Pub Date : 2025-08-12DOI: 10.1007/s12598-025-03498-2
Wen-Shuo Zhang, Chao Li, Xiao-Meng Shi, Zhi-Chao Zeng, Ya-Ping Du
Aqueous zinc-metal batteries have many advantages, including high safety, low cost, and environmental friendliness. Nevertheless, the poor cycling stability hinders their practical application. Mitigating the irreversible Zn2+ loss at the interface between the electrode and electrolyte, as well as inside the electrode, is an effective strategy to achieve high cycling stability. Herein, a novel lean-zinc anode is proposed, which is carried out by annealing LaZn bimetallic organic framework to form metal oxides and derived carbon. The anode has a low voltage hysteresis and low nucleation overpotential, further achieves high plating/stripping reversibility. The good electrochemical properties are attributed to the highly stable anode, which contains a large layer spacing La2O3 with a low lattice mismatch degree to Zn0. This anode facilitates rapid ion transport and uniform Zn0 deposition at the interface, which helps to alleviate the irreversible Zn2+ loss. On this basis, the assembled batteries can maintain excellent stability for over 3000 cycles. This illustrates the promising application of rare-earth-based bimetallic-derived anodes in aqueous zinc-metal batteries.
{"title":"Rare earth bimetallic organic framework-derived lean-zinc anodes for highly reversible zinc-metal batteries","authors":"Wen-Shuo Zhang, Chao Li, Xiao-Meng Shi, Zhi-Chao Zeng, Ya-Ping Du","doi":"10.1007/s12598-025-03498-2","DOIUrl":"10.1007/s12598-025-03498-2","url":null,"abstract":"<div><p>Aqueous zinc-metal batteries have many advantages, including high safety, low cost, and environmental friendliness. Nevertheless, the poor cycling stability hinders their practical application. Mitigating the irreversible Zn<sup>2+</sup> loss at the interface between the electrode and electrolyte, as well as inside the electrode, is an effective strategy to achieve high cycling stability. Herein, a novel lean-zinc anode is proposed, which is carried out by annealing LaZn bimetallic organic framework to form metal oxides and derived carbon. The anode has a low voltage hysteresis and low nucleation overpotential, further achieves high plating/stripping reversibility. The good electrochemical properties are attributed to the highly stable anode, which contains a large layer spacing La<sub>2</sub>O<sub>3</sub> with a low lattice mismatch degree to Zn<sup>0</sup>. This anode facilitates rapid ion transport and uniform Zn<sup>0</sup> deposition at the interface, which helps to alleviate the irreversible Zn<sup>2+</sup> loss. On this basis, the assembled batteries can maintain excellent stability for over 3000 cycles. This illustrates the promising application of rare-earth-based bimetallic-derived anodes in aqueous zinc-metal batteries.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 11","pages":"8476 - 8487"},"PeriodicalIF":11.0,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469362","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-11DOI: 10.1007/s12598-025-03513-6
Xiao-Qing Pei, Li-Na Liu, Chun Li, Hai Lin, Sha-Sha Li, Wei-Ling Yang, Fan-Ming Zeng
Eu3+-activated red phosphors are popular for their classic 5D0 → 7FJ (J = 0, 1, 2, 3, 4) emission characteristics. However, the weak emission of the 5D0 →7F4 transition and the concentration quenching caused by energy migration have become the main obstacles to achieving strong far-red emission. Herein, we report a novel Ba3Sc1-x(BO2)9: xEu3+ phosphor that simultaneously enhances 5D0 → 7F4 emission and suppresses quenching through size confinement and low phonon energy. A Sr2+ → Ba2+ substitution strategy optimizes luminescence, achieving 1.56-fold intensity enhancement and improved quantum efficiency (IQE: 83% → 92%; EQE: 38% → 40%). The improvement mechanism was revealed through the local coordination distortion of Eu3+ and the change of the band gap when Sr and Ba coexist. Structural analysis reveals enhanced thermal stability (423 K: 86% → 97%; 483 K: 78% → 95%) originates from increased lattice rigidity. Abnormal thermal quenching (303–363 K) is white light-emitting diodes (WLEDs) device prepared based on Ba2.80Sr0.20Eu(BO2)9 phosphor shows a color temperature of 4532 K and a color rendering index of 91.6. This article also explores three applications of plant growth, latent fingerprint visualization, and anti- counterfeiting QR code. This finding provides a reference for further exploring the design of high concentration quenching and efficient far-red emitting phosphors.
