and transmission electron microscope (TEM) results demonstrated that in situ serration boride layer distributes on the surface of Ti6Al4V alloy (including the outer TiB 2 layer and the inner TiB whisker layer), forming a coherent/semi‐coherent TiB 2 ‐TiB‐Ti transition interface during the heat treatment. Ti matrix grains beneath the boride layer are firmly riveted and composites achieve excellent friction coefficient about 0.40 ± 0.01. The formation mechanism of serration boride layer was discussed based on thermodynamic and diffusion kinetic analysis. Moreover, first‐principles calculations showed that the creative serrated configuration improves the interfacial bonding of the boride layer and matrix. Electron backscatter diffraction (EBSD) and geometric phase analysis (GPA) were employed to investigate the influence of the serrated boride layer on deformation behavior of composites. It revealed that the serrated boride layer reduces internal stress of interface region and can stimulate the plastic deformation of Ti matrix grains. More importantly, the strongly bonded TiB 2 ‐TiB‐Ti interface directly changes the fracture mechanism of boride layer. The current work provides a novel avenue for the fabrication of high wear‐resistant Ti alloy.
{"title":"Constructing Serrated Boride Composite Layer for Enhancing Wear Resistance of Ti6Al4V Alloy","authors":"Ying Wu, Lishi Ma, Yong‐Hua Duan, Ancang Yang, Xiang‐Ren Bai, Xiaolong Zhou, Shanju Zheng, Jia‐Wei Mi, X. L. Lu, Meng‐Nie Li","doi":"10.1002/rar2.70025","DOIUrl":"https://doi.org/10.1002/rar2.70025","url":null,"abstract":"ABSTRACT Appropriate configuration combined with strong interface bonding is the essential requirement for developing high wear‐resistant coatings. Herein, based on the powder‐pack boriding process, the properties of Ti6Al4V alloy are effectively improved by constructing a serrate tribological boride composite layer. Scanning electron microscope (SEM) and transmission electron microscope (TEM) results demonstrated that in situ serration boride layer distributes on the surface of Ti6Al4V alloy (including the outer TiB 2 layer and the inner TiB whisker layer), forming a coherent/semi‐coherent TiB 2 ‐TiB‐Ti transition interface during the heat treatment. Ti matrix grains beneath the boride layer are firmly riveted and composites achieve excellent friction coefficient about 0.40 ± 0.01. The formation mechanism of serration boride layer was discussed based on thermodynamic and diffusion kinetic analysis. Moreover, first‐principles calculations showed that the creative serrated configuration improves the interfacial bonding of the boride layer and matrix. Electron backscatter diffraction (EBSD) and geometric phase analysis (GPA) were employed to investigate the influence of the serrated boride layer on deformation behavior of composites. It revealed that the serrated boride layer reduces internal stress of interface region and can stimulate the plastic deformation of Ti matrix grains. More importantly, the strongly bonded TiB 2 ‐TiB‐Ti interface directly changes the fracture mechanism of boride layer. The current work provides a novel avenue for the fabrication of high wear‐resistant Ti alloy.","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"45 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/rar2.70025","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332837","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ABSTRACT The similar physicochemical properties of alkali metal elements make the co‐enrichment and precise separation of Cs + and Rb + in complex brine systems highly challenging. Here, an all‐inorganic strategy is proposed, which achieves efficient enrichment and precise separation of Cs + and Rb + in high‐salt systems by constructing Sr 2+ /Ba 2+ ‐based Prussian blue analogs. Two super‐sized precipitates, CsRb‐SrFC, and CsRb‐BaFC (particle sizes up to ∼5 and ∼15 μm), were successfully synthesized, significantly simplifying the complex solid–liquid separation process of traditional fine particles. Both systems exhibit rapid reaction kinetics (completed within 5 min) and efficient enrichment performance across a wide pH range (2–13). The Sr 2+ system shows maximum recovery rates of 96.08% for Cs + and 66.20% for Rb + , whereas the Ba 2+ system demonstrates stronger affinity for Rb + ( R Rb = 70.92%, R Cs = 56.26%). More importantly, CsRb‐SrFC achieves phase‐selective separation through dissolution differentiation, where water washing induces Rb + dissolution into the liquid phase, whereas Cs + remains fixed in the solid phase, enabling precise acquisition of pure Cs 2 CO 3 (purity ∼98%) through solid–liquid interfacial phase separation. Furthermore, dynamic separation experiments maintain stable and rapid ion‐specific separation characteristics (separation factor SF Cs/Rb = 353.82). This all‐inorganic process combines green economy with engineering applicability, providing theoretical support and technical pathways for targeted recovery and high‐value utilization of Cs + /Rb + resources in complex brine systems.
