Pub Date : 2025-08-18DOI: 10.1007/s12598-025-03534-1
Chen-Chang-Xiang Wang, Duo Xu, Xiao-Qi Sun, Qiang-Li Lv, Hao-Ran Guo, Xiao-Hui Chen, Hua Wang, Kong-Zhai Li, Zhi-Shan Li
Exploring earth-abundant, highly effective, and stable electrocatalysts for overall water and urea electrolysis is urgent and essential for developing hydrogen energy technology. Herein, a simple interface engineering is used to fabricate an amorphous/crystalline Rh(OH)3/NiMoO4 electrocatalyst. It exhibits an impressive trifunctional catalyst, with low overpotentials of 414 and 150 mV at 500 mA cm−2 for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), and with a low voltage of 1.457 V for urea oxidation reaction (UOR) at 500 mA cm−2. The outstanding OER, HER, and UOR activities are attributed to the unique amorphous/crystalline heterostructure of Rh(OH)3/NiMoO4, which possesses special hydrophilic features that accelerate mass transfer and provide abundant exposed active sites and appropriate defects. In situ Raman spectra reveal that the incorporation of amorphous Rh(OH)3 facilitates the catalyst reconstruction. The two-electrode electrolyzer needs cell voltages of only 1.93 and 1.59 V to achieve a current density of 500 mA cm−2 and remarkable durability for more than 50 h at 500 mA cm−2 for overall water and urea-assisted splitting. This work provides a new idea for using amorphous/crystalline heterostructure to design electrocatalysts for overall water and urea electrolysis at industrial current densities.
Graphical abstract
探索地球资源丰富、高效稳定的水、尿素整体电解电催化剂是发展氢能技术的迫切需要。本文采用简单的界面工程方法制备了非晶/结晶Rh(OH)3/NiMoO4电催化剂。在500 mA cm−2下，析氧反应（OER）和析氢反应（HER）的过电位分别为414和150 mV；在500 mA cm−2下，尿素氧化反应（UOR）的过电位为1.457 V。优异的OER、HER和UOR活性归因于Rh(OH)3/NiMoO4独特的非晶/晶体异质结构，它具有特殊的亲水特性，可以加速传质，并提供丰富的暴露活性位点和适当的缺陷。原位拉曼光谱显示，非晶态Rh(OH)3的加入促进了催化剂的重构。双电极电解槽只需要1.93和1.59 V的电池电压，以实现500 mA cm - 2的电流密度和500 mA cm - 2下超过50小时的显着耐久性，用于整体水和尿素辅助分裂。本研究为利用非晶/晶体异质结构设计工业电流密度下的全水和尿素电解电催化剂提供了新的思路。图形抽象
{"title":"Amorphous/crystalline interface-triggered electron redistribution on Rh(OH)3/NiMoO4 for high-efficient overall water and urea electrolysis at industrial current densities","authors":"Chen-Chang-Xiang Wang, Duo Xu, Xiao-Qi Sun, Qiang-Li Lv, Hao-Ran Guo, Xiao-Hui Chen, Hua Wang, Kong-Zhai Li, Zhi-Shan Li","doi":"10.1007/s12598-025-03534-1","DOIUrl":"10.1007/s12598-025-03534-1","url":null,"abstract":"<div><p>Exploring earth-abundant, highly effective, and stable electrocatalysts for overall water and urea electrolysis is urgent and essential for developing hydrogen energy technology. Herein, a simple interface engineering is used to fabricate an amorphous/crystalline Rh(OH)<sub>3</sub>/NiMoO<sub>4</sub> electrocatalyst. It exhibits an impressive trifunctional catalyst, with low overpotentials of 414 and 150 mV at 500 mA cm<sup>−2</sup> for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), and with a low voltage of 1.457 V for urea oxidation reaction (UOR) at 500 mA cm<sup>−2</sup>. The outstanding OER, HER, and UOR activities are attributed to the unique amorphous/crystalline heterostructure of Rh(OH)<sub>3</sub>/NiMoO<sub>4</sub>, which possesses special hydrophilic features that accelerate mass transfer and provide abundant exposed active sites and appropriate defects. In situ Raman spectra reveal that the incorporation of amorphous Rh(OH)<sub>3</sub> facilitates the catalyst reconstruction. The two-electrode electrolyzer needs cell voltages of only 1.93 and 1.59 V to achieve a current density of 500 mA cm<sup>−2</sup> and remarkable durability for more than 50 h at 500 mA cm<sup>−2</sup> for overall water and urea-assisted splitting. This work provides a new idea for using amorphous/crystalline heterostructure to design electrocatalysts for overall water and urea electrolysis at industrial current densities.</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":"8577 - 8592"},"PeriodicalIF":11.0,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469257","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 : 2025-08-18DOI: 10.1007/s12598-025-03540-3
Zhengtao Xu, Chen Wang, Yao Ying, Liang Qiao, Jingwu Zheng, Juan Li, Shenglei Che, Jing Yu
Metal ion interference therapy (MIIT) employs biocatalytic interference mechanisms, such as Fenton-like reactions and oxidative stress amplification, to disrupt tumor redox homeostasis. Notably, this approach demonstrates excellent therapeutic efficacy and safety. However, biocatalytic efficiency is often hampered by the strong antioxidant system of tumor cells and the catalytic efficiency of metal ions. To address this limitation, in this study, we engineered copper–zinc bimetallic sulfide nanoparticles (CZS NPs) to implement a dual-action therapeutic strategy. The Zn2+ within CZS NPs exploit the enzymatic activity of nicotinamide adenine dinucleotide phosphate (NADPH) oxidase (NOX) to amplify tumor oxidative stress, while Cu+ boosts Fenton-like catalytic activity, intensifying oxidative stress damage. These components synergistically drive the NOX/superoxide dismutase (SOD)/peroxidase (POD) nanocascade reaction, achieving the combinatorial activation of three cell death pathways: ferroptosis, cuproptosis, and apoptosis. The synthesized CZS NPs achieve remarkable therapeutic efficacy in tumor cells through a fully optimized MIIT. These findings suggest a potential strategy for MIIT-mediated biocatalytic tumor therapy.
