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

Dual-plasmonic Ag/MoO3−x nanoflowers for ultrasensitive SERS sensing of aldehyde VOCs gas 双等离子体Ag/MoO3−x纳米花用于醛类VOCs气体的超灵敏SERS检测

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

Rare Metals

Pub Date : 2025-08-29 DOI: 10.1007/s12598-025-03562-x

Xiang-Yu Meng, Long-Song Li, Jing-Jing Wu, Ao-Chi Liu, Lei Xu, Yue-Ning Wang, Yue Hu, Zhou-Xu Zhang, Lin Qiu, Xiao-Yu Song, Ai-Guo Wu, Xiao-Tian Wang, Jie Lin

The electromagnetic field coupling between two kinds of noble metal nanoparticles endows high surface-enhanced Raman scattering (SERS) activity but is accompanied by uneven hot spots. Using two-dimensional semiconductors with localized surface plasmon resonance (LSPR) effects instead of one of the noble metal components can effectively improve uniformity. Hence, the Ag nanoparticles (Ag NPs) loaded MoO_3−x nanoflowers (Ag/MoO_3−x) were engineered to exploit dual-plasmonic coupling and realize the trace detection of aldehyde volatile organic compounds (VOCs) gas. The finite-difference time-domain (FDTD) simulation results proved that there is an obvious electromagnetic field coupling effect between Ag NPs and MoO_3−x semiconductors, which can amplify the molecular dipole moment significantly. The chemical enhancement mechanism in the Ag/MoO_3−x substrate was clarified by band structure analysis, in which the free electrons accumulated at the bottom of the conduction band of the MoO_3−x semiconductor can promote the charge transfer process between Ag/MoO_3−x and the 4-aminothiophenol (4-ATP) molecule. Moreover, the electron delocalization of 4-ATP molecule was enhanced after being absorbed on Ag/MoO_3−x nanoflowers, facilitating the charge transfer between 4-ATP and Ag/MoO_3−x substrate effectively. Importantly, using the 4-ATP molecule as a probe, the trace detection of a variety of aldehyde VOCs gas was realized by Ag/MoO_3−x substrate with a low limit of detection (LOD) of 10 ppb. This work provided a new idea for the design of noble metal-plasmonic semiconductor heterostructure substrates.

Graphical abstract

两种贵金属纳米粒子之间的电磁场耦合具有较高的表面增强拉曼散射活性，但存在不均匀的热点。利用具有局域表面等离子体共振（LSPR）效应的二维半导体代替贵金属元件可以有效地改善均匀性。因此，设计了负载MoO3−x纳米花（Ag/MoO3−x）的Ag纳米粒子（Ag NPs），利用双等离子体耦合实现了醛类挥发性有机化合物（VOCs）气体的痕量检测。时域有限差分（FDTD）仿真结果证明，Ag纳米粒子与MoO3−x半导体之间存在明显的电磁场耦合效应，可以显著放大分子偶极矩。通过带结构分析阐明了Ag/MoO3−x衬底中的化学增强机制，其中在MoO3−x半导体导带底部积累的自由电子促进了Ag/MoO3−x与4-氨基噻吩（4-ATP）分子之间的电荷转移过程。此外，4-ATP分子被Ag/MoO3−x纳米花吸收后，电子离域增强，有效促进了4-ATP与Ag/MoO3−x底物之间的电荷转移。重要的是，利用4-ATP分子作为探针，Ag/MoO3−x底物实现了多种醛类VOCs气体的痕量检测，低检出限（LOD）为10 ppb。本工作为贵金属-等离子体半导体异质结构衬底的设计提供了新的思路。图形抽象

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引用次数: 0

Enhancing immunogenic cell death in lung cancer through Ferritin-based nanocarriers: a novel approach for combined immunotherapy 通过铁蛋白纳米载体增强肺癌免疫原性细胞死亡：一种联合免疫治疗的新方法

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

Rare Metals

Pub Date : 2025-08-28 DOI: 10.1007/s12598-025-03495-5

Runsen Jin, Chunxia Zhang, Xianfei Zhang, Yuqin Cao, Mingyuan Du, Jie Xiang, Kai Chen