{"title":"The synergy of structural constraints and lattice engineering endows Ba2.80Sr0.20Sc(BO2)9: Eu3+ phosphor with a concentration-free quenching effect and far-red emission","authors":"Xiao-Qing Pei, Li-Na Liu, Chun Li, Hai Lin, Sha-Sha Li, Wei-Ling Yang, Fan-Ming Zeng","doi":"10.1007/s12598-025-03513-6","DOIUrl":"10.1007/s12598-025-03513-6","url":null,"abstract":"<div><p>Eu<sup>3+</sup>-activated red phosphors are popular for their classic <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub><i>J</i></sub> (<i>J</i> = 0, 1, 2, 3, 4) emission characteristics. However, the weak emission of the <sup>5</sup>D<sub>0</sub> →<sup>7</sup>F<sub>4</sub> transition and the concentration quenching caused by energy migration have become the main obstacles to achieving strong far-red emission. Herein, we report a novel Ba<sub>3</sub>Sc<sub>1-<i>x</i></sub>(BO<sub>2</sub>)<sub>9</sub>: <i>x</i>Eu<sup>3+</sup> phosphor that simultaneously enhances <sup>5</sup>D<sub>0</sub> → <sup>7</sup>F<sub>4</sub> emission and suppresses quenching through size confinement and low phonon energy. A Sr<sup>2+</sup> → Ba<sup>2+</sup> substitution strategy optimizes luminescence, achieving 1.56-fold intensity enhancement and improved quantum efficiency (IQE: 83% → 92%; EQE: 38% → 40%). The improvement mechanism was revealed through the local coordination distortion of Eu<sup>3+</sup> and the change of the band gap when Sr and Ba coexist. Structural analysis reveals enhanced thermal stability (423 K: 86% → 97%; 483 K: 78% → 95%) originates from increased lattice rigidity. Abnormal thermal quenching (303–363 K) is white light-emitting diodes (WLEDs) device prepared based on Ba<sub>2.80</sub>Sr<sub>0.20</sub>Eu(BO<sub>2</sub>)<sub>9</sub> phosphor shows a color temperature of 4532 K and a color rendering index of 91.6. This article also explores three applications of plant growth, latent fingerprint visualization, and anti- counterfeiting QR code. This finding provides a reference for further exploring the design of high concentration quenching and efficient far-red emitting phosphors.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 11","pages":"8832 - 8848"},"PeriodicalIF":11.0,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469285","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lithium-sulfurized polyacrylonitrile (Li-SPAN) batteries are an advanced class of Li–S energy storage systems that effectively mitigate the polysulfide shuttle effect. However, conventional SPAN cathodes experience low active material retention (< 40 wt%) and sluggish electrochemical kinetics, which limit their practical application. To address these challenges, this study introduces a CoS2/NiS2@SeSPAN composite nanofiber membrane as a high-performance Li-SPAN cathode. The cathode was synthesized through electrospinning Co/Ni salts with PAN, followed by hydrothermal deposition of Ni-ZIF-67 and SeSx-assisted thermal treatment to form a CoS2/NiS2 heterostructure within the SeSPAN matrix. Experimental validation and density functional theory simulations confirmed that the cathode electrolyte interphase layer effectively encapsulated the active material, extending the solid-state reaction pathway. This hierarchical porous architecture enabled a high active material loading of 59 wt%, which considerably exceeds that of conventional SPAN-based cathodes. The three-dimensional interconnected fiber network maximized the exposure of the CoS2/NiS2 heterojunction, while the metal sulfides increased the conductivity to facilitate efficient electron and ion transport. The intrinsic electric field within the CoS2/NiS2 heterostructure further enhanced polysulfide adsorption and catalytic conversion, accelerating the electrochemical kinetics. As a result, the CoS2/NiS2@SeSPAN cathode had an initial discharge capacity of 678 mAh g−1 at 0.2C, maintaining 634 mAh g−1 at 0.5C. Remarkably, the battery maintained 98.2% of its capacity after 800 cycles, highlighting its outstanding long-term cycling stability. The substantial potential of CoS2/NiS2@SeSPAN for high-performance Li-SPAN batteries and the critical role of heterostructure engineering in next-generation energy storage technologies are highlighted in this study.
Graphical abstract