{"title":"Dual-pronged metal ion interference therapy: copper–zinc bimetallic sulfide nanoparticles synergistically disrupt redox homeostasis for enhanced tumor treatment","authors":"Zhengtao Xu, Chen Wang, Yao Ying, Liang Qiao, Jingwu Zheng, Juan Li, Shenglei Che, Jing Yu","doi":"10.1007/s12598-025-03540-3","DOIUrl":"10.1007/s12598-025-03540-3","url":null,"abstract":"<div><p>Metal ion interference therapy (MIIT) employs biocatalytic interference mechanisms, such as Fenton-like reactions and oxidative stress amplification, to disrupt tumor redox homeostasis. Notably, this approach demonstrates excellent therapeutic efficacy and safety. However, biocatalytic efficiency is often hampered by the strong antioxidant system of tumor cells and the catalytic efficiency of metal ions. To address this limitation, in this study, we engineered copper–zinc bimetallic sulfide nanoparticles (CZS NPs) to implement a dual-action therapeutic strategy. The Zn<sup>2+</sup> within CZS NPs exploit the enzymatic activity of nicotinamide adenine dinucleotide phosphate (NADPH) oxidase (NOX) to amplify tumor oxidative stress, while Cu<sup>+</sup> boosts Fenton-like catalytic activity, intensifying oxidative stress damage. These components synergistically drive the NOX/superoxide dismutase (SOD)/peroxidase (POD) nanocascade reaction, achieving the combinatorial activation of three cell death pathways: ferroptosis, cuproptosis, and apoptosis. The synthesized CZS NPs achieve remarkable therapeutic efficacy in tumor cells through a fully optimized MIIT. These findings suggest a potential strategy for MIIT-mediated biocatalytic tumor therapy.</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":"8744 - 8756"},"PeriodicalIF":11.0,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469379","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 : 2025-08-18DOI: 10.1007/s12598-025-03533-2
Zhenwei Chao, Yan Dong, Xuerong Zheng, Xu Chen, Yida Deng
Peroxymonosulphate (PMS) activation via non-radical pathways has emerged as a promising pollutant degradation method owing to its highly selective oxidation of organic pollutants and high tolerance to water matrices. However, the mechanism underlying this non-radical process remains unclear. Herein, we reveal a mechanism for the transformation phenomenon between singlet oxygen (1O2) and high-valence Mn species in a spinel MnCo2O4.5/PMS system, which aggressively enhances the degradation rate of organic contaminants and dramatically decreases PMS usage. The mechanism of the transformation is due to the increased valence of Mn via the introduction of Co into spinel Mn3O4. These results highlight the mechanism of non-radical pathways in water treatment and provide a new strategy for designing catalysts for PMS activation.
{"title":"Boosting peroxymonosulphate activation by a pathway transformation mechanism: the dominant role of high-valent Mn species","authors":"Zhenwei Chao, Yan Dong, Xuerong Zheng, Xu Chen, Yida Deng","doi":"10.1007/s12598-025-03533-2","DOIUrl":"10.1007/s12598-025-03533-2","url":null,"abstract":"<p>Peroxymonosulphate (PMS) activation via non-radical pathways has emerged as a promising pollutant degradation method owing to its highly selective oxidation of organic pollutants and high tolerance to water matrices. However, the mechanism underlying this non-radical process remains unclear. Herein, we reveal a mechanism for the transformation phenomenon between singlet oxygen (<sup>1</sup>O<sub>2</sub>) and high-valence Mn species in a spinel MnCo<sub>2</sub>O<sub>4.5</sub>/PMS system, which aggressively enhances the degradation rate of organic contaminants and dramatically decreases PMS usage. The mechanism of the transformation is due to the increased valence of Mn via the introduction of Co into spinel Mn<sub>3</sub>O<sub>4</sub>. These results highlight the mechanism of non-radical pathways in water treatment and provide a new strategy for designing catalysts for PMS activation.</p>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 11","pages":"8691 - 8700"},"PeriodicalIF":11.0,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469290","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 : 2025-08-16DOI: 10.1007/s12598-025-03493-7
Xin-Rui Li, Zhi-Ying Wang, Shao-Wen Cao, Cheng-Xiao Zhao, Xiao-Fei Yang
Two-dimensional (2D) nanomaterials have emerged as highly efficient co-catalysts in the field of photocatalytic water splitting, due to their distinct physicochemical features. Herein, a novel 2D nanomaterial, ultrathin FePS3 nanosheets, is prepared by an ultrasound-assisted delamination process in organic solvent, followed by the in situ construction of CdS nanosheet/FePS3 nanosheet hierarchical heterojunction via the solvothermal method. It is notable that the designed CdS/FePS3 photocatalyst demonstrates an efficient hydrogen-producing performance up to 7565 μmol g−1 h−1 for hydrogen production reaction (HER) under visible-light illumination, which is almost 8 times higher than that of bulk CdS. The enhancement in HER performance is attributed to the synergy of accelerated interfacial charge transfer, high specific surface area, and extended visible-light absorption originating from as-synthesized conductive few-layer FePS3 nanosheets. Furthermore, the charge transfer pathway of the constructed 2D CdS/2D FePS3 heterojunction is unveiled by in situ atomic force microscopy with Kelvin probe force microscopy (AFM-KPFM), in situ X-ray photoelectron spectroscopy (XPS), and photoelectrochemical measurements. This study offers new insight into the rational design and controllable synthesis of FePS3-based composite photocatalytic systems for efficient photocatalytic hydrogen production.
