ABSTRACT Early diagnosis of liver cancer demands high sensitivity, high specificity, convenience and real‐time monitoring capabilities. However, it encounters challenges such as low concentration of markers, numerous interfering factors, and limitations of detection technologies. This study investigates the potential of plasmonic gold nanorods (AuNRs) and rare‐earth‐based up‐conversion nanoparticles (NaYF 4 :Yb/Er/Tm UCNPs) in liver cancer surveillance and detection. A significant enhancement in Near‐infrared (NIR) fluorescence of the UCNPs was observed when the assay was used for detecting the serum biomarker Golgi protein 73 (GP73). The method enables ultra‐sensitive, quantitative detection of GP73 at concentrations as low as 5 ng mL −1 in a short period of time, using only 10 μL of serum samples. It demonstrated a sensitivity of 88.90% and a specificity of 100%, surpassing conventional immunoassays and showing strong agreement with Magnetic resonance imaging (MRI) and computed tomography (CT) in prognostic performance. Compared to existing advanced detection methods, this approach exhibited superior performance in diagnostic accuracy, cost‐effectiveness, and time efficiency, highlighting its high practical value and transformative potential. Based on the findings of this study, the rare‐earth‐plasmonic hybrid nanomaterials in the GP73 detection method show promise for future liver cancer diagnostics. Despite its simplicity, it offers potential applications in community screening, intraoperative assessment, and postoperative monitoring.
肝癌早期诊断需要高灵敏度、高特异性、便捷性和实时监测能力。然而，它面临着标记物浓度低、干扰因素多、检测技术限制等挑战。本研究探讨了等离子体金纳米棒（aunr）和基于稀土的向上转化纳米颗粒（nayf4:Yb/Er/Tm UCNPs）在肝癌监测和检测中的潜力。用该方法检测血清生物标志物高尔基蛋白73 （GP73）时，发现UCNPs的近红外（NIR）荧光显著增强。该方法能够在短时间内，仅使用10 μL血清样品，在低至5 ng mL−1的浓度下，超灵敏地定量检测GP73。它的敏感性为88.90%，特异性为100%，超过了传统的免疫测定，在预后表现上与磁共振成像（MRI）和计算机断层扫描（CT）表现出强烈的一致性。与现有的先进检测方法相比，该方法在诊断准确性、成本效益和时间效率方面表现出优异的性能，突出了其较高的实用价值和变革潜力。基于本研究的发现，GP73检测方法中的稀土等离子体杂化纳米材料有望用于未来的肝癌诊断。尽管它简单，但它在社区筛查、术中评估和术后监测方面具有潜在的应用前景。
{"title":"Plasmon‐Enhanced NaYF <sub>4</sub> :Yb/Er/Tm UCNPs Fluorescent Biosensing for Ultrasensitive Detection of GP73 in Clinical Liver Cancer Diagnosis","authors":"Changsheng Shi, Wei Cai, Zhixiang Lin, Y Xu, Liu Xu, Bingru Zheng, Wenhua Li, Hui Tong, Qing Yang, Caiping Ding, Youju Huang","doi":"10.1002/rar2.70222","DOIUrl":"https://doi.org/10.1002/rar2.70222","url":null,"abstract":"ABSTRACT Early diagnosis of liver cancer demands high sensitivity, high specificity, convenience and real‐time monitoring capabilities. However, it encounters challenges such as low concentration of markers, numerous interfering factors, and limitations of detection technologies. This study investigates the potential of plasmonic gold nanorods (AuNRs) and rare‐earth‐based up‐conversion nanoparticles (NaYF 4 :Yb/Er/Tm UCNPs) in liver cancer surveillance and detection. A significant enhancement in Near‐infrared (NIR) fluorescence of the UCNPs was observed when the assay was used for detecting the serum biomarker Golgi protein 73 (GP73). The method enables ultra‐sensitive, quantitative detection of GP73 at concentrations as low as 5 ng mL −1 in a short period of time, using only 10 μL of serum samples. It demonstrated a sensitivity of 88.90% and a specificity of 100%, surpassing conventional immunoassays and showing strong agreement with Magnetic resonance imaging (MRI) and computed tomography (CT) in prognostic performance. Compared to existing advanced detection methods, this approach exhibited superior performance in diagnostic accuracy, cost‐effectiveness, and time efficiency, highlighting its high practical value and transformative potential. Based on the findings of this study, the rare‐earth‐plasmonic hybrid nanomaterials in the GP73 detection method show promise for future liver cancer diagnostics. Despite its simplicity, it offers potential applications in community screening, intraoperative assessment, and postoperative monitoring.","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"45 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148305745","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 development of sodium‐ion batteries (SIBs) is limited by slow charge transfer kinetics and large material volume changes caused by the large radius of Na + . Leveraging the excellent physicochemical properties and unique heterostructures of metal selenides, ultrafine hetero‐CuFeSe 2 ‐CoSe 2 nanoparticles are in situ wrapped by polyvinylpyrrolidone‐derived carbon (PDC) to successfully synthesize multicomponent composite electrode materials (CuFeSe 2 ‐CoSe 2 @PDC) for SIB anodes. The carbon‐coated trimetallic selenide heterostructure synergistically enhances electronic/ionic conductivity while maintaining exceptional structural stability, thereby significantly improving