{"title":"Dissolution‐Controlled Phase Separation of Cs <sup>+</sup> /Rb <sup>+</sup> in High‐Salinity Brines via All‐Inorganic Prussian Blue Analogs","authors":"Kang Li, Ruixin Ma, Shina Li","doi":"10.1002/rar2.70077","DOIUrl":"https://doi.org/10.1002/rar2.70077","url":null,"abstract":"ABSTRACT The similar physicochemical properties of alkali metal elements make the co‐enrichment and precise separation of Cs + and Rb + in complex brine systems highly challenging. Here, an all‐inorganic strategy is proposed, which achieves efficient enrichment and precise separation of Cs + and Rb + in high‐salt systems by constructing Sr 2+ /Ba 2+ ‐based Prussian blue analogs. Two super‐sized precipitates, CsRb‐SrFC, and CsRb‐BaFC (particle sizes up to ∼5 and ∼15 μm), were successfully synthesized, significantly simplifying the complex solid–liquid separation process of traditional fine particles. Both systems exhibit rapid reaction kinetics (completed within 5 min) and efficient enrichment performance across a wide pH range (2–13). The Sr 2+ system shows maximum recovery rates of 96.08% for Cs + and 66.20% for Rb + , whereas the Ba 2+ system demonstrates stronger affinity for Rb + ( R Rb = 70.92%, R Cs = 56.26%). More importantly, CsRb‐SrFC achieves phase‐selective separation through dissolution differentiation, where water washing induces Rb + dissolution into the liquid phase, whereas Cs + remains fixed in the solid phase, enabling precise acquisition of pure Cs 2 CO 3 (purity ∼98%) through solid–liquid interfacial phase separation. Furthermore, dynamic separation experiments maintain stable and rapid ion‐specific separation characteristics (separation factor SF Cs/Rb = 353.82). This all‐inorganic process combines green economy with engineering applicability, providing theoretical support and technical pathways for targeted recovery and high‐value utilization of Cs + /Rb + resources in complex brine systems.","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/rar2.70077","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332368","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ABSTRACT The sluggish kinetics of the oxygen reduction reaction (ORR) necessitate developing oxygen electrodes with enhanced electrocatalytic activity for practical zinc–air battery applications. In this study, an iron‐doped copper sulfide electrocatalyst (CuFeNS‐PNC) anchored on metal–organic framework‐derived carbon substrates was designed, featuring a bimetallic Cu 5 FeS 4 architecture where iron electronically modulates copper sites. The performance enhancement of this copper–iron sulfide bimetallic system relative to a monometallic copper sulfide arises from synergistic Fe‐Cu interactions, as confirmed by X‐ray photoelectron spectroscopy (XPS), revealing electron transfer from iron to copper. Density functional theory (DFT) calculations demonstrate that iron incorporation downshifts the copper d‐band center, weakening OH* adsorption energy to a more optimal level, thereby boosting ORR kinetics. Consequently, the CuFeNS‐PNC catalyst achieves superior electrocatalytic performance with an ORR onset potential ( E onset ) of 0.988 V and a half‐wave potential ( E 1/2 ) of 0.874 V, significantly surpassing commercial Pt/C and conventional metallic sulfide catalysts. When integrated into a zinc–air battery, it delivers a high open‐circuit voltage (1.450 V), specific capacity (789 mAh g −1 ), and peak power density (117.9 mW cm −2 ). This work provides valuable guidelines for the rational design and synthesis of electronically modulated metallic sulfides to enhance ORR activity for energy storage and conversion applications.