{"title":"Rationally designed hierarchical 2D CdS/2D FePS3 heterojunctions for boosted photocatalytic hydrogen production","authors":"Xin-Rui Li, Zhi-Ying Wang, Shao-Wen Cao, Cheng-Xiao Zhao, Xiao-Fei Yang","doi":"10.1007/s12598-025-03493-7","DOIUrl":"10.1007/s12598-025-03493-7","url":null,"abstract":"<div><p>Two-dimensional (2D) nanomaterials have emerged as highly efficient co-catalysts in the field of photocatalytic water splitting, due to their distinct physicochemical features. Herein, a novel 2D nanomaterial, ultrathin FePS<sub>3</sub> nanosheets, is prepared by an ultrasound-assisted delamination process in organic solvent, followed by the in situ construction of CdS nanosheet/FePS<sub>3</sub> nanosheet hierarchical heterojunction via the solvothermal method. It is notable that the designed CdS/FePS<sub>3</sub> photocatalyst demonstrates an efficient hydrogen-producing performance up to 7565 μmol g<sup>−1</sup> h<sup>−1</sup> for hydrogen production reaction (HER) under visible-light illumination, which is almost 8 times higher than that of bulk CdS. The enhancement in HER performance is attributed to the synergy of accelerated interfacial charge transfer, high specific surface area, and extended visible-light absorption originating from as-synthesized conductive few-layer FePS<sub>3</sub> nanosheets. Furthermore, the charge transfer pathway of the constructed 2D CdS/2D FePS<sub>3</sub> heterojunction is unveiled by in situ atomic force microscopy with Kelvin probe force microscopy (AFM-KPFM), in situ X-ray photoelectron spectroscopy (XPS), and photoelectrochemical measurements. This study offers new insight into the rational design and controllable synthesis of FePS<sub>3</sub>-based composite photocatalytic systems for efficient photocatalytic hydrogen production.</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":"8656 - 8666"},"PeriodicalIF":11.0,"publicationDate":"2025-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469289","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 treatment of bacterial wound infection remains a significant health challenge, with the prevention of bacterial resistance and harnessing the microenvironment of lesions for biological therapy being a clinical expectation. Nanozymes, as enzyme-mimicking catalysts, provide a promising non-antibiotic strategy for bacterial elimination. However, their therapeutic potential has been constrained by acidic pH-dependent catalytic activity, cytotoxicity that impedes tissue regeneration, and insufficient understanding of their bactericidal mechanisms. In this study, a high-entropy nanozyme system was developed with antibiofilm and pro-regenerative properties via incorporating lanthanide and zinc into a clinically approved iron-based nanocrystal. This high-entropy lattice modification enabled self-adaptive catalysis via surface electron density modulation, effectively overcoming pH restrictions and enhancing peroxidase-like activity under physiological conditions. Mechanistic investigations revealed that this optimized nanozyme could effectively cleave bacterial peptidoglycan glycosidic bonds via oxidation, disrupt membrane integrity, and induce oxidative damage to biomacromolecules through reactive oxygen species (ROS) generation, demonstrating potent antimicrobial efficacy against S. aureus, E. coli, and P. aeruginosa. Notably, these high-entropy nanozymes exhibited good biocompatibility and promoted the migration and proliferation of fibroblasts, accelerating epithelialization and granulation tissue formation by modulating the wound microenvironment, as confirmed in both in vitro and infected wound models, with no observed adverse effects. This multi-element doping strategy provides valuable insights into the development of novel and efficient antimicrobial materials to combat the growing threat of bacterial resistance.
