Journal of Alloys and Compounds最新文献_第9页

Effect of tautomerism on the hydrogen storage performance of alkali metal pyridinolates 互变异构对碱金属吡啶酸酯储氢性能的影响

IF 6.3 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Journal of Alloys and Compounds

Pub Date : 2026-01-12 DOI: 10.1016/j.jallcom.2026.186148

Alexis Munyentwali , Xingchi Zhou , Jiaquan Guo , Yang Yu , Qijun Pei , Anan Wu , Teng He , Ping Chen

Alkali metal pyridinolates have recently emerged as promising materials for reversible hydrogen storage owing to their high hydrogen capacities, simple synthesis, low cost, air stability, and favorable dehydrogenation thermodynamics. Given that these compounds originate from organic precursors that exhibit tautomerism, this study investigates the effect of tautomeric equilibria on their hydrogen storage performance. Using three positional isomers of lithium pyridinolate as representative model compounds, density functional theory calculations combined with experimental results reveal divergent reactivity patterns. In lithium 2-pyridinolate, the tautomeric equilibrium favors the lithium 2-pyridonate form; however, the intrinsic amide resonance stabilization in this tautomer hinders complete hydrogenation, leading to a stable intermediate that cannot be reversibly dehydrogenated under moderate conditions. Lithium 3-pyridinolate, which exists exclusively in this form, undergoes complete hydrogenation to form lithium 3-piperidinolate; yet this hydrogen-rich compound cannot be efficiently dehydrogenated under moderate conditions because of its high thermodynamic stability. In contrast, lithium 4-pyridinolate can tautomerize to its pyridonate form, but the para-arrangement of the CO and N–Li groups in the latter reduces its stability. As a result, lithium 4-pyridinolate, being the most stable tautomer, undergoes complete hydrogenation to form lithium 4-piperidinolate, which can also be reversibly dehydrogenated with a conversion of 99.6 % at temperatures as low as 100 °C due to its favorable thermodynamics. Overall, this study demonstrates the significance of considering tautomerism in the design of organic-based hydrogen storage materials and presents the lithium 4-pyridinolate/4-piperidinolate pair as a promising new system for reversible hydrogen storage.

碱金属吡啶酸酯具有储氢容量大、合成简单、成本低、空气稳定性好、脱氢热力学好等优点，近年来成为一种很有前途的可逆储氢材料。鉴于这些化合物来源于表现出互变异构的有机前体，本研究探讨了互变异构平衡对其储氢性能的影响。使用三个位置pyridinolate锂作为代表模型化合物的同分异构体,密度泛函理论计算结合实验结果显示不同的反应模式。在2-吡啶酸锂中，互变异构平衡倾向于2-吡啶酸锂的形式；然而，这种互变异构体固有的酰胺共振稳定性阻碍了完全氢化，导致稳定的中间体在中等条件下不能可逆脱氢。仅以这种形式存在的3-吡啶酸锂完全加氢生成3-哌啶酸锂；然而，由于其较高的热力学稳定性，这种富氢化合物在中等条件下不能有效脱氢。相比之下，4-吡啶酸锂可以变异构成吡啶盐形式，但后者中C=O和N-Li基团的平行排列降低了其稳定性。因此，4-吡啶酸锂作为最稳定的互变异构体，经过完全加氢形成4-胡椒酸锂，由于其良好的热力学特性，在低至100℃的温度下，4-哌酸锂也可以以99.6%的转化率可逆脱氢。总之，本研究证明了在设计有机基储氢材料时考虑互变异构的重要性，并提出了4-吡啶酸锂/4-哌啶酸锂对作为一种有前景的可逆储氢新体系。

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引用次数: 0

Gold nanostar@nickel-cobalt layered double hydroxide nanozymes for highly sensitive colorimetric detection of H₂O₂ 金Nanostar@Nickel-Cobalt层状双氢氧化物纳米酶的高灵敏度比色检测h2o₂O₂

IF 6.3 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Journal of Alloys and Compounds