锂硫化聚丙烯腈（Li-SPAN）电池是一种先进的锂硫电池储能系统，可有效缓解多硫化物穿梭效应。然而，传统的SPAN阴极具有活性物质保留率低（40% wt%）和电化学动力学缓慢的特点，这限制了其实际应用。为了解决这些挑战，本研究引入了CoS2/NiS2@SeSPAN复合纳米纤维膜作为高性能Li-SPAN阴极。采用PAN静电纺丝Co/Ni盐合成阴极，再通过水热沉积Ni- zif -67和sesx辅助热处理，在SeSPAN基体内形成CoS2/NiS2异质结构。实验验证和密度泛函理论模拟证实，阴极电解质间相层有效封装了活性物质，延长了固态反应途径。这种分层多孔结构使活性材料负载高达59%，大大超过了传统的基于span的阴极。三维互连光纤网络最大限度地暴露了CoS2/NiS2异质结，而金属硫化物增加了电导率，促进了电子和离子的有效传递。CoS2/NiS2异质结构内的本征电场进一步增强了多硫化物的吸附和催化转化，加速了电化学动力学。结果表明，CoS2/NiS2@SeSPAN阴极在0.2C时的初始放电容量为678 mAh g−1，在0.5C时保持634 mAh g−1。值得注意的是，电池在800次循环后保持了98.2%的容量，突出了其出色的长期循环稳定性。本研究强调了CoS2/NiS2@SeSPAN在高性能Li-SPAN电池中的巨大潜力，以及异质结构工程在下一代储能技术中的关键作用。图形抽象
{"title":"Enhanced performance of lithium-sulfurized polyacrylonitrile batteries via multifunctional CoS2/NiS2 heterostructures and intrinsic electric fields","authors":"Hao Liu, Hai-Hui Liu, Qiang Xu, Xiao-Dong Shao, Xiao Zhang, Shu-Liang Lv, Zhi-Jia Zhang, Chang Ma, Yan-Mei Jin","doi":"10.1007/s12598-025-03525-2","DOIUrl":"10.1007/s12598-025-03525-2","url":null,"abstract":"<div><p>Lithium-sulfurized polyacrylonitrile (Li-SPAN) batteries are an advanced class of Li–S energy storage systems that effectively mitigate the polysulfide shuttle effect. However, conventional SPAN cathodes experience low active material retention (< 40 wt%) and sluggish electrochemical kinetics, which limit their practical application. To address these challenges, this study introduces a CoS<sub>2</sub>/NiS<sub>2</sub>@SeSPAN composite nanofiber membrane as a high-performance Li-SPAN cathode. The cathode was synthesized through electrospinning Co/Ni salts with PAN, followed by hydrothermal deposition of Ni-ZIF-67 and SeS<sub><i>x</i></sub>-assisted thermal treatment to form a CoS<sub>2</sub>/NiS<sub>2</sub> heterostructure within the SeSPAN matrix. Experimental validation and density functional theory simulations confirmed that the cathode electrolyte interphase layer effectively encapsulated the active material, extending the solid-state reaction pathway. This hierarchical porous architecture enabled a high active material loading of 59 wt%, which considerably exceeds that of conventional SPAN-based cathodes. The three-dimensional interconnected fiber network maximized the exposure of the CoS<sub>2</sub>/NiS<sub>2</sub> heterojunction, while the metal sulfides increased the conductivity to facilitate efficient electron and ion transport. The intrinsic electric field within the CoS<sub>2</sub>/NiS<sub>2</sub> heterostructure further enhanced polysulfide adsorption and catalytic conversion, accelerating the electrochemical kinetics. As a result, the CoS<sub>2</sub>/NiS<sub>2</sub>@SeSPAN cathode had an initial discharge capacity of 678 mAh g<sup>−1</sup> at 0.2C, maintaining 634 mAh g<sup>−1</sup> at 0.5C. Remarkably, the battery maintained 98.2% of its capacity after 800 cycles, highlighting its outstanding long-term cycling stability. The substantial potential of CoS<sub>2</sub>/NiS<sub>2</sub>@SeSPAN for high-performance Li-SPAN batteries and the critical role of heterostructure engineering in next-generation energy storage technologies are highlighted in this study.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 11","pages":"8429 - 8443"},"PeriodicalIF":11.0,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-11DOI: 10.1007/s12598-025-03438-0
Xinliang Zhou, Wenjing He, Menghe Jia, Mengqi Ren, Xingrui Li, Ang Cao, Dong-sheng Li, Shuang Li, Naiteng Wu, Xianming Liu
The diverse valence and spatial structure endow vanadium oxides with significant potential in the field of aqueous zinc ion batteries (AZIBs). Although the conventional ion doping method mitigates the intrinsically sluggish kinetics, it exacerbates the erosion of Zn2+/H+ and free water within the lattice structure, leading to inferior structural stability and capacity fading. Herein, a synchronous dual-modification strategy is introduced to improve the electrochemical performance of the V6O13 cathode through an ingenious hydrolysis process involving K2Cr2O7. Experimental and calculated results demonstrate that the coating layer formed by chromium oxide supports the structural firmness and strengthens the interfacial chemistry, based on increased electrochemical activity by K+ intercalation. Consequently, the optimized sample delivers a capacity of 418 mAh g−1 at 0.1 A g−1, and excellent cyclic stability of 205 mAh g−1 after 6000 cycles at 10 A g−1. It is fully charged at a small current of 0.5 A g−1 to maintain a reversible capacity of 346 mAh g−1 after 72 h in an open circuit state, and there is no obvious capacity decay, highlighting the crucial protective effect of the inactive coating layer. This work presents a straightforward and reliable approach to effectively harmonize the relationship between activity and structural stability for advanced AZIBs cathode.
