Rare Metals最新文献_第7页

Past, present, prospect: AI-driven evolution of low-dimensional material design for sustainable environmental solutions 过去，现在，前景：人工智能驱动的低维材料设计的发展，以实现可持续的环境解决方案

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-09-29 DOI: 10.1007/s12598-025-03631-1

Bo-Ru Su, Jian-Qiao Liu, Dan Zhao, Di Wu, Chu-Qiao Hu, Pei-Lun Qiu, Ya-Nan Zhang, Ce Fu, Qian-Ru Zhang

Low-dimensional materials have attracted significant interest for their unique properties, including high surface area, confined but tunable electronics and superior catalysis, making them ideal for environmental applications. Their potential to address key challenges in solar energy conversion and in-situ remediation highlights their importance in advancing environmental sustainability. However, traditional methods of low-dimensional material design face significant obstacles, such as scalability limitations, high computational costs, and the inherent difficulty in accurate prediction of material properties, underscoring the need for innovative approaches. Here, we demonstrate an AI-driven evolution of low-dimensional material design for sustainable environmental solutions, from the traditional techniques in the past, through the present transition to computational approaches, to the prospect where AI-enabled strategies exhibit the supremacy. This review covers properties of low-dimensional materials and the fundamental design principles, emphasizing the pivotal role of deep learning in optimizing and accelerating design of advanced functional materials. Further explorations focus on their applications for sustainable environmental solutions, including pollution remediation, water purification, nitrogen fixation, CO₂ reduction as well as hydrogen and hydrogen peroxide production. Ultimately, the key challenges and future trends are identified in the aspects of algorithm, intelligence and scalability for environmental applications. This work offers a comprehensive overview on the evolution pathway of design strategies for low-dimensional materials driven by AI methodology, demonstrating transformative insights that not only accelerate the discovery of low-dimensional materials, but also motivate the environmental applications in various domains.

Graphical abstract

低维材料因其独特的性能而引起了人们的极大兴趣，包括高表面积，受限但可调谐的电子器件和卓越的催化性能，使其成为环境应用的理想选择。它们在解决太阳能转换和原位修复方面的关键挑战方面的潜力突出了它们在促进环境可持续性方面的重要性。然而，传统的低维材料设计方法面临着显著的障碍，如可扩展性限制、高计算成本以及准确预测材料性能的固有困难，这凸显了对创新方法的需求。在这里，我们展示了人工智能驱动的低维材料设计的发展，以实现可持续的环境解决方案，从过去的传统技术，到现在向计算方法的过渡，再到人工智能策略表现出至高无上的前景。本文综述了低维材料的特性和基本设计原理，强调了深度学习在优化和加速先进功能材料设计中的关键作用。进一步的探索重点是它们在可持续环境解决方案中的应用，包括污染修复、水净化、固氮、二氧化碳减排以及氢气和过氧化氢的生产。最后，在环境应用的算法、智能和可扩展性方面确定了关键挑战和未来趋势。这项工作全面概述了由人工智能方法论驱动的低维材料设计策略的演变路径，展示了变革性的见解，不仅加速了低维材料的发现，而且还激发了各个领域的环境应用。图形抽象

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引用次数: 0

Emerging Fe-based catalysts for heterogeneous Fenton-like reactions: from nanoparticles to clusters and single-atom catalysts 新兴的非均相类芬顿反应的铁基催化剂：从纳米颗粒到团簇和单原子催化剂

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-09-29 DOI: 10.1007/s12598-025-03612-4

Jiang-Feng Li, Yu-Xuan Shi, Li-Shuang Wei, Sang Sang, Xiao-Xin Xia, Sheng-You Li, Yu-Zhen Liu, Kai-Ying Zhao, Guang-Tao Zan

Heterogeneous Fenton-like technology, a prominent advanced oxidation process, has gained widespread use in wastewater treatment for the removal of contaminants. The performance of this technology is highly dependent on the catalyst materials employed. Iron-based catalysts have attracted considerable attention due to their tunable properties, low cost, and environmental friendliness. However, challenges such as inadequate catalytic activity and the dissolution of iron species have limited their practical effectiveness. To address these challenges, various novel iron-based materials have been developed, ranging from diverse iron compounds to iron-based composites on different substrates, and from iron nanoparticles to iron clusters and single-atom catalysts (SACs). This review systematically examines the latest advancements in heterogeneous iron-based catalysts, focusing on two main categories: iron-based nanoparticle catalysts and iron-based clusters/SACs. We delve into the relationship between catalyst structures and catalytic performance in Fenton-like reactions, such as the nature of the substrate, catalyst size, and the interfacial interaction between the catalyst and the substrate. By emphasizing recent progress and existing limitations, this review aims to provide valuable insights for the future development and application of high-performance heterogeneous catalysts for Fenton-like reactions.