氧还原反应（ORR）的缓慢动力学要求开发具有增强电催化活性的氧电极用于实际的锌空气电池应用。在这项研究中，设计了一种铁掺杂硫化铜电催化剂（CuFeNS - PNC），锚定在金属有机框架衍生的碳衬底上，具有双金属cu5fes4结构，其中铁电子调节铜位点。X射线光电子能谱（XPS）证实，这种铜-硫化铁双金属体系相对于单金属硫化铜的性能增强是由于Fe - Cu的协同相互作用，揭示了电子从铁到铜的转移。密度泛函理论（DFT）计算表明，铁的加入降低了铜d波段中心，将OH*吸附能减弱到更理想的水平，从而提高了ORR动力学。因此，CuFeNS‐PNC催化剂的ORR起始电位（E起始电位）为0.988 V，半波电位（E 1/2）为0.874 V，显著优于商用Pt/C和传统金属硫化物催化剂，具有优异的电催化性能。当集成到锌空气电池中时，它提供高开路电压（1.450 V），比容量（789 mAh g - 1）和峰值功率密度（117.9 mW cm - 2）。这项工作为合理设计和合成电子调制金属硫化物以提高能量存储和转换应用中的ORR活性提供了有价值的指导。
{"title":"Electronic Modulation of Cu Sites via Iron Incorporation in Cu <sub>5</sub> FeS <sub>4</sub> Bimetallic Sulfide for High‐Efficiency Oxygen Reduction Reaction","authors":"Taichong Chitboonyakasem, Yi-Tian Gao, Xinbo Qiu, Jing Peng, Jian Zhou","doi":"10.1002/rar2.70108","DOIUrl":"https://doi.org/10.1002/rar2.70108","url":null,"abstract":"ABSTRACT The sluggish kinetics of the oxygen reduction reaction (ORR) necessitate developing oxygen electrodes with enhanced electrocatalytic activity for practical zinc–air battery applications. In this study, an iron‐doped copper sulfide electrocatalyst (CuFeNS‐PNC) anchored on metal–organic framework‐derived carbon substrates was designed, featuring a bimetallic Cu 5 FeS 4 architecture where iron electronically modulates copper sites. The performance enhancement of this copper–iron sulfide bimetallic system relative to a monometallic copper sulfide arises from synergistic Fe‐Cu interactions, as confirmed by X‐ray photoelectron spectroscopy (XPS), revealing electron transfer from iron to copper. Density functional theory (DFT) calculations demonstrate that iron incorporation downshifts the copper d‐band center, weakening OH* adsorption energy to a more optimal level, thereby boosting ORR kinetics. Consequently, the CuFeNS‐PNC catalyst achieves superior electrocatalytic performance with an ORR onset potential ( E onset ) of 0.988 V and a half‐wave potential ( E 1/2 ) of 0.874 V, significantly surpassing commercial Pt/C and conventional metallic sulfide catalysts. When integrated into a zinc–air battery, it delivers a high open‐circuit voltage (1.450 V), specific capacity (789 mAh g −1 ), and peak power density (117.9 mW cm −2 ). This work provides valuable guidelines for the rational design and synthesis of electronically modulated metallic sulfides to enhance ORR activity for energy storage and conversion applications.","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"45 2","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/rar2.70108","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333475","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ABSTRACT The design of nanoparticles confined in hollow N‐doped carbon structures is crucial for improving the oxygen reduction reaction (ORR) kinetics, yet achieving this remains a significant challenge. In this work, hollow porous nitrogen‐doped carbon encapsulated FeP/Fe 2 P (H‐FeP/Fe 2 P) were successfully constructed via a templating method combined with dopamine hydrochloride coating, acid etching, and subsequent high‐temperature phosphating. In situ spectroelectrochemical investigations and theoretical results demonstrate that the adsorbed hydroxyl species (*OH) can be readily released from the catalyst surface by facilitating the dissociation of oxygen–oxygen bonds at the active sites of Fe, thus accelerating the kinetics of the ORR. The optimized H‐FeP/Fe 2 P achieves a high limiting current density of 5.5 mA cm −2 and a low Tafel slope of 39 mV dec −1 in 0.1 M KOH, outperforming corresponding solid samples and most reported transition metal phosphide catalysts. Moreover, the H‐FeP/Fe 2 P‐based aqueous ZAB exhibits remarkable performance, including high peak power density (175 mW cm −2 ), large specific capacity (813 mAh g −1 Zn ), and stable charge/discharge stability over 800 h. The corresponding solid‐state zinc‐air battery also delivers a high peak power density of 101 mW cm −2 and excellent flexibility. The carbon confinement strategy proposed in this study opens new avenues for developing high‐performance and cost‐effective non‐precious metal ORR catalysts in zinc‐air batteries.