{"title":"High-entropy nanozymes with dual antibiofilm and pro-regenerative functions for wound healing","authors":"Jun-Yao Wang, Gui-Xian Shen, Xiao-Die Zeng, Jian-Ping Lu, Chun-Wei Wu, Rui-Ping Zhou, Zhi-Yong Wang","doi":"10.1007/s12598-025-03542-1","DOIUrl":"10.1007/s12598-025-03542-1","url":null,"abstract":"<div><p>The treatment of bacterial wound infection remains a significant health challenge, with the prevention of bacterial resistance and harnessing the microenvironment of lesions for biological therapy being a clinical expectation. Nanozymes, as enzyme-mimicking catalysts, provide a promising non-antibiotic strategy for bacterial elimination. However, their therapeutic potential has been constrained by acidic pH-dependent catalytic activity, cytotoxicity that impedes tissue regeneration, and insufficient understanding of their bactericidal mechanisms. In this study, a high-entropy nanozyme system was developed with antibiofilm and pro-regenerative properties via incorporating lanthanide and zinc into a clinically approved iron-based nanocrystal. This high-entropy lattice modification enabled self-adaptive catalysis via surface electron density modulation, effectively overcoming pH restrictions and enhancing peroxidase-like activity under physiological conditions. Mechanistic investigations revealed that this optimized nanozyme could effectively cleave bacterial peptidoglycan glycosidic bonds via oxidation, disrupt membrane integrity, and induce oxidative damage to biomacromolecules through reactive oxygen species (ROS) generation, demonstrating potent antimicrobial efficacy against <i>S. aureus</i>, <i>E. coli</i>, and <i>P. aeruginosa</i>. Notably, these high-entropy nanozymes exhibited good biocompatibility and promoted the migration and proliferation of fibroblasts, accelerating epithelialization and granulation tissue formation by modulating the wound microenvironment, as confirmed in both in vitro and infected wound models, with no observed adverse effects. This multi-element doping strategy provides valuable insights into the development of novel and efficient antimicrobial materials to combat the growing threat of bacterial resistance.</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":"8701 - 8719"},"PeriodicalIF":11.0,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469350","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 : 2025-08-14DOI: 10.1007/s12598-025-03536-z
Xiao-Ye Zhou, Cheng-Zhi Zu, Muhammad Irfan, Ke-Xiu Dong, Wen-Juan Yu, Min Wu, Muhammad Javid, Yuan-Liang Zhou
The precise construction of anti-electromagnetic interference composites with highly efficient absorption capability, superior self-cleaning, and excellent thermal conductivity is still challenging since the incompatibility of multi performances. Herein, FeNi@C/ZnO array nanostructures are decorated on a flexible carbon cloth backbone to solve this challenge. The carbon cloth grown with hierarchical ZnO arrays not only possesses high dielectric loss capability, but the magnetic loss also can be modulated via controlling the depositing content of FeNi@C nanoparticles (NCs). This approach effectively fulfills the appropriate impedance matching and broad effective absorption bandwidth (EAB, the reflection loss < −10 dB). Our prepared FeNi@C/ZnO/CC composite can achieve a minimum reflection loss value of -39.36 dB, and the corresponding EAB can cover the entire X-band. Moreover, it exhibits excellent self-cleaning performance with a water contact angle as high as 155°. In addition, benefiting from the exquisite nano/micro structural design, the fabric composite also possesses superior thermal management property, with a thermal conductivity of 0.23 W m−1 K−1. This study has the potential to be applied in the field of electromagnetic wave absorption (EWA) materials and multifunctional electrical devices.
Graphical abstract
由于多种性能的不相容，精确构建具有高效吸收能力、优异自洁性和优异导热性的抗电磁干扰复合材料仍然是一个挑战。本文将FeNi@C/ZnO阵列纳米结构装饰在柔性碳布骨架上，以解决这一挑战。层次化ZnO碳布不仅具有较高的介质损耗能力，而且可以通过控制FeNi@C纳米颗粒（NCs）的沉积量来调节其磁损耗。这种方法有效地实现了适当的阻抗匹配和较宽的有效吸收带宽（EAB，反射损耗<；−10 dB）。我们制备的FeNi@C/ZnO/CC复合材料可以实现最小反射损耗值-39.36 dB，相应的EAB可以覆盖整个x波段。此外，它具有优异的自清洁性能，水接触角高达155°。此外，得益于精致的纳米/微观结构设计，织物复合材料还具有优越的热管理性能，导热系数为0.23 W m−1 K−1。该研究在电磁波吸收材料和多功能电子器件领域具有潜在的应用前景。图形抽象
{"title":"Construction of hierarchical FeNi@C/ZnO array nanostructures on flexible carbon cloth for high-efficient electromagnetic absorption, self-cleaning, and thermal management","authors":"Xiao-Ye Zhou, Cheng-Zhi Zu, Muhammad Irfan, Ke-Xiu Dong, Wen-Juan Yu, Min Wu, Muhammad Javid, Yuan-Liang Zhou","doi":"10.1007/s12598-025-03536-z","DOIUrl":"10.1007/s12598-025-03536-z","url":null,"abstract":"<div><p>The precise construction of anti-electromagnetic interference composites with highly efficient absorption capability, superior self-cleaning, and excellent thermal conductivity is still challenging since the incompatibility of multi performances. Herein, FeNi@C/ZnO array nanostructures are decorated on a flexible carbon cloth backbone to solve this challenge. The carbon cloth grown with hierarchical ZnO arrays not only possesses high dielectric loss capability, but the magnetic loss also can be modulated via controlling the depositing content of FeNi@C nanoparticles (NCs). This approach effectively fulfills the appropriate impedance matching and broad effective absorption bandwidth (EAB, the reflection loss < −10 dB). Our prepared FeNi@C/ZnO/CC composite can achieve a minimum reflection loss value of -39.36 dB, and the corresponding EAB can cover the entire X-band. Moreover, it exhibits excellent self-cleaning performance with a water contact angle as high as 155°. In addition, benefiting from the exquisite nano/micro structural design, the fabric composite also possesses superior thermal management property, with a thermal conductivity of 0.23 W m<sup>−1</sup> K<sup>−1</sup>. This study has the potential to be applied in the field of electromagnetic wave absorption (EWA) materials and multifunctional electrical devices.</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":"8884 - 8898"},"PeriodicalIF":11.0,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469341","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 : 2025-08-13DOI: 10.1007/s12598-025-03497-3