Graphical abstract

非均相类芬顿技术作为一种先进的氧化工艺，在污水处理中得到了广泛的应用。该技术的性能高度依赖于所采用的催化剂材料。铁基催化剂因其可调性、低成本和环境友好性而受到广泛关注。然而，诸如催化活性不足和铁的溶解等挑战限制了它们的实际有效性。为了应对这些挑战，各种新型铁基材料已经被开发出来，从不同的铁化合物到不同衬底的铁基复合材料，从铁纳米颗粒到铁簇和单原子催化剂（SACs）。本文系统地综述了非均相铁基催化剂的最新进展，重点介绍了两大类：铁基纳米颗粒催化剂和铁基簇/SACs催化剂。我们深入研究了类芬顿反应中催化剂结构与催化性能之间的关系，如底物的性质、催化剂的尺寸以及催化剂与底物之间的界面相互作用。本文综述了近年来的研究进展和存在的局限性，旨在为今后类芬顿反应的高性能非均相催化剂的开发和应用提供有价值的见解。图形抽象

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引用次数: 0

Ultrasensitive chemical detection using amorphous MoS ₂ decorated NiS core–shell structures on nickel foam 泡沫镍表面非晶态MoS 2修饰NiS核壳结构的超灵敏化学检测

1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-09-23 DOI: 10.1007/s12598-025-03608-0

Hongquan Xu, Xiangdong Meng, Baizhi Li, Ming Gao

Abstract Surface‐enhanced Raman spectroscopy (SERS) is a highly sensitive analytical technique extensively employed in bioanalysis, chemical sensing, and environmental monitoring. Transition metal sulfides, such as molybdenum disulfide (MoS 2 ) and nickel sulfide (NiS), exhibit significant potential as SERS substrates, but their performance is often constrained by limited exposure of active sites and inefficient charge transfer, especially in complex sample matrices. In this study, we address these challenges by employing a hydrothermal strategy to synthesize amorphous MoS 2 nanoshells in an urchin‐like MoS 2 ‐NiS core–shell structure grown on nickel foam (A‐MoS 2 /NiS/NF). Further enhancement was realized via neodymium doping, yielding the x Nd‐A‐MoS 2 /NiS/NF. The optimized 0.015Nd‐A‐MoS 2 /NiS/NF substrate demonstrated a high enhancement factor (EF) of 1.56 × 10 9 for methylene blue (MB) and a detection limit as low as 10 –12 M. Density functional theory (DFT) calculations indicate that neodymium doping substantially increases the density of states (DOS) at the Fermi level, thereby enhancing charge transfer and amplifying the Raman signal. The 0.015Nd‐A‐MoS 2 /NiS/NF substrate also exhibited high sensitivity in detecting melamine in real milk samples, confirming its practical applicability. By effectively addressing the challenges of active site exposure and charge transfer in MoS 2 and NiS‐based SERS substrates, this work significantly advances the practical application of transition metal sulfides in SERS. This development paves the way for the broader deployment of these materials in environmental and bioanalytical detection, presenting a promising strategy for improving the sensitivity and versatility of SERS‐based sensors.

摘要表面增强拉曼光谱（SERS）是一种高灵敏度的分析技术，广泛应用于生物分析、化学传感和环境监测。过渡金属硫化物，如二硫化钼（MoS 2）和硫化镍（NiS），表现出作为SERS底物的巨大潜力，但它们的性能往往受到活性位点暴露有限和低效电荷转移的限制，特别是在复杂的样品基质中。在本研究中，我们采用水热策略在泡沫镍上生长的海胆状MoS 2‐NiS核壳结构（a‐MoS 2 /NiS/NF）中合成了非晶MoS 2纳米壳，从而解决了这些挑战。通过钕掺杂进一步增强，得到了x Nd‐A‐MoS 2 /NiS/NF。优化后的0.015Nd‐A‐MoS 2 /NiS/NF衬底对亚甲基蓝（MB）的增强因子（EF）高达1.56 × 10 9，检测限低至10 ~ 12 m。密度泛函理论（DFT）计算表明，钕掺杂大大增加了费米能级的态密度（DOS），从而增强了电荷转移并放大了拉曼信号。0.015Nd‐A‐MoS 2 /NiS/NF底物在检测真实牛奶样品中的三聚氰胺时也表现出很高的灵敏度，证实了其实用性。通过有效地解决MoS 2和NiS基SERS衬底的活性位点暴露和电荷转移的挑战，本工作显著推进了过渡金属硫化物在SERS中的实际应用。这一发展为这些材料在环境和生物分析检测中的广泛应用铺平了道路，为提高基于SERS的传感器的灵敏度和多功能性提供了一个有前途的策略。