纳米颗粒的设计局限在空心N掺杂碳结构中，对于改善氧还原反应（ORR）动力学至关重要，但实现这一目标仍然是一个重大挑战。在这项工作中，通过模板法结合盐酸多巴胺涂层，酸蚀和随后的高温磷化，成功构建了空心多孔氮掺杂碳封装FeP/ fe2p （H‐FeP/ fe2p）。原位光谱电化学研究和理论结果表明，吸附的羟基（*OH）可以通过促进Fe活性位点的氧键解离而很容易从催化剂表面释放出来，从而加速ORR动力学。优化后的H - FeP/ fe2p在0.1 M KOH条件下具有5.5 mA cm−2的高极限电流密度和39 mV dec−1的低Tafel斜率，优于相应的固体样品和大多数报道的过渡金属磷化物催化剂。此外，基于H - FeP/ fe2p的水溶液ZAB表现出卓越的性能，包括高峰值功率密度（175 mW cm - 2），大比容量（813 mAh g - 1 Zn）和超过800 H的稳定充放电稳定性。相应的固态锌-空气电池也具有101 mW cm - 2的峰值功率密度和优异的灵活性。本研究提出的碳约束策略为开发锌空气电池中高性能和低成本的非贵金属ORR催化剂开辟了新的途径。
{"title":"Hollow Porous Nitrogen‐Doped Carbon‐Confined FeP/Fe <sub>2</sub> P Nanoparticle‐Armored Catalyst for Efficient Oxygen Reduction Reaction in Aqueous/Flexible Zinc‐Air Batteries","authors":"Lixia Wang, Jia‐Sui Huang, Xiao‐yang Cheng, Zhi‐Yang Huang, A‐Lin Zhou, Shu‐Hui Sun, Xia Yang, Tian‐Xiao Sun, Bin Wu","doi":"10.1002/rar2.70023","DOIUrl":"https://doi.org/10.1002/rar2.70023","url":null,"abstract":"ABSTRACT The design of nanoparticles confined in hollow N‐doped carbon structures is crucial for improving the oxygen reduction reaction (ORR) kinetics, yet achieving this remains a significant challenge. In this work, hollow porous nitrogen‐doped carbon encapsulated FeP/Fe 2 P (H‐FeP/Fe 2 P) were successfully constructed via a templating method combined with dopamine hydrochloride coating, acid etching, and subsequent high‐temperature phosphating. In situ spectroelectrochemical investigations and theoretical results demonstrate that the adsorbed hydroxyl species (*OH) can be readily released from the catalyst surface by facilitating the dissociation of oxygen–oxygen bonds at the active sites of Fe, thus accelerating the kinetics of the ORR. The optimized H‐FeP/Fe 2 P achieves a high limiting current density of 5.5 mA cm −2 and a low Tafel slope of 39 mV dec −1 in 0.1 M KOH, outperforming corresponding solid samples and most reported transition metal phosphide catalysts. Moreover, the H‐FeP/Fe 2 P‐based aqueous ZAB exhibits remarkable performance, including high peak power density (175 mW cm −2 ), large specific capacity (813 mAh g −1 Zn ), and stable charge/discharge stability over 800 h. The corresponding solid‐state zinc‐air battery also delivers a high peak power density of 101 mW cm −2 and excellent flexibility. The carbon confinement strategy proposed in this study opens new avenues for developing high‐performance and cost‐effective non‐precious metal ORR catalysts in zinc‐air batteries.","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"45 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/rar2.70023","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333076","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ya‐Ke Wu, Kai Jia, Fu-Ying Wu, Bei‐Bei Xiao, Ting Bian, Hu Liu, Hong Li, Liu‐Ting Zhang
ABSTRACT Weakening the electrostatic attraction between Mg 2+ ions and H − ions in MgH 2 is vital for improving the kinetic performance of MgH 2 for hydrogen storage. Herein, a multivalent microenvironment is synergistically created by Mn and Mg 2 Ni to break the stable structure of MgH 2 , enabling rapid and stable de/hydrogenation performance. Specifically, the catalyzed MgH 2 system rapidly emits 5.98 wt% H 2 at 265°C within just 20 min and swiftly absorbs 6.24 wt% H 2 at 150°C in a mere 10 min. Microscopic characterization shows that a tight interface is formed between Ni and Mn 2 O 3 , which provides a stable anchor point for the formation of hydrogen pumps. Additionally, the multivalency of Mn and abundant oxygen vacancies accelerate the electron transfer and provide the shortest path for H dissociation. Moreover, density functional theory (DFT) indicates that Mg‐H is extracted from 0.173 to 0.204 nm after modification, achieving a reduced decomposition energy of MgH 2 . Besides, 97.8% reversible hydrogen storage capacity was maintained after 30 cycles, presenting prominent potential for practical applications.