Immunogenic cell death (ICD) represents a crucial mechanism in cancer therapy, providing a pathway to trigger antitumor immune responses. Recent advancements in understanding and applying ICD for lung cancer therapy have identified traditional chemotherapy agents as potent ICD inducers. Despite their efficacy, the systemic toxicity and potential for inducing drug resistance limit their clinical application. This study introduces a novel approach utilizing ferritin-based nanocarriers [HFn(+)] for the targeted delivery of doxorubicin (DOX), combined with CpG oligodeoxynucleotides as an immune adjuvant, to enhance the immunogenicity and therapeutic efficacy against lung cancer. The engineered HFn(+) nanocarriers exploit the tumor-targeting ability of ferritin, capitalizing on its preferential uptake via transferrin receptor 1 (TfR1) overexpression on tumor cells. We comprehensively evaluate the preparation, characterization, and in vitro and in vivo efficacy of pHFn(+)@CpG/DOX complexes. The study confirms the potent antitumor activity of pHFn(+)@CpG/DOX in a lung cancer model, presenting a promising strategy for combined tumor immunotherapy with minimal systemic toxicity. This approach not only underscores the potential of nanocarrier-based drug delivery systems in cancer therapy but also opens new avenues for developing more effective and targeted cancer treatment modalities.

Graphical Abstract

免疫原性细胞死亡（Immunogenic cell death， ICD）是癌症治疗中的一个重要机制，它提供了一种触发抗肿瘤免疫反应的途径。在了解和应用ICD治疗肺癌方面的最新进展已确定传统化疗药物是有效的ICD诱导剂。尽管其疗效显著，但全身性毒性和诱导耐药的潜力限制了其临床应用。本研究介绍了一种利用铁蛋白纳米载体[HFn(+)]靶向递送多柔比星（DOX）的新方法，并联合CpG寡脱氧核苷酸作为免疫佐剂，以提高肺癌的免疫原性和治疗效果。设计的HFn（+）纳米载体利用铁蛋白的肿瘤靶向能力，通过肿瘤细胞上过表达的转铁蛋白受体1 （TfR1）优先摄取铁蛋白。我们综合评价了pHFn(+)@CpG/DOX配合物的制备、表征及其体外和体内功效。该研究证实了pHFn(+)@CpG/DOX在肺癌模型中的有效抗肿瘤活性，提出了一种具有最小全身毒性的联合肿瘤免疫治疗策略。这种方法不仅强调了基于纳米载体的药物输送系统在癌症治疗中的潜力，而且为开发更有效和更有针对性的癌症治疗方式开辟了新的途径。图形抽象

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引用次数: 0

Reactive hydrogen species behaviors on Cu-doped Co3O4 nanoneedles enhance nitrate electroreduction at high current density 在高电流密度下，cu掺杂Co3O4纳米针上的活性氢行为增强了硝酸盐的电还原

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

Rare Metals

Pub Date : 2025-08-27 DOI: 10.1007/s12598-025-03576-5

Yan-Qiu Wu, Shuai Niu, Bin Wu, Feng Wu, Ying Yuan, Juan Zhang, Jia-Wei Wang, Liang Chen, Xu Wu

The electrochemical conversion of nitrate, commonly found in industrial effluents and contaminated groundwater, into ammonia offers a sustainable strategy for both wastewater remediation and ammonia production. However, most existing catalysts exhibit limited activity and stability, particularly under industrial-level current density. Here we present a straightforward hydrothermal–calcination method to in situ fabricate Cu-doped Co₃O₄ nanoneedle arrays on three-dimensional porous copper foam (Cu-Co₃O₄/CF). The resulting electrode delivers an industrial-scale current density of ~ 1000 mA cm⁻², a high NH₃ yield rate of 58.4 mg h⁻¹ cm⁻², and a Faradaic efficiency of 98.3% at −0.5 V versus RHE. The outstanding performance under high current density highlights the significant practical potential of Cu-Co₃O₄/CF for large-scale applications. Density functional theory (DFT) calculations combined with experimental analysis demonstrate that Cu incorporation optimizes NO₃⁻ adsorption energy. More importantly, the doping of Cu accelerates the kinetics of the Volmer step (H₂O → *H + *OH), which provides protons for the hydrogenation pathway. This promotes the selective formation of NH₃ during the electrochemical nitrate reduction reaction (NO₃RR). Overall, this work provides fundamental insights into designing efficient transition metal oxide catalysts for nitrate valorization.