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引用次数: 0

Engineered Hf0.7Ti0.3O2 nanoparticles for efficient radiotherapy on rectal cancer via synergistically enhanced radiation deposition and ROS production 设计的Hf0.7Ti0.3O2纳米颗粒通过协同增强辐射沉积和ROS的产生对直肠癌进行有效放疗

1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-09-23 DOI: 10.1007/s12598-025-03595-2

Juan Du, Yong-Long Ye, Chao Xie, Jun Luo, Kaiwei Xu, Yabing Sun, Liangxue Lai, Wenzhi Ren, Junming Guo, Aiguo Wu, Kaitai Liu

Preoperative radiotherapy is a cornerstone of treatment for locally advanced rectal cancer, but intrinsic tumor cell radio resistance remains a primary obstacle limiting therapeutic efficacy. Herein, for the first time, we successfully constructed Hf0.7Ti0.3O2@PEG (HT) nanoparticles by introducing titanium (Ti) into hafnium dioxide (HfO2). These HT nanoparticles synergistically combined the superior X-ray energy deposition capability of Hf and the efficient radiation-induced ROS generation performance of Ti, leading to a 1.4-fold higher ROS yield compared to HfO2. Moreover, HT nanoparticles significantly enhanced radiosensitivity by inducing extensive DNA damage and oxidative stress in tumor cells. This resulted in a tumor inhibition rate of 87.7% ± 2.1% in mouse models. Notably, HT nanoparticles enabled a marked reduction in radiation dose while maintaining therapeutic efficacy and safety, overcoming the major limitation of conventional HfO2 nanoradiosensitizers in ROS generation. This study presents a promising new approach for rectal cancer radiotherapy and holds significant potential for improving outcomes in radioresistant rectal cancer.

术前放疗是局部晚期直肠癌治疗的基石，但肿瘤细胞固有的放射抵抗仍然是限制治疗效果的主要障碍。本文首次将钛（Ti）引入二氧化铪（HfO2）中，成功构建了Hf0.7Ti0.3O2@PEG （HT）纳米颗粒。这些高温纳米粒子协同结合了Hf优越的x射线能量沉积能力和Ti高效的辐射诱导ROS生成性能，导致ROS产率比HfO2高1.4倍。此外，HT纳米颗粒通过诱导肿瘤细胞广泛的DNA损伤和氧化应激显著增强放射敏感性。小鼠模型的肿瘤抑制率为87.7%±2.1%。值得注意的是，HT纳米颗粒能够显著降低辐射剂量，同时保持治疗效果和安全性，克服了传统HfO2纳米辐射增敏剂在ROS生成中的主要局限性。这项研究为直肠癌放疗提供了一种有希望的新方法，并具有显著的改善放射耐药直肠癌预后的潜力。

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引用次数: 0

Structural engineering of bimetallic copper molybdate with high energy storage performance for long-life hybrid supercapacitors 长寿命混合超级电容器用高储能双金属钼酸铜结构工程

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-09-23 DOI: 10.1007/s12598-025-03583-6