{"title":"Constructing a Favorable Microenvironment for Robust Hydrogen Storage in MgH <sub>2</sub> Through Synergistic Cooperation With Mn and Mg <sub>2</sub> Ni","authors":"Ya‐Ke Wu, Kai Jia, Fu-Ying Wu, Bei‐Bei Xiao, Ting Bian, Hu Liu, Hong Li, Liu‐Ting Zhang","doi":"10.1002/rar2.70038","DOIUrl":"https://doi.org/10.1002/rar2.70038","url":null,"abstract":"ABSTRACT Weakening the electrostatic attraction between Mg 2+ ions and H − ions in MgH 2 is vital for improving the kinetic performance of MgH 2 for hydrogen storage. Herein, a multivalent microenvironment is synergistically created by Mn and Mg 2 Ni to break the stable structure of MgH 2 , enabling rapid and stable de/hydrogenation performance. Specifically, the catalyzed MgH 2 system rapidly emits 5.98 wt% H 2 at 265°C within just 20 min and swiftly absorbs 6.24 wt% H 2 at 150°C in a mere 10 min. Microscopic characterization shows that a tight interface is formed between Ni and Mn 2 O 3 , which provides a stable anchor point for the formation of hydrogen pumps. Additionally, the multivalency of Mn and abundant oxygen vacancies accelerate the electron transfer and provide the shortest path for H dissociation. Moreover, density functional theory (DFT) indicates that Mg‐H is extracted from 0.173 to 0.204 nm after modification, achieving a reduced decomposition energy of MgH 2 . Besides, 97.8% reversible hydrogen storage capacity was maintained after 30 cycles, presenting prominent potential for practical applications.","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"45 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/rar2.70038","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332781","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bin Wang, Shun‐Jie Wu, Xin‐Lin Lu, Yong Ge, Yue Zhang, Zhi‐Xiang Ma, Bin Xu, Paul‐K. Chu, Yuanzhang Zhao
ABSTRACT The limited osteogenic capacity of magnesium phosphate cement (MPC) has constrained its biomedical applications, underscoring the necessity to develop MPC with enhanced physical properties and bone‐forming capabilities. In this study, a multifunctional MPC system was developed by incorporating zoledronic acid‐loaded near‐infrared (NIR)‐responsive nanocarriers, strontium oxide (SrO), and hyaluronic acid (HA). The nanocarriers were constructed using dual‐layer poly‐dopamine (PDA) modification of mesoporous silica nanoparticles (MSNs), enabling controlled drug release and antibacterial efficacy under NIR stimulation. The optimized Sr‐ZMP‐HA MPC demonstrated prolonged setting time, near‐neutral pH, superior injectability, and improved compressive strength. Immersion tests revealed its sustained degradation resistance. This composite material exhibited excellent biocompatibility along with enhanced osteogenic and angiogenic properties, particularly when activated by NIR irradiation. The experiments demonstrated that NIR‐triggered Sr‐ZMP‐HA MPC promoted osteoblast‐derived exosome secretion. These exosomes mediated miRNA transfer to osteoclasts, effectively suppressing their proliferation and differentiation while delaying bone tissue senescence. This dual‐functional system, combining NIR‐responsive nanomedicine with exosome‐mediated intercellular communication, provided a novel strategy for developing advanced bone repair materials, potentially addressing current limitations in orthopedic applications through synergistic mechanical reinforcement and biological activation mechanisms.