Graphical abstract

硝酸盐通常存在于工业废水和受污染的地下水中，其电化学转化为氨为废水修复和氨生产提供了一种可持续的策略。然而，大多数现有的催化剂表现出有限的活性和稳定性，特别是在工业水平的电流密度下。本文提出了一种在三维多孔泡沫铜（Cu-Co3O4/CF）上原位制备cu掺杂Co3O4纳米针阵列的直接水热煅烧方法。该电极的电流密度可达~ 1000 mA cm−2，NH3产率高达58.4 mg h−1 cm−2，与RHE相比，在−0.5 V下的法拉第效率可达98.3%。Cu-Co3O4/CF在高电流密度下的优异性能凸显了Cu-Co3O4/CF在大规模应用中的巨大应用潜力。密度泛函理论（DFT）计算结合实验分析表明，Cu的掺入优化了NO3−吸附能。更重要的是，Cu的掺杂加速了Volmer步骤（H2O→*H + *OH）的动力学，为加氢途径提供了质子。这促进了电化学硝酸还原反应（NO3RR）中NH3的选择性形成。总的来说，这项工作为设计有效的过渡金属氧化物催化剂提供了基本的见解。图形抽象

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引用次数: 0

Polymorphic reactive oxygen species (ROS) storm for enhanced tumor therapy 多态活性氧（ROS）风暴增强肿瘤治疗

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

Rare Metals

Pub Date : 2025-08-25 DOI: 10.1007/s12598-025-03510-9

Yanhong Sun, Sihuai Xiong, Xingwu Jiang, Jing Jin, Tianlin Song, Fan Wu, Fei Chen, Di Wu, Yuanchen Wang, Xianfu Meng, Wenbin Zou, Zhuan Liao, Wenbo Bu

Generating excessively reactive oxygen species (ROS) within tumor cells is a widely adopted therapeutic strategy. However, single-type ROS exhibit fixed attack sites and mechanisms of action in tumor cells, rendering them susceptible to resistance via cellular repair mechanisms. To overcome this limitation, this study proposes a polymorphic ROS strategy that simultaneously induces multiple types of ROS to enhance the therapeutic efficacy. A nanoplatform named as AuPd@Mn_xO_y/L/DOX (AP-M@L/D) is developed. AuPd core can catalyze oxygen to generate superoxide anions (O₂^·−), and the released multivalent manganese ions in tumor can trigger the production of singlet oxygen (¹O₂) and hydroxyl radicals (·OH). The polymorphic ROS (O₂^·−, ¹O₂, ·OH) with different reactivity, lifetime, and diffusion capacity can achieve multifaceted oxidative damage, significantly improving tumor eradication. Concurrently, photothermal heating and DOX release can enhance catalytic reaction rate and intracellular hydrogen peroxide levels, further amplifying polymorphic ROS generation. Both in vitro and in vivo experiments demonstrate that AP-M@L/D induces significant intracellular oxidative stress and enhances cell-killing efficiency by activating the apoptotic pathway. In summary, the spatiotemporally controllable polymorphic ROS can enhance antitumor efficacy and provide a guidance for ROS therapy.

在肿瘤细胞内产生过多的活性氧（ROS）是一种被广泛采用的治疗策略。然而，单型ROS在肿瘤细胞中表现出固定的攻击位点和作用机制，使其容易通过细胞修复机制产生耐药性。为了克服这一限制，本研究提出了一种多态ROS策略，同时诱导多种类型的ROS来提高治疗效果。开发了一个纳米平台AuPd@MnxOy/L/DOX （AP-M@L/D）。AuPd核可以催化氧生成超氧阴离子（O2·−），在肿瘤中释放的多价锰离子可以触发单线态氧（1O2）和羟基自由基（·OH）的产生。具有不同反应活性、寿命和扩散能力的多态ROS （O2·−、1O2、·OH）可实现多方面的氧化损伤，显著促进肿瘤根除。同时，光热加热和DOX释放可以提高催化反应速率和细胞内过氧化氢水平，进一步放大多态ROS的生成。体外和体内实验均表明AP-M@L/D通过激活凋亡通路诱导细胞内氧化应激，提高细胞杀伤效率。综上所述，时空可控的多态ROS可以增强抗肿瘤疗效，为ROS治疗提供指导。