Graphical abstract
不同的价态和空间结构赋予了钒氧化物在水锌离子电池领域的巨大潜力。虽然传统的离子掺杂方法减轻了内在缓慢的动力学，但它加剧了晶格结构内Zn2+/H+和自由水的侵蚀，导致结构稳定性差和容量衰退。本文提出了一种同步双改性策略，通过巧妙的K2Cr2O7水解工艺来提高V6O13阴极的电化学性能。实验和计算结果表明，通过K+的插入，氧化铬形成的涂层支持了结构的坚固性，增强了界面化学性质。因此，优化后的样品在0.1 a g−1下提供418 mAh g−1的容量，在10 a g−1下循环6000次后提供205 mAh g−1的优异循环稳定性。在0.5 a g−1的小电流下充满电，在开路状态下72 h后仍保持346 mAh g−1的可逆容量，并且没有明显的容量衰减，突出了非活性涂层的关键保护作用。本文提出了一种简单可靠的方法来有效地协调先进azib阴极的活性与结构稳定性之间的关系。图形抽象
{"title":"Synchronous dual-modification strategy of K+ intercalation and CrOx coating enabling durable zinc-ion storage in vanadium oxide","authors":"Xinliang Zhou, Wenjing He, Menghe Jia, Mengqi Ren, Xingrui Li, Ang Cao, Dong-sheng Li, Shuang Li, Naiteng Wu, Xianming Liu","doi":"10.1007/s12598-025-03438-0","DOIUrl":"10.1007/s12598-025-03438-0","url":null,"abstract":"<div><p>The diverse valence and spatial structure endow vanadium oxides with significant potential in the field of aqueous zinc ion batteries (AZIBs). Although the conventional ion doping method mitigates the intrinsically sluggish kinetics, it exacerbates the erosion of Zn<sup>2+</sup>/H<sup>+</sup> and free water within the lattice structure, leading to inferior structural stability and capacity fading. Herein, a synchronous dual-modification strategy is introduced to improve the electrochemical performance of the V<sub>6</sub>O<sub>13</sub> cathode through an ingenious hydrolysis process involving K<sub>2</sub>Cr<sub>2</sub>O<sub>7</sub>. Experimental and calculated results demonstrate that the coating layer formed by chromium oxide supports the structural firmness and strengthens the interfacial chemistry, based on increased electrochemical activity by K<sup>+</sup> intercalation. Consequently, the optimized sample delivers a capacity of 418 mAh g<sup>−1</sup> at 0.1 A g<sup>−1</sup>, and excellent cyclic stability of 205 mAh g<sup>−1</sup> after 6000 cycles at 10 A g<sup>−1</sup>. It is fully charged at a small current of 0.5 A g<sup>−1</sup> to maintain a reversible capacity of 346 mAh g<sup>−1</sup> after 72 h in an open circuit state, and there is no obvious capacity decay, highlighting the crucial protective effect of the inactive coating layer. This work presents a straightforward and reliable approach to effectively harmonize the relationship between activity and structural stability for advanced AZIBs cathode.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 11","pages":"8525 - 8535"},"PeriodicalIF":11.0,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469222","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The field of disease smelling diagnosis has experienced a major breakthrough with the development of the electronic nose (E-nose) that utilizes thiol-capped gold nanoparticles (GNPs). This study focuses on overcoming the challenges of sensors to detect VOCs stably confounding with interferents of humidity and pressure, and clarifying their essential mechanism. An innovative and straightforward method for synthesizing GNPs and modifying their surface has been developed. This unique approach deviates from the conventional Brust method by completely removing any traces of tetraoctylammonium bromide (TOAB), ensuring reproducibility and simplicity of use. This modification enhances the sensor’s responsiveness to both polar and non-polar VOCs, as well as strengthen selectivity and anti-interferant capabilities. The mechanism of generating sensing cross-talk from TOAB residue is proposed through rigorous sensing experiments, X-ray photoelectron spectroscopy (XPS) results, and theoretical analysis. Thus, this study enhances the responsiveness of the sensor to both polar and non-polar VOCs, while also strengthening its selectivity and anti-interferent capabilities. This could potentially revolutionize the practical applications of E-nose in smelling diagnosis.
{"title":"Confronting pressure and humidity limitations in gold nanoparticle sensors array for enhancing electronic nose technology in real-world applications","authors":"Xue Jiang, Dan-Yao Qu, Jun-Nan Zhang, Viki Kloper, Ke-Fan Zhang, Guang-Jian Zhang, Lei Wang, Ming-Hu Pan, Quan-Min Guo, Li Chen, Wei-Tian Huang, Jian-Zhi Gao, Hossam Haick, Wei-Wei Wu","doi":"10.1007/s12598-025-03521-6","DOIUrl":"10.1007/s12598-025-03521-6","url":null,"abstract":"<div><p>The field of disease smelling diagnosis has experienced a major breakthrough with the development of the electronic nose (E-nose) that utilizes thiol-capped gold nanoparticles (GNPs). This study focuses on overcoming the challenges of sensors to detect VOCs stably confounding with interferents of humidity and pressure, and clarifying their essential mechanism. An innovative and straightforward method for synthesizing GNPs and modifying their surface has been developed. This unique approach deviates from the conventional Brust method by completely removing any traces of tetraoctylammonium bromide (TOAB), ensuring reproducibility and simplicity of use. This modification enhances the sensor’s responsiveness to both polar and non-polar VOCs, as well as strengthen selectivity and anti-interferant capabilities. The mechanism of generating sensing cross-talk from TOAB residue is proposed through rigorous sensing experiments, X-ray photoelectron spectroscopy (XPS) results, and theoretical analysis. Thus, this study enhances the responsiveness of the sensor to both polar and non-polar VOCs, while also strengthening its selectivity and anti-interferent capabilities. This could potentially revolutionize the practical applications of E-nose in smelling diagnosis.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 11","pages":"8789 - 8801"},"PeriodicalIF":11.0,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469366","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-08DOI: 10.1007/s12598-025-03479-5
Lu Liu, Qi An, Hai-Ye Zhu, Lei Qiu, Qing Liu, Hong Guo
The application of a piezoelectric field based on photocatalytic CO2 reduction reaction is a new strategy to overcome the rapid charge recombination. Herein, NaNbO3–Ag–AgBr heterojunction synergizing piezoelectric polarization and the localized surface plasmon resonance (LSPR) effect is designed. Under the simultaneous excitation of light and ultrasound, piezoelectric field drives the separation of directional charge, and Ag nanoparticles enhance the absorption of visible light and the injection of hot electrons. Meanwhile, the mechanism of carrier transport in heterojunction under the synergistic action of piezoelectric field and LSPR effect is also studied. The research shows the CO yield of NaNbO3-Ag-AgBr is 153.21 µmol g−1 and nearly 17 times higher than that of NaNbO3. In situ infrared spectroscopy, piezoresponse force microscopy (PFM) and Kelvin probe force microscopy (KPFM) results show that piezoelectric polarization reduces the Schottky barrier at the interface, promotes the transfer of hot electrons and inhibits the rapid bulk phase charge recombination. Thus, the piezoelectric photocatalytic system provides more profound insights for photocatalytic CO2RR.