Muneerah Al-Aqeel

Morphologically controlled synthesis of metal oxide-based materials has attracted significant attention to enable the capacity and redox performance of faradaic-type hybrid supercapacitors (H-SCs). In this work, we designed hollow-structured copper molybdate (Cu₃Mo₂O₉) with hollow flowers (CM HFs) and hollow spheres (HSs) were facilely prepared by solvent-mediated hydrothermal method. The aqueous environment in the hydrothermal system facilitates anisotropic crystal growth and self-assembly of nanoplates into three-dimensional CM HFs architecture, which showed high surface area and enhanced electrolyte accessibility. The electrochemical performance revealed that the CM HFs showed better redox behavior with longer charge–discharge times, and lower resistance compared to CM HSs. As a result, the CM HFs showed a higher specific capacitance of 530 F g⁻¹ at 2 A g⁻¹ and faster ion diffusion with a capacitance retention of 94.1% after 10,000 cycles. Moreover, a two-electrode H-SC was fabricated using CM HFs as the positive electrode and activated carbon as the negative electrode, which achieved a high energy density of 33.24 Wh kg⁻¹ and a power density of 5250 W kg⁻¹ along with excellent cycling stability. Aiding from the high energy storage performance of H-SC, the devices in series successfully powered LEDs, demonstrating their potential for flexible and durable energy storage applications.

Graphical Abstract

金属氧化物基材料的形态控制合成为法拉第型混合超级电容器（H-SCs）的容量和氧化还原性能提供了重要的研究方向。本文设计了具有空心花结构的钼酸铜（Cu3Mo2O9），并采用溶剂介导水热法制备了空心球。水热体系中的水环境有利于纳米板的各向异性晶体生长和自组装成三维CM - HFs结构，具有高的比表面积和增强的电解质可及性。电化学性能表明，与CM HFs相比，CM HFs具有更长的充放电时间和更低的电阻，具有更好的氧化还原性能。结果表明，CM HFs在2 a g−1时具有较高的比电容，达到530 F g−1，离子扩散速度更快，循环10,000次后电容保持率为94.1%。此外，以CM hf为正极，活性炭为负极制备了双电极H-SC，其能量密度为33.24 Wh kg - 1，功率密度为5250 W kg - 1，具有良好的循环稳定性。得益于H-SC的高能量存储性能，该系列器件成功地为led供电，展示了其灵活耐用的能量存储应用潜力。图形抽象

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引用次数: 0

2D sp2 carbon-conjugated covalent organic frameworks: photocatalytic platforms for solar energy conversion 二维sp2碳共轭共价有机框架：太阳能转换的光催化平台

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-09-18 DOI: 10.1007/s12598-025-03604-4

Bin Qi, Rongchen Shen, Ziyang Ke, Song Wang, Youji Li, Peng Zhang, Difa Xu, Xin Li

The unique fully conjugated architecture and tunable electronic properties of 2D sp² carbon-conjugated covalent organic frameworks (sp²c-COFs) have established them as promising photocatalysts. This review systematically summarizes the synthetic strategies, photocatalytic applications and performance modulation mechanisms of sp²c-COFs, and provides an outlook on future research directions. First, we introduce the main synthetic methods for sp²c-COFs, including Knoevenagel condensation, Aldol condensation and Horner-Wadsworth-Emmons reactions. Subsequently, we discuss in detail their photocatalytic applications in H₂ evolution, CO₂ reduction, H₂O₂ production, pollutant degradation, and selective organic transformations. Additionally, this review comprehensively discusses key photocatalytic regulation mechanisms, revealing how molecular design strategies can precisely control electronic structures, active site accessibility, and interfacial charge dynamics to enhance photocatalytic performance. Finally, we analyze the current challenges in the field and propose future research directions, including the development of novel synthetic strategies, deeper understanding of photocatalytic mechanisms, and the expansion of their applications in energy and environmental technologies. This work provides fundamental insights into structure–property relationships and paves the way for future photocatalytic systems.

Graphical abstract

二维sp2碳共轭共价有机骨架（sp2c-COFs）独特的全共轭结构和可调的电子性质使其成为一种很有前途的光催化剂。本文系统综述了sp2c-COFs的合成策略、光催化应用及性能调节机制，并对未来的研究方向进行了展望。首先介绍了sp2c-COFs的主要合成方法，包括Knoevenagel缩合、Aldol缩合和Horner-Wadsworth-Emmons反应。随后，我们详细讨论了它们在H2演化、CO2还原、H2O2生成、污染物降解和选择性有机转化等方面的光催化应用。此外，本文还全面讨论了关键的光催化调控机制，揭示了分子设计策略如何精确控制电子结构、活性位点可及性和界面电荷动力学以提高光催化性能。最后，我们分析了该领域目前面临的挑战，并提出了未来的研究方向，包括开发新的合成策略，加深对光催化机理的理解，以及扩大其在能源和环境技术中的应用。这项工作为结构-性质关系提供了基本的见解，并为未来的光催化系统铺平了道路。图形抽象