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引用次数: 0

Modulating electronic structure to expedite Na4Fe3(PO4)2P2O7 reaction kinetics for high-power Na-ion batteries 调制电子结构加快大功率钠离子电池Na4Fe3(PO4)2P2O7反应动力学

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

Rare Metals

Pub Date : 2025-08-25 DOI: 10.1007/s12598-025-03552-z

Ning-Chun Li, Chen-Wei Li, Michal Sedlačík, Petr Saha, Qi-Lin Cheng, Hai-Feng Yu, Hao Jiang

The Na₄Fe₃(PO₄)₂P₂O₇ (NFPP) has considered as a very attractive cathode material for Na-ion batteries mainly due to its cheap price and high security. Its low electron transfer rate is usually improved by coating a layer of hard carbon, which however exhibits a low graphitization degree because of the relatively low NFPP synthesis temperature (~ 500 °C). In this study, a highly-conductive hybrid carbon has been employed to accelerate redox reaction kinetics of NFPP by modulating electronic structure for achieving high-power Na-ion batteries. The hybrid carbon is derived from the mixed polyethylene glycol (PEG) and glucose, in which the low ether bond energy (~ 340 kJ mol⁻¹) of PEG facilitates the free radical generation during pyrolysis with high graphitization degree while glucose improves the uniformity of the carbon coating. As a result, the optimized cathode exhibits a very high reversible capacity of 90.8 mAh g⁻¹ at 20C within 2.0–4.0 V with 85.3% capacity retention after 10,000 cycles, highlighting huge application potentials in two-wheeled electric vehicles, backup energy storage, and so forth.

Graphic Abstract

Na4Fe3(PO4)2P2O7 （NFPP）被认为是一种非常有吸引力的钠离子电池正极材料，主要是因为它价格便宜，安全性高。其低电子转移率通常通过涂覆一层硬碳来改善，但由于NFPP合成温度相对较低（~ 500℃），其石墨化程度较低。在这项研究中，高导电杂化碳通过调节电子结构来加速NFPP的氧化还原反应动力学，从而实现高功率na离子电池。杂化碳是由聚乙二醇（PEG）和葡萄糖混合而成，其中聚乙二醇的醚键能低（~ 340 kJ mol−1），有利于热解过程中自由基的生成，石墨化程度高，葡萄糖提高了碳包层的均匀性。结果表明，优化后的阴极在2.0-4.0 V范围内，在20C条件下具有90.8 mAh g−1的高可逆容量，10000次循环后容量保持率为85.3%，在两轮电动汽车、备用储能等领域具有巨大的应用潜力。图形抽象

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引用次数: 0

Optimizing electrochemical microenvironment of Ni sites by constructing Ni–WO2 heterostructure for promoting electrocatalytic conversion of methanol to formate via direct electrooxidation path 通过构建Ni - wo2异质结构，优化Ni位点的电化学微环境，促进直接电氧化途径电催化甲醇转化为甲酸酯

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

Rare Metals

Pub Date : 2025-08-25 DOI: 10.1007/s12598-025-03544-z

Shuai He, Man Zhao, Peipei Zhao, Jiamin Ma, Chunmei Liu, He Xiao, Li Zhang, Junming Zhang, Tianjun Hu, Shengxiang Wang, Huan Pang, Jianfeng Jia