Graphical abstract
基于光催化CO2还原反应的压电场的应用是克服快速电荷复合的新策略。本文设计了NaNbO3-Ag-AgBr异质结协同压电极化和局域表面等离子体共振（LSPR）效应。在光和超声的同时激发下，压电场驱动定向电荷的分离，Ag纳米粒子增强了对可见光的吸收和热电子的注入。同时，研究了压电场和LSPR效应协同作用下异质结中载流子输运的机理。研究表明，NaNbO3- ag - agbr的CO产率为153.21µmol g−1，是NaNbO3的近17倍。原位红外光谱、压电响应力显微镜（PFM）和开尔文探针力显微镜（KPFM）结果表明，压电极化降低了界面处的肖特基势垒，促进了热电子的转移，抑制了体相电荷的快速复合。因此，压电光催化系统为光催化CO2RR提供了更深刻的见解。图形抽象
{"title":"Synergistic effect of piezoelectricity and LSPR effect to boost efficient photocatalytic CO2RR","authors":"Lu Liu, Qi An, Hai-Ye Zhu, Lei Qiu, Qing Liu, Hong Guo","doi":"10.1007/s12598-025-03479-5","DOIUrl":"10.1007/s12598-025-03479-5","url":null,"abstract":"<div><p>The application of a piezoelectric field based on photocatalytic CO<sub>2</sub> reduction reaction is a new strategy to overcome the rapid charge recombination. Herein, NaNbO<sub>3</sub>–Ag–AgBr heterojunction synergizing piezoelectric polarization and the localized surface plasmon resonance (LSPR) effect is designed. Under the simultaneous excitation of light and ultrasound, piezoelectric field drives the separation of directional charge, and Ag nanoparticles enhance the absorption of visible light and the injection of hot electrons. Meanwhile, the mechanism of carrier transport in heterojunction under the synergistic action of piezoelectric field and LSPR effect is also studied. The research shows the CO yield of NaNbO<sub>3</sub>-Ag-AgBr is 153.21 µmol g<sup>−1</sup> and nearly 17 times higher than that of NaNbO<sub>3</sub>. In situ infrared spectroscopy, piezoresponse force microscopy (PFM) and Kelvin probe force microscopy (KPFM) results show that piezoelectric polarization reduces the Schottky barrier at the interface, promotes the transfer of hot electrons and inhibits the rapid bulk phase charge recombination. Thus, the piezoelectric photocatalytic system provides more profound insights for photocatalytic CO<sub>2</sub>RR.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 11","pages":"8667 - 8679"},"PeriodicalIF":11.0,"publicationDate":"2025-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469349","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-07DOI: 10.1007/s12598-025-03470-0
Jie Ma, Han Zhang, Bai Yang, Xu-Feng Li, Rong-Hai Yu, Xi-Xiang Zhang, Ran Li
It is crucial to improve the antioxidant ability and structural stability of high-performance rare earth (RE) metal nanoalloys for their potential wide applications. In this work, an efficient functional surface carbon modification method has been provided to fabricate high-stability RE alloy/carbon nanostructures as high-performance electromagnetic materials. Specifically, graphite-encapsulated Y2Co17 nanoalloys constructed with high-purity Y2Co17 nanoparticles entirely coated with dense ultrathin N-doped graphite carbon (NGC) nanolayers to form antioxidative Y2Co17@NGC nanostructures are fabricated by a precisely controlled calcium thermic reduction of well-designed crystalline CoO-Co-Y2O3/C precursors. Another similarly structured Y2Co17@defect-rich graphite carbon (DGC) nanostructure is obtained by replacing NGC in Y2Co17@NGC with DGC by the same calcium thermic reduction but adjusting the carbon sources in the precursors. The excellent oxidation resistance and stable structures for these graphite-encapsulated Y2Co17 nanostructures facilitate the formation of ultrapure magnetic planar-anisotropy Y2Co17 phase, which results in their good soft magnetism with ultrahigh saturation magnetization values of 112.1–113.3 A m2 kg−1. Y2Co17@NGC nanostructures exhibit a favorable C band microwave absorption with a high minimum reflection loss (RLmin) value up to −80.16 dB at 4.30 GHz with a 4.03-mm-thick and Y2Co17@DGC nanostructures show a typical Ku band absorption with a RLmin value of −52.59 dB at 16.71 GHz with a 1.34 mm thickness. The good switchable electromagnetic properties of these graphite-encapsulated Y2Co17 nanostructures are demonstrated to arise from their different surface carbon defects. This work provides a surface carbon treatment strategy for fundamentally improving the oxidation resistance and structural stability of the easily oxidized RE nanoalloys and further constructing novelly structured functionalized RE alloy/carbon nanostructures.