the reaction kinetics of active materials. In addition, the exceptionally high pseudocapacitive contribution (97% at 1.0 mV s −1 ) plays a pivotal role in achieving high reversible specific capacity, excellent cycling stability, and superior rate capability. Benefiting from the multicomponent synergistic effects, the electrode delivers an exceptional specific capacity of 457.88 mAh g −1 after 1000 cycles at 2 A g −1 , with an ultralow average capacity decay rate of merely 0.0021% per cycle. Density functional theory (DFT) calculations further elucidate that the CuFeSe 2 ‐CoSe 2 heterointerface induces electronic structure reconstruction, and the generated built‐in electric field promotes interfacial electrochemical kinetics. Ex situ X‐ray diffraction (XRD) further revealed the reversible phase transformation reaction mechanism and confirmed the remarkable structural stability of CuFeSe 2 ‐CoSe 2 @PDC. This offers a feasible strategy to design high‐performance electrodes capable of rapid and stable Na + storage.
{"title":"Multiscale Study of a Synergistic System in Carbon‐Coated Multimetal‐Based Selenides Toward Rapid and Highly Stable Sodium Storage","authors":"Ying Zhu, Xiuzhen Wang, Lei Dong, Yilin Cao, Zhang‐Cheng Cao, Liu‐Ting Zhang","doi":"10.1002/rar2.70135","DOIUrl":"https://doi.org/10.1002/rar2.70135","url":null,"abstract":"ABSTRACT The development of sodium‐ion batteries (SIBs) is limited by slow charge transfer kinetics and large material volume changes caused by the large radius of Na + . Leveraging the excellent physicochemical properties and unique heterostructures of metal selenides, ultrafine hetero‐CuFeSe 2 ‐CoSe 2 nanoparticles are in situ wrapped by polyvinylpyrrolidone‐derived carbon (PDC) to successfully synthesize multicomponent composite electrode materials (CuFeSe 2 ‐CoSe 2 @PDC) for SIB anodes. The carbon‐coated trimetallic selenide heterostructure synergistically enhances electronic/ionic conductivity while maintaining exceptional structural stability, thereby significantly improving the reaction kinetics of active materials. In addition, the exceptionally high pseudocapacitive contribution (97% at 1.0 mV s −1 ) plays a pivotal role in achieving high reversible specific capacity, excellent cycling stability, and superior rate capability. Benefiting from the multicomponent synergistic effects, the electrode delivers an exceptional specific capacity of 457.88 mAh g −1 after 1000 cycles at 2 A g −1 , with an ultralow average capacity decay rate of merely 0.0021% per cycle. Density functional theory (DFT) calculations further elucidate that the CuFeSe 2 ‐CoSe 2 heterointerface induces electronic structure reconstruction, and the generated built‐in electric field promotes interfacial electrochemical kinetics. Ex situ X‐ray diffraction (XRD) further revealed the reversible phase transformation reaction mechanism and confirmed the remarkable structural stability of CuFeSe 2 ‐CoSe 2 @PDC. This offers a feasible strategy to design high‐performance electrodes capable of rapid and stable Na + storage.","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"45 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147881938","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 High‐entropy alloys (HEAs) have attracted considerable interest from researchers owing to their tunable chemical compositions, exceptional structural stability, and promising catalytic properties. However, their large‐scale application is often hindered by complex manufacturing techniques and poor durability. Herein, we report a simple and cost‐effective three‐dimensional (3D) printing strategy to fabricate a 3D‐FeMnCrCo HEA catalyst with precisely controlled composition, structure, and porosity. The as‐prepared 3D‐FeMnCrCo catalyst exhibits high printing accuracy, excellent compression resistance, and remarkable efficiency in degrading organic contaminants using peroxymonosulfate (PMS) activation. Notably, the catalyst maintains outstanding catalytic stability over 100 consecutive cycles, which outperforms most of its powdered counterparts. Theoretical calculations and controlled experiments reveal that a synergistic combination of Fe/Mn electron donation, Co‐mediated charge buffering, and Cr‐driven orbital hybridization lowers the electron transfer energy barrier, thereby enhancing PMS activation. Mechanistic studies further show that singlet oxygen is the predominant reactive species in the 3D‐FeMnCrCo/PMS system. The biotoxicity of degraded pollutants and the catalyst's performance in treating actual wastewater are also systematically evaluated. This work provides critical insights into the practical application of HEAs in water treatment and guides the design of efficient, stable, and easily recoverable catalysts for environmental remediation.