磷酸镁水泥（MPC）有限的成骨能力限制了其生物医学应用，强调了开发具有增强物理性能和骨形成能力的MPC的必要性。在这项研究中，通过加入唑来膦酸负载的近红外（NIR）响应纳米载体、氧化锶（SrO）和透明质酸（HA），开发了多功能MPC系统。采用双层聚多巴胺（PDA）修饰介孔二氧化硅纳米颗粒（MSNs）构建纳米载体，使其在近红外刺激下具有可控的药物释放和抗菌效果。优化后的Sr - ZMP - HA MPC具有凝固时间延长、pH值接近中性、注射性好、抗压强度提高等特点。浸渍试验表明其具有持续的抗降解能力。这种复合材料表现出优异的生物相容性以及增强的成骨和血管生成性能，特别是在近红外照射下激活时。实验表明，近红外触发的Sr - ZMP - HA MPC促进了成骨细胞来源的外泌体分泌。这些外泌体介导miRNA转移到破骨细胞，有效抑制其增殖和分化，同时延缓骨组织衰老。这种双功能系统结合了近红外响应纳米药物和外泌体介导的细胞间通讯，为开发先进的骨修复材料提供了一种新的策略，有可能通过协同机械增强和生物激活机制解决目前骨科应用中的局限性。
{"title":"NIR‐Responsive Nano‐Integrated Magnesium Phosphate Cement Promotes Bone Regeneration via Osteoblast‐Exosome‐Osteoclast Crosstalk","authors":"Bin Wang, Shun‐Jie Wu, Xin‐Lin Lu, Yong Ge, Yue Zhang, Zhi‐Xiang Ma, Bin Xu, Paul‐K. Chu, Yuanzhang Zhao","doi":"10.1002/rar2.70103","DOIUrl":"https://doi.org/10.1002/rar2.70103","url":null,"abstract":"ABSTRACT The limited osteogenic capacity of magnesium phosphate cement (MPC) has constrained its biomedical applications, underscoring the necessity to develop MPC with enhanced physical properties and bone‐forming capabilities. In this study, a multifunctional MPC system was developed by incorporating zoledronic acid‐loaded near‐infrared (NIR)‐responsive nanocarriers, strontium oxide (SrO), and hyaluronic acid (HA). The nanocarriers were constructed using dual‐layer poly‐dopamine (PDA) modification of mesoporous silica nanoparticles (MSNs), enabling controlled drug release and antibacterial efficacy under NIR stimulation. The optimized Sr‐ZMP‐HA MPC demonstrated prolonged setting time, near‐neutral pH, superior injectability, and improved compressive strength. Immersion tests revealed its sustained degradation resistance. This composite material exhibited excellent biocompatibility along with enhanced osteogenic and angiogenic properties, particularly when activated by NIR irradiation. The experiments demonstrated that NIR‐triggered Sr‐ZMP‐HA MPC promoted osteoblast‐derived exosome secretion. These exosomes mediated miRNA transfer to osteoclasts, effectively suppressing their proliferation and differentiation while delaying bone tissue senescence. This dual‐functional system, combining NIR‐responsive nanomedicine with exosome‐mediated intercellular communication, provided a novel strategy for developing advanced bone repair materials, potentially addressing current limitations in orthopedic applications through synergistic mechanical reinforcement and biological activation mechanisms.","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"45 2","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334186","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ABSTRACT Transition metal carbides demonstrate exceptional mechanical properties but confront a critical hardness–toughness trade‐off. Spinodal decomposition‐mediated phase separation is an effective approach to enhance mechanical properties in carbide ceramics through high‐temperature treatment. Guided by thermodynamic phase diagrams, this study designed a novel (V, Nb)C system wherein nanoscale phase separation was realized via controlled aging processes. Unlike traditional carbide ceramics, the aged (V, Nb)C carbides present a unique dual‐scale microstructure: nanoscale intragranular spinodal decomposition coexists synergistically with a grain‐boundary dislocation network associated with locally ordered phases. This unique structure effectively impedes dislocation motion, leading to superior mechanical performance enhancement compared to conventional carbide ceramics. Following controlled aging treatments, the material achieves a simultaneous enhancement of hardness (45% increase) and fracture toughness (25% improvement) relative to the as‐fabricated state, thereby overcoming the intrinsic hardness–toughness trade‐off inherent to carbide systems. This study elucidates the crucial role of spinodal decomposition in the microstructural evolution of composite carbides and highlights the efficacy of the chemically ordered dislocation network in suppressing diffusion and dislocation motion. These insights establish a robust theoretical framework for optimizing mechanical properties and designing ceramic materials with exceptional service performance.