Pub Date : 2026-01-12 DOI: 10.1016/j.jallcom.2026.186146

Dongxiao Lu, Xiuyu Li, Xuanxiong Zeng, Lin Yuan, Jinhua Li

Layered double hydroxides (LDHs) are an important class of nanozyme materials widely used for colorimetric detection of H₂O₂, owing to their layered architecture, abundant surface-active sites, and tunable electronic properties. However, individual LDH components often exhibit insufficient nanozyme activity toward the catalytic decomposition of H₂O₂. Here, we report a heterostructured nanozyme comprising gold nanostars intercalated into nickel–cobalt layered double hydroxides (AuSTs@LDH) for H₂O₂ colorimetric detection. The AuSTs@LDH interface markedly enhances electron transfer efficiency associated with the Co^2 + /Co³⁺ redox couple, delivering superior catalytic performance characterized by a markedly low Michaelis-Menten constant (K_m(H₂O₂) = 0.0008 mM), which represents an approximate 80.5 % reduction compared to pristine LDH material. Moreover, the sensing system based on AuSTs@LDH nanozyme enables accurate H₂O₂ detection with a detection limit of 9.72 μM (S/N = 3). The nanozyme exhibits high selectivity and anti-interference ability. In the presence of interferents (aspartic acid, urea, glycine, threonine, and glutamic acid), the variation in the H₂O₂ detection signal intensity is less than 3 %. Notably, integrating the AuSTs@LDH nanozyme with a hydrogel matrix yields a portable detection device, thereby achieving rapid on-site H₂O₂ detection. Overall, this work offers feasible design for high-performance nanozymes and presents a viable solution for H₂O₂ detection in biomedical diagnostics and environmental monitoring.

层状双氢氧化物（LDHs）是一类重要的纳米酶材料，由于其层状结构、丰富的表面活性位点和可调的电子性质，被广泛用于H2O2的比色检测。然而，单个LDH组分往往表现出对H2O2催化分解的纳米酶活性不足。在这里，我们报道了一种异质结构的纳米酶，它包含嵌入镍钴层状双氢氧化物的金纳米星（AuSTs@LDH），用于H2O2比色检测。AuSTs@LDH界面明显提高与二氧化碳相关的电子转移效率+ /二氧化碳+氧化还原电对,提供优越的催化性能具有明显低Michaelis-Menten常数(公里(过氧化氢)= 0.0008毫米),代表一个近似原始的LDH材料相比减少80.5%。此外，基于AuSTs@LDH纳米酶的传感系统能够准确检测H2O2，检测限为9.72μM （S/N = 3）。纳米酶具有高选择性和抗干扰能力。在干扰物（天冬氨酸、尿素、甘氨酸、苏氨酸和谷氨酸）存在的情况下，H2O2检测信号强度的变化小于3%。值得注意的是，将AuSTs@LDH纳米酶与水凝胶基质结合在一起，产生了一种便携式检测装置，从而实现了快速的现场H2O2检测。总的来说，这项工作为高性能纳米酶提供了可行的设计，并为生物医学诊断和环境监测中的H2O2检测提供了可行的解决方案。

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引用次数: 0

A novel Ca3Y2Si3O12:Sm3 + /Eu3+ phosphor with anti-thermal quenching for ratiometric thermometry 用于比例测温的新型抗热猝灭Ca3Y2Si3O12:Sm3+/Eu3+荧光粉

IF 6.3 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Journal of Alloys and Compounds

Pub Date : 2026-01-12 DOI: 10.1016/j.jallcom.2026.186178

Xiuying Tian , Yanling Wu , Suhua Wang , Jin Wen , Changyan Ji , Zhi Huang , Fei Luo , Xin Liu , Jing Li , Hongxia Peng , Shuying Zhou , Guowen Li , Hua-Tay Lin