{"title":"3D‐Printed Porous High‐Entropy Alloy Boosts Peroxymonosulfate Activation for Long‐Term Organic Pollutant Degradation","authors":"Sheng Guo, Mengmeng Yang, Xizi Gao, Huang Yi, Yushan Huang, Liming You, Changjun Han, Chao Cai, Fengxi Chen, Rong Chen","doi":"10.1002/rar2.70134","DOIUrl":"https://doi.org/10.1002/rar2.70134","url":null,"abstract":"ABSTRACT High‐entropy alloys (HEAs) have attracted considerable interest from researchers owing to their tunable chemical compositions, exceptional structural stability, and promising catalytic properties. However, their large‐scale application is often hindered by complex manufacturing techniques and poor durability. Herein, we report a simple and cost‐effective three‐dimensional (3D) printing strategy to fabricate a 3D‐FeMnCrCo HEA catalyst with precisely controlled composition, structure, and porosity. The as‐prepared 3D‐FeMnCrCo catalyst exhibits high printing accuracy, excellent compression resistance, and remarkable efficiency in degrading organic contaminants using peroxymonosulfate (PMS) activation. Notably, the catalyst maintains outstanding catalytic stability over 100 consecutive cycles, which outperforms most of its powdered counterparts. Theoretical calculations and controlled experiments reveal that a synergistic combination of Fe/Mn electron donation, Co‐mediated charge buffering, and Cr‐driven orbital hybridization lowers the electron transfer energy barrier, thereby enhancing PMS activation. Mechanistic studies further show that singlet oxygen is the predominant reactive species in the 3D‐FeMnCrCo/PMS system. The biotoxicity of degraded pollutants and the catalyst's performance in treating actual wastewater are also systematically evaluated. This work provides critical insights into the practical application of HEAs in water treatment and guides the design of efficient, stable, and easily recoverable catalysts for environmental remediation.","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"45 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/rar2.70134","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147889040","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}
Hao Liang, Yu Liang, Rubiao Qiu, Kunpeng Duan, Jiaxiao Li, Yan Liu, Xiaowen Li, Xiaowen Li, L. Wang, Lingling Liang, Mingyang Jiang, C WANG, G. CHEN, Ming Gao, Xiaojie Li, Xiaojie Li, Tao Qin
ABSTRACT Periodontitis is a chronic infectious oral disease triggered by periodontopathogenic bacteria, resulting in the progressive inflammation and destruction of the tissues surrounding teeth. To achieve reprogramming of the infectious microenvironment for periodontitis therapy, a nanoformulation was proposed by loading polydopamine (PDA) with ultrasmall strontium through in situ reduction and arginine by Michael addition, defined as PA. Combined with near infrared (NIR) irradiation, it could efficiently scavenge reactive oxygen species (ROS), and downregulate inflammatory factors expression through inhibiting NF‐κB pathway. In addition, it also confirmed the effective bacteria killing in NIR stimulated PA by photothermal effects and nitric oxide (NO) generation. Significantly, PA + NIR was also verified to promote alveolar bone tissue repair through strontium ions (Sr 2+ ) and NO induced angiogenesis, together with Sr 2+ mediated osteogenesis. The administration strategy was finally verified to alleviate the oxidative stress derived inflammation, suppress bacterial growth and biofilm formation, as well as promote bone regeneration with high efficacy and biosafety in the periodontitis rat models. All the above findings contributed to the NIR enhanced synergistic treatment of periodontitis, and it may serve as a promising strategy for the treatment of other inflammation related diseases.