Ting Chen, Qian-Hui Wu, Mei Shi, Xin Chen, Shun-Rui Luo, Lei-Ming Lang, Zhi-Dong Chen, Huan Pang
Vanadium-based materials are recognized as promising cathodes for high-energy-density aqueous zinc-ion batteries (AZIBs). However, their inherent low intrinsic conductivities and sluggish reaction kinetics curtail their capacity release. Here, we enhanced the electron and ion transport properties of vanadium-based cathodes through heterojunction engineering, coupled with in situ electrochemical activation, significantly enhancing an unprecedented zinc-ion storage capacity and rapid kinetic performance. A heterostructured V2O3/g-C3N4 (V2O3/CN) precursor was synthesized via a calcination process firstly. When employed as a cathode in AZIBs, this precursor undergoes an in situ phase transformation into Zn3(OH)2V2O7·2H2O/C3N4 (ZVOH/CN) during the inaugural charging process, while retaining its heterojunction structure. Both electrochemical assessments and theoretical calculations revealed that ZVOH/CN exhibits superior zinc-ion adsorption and migration capabilities compared to conventional vanadium-based cathodes. The formation of the heterojunction amplifies the material’s electronic conductivity and ion diffusion kinetics. As a result, the optimal ZVOH/CN composite electrode showcases a remarkable capacity of 518.5 mAh g−1 at 0.5 A g−1, superior rate performance of 177.8 mAh g−1 at 20 A g−1, and impressive cycling stability. This work offers a novel design strategy for vanadium-based composite materials as high-performance AZIB cathodes.
Graphical abstract
钒基材料被认为是高能量密度水性锌离子电池（azib）极具前景的阴极材料。然而，它们固有的低固有电导率和缓慢的反应动力学限制了它们的容量释放。在这里，我们通过异质结工程增强了钒基阴极的电子和离子输运特性，再加上原位电化学活化，显著提高了前所未有的锌离子存储容量和快速动力学性能。采用煅烧法首次合成了异质结构的V2O3/g-C3N4 （V2O3/CN）前驱体。在AZIBs中用作阴极时，该前驱体在初始充电过程中原位相变为Zn3(OH)2V2O7·2H2O/C3N4 (ZVOH/CN)，同时保持其异质结结构。电化学评价和理论计算表明，与传统的钒基阴极相比，ZVOH/CN具有更好的锌离子吸附和迁移能力。异质结的形成放大了材料的电子导电性和离子扩散动力学。结果表明，ZVOH/CN复合电极在0.5 a g−1时的容量为518.5 mAh g−1，在20 a g−1时的倍率性能为177.8 mAh g−1，并且具有令人印象深刻的循环稳定性。这项工作为钒基复合材料作为高性能AZIB阴极提供了一种新的设计策略。图形抽象
{"title":"Heterostructure engineering coupled with in situ activation enables ultra-high capacity and fast zinc-ion storage kinetics in vanadium-based cathodes","authors":"Ting Chen, Qian-Hui Wu, Mei Shi, Xin Chen, Shun-Rui Luo, Lei-Ming Lang, Zhi-Dong Chen, Huan Pang","doi":"10.1007/s12598-025-03497-3","DOIUrl":"10.1007/s12598-025-03497-3","url":null,"abstract":"<div><p>Vanadium-based materials are recognized as promising cathodes for high-energy-density aqueous zinc-ion batteries (AZIBs). However, their inherent low intrinsic conductivities and sluggish reaction kinetics curtail their capacity release. Here, we enhanced the electron and ion transport properties of vanadium-based cathodes through heterojunction engineering, coupled with in situ electrochemical activation, significantly enhancing an unprecedented zinc-ion storage capacity and rapid kinetic performance. A heterostructured V<sub>2</sub>O<sub>3</sub>/g-C<sub>3</sub>N<sub>4</sub> (V<sub>2</sub>O<sub>3</sub>/CN) precursor was synthesized via a calcination process firstly. When employed as a cathode in AZIBs, this precursor undergoes an in situ phase transformation into Zn<sub>3</sub>(OH)<sub>2</sub>V<sub>2</sub>O<sub>7</sub>·2H<sub>2</sub>O/C<sub>3</sub>N<sub>4</sub> (ZVOH/CN) during the inaugural charging process, while retaining its heterojunction structure. Both electrochemical assessments and theoretical calculations revealed that ZVOH/CN exhibits superior zinc-ion adsorption and migration capabilities compared to conventional vanadium-based cathodes. The formation of the heterojunction amplifies the material’s electronic conductivity and ion diffusion kinetics. As a result, the optimal ZVOH/CN composite electrode showcases a remarkable capacity of 518.5 mAh g<sup>−1</sup> at 0.5 A g<sup>−1</sup>, superior rate performance of 177.8 mAh g<sup>−1</sup> at 20 A g<sup>−1</sup>, and impressive cycling stability. This work offers a novel design strategy for vanadium-based composite materials as high-performance AZIB cathodes.</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":"8500 - 8513"},"PeriodicalIF":11.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469377","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 : 2025-08-13DOI: 10.1007/s12598-025-03413-9
Ayça Coşkun, Ahmet Serdar Kopar, Zeynep Elif Özerbaş, Muhammet Ayhan Işık, Kamer Özge Erişmiş, Murat An, Mehtap Aygün Çağlar, Bülent Çakmak, Mehmet Ertuğrul, Güven Turgut