The syntheses of Ca₃Y₂Si₃O₁₂: Sm³⁺/Eu³⁺ phosphors were undertaken in this study via a solid-state reaction for optical thermometry applications. Structural characterization via the use of XRD suggested an orthorhombic silico-carnotite structure, with Sm³⁺ and Eu³⁺ ions effectively incorporating into Y³⁺ sites. Structural analysis further suggested a preferential occupancy of Sm³⁺ and Eu³⁺ ions at A sites within host material of AB₂C₂(SiO₄)₃. The synthesized phosphors exhibited efficient energy transfer (ET) from Sm³⁺ to Eu³⁺, with a mechanism dominated by electric dipole-dipole interaction and a maximum transfer efficiency of 32.3 %. Temperature-dependent photoluminescence studies and corresponding contour maps revealed a unique anti-thermal quenching property of Eu³⁺ at 534 nm, attributed to ⁵D₁→⁷F₁ transition, while the emission of Eu³⁺ at 613 nm, assigned to ⁵D₀→⁷F₂ transition, followed conventional thermal quenching. Leveraging these contrasting thermal responses, an innovative thermometry scheme based on luminescence intensity ratio (LIR) was established. The optimized phosphor displayed a maximum relative sensitivity (Sᵣ) of 0.703 % K⁻¹ at 573 K and δT of 0.711 K at 573 K under 395 nm excitation, surpassing most of the reported thermometric phosphors, which highlighted the great applicational potential of the developed material for optical temperature sensing under high-temperature conditions.

本研究通过固相反应合成了用于光学测温的Ca3Y2Si3O12: Sm3+/Eu3+荧光粉。通过XRD进行的结构表征表明其为正交硅-卡诺岩结构，Sm3+和Eu3+离子有效地结合到Y3+位点上。结构分析进一步表明Sm3+和Eu3+离子优先占据AB2C2(SiO4)3的a位点。所合成的荧光粉具有从Sm3+到Eu3+的高效能量转移（ET）机制，以电偶极子-偶极子相互作用为主，最大转移效率为32.3%。温度相关的光致发光研究和相应的等高线图显示，534nm处的Eu3+具有独特的抗热猝灭特性，归因于5D1→7F1跃迁，而613nm处的Eu3+的发射归因于5D0→7F2跃迁，遵循常规热猝灭。利用这些对比热响应，建立了一种基于发光强度比（LIR）的创新测温方案。在395nm激发下，优化后的荧光粉在573K处的最大相对灵敏度（Sᵣ）为0.703% K-1，在573K处的δT为0.711K，超过了目前报道的大多数测温荧光粉，显示了该材料在高温条件下光学测温方面的巨大应用潜力。

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引用次数: 0

Facile fabrication of WO3/CuMoO4 heterojunction nanocomposite as a dual-functional S-scheme photocatalyst for hydrogen evolution and degradation of organic pollutants WO3/CuMoO4异质结纳米复合材料的制备及其作为双功能S-scheme光催化剂的析氢和降解有机污染物

IF 6.2 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Journal of Alloys and Compounds

Pub Date : 2026-01-12 DOI: 10.1016/j.jallcom.2026.186170

Ghader Hosseinzadeh, Alireza Yousefi, Seyed Mehdi Sajjadi, Reza Hadjiaghaie Vafaie, Sobhan Sheykhivand, Reza Hosseinzadeh, Javad Yekrang, Jamal Dabbagh