{"title":"An Ultrasmall Strontium‐Loaded Polydopamine Nanoformulation for Near‐Infrared‐Enhanced Periodontitis Therapy via Photodynamic Gas‐Promoted Antibacterial and Bone Repair","authors":"Hao Liang, Yu Liang, Rubiao Qiu, Kunpeng Duan, Jiaxiao Li, Yan Liu, Xiaowen Li, Xiaowen Li, L. Wang, Lingling Liang, Mingyang Jiang, C WANG, G. CHEN, Ming Gao, Xiaojie Li, Xiaojie Li, Tao Qin","doi":"10.1002/rar2.70148","DOIUrl":"https://doi.org/10.1002/rar2.70148","url":null,"abstract":"ABSTRACT Periodontitis is a chronic infectious oral disease triggered by periodontopathogenic bacteria, resulting in the progressive inflammation and destruction of the tissues surrounding teeth. To achieve reprogramming of the infectious microenvironment for periodontitis therapy, a nanoformulation was proposed by loading polydopamine (PDA) with ultrasmall strontium through in situ reduction and arginine by Michael addition, defined as PA. Combined with near infrared (NIR) irradiation, it could efficiently scavenge reactive oxygen species (ROS), and downregulate inflammatory factors expression through inhibiting NF‐κB pathway. In addition, it also confirmed the effective bacteria killing in NIR stimulated PA by photothermal effects and nitric oxide (NO) generation. Significantly, PA + NIR was also verified to promote alveolar bone tissue repair through strontium ions (Sr 2+ ) and NO induced angiogenesis, together with Sr 2+ mediated osteogenesis. The administration strategy was finally verified to alleviate the oxidative stress derived inflammation, suppress bacterial growth and biofilm formation, as well as promote bone regeneration with high efficacy and biosafety in the periodontitis rat models. All the above findings contributed to the NIR enhanced synergistic treatment of periodontitis, and it may serve as a promising strategy for the treatment of other inflammation related diseases.","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"45 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/rar2.70148","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147903235","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 X‐ray delayed imaging technology leverages an “irradiation‐storage‐thermally stimulated readout” mode, demonstrating unique advantages in intermittent monitoring scenarios such as high‐temperature/high‐radiation environments. This typically requires materials combining abundant carrier‐trapping energy levels with structural thermostability. Herein, Cr 3+ ‐doped ZnGa 2 O 4 glass ceramics (ZGC GCs) serve as a functional platform, utilizing their deep trap energy levels (main peak 197.7°C) to efficiently capture and store X‐ray imaging information, and achieve high‐brightness X‐ray delayed imaging by modulating the thermally stimulated detrapping rates. Under its exceptional structural thermostability and deep trap characteristics, ZGC GCs maintain high‐quality delayed imaging capability by thermal stimulation even after 180°C irradiation, highlighting their potential for high‐temperature nondestructive testing and surpassing the high‐temperature failure threshold of conventional scintillators. This work pioneers functional applications of glass ceramics in high‐temperature irradiation scenarios and offers a novel perspective for selecting harsh‐environment‐adapted X‐ray imaging materials.