Nickel-based catalysts display promising potential in integrated hydrogen production through methanol electrooxidation (MOR). The unavoidable self-oxidation from Ni(OH)₂ to NiOOH severely restricts their MOR performance. To inspire the progress of MOR before self-oxidation of Ni species by altering reaction pathways, a heterostructured Ni–WO₂ catalyst is constructed to follow the direct electrooxidation pathway of methanol. In-situ/ex-situ characterization techniques combined with density functional theory calculations reveal the constructed Ni–WO₂ heterostructure alters the electronic structure of Ni site. It’s found Ni–Ni bond in Ni–WO₂ becomes longer and the electrons transfer from Ni sites to W sites. This results in upshifted d band center of Ni site and its closing to the Fermi energy level, which optimizes the CH₃OH adsorption and the deprotonation of *CH₃O into *CH₂O in potential-determining step. Moreover, the formed asymmetric adsorption sites increase the polarity of the methanol and the intermediate. As expected, CH₃OH molecule is highly converted into HCOOH via direct electrooxidation pathway. This obtained Ni–WO₂ exhibits superior MOR activity with high peak current density of 325.26 mA cm⁻² and performs long term of 90 h at 10 mA cm⁻² in hydrogen production. This work provides an important guidance for designing efficient Ni-based samples for direct electrooxidation of methanol.

Graphical abstract

镍基催化剂在甲醇电氧化综合制氢（MOR）中具有广阔的应用前景。Ni(OH)2不可避免的自氧化生成NiOOH，严重制约了其MOR性能。为了通过改变反应途径来激发Ni在自氧化前的MOR进展，构建了一种异质结构的Ni - wo2催化剂，遵循甲醇的直接电氧化途径。原位/非原位表征技术结合密度泛函理论计算表明，构建的Ni - wo2异质结构改变了Ni位点的电子结构。发现Ni - wo2中的Ni - Ni键变长，电子从Ni位转移到W位。这使得Ni位点的d带中心上移，并接近费米能级，从而优化了CH3OH的吸附，并在电位决定步骤中使* ch30脱质子为*CH2O。此外，形成的不对称吸附位点增加了甲醇和中间体的极性。正如预期的那样，CH3OH分子通过直接电氧化途径高度转化为HCOOH。得到的Ni-WO2具有较高的MOR活性，峰值电流密度为325.26 mA cm−2，在10 mA cm−2下可长时间产氢90 h。这项工作为设计高效的镍基样品用于甲醇的直接电氧化提供了重要的指导。图形抽象

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引用次数: 0

Synergistic defect engineering and gradient pore structure induce tellurium nanoclusters for high-performance aqueous zinc-tellurium batteries 协同缺陷工程和梯度孔结构诱导制备高性能锌碲水电池用碲纳米团簇

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

Rare Metals

Pub Date : 2025-08-22 DOI: 10.1007/s12598-025-03551-0

Yan-Ping Guo, Heng-Rui Guo, Long-Sheng Liang, Hao Luo, Xue-Ying Su, Rong-Sheng Zheng, Kun-Wei Zheng, Kai-Ying Wang, Zai-Jun Cheng

Aqueous zinc-tellurium (Zn-Te) batteries have garnered much attention due to their inherent safety and high specific capacity. Unfortunately, the problem of low utilization and severe volume expansion represents a significant obstacle to the development of aqueous Zn-Te batteries. Herein, a synergistic defect engineering and gradient pore structure strategy is proposed to construct tellurium nanoclusters/carbon composite cathode materials (DP-C/Te) for high-performance aqueous Zn-Te batteries. The gradient pore structure supplies confinement spaces that restrict crystalline tellurium formation, facilitating high-activity tellurium nanoclusters and enhancing structural stability. A defect-rich structure can accelerate the migration and aggregation of tellurium, not only leading to the formation of tellurium nanoclusters but also boosting the redox reaction of aqueous Zn-Te batteries. Additionally, robust C–O bonds can further facilitate the interfacial electron transfer. Consequently, the DP-C/Te cathode for aqueous zinc-tellurium batteries demonstrates sufficient specific capacity (481.75 mAh g⁻¹ at 0.1 A g⁻¹), superior rate performance (114 mAh g⁻¹ even at 3 A g⁻¹) and reliable cycling stability (81% capacity retention at 1 A g⁻¹ after 1100 cycles). Furthermore, this work offers a promising perspective for high-performance aqueous Zn-Te batteries.