In this study, WO3/CuMoO4 heterojunction nanocomposites were developed by combining WO3 micro hallow sphere, and CuMoO4 nanoparticles using a hydrothermal method, and were applied as a dual-functional S-scheme photocatalyst for simultaneous degradation of RhB organic pollutants and hydrogen evolution under simulated sunlight irradiation. The findings indicated that such a heterojunction sample exhibited the improved photocatalytic properties, and maximum H2 evolution efficiency of 2.95 mmol g-1 h-1 was achieved for the WO3-40CuMoO4 sample with 40 w/w% of CuMoO4. The enhancement in the photocatalytic activities of these heterojunctions are originated from the reduction in the rate of recombination of the photogenerated charge carriers, enhanced sunlight absorption, and effective generation of reductant (e.g. e for H2 evolution) and oxidant species (such as O2•− and •OH radicals for the dye degradation). The S-scheme charge separation pathway was found to account for the improved photocatalytic properties of the heterojunction samples. In the S-scheme charge mechanism, formation of heterojunction contact between two the WO3 and CuMoO4 semiconductors, facilitates electron transfer between these semiconductors, which leads to improved charge separation, extended lifetimes of electrons and holes, and enhanced photocatalytic efficiency. The synthesized nanocomposite demonstrates satisfactory stability and can be effectively employed as a bifunctional S-scheme photocatalyst for simultaneous degradation of organic pollutants and hydrogen production.

本研究采用水热法将WO3微空心球与CuMoO4纳米颗粒结合，制备了WO3/CuMoO4异质结纳米复合材料，并将其作为双功能s型光催化剂应用于模拟阳光照射下RhB有机污染物的同时降解和析氢。结果表明，该异质结样品具有更好的光催化性能，当CuMoO4含量为40 w/w%时，WO3-40CuMoO4样品的析氢效率最高为2.95 mmol g-1 h-1。这些异质结的光催化活性的增强源于光生成的载流子的重组速率的降低，增强的阳光吸收，以及还原剂（例如用于H2演化的e）和氧化剂（例如用于染料降解的O2•−和•OH自由基）的有效生成。发现S-scheme电荷分离途径可以解释异质结样品光催化性能的改善。在S-scheme电荷机制中，WO3和CuMoO4半导体之间形成异质结接触，促进了半导体之间的电子转移，从而改善了电荷分离，延长了电子和空穴的寿命，提高了光催化效率。所合成的纳米复合材料具有良好的稳定性，可以有效地作为双功能s型光催化剂，同时降解有机污染物和制氢。

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引用次数: 0

Effects of site preference on crystal structure, magnetism, and magnetocaloric performance in Zn/Cd-doped EuAl4 位置偏好对Zn/ cd掺杂EuAl4晶体结构、磁性和磁热性能的影响

IF 6.3 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Journal of Alloys and Compounds

Pub Date : 2026-01-12 DOI: 10.1016/j.jallcom.2026.186154

Sujuan Wang , Yuqing Bai , Xiaohua Luo , Chunsheng Fang , Huiyang Yang , Rui Zhong , Qing Luo , Changcai Chen , Ihor Bulyk , Shengcan Ma

We report the effects of doping transition metal Zn and Cd on the crystal structure, magnetic properties and magnetocaloric effects of EuAl₄. Single crystals of EuAl_4-xZn_x and EuAl_4-yCd_y were successfully synthesized via the Al-flux method. These compounds crystallize in the tetragonal BaAl₄-type structure with the space group I4/mmm. Despite Zn and Cd belonging to the same group in the periodic table, their distinct atomic sizes lead to different site preferences within the EuAl₄ lattice, thereby inducing significant alterations in the lattice parameters and magnetic behaviors. Specifically, Zn atoms predominantly substitute for Al atoms at the 4e site, whereas Cd atoms occupy both the 4e and 4d sites equally. Upon Zn doping, compared to the pristine EuAl₄, the lattice parameter a decreases while the c increases. In contrast, Cd doping results in an almost unchanged a value and an increase in c. Both Zn and Cd doping contribute to the enhancement of ferromagnetic interactions and magnetocaloric properties. Notably, after Zn doping, the easy magnetization direction shifts from the ab plane to the c axis. Conversely, Cd doping weakens the magnetic anisotropy of the compounds. EuAl_3.51Zn_0.49, EuAl_3.27Zn_0.73 and EuAl_3.65Cd_0.35 compounds exhibit ferromagnetic characteristics along both the ab plane and the c axis. However, EuAl_3.77Cd_0.23 shows a pronounced magnetic field-induced first-order metamagnetic transition. Under the magnetic field change of 0–20 kOe, the maximum magnetic entropy change increases from −8.4 J/kg K for EuAl₄ to −14.2 J/kg K for EuAl_3.27Zn_0.73 and −16.3 J/kg K for EuAl_3.65Cd_0.35. The corresponding refrigeration capacity is 67, 120 and 128 J/kg, respectively. These outstanding magnetocaloric properties strongly suggest that EuAl_4-xZn_x and EuAl_4-yCd_y compounds are competitively performing materials for magnetic refrigeration applications in the liquid helium temperature region.