{"title":"High‐Brightness Delayed Imaging Realized by Embedding Zinc Gallate Nanocrystals Into Glass","authors":"Jing Wu, Xing‐Liang Luo, Pu‐Wei Zhai, Ming‐Hui Long, Yuan Xue, Xiu‐Xia Yang, Xu‐Hui Xu","doi":"10.1002/rar2.70121","DOIUrl":"https://doi.org/10.1002/rar2.70121","url":null,"abstract":"ABSTRACT X‐ray delayed imaging technology leverages an “irradiation‐storage‐thermally stimulated readout” mode, demonstrating unique advantages in intermittent monitoring scenarios such as high‐temperature/high‐radiation environments. This typically requires materials combining abundant carrier‐trapping energy levels with structural thermostability. Herein, Cr 3+ ‐doped ZnGa 2 O 4 glass ceramics (ZGC GCs) serve as a functional platform, utilizing their deep trap energy levels (main peak 197.7°C) to efficiently capture and store X‐ray imaging information, and achieve high‐brightness X‐ray delayed imaging by modulating the thermally stimulated detrapping rates. Under its exceptional structural thermostability and deep trap characteristics, ZGC GCs maintain high‐quality delayed imaging capability by thermal stimulation even after 180°C irradiation, highlighting their potential for high‐temperature nondestructive testing and surpassing the high‐temperature failure threshold of conventional scintillators. This work pioneers functional applications of glass ceramics in high‐temperature irradiation scenarios and offers a novel perspective for selecting harsh‐environment‐adapted X‐ray imaging materials.","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"45 3","pages":""},"PeriodicalIF":0.0,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/rar2.70121","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147898655","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 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}
Lei Zhang, Jianhao Qiu, Biyao Fang, Guanglu Xia, Chen Chen, Meng Liu, Yixin Li, Yuehua Chen, Jianfeng Yao
ABSTRACT Defects can tune the band structure of semiconductors, thereby reconfiguring the corresponding heterojunctions. In this study, coralloidal Bi 2 S 3 @In 2 S 3 heterostructures rich in sulfur vacancies were successfully developed via a one‐step hydrothermal method with content regulation of the sulfur source. In 2 S 3 nanosheets are evenly distributed along Bi 2 S 3 nanorod clusters, imparting a unique coralloidal structure and compact interfacial contact that accelerates the transportation of photoinduced electrons and holes. Moreover, the sulfur vacancy strengthens the light absorption and enables staggered energy band alignment for Bi 2 S 3 @In 2 S 3 heterostructures, which further promotes charge carrier separation. Owing to these favorable features, the coralloidal Bi 2 S 3 @In 2 S 3 heterostructure with rich sulfur vacancies exhibited a high photocatalytic efficiency for Cr(VI) reduction, whose reaction rate constant is 34.9, 8.1 and 1.9‐fold enhancements compared with those of Bi 2 S 3 , In 2 S 3 , and the Bi 2 S 3 @In 2 S 3 heterostructure with poor sulfur vacancies, respectively. For simultaneous Cr(VI) reduction and antibiotic (tetracycline and ciprofloxacin) degradation under visible light, the excellent Cr(VI) reduction performance was kept and the degradation rates of the antibiotics clearly increased (more than 25%) compared with those of the reactions in the corresponding solo system, which was due to the synergistic effect of efficient utilization of photoinduced electrons and holes. This article provides valuable insight and guidance for the design of defective heterostructures and the treatment of complex water pollutants.
{"title":"Sulfur Vacancy Engineering of Coralloidal Bi <sub>2</sub> S <sub>3</sub> @In <sub>2</sub> S <sub>3</sub> Heterojunction for Enhanced Photocatalytic Removal of Cr(VI)/Antibiotic Mixed Pollutants","authors":"Lei Zhang, Jianhao Qiu, Biyao Fang, Guanglu Xia, Chen Chen, Meng Liu, Yixin Li, Yuehua Chen, Jianfeng Yao","doi":"10.1002/rar2.70028","DOIUrl":"https://doi.org/10.1002/rar2.70028","url":null,"abstract":"ABSTRACT Defects can tune the band structure of semiconductors, thereby reconfiguring the corresponding heterojunctions. In this study, coralloidal Bi 2 S 3 @In 2 S 3 heterostructures rich in sulfur vacancies were successfully developed via a one‐step hydrothermal method with content regulation of the sulfur source. In 2 S 3 nanosheets are evenly distributed along Bi 2 S 3 nanorod clusters, imparting a unique coralloidal structure and compact interfacial contact that accelerates the transportation of photoinduced electrons and holes. Moreover, the sulfur vacancy strengthens the light absorption and enables staggered energy band alignment for Bi 2 S 3 @In 2 S 3 heterostructures, which further promotes charge carrier separation. Owing to these favorable features, the coralloidal Bi 2 S 3 @In 2 S 3 heterostructure with rich sulfur vacancies exhibited a high photocatalytic efficiency for Cr(VI) reduction, whose reaction rate constant is 34.9, 8.1 and 1.9‐fold enhancements compared with those of Bi 2 S 3 , In 2 S 3 , and the Bi 2 S 3 @In 2 S 3 heterostructure with poor sulfur vacancies, respectively. For simultaneous Cr(VI) reduction and antibiotic (tetracycline and ciprofloxacin) degradation under visible light, the excellent Cr(VI) reduction performance was kept and the degradation rates of the antibiotics clearly increased (more than 25%) compared with those of the reactions in the corresponding solo system, which was due to the synergistic effect of efficient utilization of photoinduced electrons and holes. This article provides valuable insight and guidance for the design of defective heterostructures and the treatment of complex water pollutants.","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"45 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/rar2.70028","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147903751","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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