{"title":"Ultrathin graphite-encapsulated Y2Co17 nanostructures with good structural stability and switchable microwave absorption","authors":"Jie Ma, Han Zhang, Bai Yang, Xu-Feng Li, Rong-Hai Yu, Xi-Xiang Zhang, Ran Li","doi":"10.1007/s12598-025-03470-0","DOIUrl":"10.1007/s12598-025-03470-0","url":null,"abstract":"<p>It is crucial to improve the antioxidant ability and structural stability of high-performance rare earth (RE) metal nanoalloys for their potential wide applications. In this work, an efficient functional surface carbon modification method has been provided to fabricate high-stability RE alloy/carbon nanostructures as high-performance electromagnetic materials. Specifically, graphite-encapsulated Y<sub>2</sub>Co<sub>17</sub> nanoalloys constructed with high-purity Y<sub>2</sub>Co<sub>17</sub> nanoparticles entirely coated with dense ultrathin N-doped graphite carbon (NGC) nanolayers to form antioxidative Y<sub>2</sub>Co<sub>17</sub>@NGC nanostructures are fabricated by a precisely controlled calcium thermic reduction of well-designed crystalline CoO-Co-Y<sub>2</sub>O<sub>3</sub>/C precursors. Another similarly structured Y<sub>2</sub>Co<sub>17</sub>@defect-rich graphite carbon (DGC) nanostructure is obtained by replacing NGC in Y<sub>2</sub>Co<sub>17</sub>@NGC with DGC by the same calcium thermic reduction but adjusting the carbon sources in the precursors. The excellent oxidation resistance and stable structures for these graphite-encapsulated Y<sub>2</sub>Co<sub>17</sub> nanostructures facilitate the formation of ultrapure magnetic planar-anisotropy Y<sub>2</sub>Co<sub>17</sub> phase, which results in their good soft magnetism with ultrahigh saturation magnetization values of 112.1–113.3 A m<sup>2</sup> kg<sup>−1</sup>. Y<sub>2</sub>Co<sub>17</sub>@NGC nanostructures exhibit a favorable C band microwave absorption with a high minimum reflection loss (<i>RL</i><sub>min</sub>) value up to −80.16 dB at 4.30 GHz with a 4.03-mm-thick and Y<sub>2</sub>Co<sub>17</sub>@DGC nanostructures show a typical Ku band absorption with a <i>RL</i><sub>min</sub> value of −52.59 dB at 16.71 GHz with a 1.34 mm thickness. The good switchable electromagnetic properties of these graphite-encapsulated Y<sub>2</sub>Co<sub>17</sub> nanostructures are demonstrated to arise from their different surface carbon defects. This work provides a surface carbon treatment strategy for fundamentally improving the oxidation resistance and structural stability of the easily oxidized RE nanoalloys and further constructing novelly structured functionalized RE alloy/carbon nanostructures.</p>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 11","pages":"8863 - 8883"},"PeriodicalIF":11.0,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469310","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-07DOI: 10.1007/s12598-025-03469-7
Ling-Jun Li, Pan-Qing Wang, Niu Zhao, Xiao-Xue Tan, Ke-Chen Liu, Yu-Heng Wang, Tian-Xiang Ning, Lei Tan, Kang-Yu Zou
The introduction of Co and Mn is regarded as an effective strategy to enhance the cycling stability of LiNixM1−xO2 (x ≥ 0.9) cathodes. However, since the delithiation degrees of respective LiNixM1−xO2 cathodes measured at the fixed cutoff voltage are different, it is necessary to design the appropriate systems to evaluate the specific roles of Co and Mn elements in cyclic stability. Therefore, three LiNixM1−xO2 cathodes, including LiNiO2 (LNO), LiNi0.9Co0.1O2 (NC91), and LiNi0.9Mn0.1O2 (NM91) have been chosen for systematically investigating the effect of Co and Mn on cycle durability, which are controlled at the same delithiation state during the electrochemical processes. It is found that the order of cycling stability among the three cathodes is NC91 > LNO > NM91 in the 80 mol% delithiation state. Co substitution suppresses lattice distortion, mitigates transition metal dissolution and structural degradation, further enhancing structural/interface stability, which brings out outstanding cycle stability of NC91. Notably, cycling stability is mainly determined by interfacial stability. Although NM91 exhibits superior structural stability compared to NC91, the worst cycling performance of NM91 is presented, which is attributed to the deteriorated interfacial stability resulting from the Jahn–Teller from Mn3+. This study elucidates the effect of Co and Mn on the cycle stability in LiNixM1−xO2 cathodes under the same delithiation state, thereby delivering reasonable guidance for designing advanced ultrahigh-nickel cathodes.