本文报道了过渡金属Zn和Cd掺杂对EuAl4晶体结构、磁性能和磁热效应的影响。采用Al-flux法成功合成了EuAl4-xZnx和EuAl4-yCdy单晶。这些化合物结晶为具有空间基I4/mmm的四方baal4型结构。尽管Zn和Cd在元素周期表中属于同一族，但它们不同的原子尺寸导致了EuAl4晶格中不同的位置偏好，从而导致了晶格参数和磁性行为的显著变化。具体来说，Zn原子主要取代Al原子在4e位点，而Cd原子同时占据4e和4d位点。与未掺杂的EuAl4相比，掺杂Zn后晶格参数a减小，c增大。相比之下，镉掺杂导致的a值几乎不变，而c值增加。锌和镉掺杂都有助于增强铁磁相互作用和磁热学性能。值得注意的是，锌掺杂后易磁化方向由ab平面向c轴方向偏移。相反，镉的掺杂削弱了化合物的磁各向异性。EuAl3.51Zn0.49、EuAl3.27Zn0.73和EuAl3.65Cd0.35化合物在ab平面和c轴上均表现出铁磁特性。而EuAl3.77Cd0.23表现出明显的磁场诱导的一阶偏磁跃迁。在0 ~ 20 kOe的磁场变化下，EuAl4的最大磁熵变化从-8.4 J/kg K增加到-14.2 J/kg K, EuAl3.27Zn0.73和EuAl3.65Cd0.35分别增加到-16.3 J/kg K。制冷量分别为67、120和128 J/kg。这些突出的磁热学性质强烈表明，EuAl4-xZnx和EuAl4-yCdy化合物是在液氦温度区域磁制冷应用中具有竞争力的材料。

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引用次数: 0

Rapid oxidative etching-induced active interfaces for constructing dense Ag-modified zinc anodes 构建致密银修饰锌阳极的快速氧化蚀刻诱导活性界面

IF 6.3 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Journal of Alloys and Compounds

Pub Date : 2026-01-12 DOI: 10.1016/j.jallcom.2026.186158

Yiyang Bi, Fuyu Jiang, PeiLin Liu, Yuchun Wan, Lianshan Sun, Wanqiang Liu

Aqueous zinc-ion batteries (AZIBs) are viewed as competitive candidates for high-energy-density storage. However, the performance of AZIBs is impeded by dendrite growth and side reactions on the zinc anode surface. Herein, a facile in situ galvanic replacement strategy assisted by ammonium persulfate (APS)-assisted surface etching is proposed to construct a zincophilic Ag-modified interface on Zn metal, enabling dynamic regulation of Zn²⁺ nucleation and deposition behavior. As a result, the Zn@Ag anode exhibits a significantly reduced Zn²⁺ nucleation energy barrier (from 47.2 to 31.2 kJ mol⁻¹), enabling uniform and dense Zn deposition while effectively suppressing dendrite formation and interfacial side reactions. Meanwhile, COMSOL simulations based on the finite element method verified the key role of the Ag-modified interface in suppressing dendrite formation and mitigating interfacial corrosion. At current densities of 1 mAh cm⁻², a symmetric cell with the Zn@Ag interfacial layer as the anode achieved a cycle life of 1757 h (39 times that of bare Zn). Moreover, the Zn@Ag || V₂O₅ full cell has a cycle stability of over 2800 cycles. This method provides a new strategy for the design of anodes in AZIBs.