The studies on the synthesis of two-dimensional (2D) Janus materials have made significant progress over the years. They offer new opportunities to increase the potential usage of Janus transition metal dichalcogenide (TMDC) materials in different application areas due to their unique structural, electrical, optical and mechanical properties. However, the difficulties in synthesizing these materials stand out as a critical factor for further research in this field. This manuscript aims to provide a comprehensive overview of this rapidly developing field by reviewing studies in which Janus TMDC structures have been experimentally obtained. Within the scope of the research, the synthesis methods such as chemical vapor deposition (CVD), pulsed laser deposition (PLD), selective epitaxial atomic replacement (SEAR), plasma-assisted selenization process (PASP) and room temperature atomic layer selenization (RT-ALS) have been handled in detail. The analysis results obtained by various characterization methods such as Raman spectroscopy, photoluminescence (PL), atomic force microscopy (AFM), Kelvin probe force microscopy (KPFM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), piezoelectric properties, mechanical properties and second harmonic generation (SHG) have been looked into. Moreover, the kinetic mechanisms of the synthesis processes have been particularly discussed so that the synthesis processes of the materials can be optimized and more controlled synthesis techniques can be developed. As a result of literature review, we can conclude that Janus TMDC structures should have a much wider range of applications despite the difficulties in their synthesis and novel strategies should be developed to synthesize new kind of Janus materials.
{"title":"Experimental insights into characteristic properties and applications of two-dimensional Janus transition metal dichalcogenide (TMDC) materials: a comprehensive review","authors":"Ayça Coşkun, Ahmet Serdar Kopar, Zeynep Elif Özerbaş, Muhammet Ayhan Işık, Kamer Özge Erişmiş, Murat An, Mehtap Aygün Çağlar, Bülent Çakmak, Mehmet Ertuğrul, Güven Turgut","doi":"10.1007/s12598-025-03413-9","DOIUrl":"10.1007/s12598-025-03413-9","url":null,"abstract":"<div><p>The studies on the synthesis of two-dimensional (2D) Janus materials have made significant progress over the years. They offer new opportunities to increase the potential usage of Janus transition metal dichalcogenide (TMDC) materials in different application areas due to their unique structural, electrical, optical and mechanical properties. However, the difficulties in synthesizing these materials stand out as a critical factor for further research in this field. This manuscript aims to provide a comprehensive overview of this rapidly developing field by reviewing studies in which Janus TMDC structures have been experimentally obtained. Within the scope of the research, the synthesis methods such as chemical vapor deposition (CVD), pulsed laser deposition (PLD), selective epitaxial atomic replacement (SEAR), plasma-assisted selenization process (PASP) and room temperature atomic layer selenization (RT-ALS) have been handled in detail. The analysis results obtained by various characterization methods such as Raman spectroscopy, photoluminescence (PL), atomic force microscopy (AFM), Kelvin probe force microscopy (KPFM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), piezoelectric properties, mechanical properties and second harmonic generation (SHG) have been looked into. Moreover, the kinetic mechanisms of the synthesis processes have been particularly discussed so that the synthesis processes of the materials can be optimized and more controlled synthesis techniques can be developed. As a result of literature review, we can conclude that Janus TMDC structures should have a much wider range of applications despite the difficulties in their synthesis and novel strategies should be developed to synthesize new kind of Janus 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":"8161 - 8197"},"PeriodicalIF":11.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s12598-025-03413-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469342","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}
Lithium metal anode with a high theoretical capacity (3860 mAh g−1) is the most ideal anode for high-energy density rechargeable batteries. However, lithium dendrite growth and unstable electrode/electrolyte interfaces have limited commercialization applications. Here, potassium trifluoroacetate (KTFA), as a functional additive, was introduced into the electrolytes. The K+ adsorbed at the tip of the lithium metal anode surface forms a charge shielding effect at low concentrations, forcing Li+ to deposit far from the tip, effectively regulating the behaviour and inhibiting the growth of lithium dendrites. Moreover, the TFA− anions with the lowest unoccupied molecular orbital (LUMO) energy levels can preferentially form a LiF-rich and Li2O-rich solid−electrolyte interphase (SEI) layer and stabilize the lithium electrode/electrolyte interface. Thus, Li||Cu cells have superior cycling stability for 1200 cycles and 800 cycles at 0.5 mA cm−2 and 1.0 mA cm−2 in the E3 electrolyte, respectively. Encouragingly, the Li||LiFePO4 (LFP) full cell maintained greater capacity retention after 800 cycles at 2.0C. The Li||LiNi0.8Co0.1Mn0.1O2 (NCM811) full cell also retained an initial capacity of 87.04% after 500 cycles at 1.0C, and the practical 1.0 Ah Li||NCM811 pouch cell, with a capacity retention of 96.65% after 80 cycles, exhibited excellent cycle reversibility and potential for practical application. This work provides a simple and practical strategy for preparing high-performance lithium metal batteries (LMBs).