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引用次数: 0

Adsorption of dithiophosphate‐type collectors with different substituent types on the acanthite surface in the CaO system 不同取代基类型的二硫代磷酸盐型捕收剂在CaO体系棘石表面的吸附

1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-09-18 DOI: 10.1007/s12598-025-03560-z

Kaiwei Ding, Guanfei Zhao, Tingsheng Qiu, Xianhui Qiu, Huashan Yan, Hao Wu, Wenhui Yang, Shunde Yan, Liqiang Lin

Abstract Silver is a crucial rare and valuable metal in industrial applications, primarily found in polymetallic sulfide deposits as sulfides. The adsorption compatibility between various types of associated silver ores and collectors has not been extensively studied. This research focuses on acanthite (Ag 2 S), the predominant mineral in such ores. The study systematically investigates the adsorption compatibility differences between dithiophosphate collectors with five distinct substituents and associated silver ores. This investigation combines computational chemistry simulations with experimental validations. The findings reveal that the −N 2 PS 2 − ‐type collector exhibits superior surface matching with acanthite (100) surface compared to the −O 2 PS 2 − ‐type collector. Moreover, the presence of −C−O−C− bonds and benzene rings enhances the effectiveness of dithiophosphate‐type collectors for acanthite. In contrast, the compatibility of the −C 2 PS 2 − ‐type 3418A collector, lacking characteristic groups, is relatively poor. In high‐alkali processes, the adsorption of Ca(OH) + hinders the reactivity of silver atoms with the collector. The presence of benzene rings and −NH− groups in the substituents intensifies the impact of Ca(OH) + on the collector, thereby diminishing its adsorption strength. The introduction of −C−O−C− does not modify the sensitivity of the −O 2 PS 2 − ‐type collector to Ca(OH) + . Furthermore, the adsorption of alkane −C 2 PS 2 − ‐type collectors on mineral surfaces remains unaffected by the attenuating effect of Ca(OH) + . The results of the flotation tests, Zeta potential, and adsorption capacity assessments further validated the conclusions derived from computational chemistry analyses. The results provide valuable insights for the future design and advancement of innovative collectors customized for silver ore applications.

银是一种重要的稀有贵重金属，主要以硫化物形式存在于多金属硫化物矿床中。不同类型伴生银矿与捕收剂之间的吸附相容性尚未得到广泛的研究。本研究的重点是棘长石（ag2s），这是这类矿石中的主要矿物。本研究系统地考察了五种不同取代基的二硫代磷酸盐捕收剂与伴生银矿的吸附相容性差异。这项研究结合了计算化学模拟和实验验证。结果表明，与−O 2 PS 2−型捕收剂相比，−N 2 PS 2−型捕收剂与棘石（100）表面具有更好的表面匹配性。此外，−C−O−C−键和苯环的存在提高了二硫代磷酸盐型捕收剂对棘石的捕收效果。相比之下，−C 2 PS 2−型3418A集电极由于缺乏特征组，兼容性相对较差。在高碱过程中，Ca(OH) +的吸附阻碍了银原子与捕收剂的反应性。取代基中苯环和- NH -基团的存在增强了Ca(OH) +对捕收剂的影响，从而降低了捕收剂的吸附强度。−C−O−C−的引入不会改变−O 2 PS 2−型收集器对Ca(OH) +的灵敏度。此外，烷烃- c2ps2 -型捕收剂在矿物表面的吸附不受Ca(OH) +的衰减作用的影响。浮选试验、Zeta电位和吸附容量评估的结果进一步验证了计算化学分析得出的结论。研究结果为未来设计和开发针对银矿应用定制的创新型捕收剂提供了有价值的见解。

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引用次数: 1

The roadmap of carbon-based single-atom catalysts: rational design and electrochemical applications 碳基单原子催化剂的发展轨迹：合理设计与电化学应用

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-09-18 DOI: 10.1007/s12598-025-03477-7

Kaiyuan Liu, Liping Wang, Wenxing Chen, Zhiyi Sun, Huilong Geng, Yinqi Li, Ziwei Deng, Shuai Jiang, Boran Zhou, Kedi Yu, Liyuan Wei, Xin Gao, Zhuo Chen, Huazhang Zhai, Zhengbo Chen, Yahe Wu, Dingsheng Wang, Pengwan Chen