Graphical Abstract

锌碲（Zn-Te）水电池因其固有的安全性和高比容量而备受关注。不幸的是，低利用率和严重的体积膨胀问题是阻碍水性锌- te电池发展的一个重要障碍。本文提出了一种缺陷工程和梯度孔结构协同策略，用于构建高性能水性锌碲电池用碲纳米团簇/碳复合正极材料（DP-C/Te）。梯度孔隙结构提供了限制碲晶体形成的约束空间，促进了高活性碲纳米团簇的形成，提高了结构的稳定性。富缺陷结构可以加速碲的迁移和聚集，不仅可以形成碲纳米团簇，还可以促进水相Zn-Te电池的氧化还原反应。此外，强大的C-O键可以进一步促进界面电子转移。因此，用于水相锌碲电池的DP-C/Te阴极具有足够的比容量（在0.1 A g−1时为481.75 mAh g−1），优越的倍率性能（即使在3 A g−1时为114 mAh g−1）和可靠的循环稳定性（在1100次循环后在1 A g−1时容量保持81%）。此外，这项工作为高性能水性锌碲电池提供了一个有希望的前景。图形抽象

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引用次数: 0

Review of additively manufactured zinc alloys by laser powder bed fusion for biomedical applications 激光粉末床熔合增材制造锌合金在生物医学领域的研究进展

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

Rare Metals

Pub Date : 2025-08-22 DOI: 10.1007/s12598-025-03518-1

Xuan Yang, Zaimao Peng, Yan Fang, Yunlong Tang, Hsin-Hui Shen, Yuman Zhu

Zinc (Zn) and its alloys have emerged as promising candidates for biomedical materials, owing to their controlled degradation kinetics, intrinsic biocompatibility, and the release Zn²⁺ ions which are known to promote bone regeneration and tissue healing. Despite their potential, the widespread clinical adoption of Zn alloys has been hindered by insufficient mechanical properties, design limitations of traditional manufacturing, and limited clinical validation. Recent advances in additive manufacturing (AM), particularly laser powder bed fusion (LPBF), are revolutionizing the production of Zn alloy implants. LPBF enables unprecedented design freedom and accuracy, allowing the fabrication of patient-specific, geometrically-intricate and porous structures with unique functionality that are previously unattainable. This review aims to provide a comprehensive overview of the latest progress in LPBF processing of Zn alloys, focusing on structure design, fabrication, microstructural characteristics, and mechanical and biological properties—critical factors for real applications of functional implants, particularly in cardiovascular and orthopedic fields. Additionally, this review examines the role of post-processing treatments, such as heat treatments and surface modifications, in adjusting degradation rate, controlling Zn²⁺ ion release, and improving cell viability, proliferation and differentiation, all of which are vital for achieving predictable and reliable in vivo outcomes. Further, the review seeks to synthesize these advances and their interplays to provide a strategic insight for translating patient-specific, biodegradable Zn implants into clinical practice.

Graphical abstract

锌（Zn）及其合金因其可控制的降解动力学、内在的生物相容性以及释放的Zn2+离子（已知可促进骨再生和组织愈合）而成为生物医学材料的有希望的候选者。尽管具有潜力，锌合金的广泛临床应用受到机械性能不足、传统制造的设计限制和有限的临床验证的阻碍。增材制造（AM）的最新进展，特别是激光粉末床熔融（LPBF），正在彻底改变锌合金植入物的生产。LPBF实现了前所未有的设计自由度和精度，允许制造患者特定的、几何复杂的、具有独特功能的多孔结构，这是以前无法实现的。本文综述了锌合金LPBF加工的最新进展，重点介绍了结构设计、制造、微观结构特征、力学和生物学特性等方面的研究进展，这些都是功能植入物，特别是心血管和骨科领域应用的关键因素。此外，本文还探讨了后处理（如热处理和表面修饰）在调节降解速率、控制Zn2+离子释放、提高细胞活力、增殖和分化方面的作用，这些都是实现可预测和可靠的体内结果的关键。此外，该综述旨在综合这些进展及其相互作用，为将患者特异性、可生物降解的锌植入物转化为临床实践提供战略见解。图形抽象