{"title":"Insights into effects of Co and Mn elements on the cycle stability of ultrahigh-nickel cathodes charged at same delithiation state","authors":"Ling-Jun Li, Pan-Qing Wang, Niu Zhao, Xiao-Xue Tan, Ke-Chen Liu, Yu-Heng Wang, Tian-Xiang Ning, Lei Tan, Kang-Yu Zou","doi":"10.1007/s12598-025-03469-7","DOIUrl":"10.1007/s12598-025-03469-7","url":null,"abstract":"<div><p>The introduction of Co and Mn is regarded as an effective strategy to enhance the cycling stability of LiNi<sub><i>x</i></sub>M<sub>1−<i>x</i></sub>O<sub>2</sub> (<i>x</i> ≥ 0.9) cathodes. However, since the delithiation degrees of respective LiNi<sub><i>x</i></sub>M<sub>1−<i>x</i></sub>O<sub>2</sub> cathodes measured at the fixed cutoff voltage are different, it is necessary to design the appropriate systems to evaluate the specific roles of Co and Mn elements in cyclic stability. Therefore, three LiNi<sub><i>x</i></sub>M<sub>1−<i>x</i></sub>O<sub>2</sub> cathodes, including LiNiO<sub>2</sub> (LNO), LiNi<sub>0.9</sub>Co<sub>0.1</sub>O<sub>2</sub> (NC91), and LiNi<sub>0.9</sub>Mn<sub>0.1</sub>O<sub>2</sub> (NM91) have been chosen for systematically investigating the effect of Co and Mn on cycle durability, which are controlled at the same delithiation state during the electrochemical processes. It is found that the order of cycling stability among the three cathodes is NC91 > LNO > NM91 in the 80 mol% delithiation state. Co substitution suppresses lattice distortion, mitigates transition metal dissolution and structural degradation, further enhancing structural/interface stability, which brings out outstanding cycle stability of NC91. Notably, cycling stability is mainly determined by interfacial stability. Although NM91 exhibits superior structural stability compared to NC91, the worst cycling performance of NM91 is presented, which is attributed to the deteriorated interfacial stability resulting from the Jahn–Teller from Mn<sup>3+</sup>. This study elucidates the effect of Co and Mn on the cycle stability in LiNi<sub><i>x</i></sub>M<sub>1−<i>x</i></sub>O<sub>2</sub> cathodes under the same delithiation state, thereby delivering reasonable guidance for designing advanced ultrahigh-nickel cathodes.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 11","pages":"8404 - 8415"},"PeriodicalIF":11.0,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-07DOI: 10.1007/s12598-025-03506-5
Yongkang Zhang, Chuanyin Xiong, Qiancheng Xiong, Qing Xiong, Mengjie Zhao, Bo Wang, Mengxia Shen, Qiusheng Zhou, Yonghao Ni
Increasing the interlayer spacing of metal–organic frameworks (MOFs) through multi-metal ion doping has emerged as an effective strategy to enhance electrolyte-ion transport within the MOF unit cell, enabling the design of nickel-based MOF materials with high capacity and energy density. In this work, a series of NiCo-MOF-x (x = 1–5) were synthesized by incorporating Co2+ ions into Ni-MOF. The introduction of Co2+ modulated the unit cell structure and governed the stacking configuration of MOF nanosheets. At an optimal Ni/Co molar ratio of 4:1, the NiCo-MOF-2 sample demonstrates superior electrochemical performance, delivering a specific capacitance of 1238.6 F g−1 at 0.2 A g−1. Subsequently, NiCo-MOF-2 was grown in situ on carbonized wood (CW) to fabricate a NiCo-MOF@CW composite, which exhibits an areal capacitance of 4960 mF cm−2 at 0.6 mA cm−2. An asymmetric supercapacitor (NiCo-MOF@CW//AC) was assembled using NiCo-MOF@CW as the positive electrode and activated carbon (AC) as the negative electrode. The device achieves an areal energy density of 1.88 mWh cm−2 at a power density of 2.88 mW cm−2 (1 mA cm−2), with 83.6% capacitance retention after 2000 charge–discharge cycles. Notably, two serially connected NiCo-MOF@CW//AC devices successfully illuminate a red LED (operating voltage: 1.6–1.75 V) for 20 min. The multi-metal ion doping strategy combined with binder-free, self-supporting electrode architecture presents a novel approach for synthesizing high-performance energy storage materials.