Carbon-based single-atom catalysts (SACs) have arisen as a revolutionary category of materials in electrocatalytic energy transformation, due to the atomically dispersed metal active sites, tunable coordination microenvironments, and ideal catalytic efficiency. This review systematically examines the rational design strategies and electrochemical applications on nitrogen-doped carbon-based SACs within a rational design, activity elucidation, and application development framework, focusing on critical reactions including hydrogen evolution, oxygen reduction, nitrogen reduction, oxygen evolution, and CO₂ reduction. Special emphasis is placed on innovative coordination engineering approaches, such as asymmetrical MN_x sites, axial coordination modulation, and bimetallic synergistic sites. These strategies elucidate the mechanisms of symmetry-breaking coordination and multi-ligand coupling in tailoring electronic configurations and intermediate adsorption energetics. Complementary insights from aberration-corrected scanning transmission electron microscopy, synchrotron-based X-ray absorption spectroscopy, and density functional theory calculations are integrated to establish dynamic correlations between atomic-level structural descriptors (coordination number, bond length/angle) and electronic states (d-band center, charge transfer). This synthesis advances quantitative structure–activity relationship models linking coordination environment–electronic properties–catalytic performance. In the future, prospects center on interdisciplinary integration harnessing high-throughput robotic synthesis, artificial intelligence-driven design, and life cycle assessment frameworks to bridge atomic-scale precision with device-level implementation. Such efforts will accelerate the translation of SACs into transformative solutions for fuel cells, green hydrogen production, and carbon–neutral technologies, ultimately reshaping sustainable energy conversion landscapes.

Graphical abstract

碳基单原子催化剂（SACs）由于其原子分散的金属活性位点、可调节的配位微环境和理想的催化效率，已成为电催化能量转化领域的一种革命性材料。本文从合理设计、活性阐明和应用开发的角度，系统地探讨了氮掺杂碳基SACs的合理设计策略和电化学应用，重点研究了析氢、氧还原、氮还原、析氧和CO2还原等关键反应。特别强调创新的协调工程方法，如不对称的MNx位点、轴向协调调制和双金属协同位点。这些策略阐明了对称破缺配位和多配体耦合在裁剪电子构型和中间吸附能量学中的机制。来自像差校正扫描透射电子显微镜、基于同步加速器的x射线吸收光谱和密度泛函理论计算的互补见解被整合在一起，以建立原子级结构描述符（配位数、键长/角度）和电子状态（d波段中心、电荷转移）之间的动态相关性。本文提出了连接配位环境-电子性能-催化性能的定量构效关系模型。在未来，前景集中在跨学科集成利用高通量机器人合成，人工智能驱动的设计和生命周期评估框架，以架起原子尺度精度与设备级实现之间的桥梁。这些努力将加速将sac转化为燃料电池、绿色制氢和碳中和技术的变革性解决方案，最终重塑可持续能源转换的格局。图形抽象

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引用次数: 0

An insight into intrinsic mechanism of voltage decay in Mn-full Li-rich layered cathodes for lithium-ion batteries 锂离子电池富锰层状阴极电压衰减内在机制的研究

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-09-15 DOI: 10.1007/s12598-025-03593-4

Yong Chen, Xiao-La Li, Xuan-He Yang, Wen-Zhao Huang, Yuan Xiao, Hua-Jun Xu, Juan-Juan Cheng, Dong Luo

The widespread application of Li-rich manganese-based layered oxides (LROs), distinguished by their high energy density and low cost, is significantly constrained by voltage decay. The presently unresolved mechanism underlying this phenomenon impedes the development of effective countermeasures. Extensive research has established that voltage decay originates from irreversible oxygen release and structural evolution, but the relationship between these two factors remains incompletely characterized. This study investigates the impact of oxygen (O) redox and transition metal (TM) redox on voltage decay using Ni/Co-free Mn-full Li-rich layered oxides (MFLROs), which mitigates the confounding effects of concurrent Ni/Co redox and O redox. Electrochemical analysis demonstrates that stabilizing the O redox through Ti doping significantly inhibits voltage decay. Critically, multiple ex/in situ measurements and first-principles calculations reveal irreversible oxygen release as the dominant factor driving voltage decay. This insight establishes a foundational framework for addressing voltage decay in future research.