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引用次数: 0

Boosting hydrogen spillover over carbon nanotube anchored ultrafine Co/Co2O3 nanoparticles for efficient neutral H2O2 electrosynthesis 碳纳米管锚定的超细Co/Co2O3纳米颗粒促进氢溢出，用于高效的中性H2O2电合成

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

Rare Metals

Pub Date : 2025-08-22 DOI: 10.1007/s12598-025-03557-8

Zhuoqi Zhou, Yu Han, Manman Zou, Ronglan Pan, Xin Ge, Chuanxun Du, Jili Yuan, Tao Wang, Hao Zhang, Hu Li, Jian Zhang

Neutral H₂O₂ electrosynthesis via two-electron oxygen reduction reaction (2e⁻-ORR) is a promising alternative to replace traditional anthraquinone processes. However, it still remains significantly challenging to develop efficient electrocatalysts due to sluggish neutral 2e⁻-ORR kinetics. Herein, we reported abundant ultrafine Co/Co₂O₃ nanoparticles (NPs) anchored oxidic nitrogen-doped carbon nanotubes (Co/Co₂O₃@OCNT) derived from the pyrolysis of the mixed OCNT and Co@Tpy, presenting synergistical enhancement effect on the water dissociation to supply active hydrogen coupling with O₂ to produce H₂O₂ at positive onset potential of 0.66 V vs. RHE. As a result, Co/Co₂O₃@OCNT achieves a record current density of 4.0 mA cm⁻² at 0.2 V vs. RHE and nearly 100% H₂O₂ selectivity at the potential from 0 to 0.5 V vs. RHE. In situ observations demonstrated that ultrafine Co/Co₂O₃ NPs and nitrogen-doped carbon supports would synergistically improve the active hydrogen feeding further to facilitate the formation of key intermediate *OOH. Furthermore, based on the sandwiched configuration of the flow cell, Co/Co₂O₃@OCNT shows a superior performance with the yield rate of salt-free aqueous H₂O₂ solution around 63.4 mol g_cat⁻¹ h⁻¹ at 200 mA cm⁻² and the corresponding Faradaic efficiency of 85%. Moreover, integration of Co/Co₂O₃@OCNT into this cell achieves high real-time production concentration of H₂O₂ around 20 mM at 200 mA cm⁻² by varying the pure water flow rate to 1 mL min⁻¹, suggesting the huge potential of salt-free H₂O₂ solution production. This work provides a novel strategy for developing efficient neutral electrocatalysts and feasible process of neutral H₂O₂ production.

Graphical Abstract

双电子氧还原反应（2e−-ORR）电合成中性H2O2是一种很有前途的替代传统蒽醌工艺的方法。然而，由于中性2e−-ORR动力学缓慢，开发高效电催化剂仍然具有很大的挑战性。在此，我们报道了大量的超细Co/Co2O3纳米颗粒（NPs）锚定氧化氮掺杂碳纳米管（Co/Co2O3@OCNT），来自混合OCNT和Co@Tpy的热解，对水解离具有协同增强作用，提供活性氢偶联与O2产生H2O2，与RHE相比，正电位为0.66 V。结果，Co/Co2O3@OCNT在0.2 V vs. RHE电位下达到了创纪录的4.0 mA cm - 2电流密度，在0 ~ 0.5 V电位下达到了接近100%的H2O2选择性。原位观察表明，超细Co/Co2O3 NPs和氮掺杂碳载体将进一步协同提高活性氢的供能，促进关键中间体*OOH的形成。此外，基于夹层结构的流动电池，Co/Co2O3@OCNT表现出优异的性能，在200 mA cm−2下，无盐H2O2水溶液的产率约为63.4 mol gcat−1 h−1，相应的法拉第效率为85%。此外，将Co/Co2O3@OCNT整合到该电池中，通过将纯水流速改变为1 mL min - 1，在200 mA cm - 2下实现了高的H2O2实时生产浓度，约为20 mM，这表明无盐H2O2溶液生产的巨大潜力。本研究为开发高效的中性电催化剂和生产中性H2O2的可行工艺提供了新的思路。图形抽象

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