水锌离子电池（azib）被认为是高能量密度存储的有竞争力的候选人。然而，锌阳极表面的枝晶生长和副反应阻碍了azib的性能。本文提出了一种简单的原位电替换策略，在过硫酸铵（APS）辅助表面蚀刻的辅助下，在Zn金属上构建亲锌的ag修饰界面，从而动态调节Zn2+的成核和沉积行为。结果，Zn@Ag阳极表现出显著降低的Zn2+成核能垒（从47.2 kJ mol-1降至31.2 kJ mol-1），使Zn沉积均匀致密，同时有效抑制了枝晶的形成和界面副反应。同时，基于有限元方法的COMSOL模拟验证了ag修饰界面在抑制枝晶形成和减轻界面腐蚀方面的关键作用。在电流密度为1mah cm-2时，以Zn@Ag界面层为阳极的对称电池的循环寿命达到了1757小时（是裸锌的39倍）。此外，Zn@Ag || V2O5全电池具有超过2800次循环的循环稳定性。该方法为azib阳极的设计提供了一种新的策略。

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引用次数: 0

Breaking kinetic and thermodynamic barriers: CeO2-Ni-rGO synergistic catalysis for comprehensively enhanced hydrogen storage performance of MgH2 打破动力学和热力学障碍：CeO2-Ni-rGO协同催化全面增强MgH2储氢性能

IF 6.3 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Journal of Alloys and Compounds

Pub Date : 2026-01-12 DOI: 10.1016/j.jallcom.2026.186167

Hanqing Wang , Jing Sun , Hui Shang

As a promising high-capacity hydrogen storage material, the practical application of MgH₂ is impeded by sluggish reaction kinetics and high thermodynamic stability. In this study, a ternary CeO₂-Ni-rGO catalyst was designed to synergistically address both challenges. Electronic coupling between CeO₂ and Ni promotes the generation of abundant oxygen vacancies, which weaken the Mg-H bond and significantly reduce the dehydrogenation temperature. Meanwhile, Ni acts as an active site for H₂ dissociation and establishes a reversible Mg₂Ni/Mg₂NiH₄ “hydrogen pump”, thereby accelerating hydrogenation and dehydrogenation kinetics. The conductive rGO framework further facilitates interfacial charge transfer and prevents catalyst agglomeration. With the addition of 10 wt% CeO₂-Ni-rGO, the MgH₂ composite attains 4.0 wt% hydrogen uptake within 60 s at 100 ℃, with its hydrogenation activation energy decreasing to 52.45 kJ/mol. Concurrently, the onset dehydrogenation temperature drops to 195 ℃, with the corresponding dehydrogenation activation energy dramatically reduced from 144.4 kJ/mol to 58.9 kJ/mol. Moreover, the composite retains 97 % of its initial capacity after 30 cycles, demonstrating excellent cycling durability. Density functional theory (DFT) calculations reveal that Ni 3d states markedly increase the electronic density near the Fermi level and strengthen orbital hybridization with CeO₂, rGO, and MgH₂, enabling accelerated interfacial electron migration and facilitating both vacancy formation and H⁻ transport. These results confirm that the CeO₂-Ni-rGO ternary catalyst effectively overcomes both kinetic and thermodynamic barriers, offering a robust and promising strategy for advancing MgH₂-based solid-state hydrogen storage.