{"title":"Breaking Hardness–Toughness Trade‐Off in Novel (V, Nb)C Carbides via Nanoscale Phase Separation and Local‐Chemical‐Order Dislocation Network","authors":"Zhi‐Xuan Zhang, Na Li, Guo‐Rui Chang, Zongyao Zhang, Wei‐Li Wang, Chao Yuan, Wen Zhang","doi":"10.1002/rar2.70006","DOIUrl":"https://doi.org/10.1002/rar2.70006","url":null,"abstract":"ABSTRACT Transition metal carbides demonstrate exceptional mechanical properties but confront a critical hardness–toughness trade‐off. Spinodal decomposition‐mediated phase separation is an effective approach to enhance mechanical properties in carbide ceramics through high‐temperature treatment. Guided by thermodynamic phase diagrams, this study designed a novel (V, Nb)C system wherein nanoscale phase separation was realized via controlled aging processes. Unlike traditional carbide ceramics, the aged (V, Nb)C carbides present a unique dual‐scale microstructure: nanoscale intragranular spinodal decomposition coexists synergistically with a grain‐boundary dislocation network associated with locally ordered phases. This unique structure effectively impedes dislocation motion, leading to superior mechanical performance enhancement compared to conventional carbide ceramics. Following controlled aging treatments, the material achieves a simultaneous enhancement of hardness (45% increase) and fracture toughness (25% improvement) relative to the as‐fabricated state, thereby overcoming the intrinsic hardness–toughness trade‐off inherent to carbide systems. This study elucidates the crucial role of spinodal decomposition in the microstructural evolution of composite carbides and highlights the efficacy of the chemically ordered dislocation network in suppressing diffusion and dislocation motion. These insights establish a robust theoretical framework for optimizing mechanical properties and designing ceramic materials with exceptional service performance.","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"45 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/rar2.70006","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147334158","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jie Yang, Xin‐Yan Huang, Rong‐Zhi Zhao, Tong Gao, Jia‐Chang Ruan, Shen‐Qi Han, Lei Wang, Jin‐Biao Shu, Y. Zhang
ABSTRACT Silver nanoparticles (AgNPs) are extensively employed for electromagnetic interference (EMI) shielding owing to their remarkable conductivity, and are commonly incorporated into polymer matrices. Therefore, the uniformity of the AgNP distribution within the polymer matrix is a crucial factor that affects the EMI shielding performance. This study demonstrates the impact of the surface morphology of AgNPs on the uniformity of the filling in electromagnetic interference shielding patches. The AgNPs were synthesized through a liquid‐phase reduction process, regulating the surface shape by thermal treatment at varying temperatures. The morphology transitioned from a flower‐spherical shape to a coarse‐strip shape when the heat treatment temperature increased from 20°C to 250°C. The morphological alteration of the AgNPs was ascribed to the interplay between their surface effects and sintering kinetics. The results indicated that after heat treatment at 100°C, AgNPs with a spherical surface morphology demonstrated remarkably superior filling uniformity. The EMI patch containing AgNPs subjected to heat treatment at 100°C demonstrated superior EMI shielding efficacy. Its efficacy was further validated in practical electronic equipment by applying surface electromagnetic radiation scanning techniques. These findings offer significant insights into the practical design of EMI shielding patches for real‐world applications using the morphology‐regulated filling uniformity method.