Graphical abstract
通过多金属离子掺杂增加金属有机骨架（MOF）的层间间距已成为提高MOF单元电池内电解质离子传输的有效策略，使镍基MOF材料具有高容量和高能量密度。本文通过将Co2+离子掺入Ni-MOF中，合成了一系列NiCo-MOF-x （x = 1-5）。Co2+的引入调节了MOF纳米片的单胞结构，控制了MOF纳米片的堆叠构型。在最佳的Ni/Co摩尔比为4:1时，NiCo-MOF-2样品表现出优异的电化学性能，在0.2 a g−1时提供了1238.6 F g−1的比电容。随后，NiCo-MOF-2在碳化木材（CW）上原位生长，制备了NiCo-MOF@CW复合材料，该复合材料在0.6 mA cm -2下的面电容为4960 mF cm -2。以NiCo-MOF@CW为正极，活性炭（AC）为负极，组装了一个不对称超级电容器（NiCo-MOF@CW//AC）。该器件在2.88 mW cm - 2 （1 mA cm - 2）的功率密度下实现了1.88 mWh cm - 2的面能量密度，2000次充放电循环后电容保持率为83.6%。值得注意的是，两个串联的NiCo-MOF@CW//AC器件成功地照亮了一个红色LED（工作电压：1.6-1.75 V） 20分钟。多金属离子掺杂策略与无粘结剂、自支撑电极结构相结合，为合成高性能储能材料提供了一种新的途径。图形抽象
{"title":"Ni, Co bimetallic MOF of dual-controlled by micro-morphology and unit cell structure for biomass-based self-supporting energy storage device","authors":"Yongkang Zhang, Chuanyin Xiong, Qiancheng Xiong, Qing Xiong, Mengjie Zhao, Bo Wang, Mengxia Shen, Qiusheng Zhou, Yonghao Ni","doi":"10.1007/s12598-025-03506-5","DOIUrl":"10.1007/s12598-025-03506-5","url":null,"abstract":"<div><p>Increasing the interlayer spacing of metal–organic frameworks (MOFs) through multi-metal ion doping has emerged as an effective strategy to enhance electrolyte-ion transport within the MOF unit cell, enabling the design of nickel-based MOF materials with high capacity and energy density. In this work, a series of NiCo-MOF-<i>x</i> (<i>x</i> = 1–5) were synthesized by incorporating Co<sup>2+</sup> ions into Ni-MOF. The introduction of Co<sup>2+</sup> modulated the unit cell structure and governed the stacking configuration of MOF nanosheets. At an optimal Ni/Co molar ratio of 4:1, the NiCo-MOF-2 sample demonstrates superior electrochemical performance, delivering a specific capacitance of 1238.6 F g<sup>−1</sup> at 0.2 A g<sup>−1</sup>. Subsequently, NiCo-MOF-2 was grown in situ on carbonized wood (CW) to fabricate a NiCo-MOF@CW composite, which exhibits an areal capacitance of 4960 mF cm<sup>−2</sup> at 0.6 mA cm<sup>−2</sup>. An asymmetric supercapacitor (NiCo-MOF@CW//AC) was assembled using NiCo-MOF@CW as the positive electrode and activated carbon (AC) as the negative electrode. The device achieves an areal energy density of 1.88 mWh cm<sup>−2</sup> at a power density of 2.88 mW cm<sup>−2</sup> (1 mA cm<sup>−2</sup>), with 83.6% capacitance retention after 2000 charge–discharge cycles. Notably, two serially connected NiCo-MOF@CW//AC devices successfully illuminate a red LED (operating voltage: 1.6–1.75 V) for 20 min. The multi-metal ion doping strategy combined with binder-free, self-supporting electrode architecture presents a novel approach for synthesizing high-performance energy storage materials.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 11","pages":"8536 - 8547"},"PeriodicalIF":11.0,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469237","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The limited biocompatibility, high preparation costs, and non-reusability of noble metal surface-enhanced Raman scattering (SERS) substrates impede their large-scale application. Consequently, the development of non-noble metal substrates with excellent SERS performance remains a priority. Although quasi-metal SERS substrates represented by carbides have demonstrated remarkable SERS performance, their enhancement capabilities still require further improvement. In this study, the SERS performance of tungsten carbide (WC) substrates was enhanced by doping with tantalum (Ta) elements. The WC doped with 2 wt% Ta (WC-2T) exhibited a superior enhancement effect for probe molecules like rhodamine 6G (R6G), crystal violet, methylene blue, and malachite green compared to the undoped WC (WC-0T), with the enhancement factor for R6G molecules more than doubling. The excellent SERS performance of WC-2T can be attributed to its higher adsorption energy for probe molecules and a more efficient charge transfer process between the probe molecules. Additionally, the SERS effect of WC-2T remained robust even when exposed to strong acids and alkalis. This study successfully enhanced the SERS activity of WC via doping modification, providing a strategy for optimizing carbide quasi-metal SERS-active materials.
{"title":"Tantalum-doped tungsten carbide nanostructures with efficient charge transfer for superior SERS performance","authors":"Meng-En Hu, Zhen Wang, Xin-Can Gao, Xian Dang, Cheng-Wan Yang, Ke-Wei Li, Di-Long Liu, Xiao-Ye Hu, Yue Li, Ke Li, Zhu-Lin Huang, Guo-Wen Meng","doi":"10.1007/s12598-025-03522-5","DOIUrl":"10.1007/s12598-025-03522-5","url":null,"abstract":"<div><p>The limited biocompatibility, high preparation costs, and non-reusability of noble metal surface-enhanced Raman scattering (SERS) substrates impede their large-scale application. Consequently, the development of non-noble metal substrates with excellent SERS performance remains a priority. Although quasi-metal SERS substrates represented by carbides have demonstrated remarkable SERS performance, their enhancement capabilities still require further improvement. In this study, the SERS performance of tungsten carbide (WC) substrates was enhanced by doping with tantalum (Ta) elements. The WC doped with 2 wt% Ta (WC-2T) exhibited a superior enhancement effect for probe molecules like rhodamine 6G (R6G), crystal violet, methylene blue, and malachite green compared to the undoped WC (WC-0T), with the enhancement factor for R6G molecules more than doubling. The excellent SERS performance of WC-2T can be attributed to its higher adsorption energy for probe molecules and a more efficient charge transfer process between the probe molecules. Additionally, the SERS effect of WC-2T remained robust even when exposed to strong acids and alkalis. This study successfully enhanced the SERS activity of WC via doping modification, providing a strategy for optimizing carbide quasi-metal SERS-active materials.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 11","pages":"8802 - 8812"},"PeriodicalIF":11.0,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469284","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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