Graphical abstract

富锂锰基层状氧化物（LROs）具有高能量密度和低成本的特点，但其广泛应用受到电压衰减的极大限制。目前尚未解决的这一现象背后的机制阻碍了有效对策的发展。广泛的研究表明，电压衰减源于不可逆的氧释放和结构演化，但这两个因素之间的关系尚未完全确定。本文研究了氧(O)氧化还原和过渡金属（TM）氧化还原对电压衰减的影响，利用无Ni/Co-free Mn-full - Li-rich层状氧化物（MFLROs）减轻了Ni/Co氧化还原和O氧化还原同时发生的混淆效应。电化学分析表明，通过Ti掺杂稳定O氧化还原可以显著抑制电压衰减。重要的是，多次原位/原位测量和第一性原理计算表明，不可逆氧释放是驱动电压衰减的主要因素。这一见解为解决未来研究中的电压衰减建立了基础框架。图形抽象

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引用次数: 0

Flow-engineered multiscale porous electrode design for promoting bubbles removal efficiency toward high-current–density hydrogen evolution reaction 流动工程多尺度多孔电极设计，以提高高电流密度析氢反应的气泡去除效率

IF 11 1区材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY

Rare Metals

Pub Date : 2025-09-15 DOI: 10.1007/s12598-025-03586-3

Qing-Peng Sun, Ting-Ting Wang, Lu-Yi Shi, Yue Deng, Shao-Fei Zhang, Jin-Feng Sun, Jian-Li Kang, Tian-Tian Li, Man Li, Qi-Feng Mu

Large-scale hydrogen production through water electrolysis at high current densities encounters significant challenges due to the sluggish bubble dynamics on tortuous nanoporous electrodes, which lead to increased activation loss and structural degradation. Drawing inspiration from the directional fluid transport properties of pipeline structures, this study introduces a bubble-guiding electrode design by integrating periodic, vertically aligned porous channels into dealloyed nanoporous NiCo alloy (denoted as PA_x-npNiCo, where x refers to the periodic spacing). The vertically aligned macro-channels create a split-path effect for both gas bubbles and electrolyte flow, maintaining stable bubble diffusion velocity and reducing the risk of bubble coalescence. Moreover, nanopores formed through chemical dealloying provide a high density of active sites, significantly boosting hydrogen evolution reaction (HER) performance. By combining high-speed camera observations with computational fluid dynamics (CFD) simulations, the optimized geometry of the flow-engineered channels has been identified, demonstrating exceptional bubble-guiding capabilities. The optimized PA₂₀₀-npNiCo electrode, featuring vertically aligned channels with a 200 µm period and three-dimensional (3D) nanopores on the ligaments, achieves a record current density of 981 mA cm⁻² at a low overpotential of 223 mV, while maintaining long-term stability over 450 h at 500 mA cm⁻². When using PA₂₀₀-npNiCo as both the cathode and anode in an electrolyzer, it requires only 1.97 V to achieve 400 mA cm⁻² and exhibits stable operation for 100 h at 1000 mA cm⁻². This work offers valuable insights into bubble dynamics for HER and highlights the significance of multiscale porous electrode architecture design for broader electrocatalytic gas-evolving applications.

Graphic Abstract

由于弯曲纳米孔电极上的气泡动力学缓慢，导致活化损失和结构降解增加，因此在高电流密度下通过水电解大规模制氢面临重大挑战。受管道结构定向流体输运特性的启发，本研究引入了一种气泡引导电极设计，将周期性、垂直排列的多孔通道集成到合金纳米多孔NiCo合金中（标记为PAx-npNiCo，其中x为周期间距）。垂直排列的宏观通道对气泡和电解质流动都产生了分路效应，保持了稳定的气泡扩散速度，降低了气泡聚并的风险。此外，通过化学合金化形成的纳米孔提供了高密度的活性位点，显著提高了析氢反应（HER）的性能。通过将高速摄像机观测与计算流体动力学（CFD）模拟相结合，确定了流动工程通道的优化几何形状，展示了卓越的气泡引导能力。优化后的PA200-npNiCo电极具有200µm周期的垂直排列通道和韧带上的三维纳米孔，在223 mV的低过电位下达到创纪录的981 mA cm - 2电流密度，同时在500 mA cm - 2下保持450小时的长期稳定性。当在电解槽中使用PA200-npNiCo作为阴极和阳极时，只需要1.97 V就可以达到400 mA cm - 2，并且在1000 mA cm - 2下稳定运行100小时。这项工作为HER的气泡动力学提供了有价值的见解，并强调了多尺度多孔电极结构设计对更广泛的电催化气体演化应用的重要性。图形抽象

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