Graphical abstract
锂金属阳极具有较高的理论容量（3860 mAh g−1），是高能密度可充电电池最理想的阳极。然而，锂枝晶生长和不稳定的电极/电解质界面限制了商业化应用。本文将三氟乙酸钾（KTFA）作为功能添加剂引入电解质中。在低浓度下，吸附在锂金属阳极表面尖端的K+形成电荷屏蔽效应，迫使Li+沉积在远离尖端的地方，有效地调节了锂枝晶的行为，抑制了锂枝晶的生长。此外，具有最低未占据分子轨道（LUMO）能级的TFA -阴离子可以优先形成富liff和富li2o的固体-电解质界面（SEI）层，并稳定锂电极/电解质界面。因此，Li||Cu电池在E3电解液中分别在0.5 mA cm - 2和1.0 mA cm - 2下具有优越的1200次和800次循环稳定性。令人鼓舞的是，Li||LiFePO4 （LFP）充满电池在2.0C下循环800次后保持了更大的容量保持。在1.0℃下循环500次后，Li||LiNi0.8Co0.1Mn0.1O2 （NCM811）完整电池的初始容量保持在87.04%，实用的1.0 Ah Li||NCM811袋状电池在80次循环后的容量保持在96.65%，具有良好的循环可逆性和实际应用潜力。本研究为制备高性能锂金属电池（lmb）提供了一种简单实用的方法。图形抽象
{"title":"KTFA as an interface-stable and dendrite-inhibiting additive in high-performance lithium metal batteries","authors":"Yi Liang, Yangtao Zhou, Tao Wei, Guangda Yin, Yuan Yao, Qichang Pan, Fenghua Zheng, Hongqiang Wang, Qingyu Li, Sijiang Hu, Dequan Huang","doi":"10.1007/s12598-025-03535-0","DOIUrl":"10.1007/s12598-025-03535-0","url":null,"abstract":"<div><p>Lithium metal anode with a high theoretical capacity (3860 mAh g<sup>−1</sup>) is the most ideal anode for high-energy density rechargeable batteries. However, lithium dendrite growth and unstable electrode/electrolyte interfaces have limited commercialization applications. Here, potassium trifluoroacetate (KTFA), as a functional additive, was introduced into the electrolytes. The K<sup>+</sup> adsorbed at the tip of the lithium metal anode surface forms a charge shielding effect at low concentrations, forcing Li<sup>+</sup> to deposit far from the tip, effectively regulating the behaviour and inhibiting the growth of lithium dendrites. Moreover, the TFA<sup>−</sup> anions with the lowest unoccupied molecular orbital (LUMO) energy levels can preferentially form a LiF-rich and Li<sub>2</sub>O-rich solid−electrolyte interphase (SEI) layer and stabilize the lithium electrode/electrolyte interface. Thus, Li||Cu cells have superior cycling stability for 1200 cycles and 800 cycles at 0.5 mA cm<sup>−2</sup> and 1.0 mA cm<sup>−2</sup> in the E3 electrolyte, respectively. Encouragingly, the Li||LiFePO<sub>4</sub> (LFP) full cell maintained greater capacity retention after 800 cycles at 2.0C. The Li||LiNi<sub>0.8</sub>Co<sub>0.1</sub>Mn<sub>0.1</sub>O<sub>2</sub> (NCM811) full cell also retained an initial capacity of 87.04% after 500 cycles at 1.0C, and the practical 1.0 Ah Li||NCM811 pouch cell, with a capacity retention of 96.65% after 80 cycles, exhibited excellent cycle reversibility and potential for practical application. This work provides a simple and practical strategy for preparing high-performance lithium metal batteries (LMBs).</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":"8416 - 8428"},"PeriodicalIF":11.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469384","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 : 2025-08-13DOI: 10.1007/s12598-025-03511-8
Mohammad Arishi
Engineering the morphology of spinel mixed metal oxides is a critical strategy for developing high-performance hybrid supercapacitors as they enhance both energy storage performance and cyclic stability. Herein, we present a simple, binder-free method to fabricate hierarchical, pineapple-like CuCo2O4 nanostructures on carbon fibers via low-temperature wet-chemical method. By utilizing a combination of hexamine and urea, we tailored the morphology and crystallinity of CuCo2O4, improving ion accessibility and interconnectivity, which led to superior electrochemical performance compared to individual components. Particularly, the pineapple-like CuCo2O4 demonstrated diffusion-dominated behavior, achieving a higher specific capacitance of 745 F g−1 at 1 A g−1 and excellent cycling stability. Moreover, a hybrid supercapacitor was fabricated using diffusion-type CuCo2O4 electrode and activated carbon as the capacitive electrode, which exhibited good synergy in delivering excellent energy storage performance. The device achieved a specific capacity of 140.5 C g−1 at 0.5 A g−1 and an energy density of 45.5 Wh kg−1 with a high-power density of 5950 W kg−1. Even at a high current density of 10 A g−1, the hybrid supercapacitor maintained excellent rate capability and remarkable cycling stability (89.6% retention after 10,000 cycles), demonstrating efficient charge storage and transfer. Benefiting from high voltage and energy density, the fabricated hybrid supercapacitors successfully powered various LEDs, illustrating their potential for real-world applications. Our work demonstrates the importance of spinal-type nanostructure engineering to achieve enhanced electrochemical performance, providing a straightforward pathway for developing next-generation supercapacitors and battery materials.