{"title":"Filling Uniformity of AgNPs in EMI Shielding Patch Regulated by Surface Morphology","authors":"Jie Yang, Xin‐Yan Huang, Rong‐Zhi Zhao, Tong Gao, Jia‐Chang Ruan, Shen‐Qi Han, Lei Wang, Jin‐Biao Shu, Y. Zhang","doi":"10.1002/rar2.70040","DOIUrl":"https://doi.org/10.1002/rar2.70040","url":null,"abstract":"ABSTRACT Silver nanoparticles (AgNPs) are extensively employed for electromagnetic interference (EMI) shielding owing to their remarkable conductivity, and are commonly incorporated into polymer matrices. Therefore, the uniformity of the AgNP distribution within the polymer matrix is a crucial factor that affects the EMI shielding performance. This study demonstrates the impact of the surface morphology of AgNPs on the uniformity of the filling in electromagnetic interference shielding patches. The AgNPs were synthesized through a liquid‐phase reduction process, regulating the surface shape by thermal treatment at varying temperatures. The morphology transitioned from a flower‐spherical shape to a coarse‐strip shape when the heat treatment temperature increased from 20°C to 250°C. The morphological alteration of the AgNPs was ascribed to the interplay between their surface effects and sintering kinetics. The results indicated that after heat treatment at 100°C, AgNPs with a spherical surface morphology demonstrated remarkably superior filling uniformity. The EMI patch containing AgNPs subjected to heat treatment at 100°C demonstrated superior EMI shielding efficacy. Its efficacy was further validated in practical electronic equipment by applying surface electromagnetic radiation scanning techniques. These findings offer significant insights into the practical design of EMI shielding patches for real‐world applications using the morphology‐regulated filling uniformity method.","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"45 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/rar2.70040","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333724","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhenxuan Ma, Jia‐Guang Zheng, Meiling Lv, Chuanyue Li, Chih-Hao Wu, Panpan Zhou, Chao Su, Lei Ge
ABSTRACT This research uncovered the influence of nitrogen‐doped MXene Ti 3 CN on the reversible hydrogen storage properties of Mg(BH 4 ) 2 . The Mg(BH 4 ) 2 ‐20Ti 3 CN composite began releasing hydrogen at a temperature of 80°C. In addition, the composite discharged over 8.8 wt% hydrogen at a comparatively lower temperature of 270°C, whereas the pure Mg(BH 4 ) 2 emitted merely 5.9 wt% hydrogen under identical circumstances, which exhibited remarkably enhanced dehydrogenation kinetics. Furthermore, upon completion of four cycles, Mg(BH 4 ) 2 ‐20Ti 3 CN retained a reversible hydrogen storage capacity of 4.5 wt%, representing an 80% improvement over the undoped Mg(BH 4 ) 2 . In the course of the dehydrogenation phase, the boron atoms in Mg(BH 4 ) 2 were anchored by nitrogen atoms in Ti 3 CN to form B‐N bonds, which helped suppress the formation of MgB 12 H 12 . During the subsequent rehydrogenation process, the B‐N bonds broke, and the boron atoms reparticipated in the reversible transformation into [BH 4 ] − clusters. Meanwhile, the formation of Ti 0 by the reaction of Mg(BH 4 ) 2 with Ti 3 CN weakened the B‐H bond energy, and the layered structure provided an effective way for hydrogen spillover. These factors collectively improved the reversible hydrogen storage capabilities of Mg(BH 4 ) 2 .
{"title":"Nitrogen Anchoring Effect Triggering Improved Reversible Hydrogen Storage of Mg(BH <sub>4</sub> ) <sub>2</sub>","authors":"Zhenxuan Ma, Jia‐Guang Zheng, Meiling Lv, Chuanyue Li, Chih-Hao Wu, Panpan Zhou, Chao Su, Lei Ge","doi":"10.1002/rar2.70017","DOIUrl":"https://doi.org/10.1002/rar2.70017","url":null,"abstract":"ABSTRACT This research uncovered the influence of nitrogen‐doped MXene Ti 3 CN on the reversible hydrogen storage properties of Mg(BH 4 ) 2 . The Mg(BH 4 ) 2 ‐20Ti 3 CN composite began releasing hydrogen at a temperature of 80°C. In addition, the composite discharged over 8.8 wt% hydrogen at a comparatively lower temperature of 270°C, whereas the pure Mg(BH 4 ) 2 emitted merely 5.9 wt% hydrogen under identical circumstances, which exhibited remarkably enhanced dehydrogenation kinetics. Furthermore, upon completion of four cycles, Mg(BH 4 ) 2 ‐20Ti 3 CN retained a reversible hydrogen storage capacity of 4.5 wt%, representing an 80% improvement over the undoped Mg(BH 4 ) 2 . In the course of the dehydrogenation phase, the boron atoms in Mg(BH 4 ) 2 were anchored by nitrogen atoms in Ti 3 CN to form B‐N bonds, which helped suppress the formation of MgB 12 H 12 . During the subsequent rehydrogenation process, the B‐N bonds broke, and the boron atoms reparticipated in the reversible transformation into [BH 4 ] − clusters. Meanwhile, the formation of Ti 0 by the reaction of Mg(BH 4 ) 2 with Ti 3 CN weakened the B‐H bond energy, and the layered structure provided an effective way for hydrogen spillover. These factors collectively improved the reversible hydrogen storage capabilities of Mg(BH 4 ) 2 .","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"45 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/rar2.70017","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147332120","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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