Graphical abstract
尖晶石混合金属氧化物的形态工程是开发高性能混合超级电容器的关键策略，因为它们可以提高储能性能和循环稳定性。在此，我们提出了一种简单的、无粘合剂的方法，通过低温湿化学方法在碳纤维上制造分层的、菠萝状的CuCo2O4纳米结构。通过使用hexamine和尿素的组合，我们定制了CuCo2O4的形态和结晶度，提高了离子的可及性和互联性，从而获得了与单个组分相比优越的电化学性能。特别是，菠萝状的CuCo2O4表现出扩散主导行为，在1 a g−1时实现了745 F g−1的较高比电容和出色的循环稳定性。此外，采用扩散型CuCo2O4电极和活性炭作为电容电极制备了混合超级电容器，两者协同作用良好，具有优异的储能性能。该器件在0.5 a g−1时的比容量为140.5 C g−1，能量密度为45.5 Wh kg−1，高功率密度为5950 W kg−1。即使在10 ag−1的高电流密度下，混合超级电容器也保持了出色的倍率能力和显着的循环稳定性（10,000次循环后保持89.6%），证明了高效的电荷存储和转移。得益于高电压和能量密度，制造的混合超级电容器成功地为各种led供电，说明了它们在实际应用中的潜力。我们的工作证明了脊髓型纳米结构工程对提高电化学性能的重要性，为开发下一代超级电容器和电池材料提供了一条直接的途径。图形抽象
{"title":"Morphologically engineered mixed metal oxides on carbon fibers as a binder-free electrode for diffusion capacitance-dominated hybrid supercapacitors","authors":"Mohammad Arishi","doi":"10.1007/s12598-025-03511-8","DOIUrl":"10.1007/s12598-025-03511-8","url":null,"abstract":"<div><p>Engineering the morphology of spinel mixed metal oxides is a critical strategy for developing high-performance hybrid supercapacitors as they enhance both energy storage performance and cyclic stability. Herein, we present a simple, binder-free method to fabricate hierarchical, pineapple-like CuCo<sub>2</sub>O<sub>4</sub> nanostructures on carbon fibers via low-temperature wet-chemical method. By utilizing a combination of hexamine and urea, we tailored the morphology and crystallinity of CuCo<sub>2</sub>O<sub>4</sub>, improving ion accessibility and interconnectivity, which led to superior electrochemical performance compared to individual components. Particularly, the pineapple-like CuCo<sub>2</sub>O<sub>4</sub> demonstrated diffusion-dominated behavior, achieving a higher specific capacitance of 745 F g<sup>−1</sup> at 1 A g<sup>−1</sup> and excellent cycling stability. Moreover, a hybrid supercapacitor was fabricated using diffusion-type CuCo<sub>2</sub>O<sub>4</sub> electrode and activated carbon as the capacitive electrode, which exhibited good synergy in delivering excellent energy storage performance. The device achieved a specific capacity of 140.5 C g<sup>−1</sup> at 0.5 A g<sup>−1</sup> and an energy density of 45.5 Wh kg<sup>−1</sup> with a high-power density of 5950 W kg<sup>−1</sup>. Even at a high current density of 10 A g<sup>−1</sup>, the hybrid supercapacitor maintained excellent rate capability and remarkable cycling stability (89.6% retention after 10,000 cycles), demonstrating efficient charge storage and transfer. Benefiting from high voltage and energy density, the fabricated hybrid supercapacitors successfully powered various LEDs, illustrating their potential for real-world applications. Our work demonstrates the importance of spinal-type nanostructure engineering to achieve enhanced electrochemical performance, providing a straightforward pathway for developing next-generation supercapacitors and battery 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":"8548 - 8564"},"PeriodicalIF":11.0,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145469256","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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