作为一种很有前途的大容量储氢材料，MgH2的实际应用受到反应动力学缓慢和热力学稳定性高的制约。在本研究中，设计了一种三元CeO2-Ni-rGO催化剂来协同解决这两个挑战。CeO2与Ni之间的电子耦合促进了丰富的氧空位的产生，从而削弱了Mg-H键，显著降低了脱氢温度。同时，Ni作为H2解离的活性位点，建立可逆的Mg2Ni/Mg2NiH4“氢泵”，从而加速加氢和脱氢动力学。导电还原氧化石墨烯框架进一步促进界面电荷转移，防止催化剂团聚。加上10wt。% CeO2-Ni-rGO， MgH2复合材料达到4.0wt。在100℃条件下，60秒内吸氢率为%，加氢活化能降至52.45kJ/mol。同时，脱氢起始温度降至195℃，脱氢活化能从144.4kJ/mol大幅降至58.9kJ/mol。此外，该复合材料在30次循环后仍能保持97%的初始容量，表现出优异的循环耐久性。密度泛函理论（DFT）计算表明，Ni三维态显著增加了费米能级附近的电子密度，加强了与CeO2、rGO和MgH2的轨道杂化，加速了界面电子迁移，促进了空位的形成和H -⁻迁移。这些结果证实，CeO2-Ni-rGO三元催化剂有效地克服了动力学和热力学障碍，为推进基于mgh2的固态储氢提供了一种强大且可扩展的策略。

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引用次数: 0

Formation of (Ti,W)Fe2 C14 Laves Phase in the W-Ti-Fe System and the Impact on Mechanical Properties W-Ti- fe体系中（Ti，W）Fe2 C14相变相的形成及其对力学性能的影响

IF 6.2 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Journal of Alloys and Compounds

Pub Date : 2026-01-12 DOI: 10.1016/j.jallcom.2026.186169

Matthew J. Lloyd, Kan Ma, Andrew J. London, James Gibson, Andy Watson, Chris Hardie, Alexander Knowles

Tungsten-based alloys utilising coherent intermetallic strengthening offer a route to improved high temperature strength. Recently proposed W-Ti-Fe alloys employ B2 TiFe phase in an A2 BCC matrix to achieve this strengthening, however, other phases such as the TiFe₂ Laves phase can form at higher temperatures. In this study, the formation of the (Ti,W)Fe₂ C14 phase in a BCC W-rich matrix is observed in a W–16Ti–4Fe (at.%) alloy produced by vacuum arc-melting and annealing at 1400 ^oC. There was no evidence for the formation of either the TiFe B2 or W₆Fe₇ μ phase from analysis of the TEM diffraction patterns. The C14 Laves phase was found to have a composition of 8.8 ± 0.2 W, 23.3 ± 0.2Ti and 68.0 ± 0.8Fe (at.%) consistent with (Ti,W)Fe₂. This formed a continuous region along the boundaries between the W-rich BCC prior-dendrites, as well as in smaller isolated precipitates. The prior dendritic regions consisted of W-rich BCC phase with a composition of 84.10±0.41 W, 13.94 ± 0.73Ti and 1.94 ± 0.73Fe (at.%). Thermodynamic calculations using CALPHAD predicted the formation of a W rich BCC phase and a Ti and Fe rich liquid phase initially, which was not consistent with the presented experimental findings. A revised calculation which reduced the stability of the μ phase at high temperatures led to an improved prediction, consistent with the experimental results. To investigate the mechanical impact of the C14 phase, a combination of Continuous Stiffness Measurement (CSM) nanoindentation and high-speed nanoindentation mapping was used to measure the comparative hardness of the matrix and precipitate phases, which showed that the C14 phase exhibits a very high hardness relative to the W-rich matrix phase. An average nanohardness of 6.25 ± 0.03 GPa was measured at depth of 1.5 μm using CSM nanoindentation, which is higher than comparable B2 reinforced WTiFe alloys.

利用相干金属间强化的钨基合金为提高高温强度提供了一条途径。最近提出的W-Ti-Fe合金在A2 BCC基体中采用B2 TiFe相来实现这种强化，然而，在更高的温度下可以形成其他相，如TiFe2 Laves相。在1400℃真空电弧熔炼退火制备的W- 16ti - 4fe （at.%）合金中，观察到BCC富W基体中（Ti，W）Fe2 C14相的形成。TEM衍射图分析未发现TiFe B2和W6Fe7 μ相的形成。C14 Laves相的组成为8.8±0.2 W, 23.3±0.2Ti和68.0±0.8Fe (at.%)，与（Ti，W）Fe2相一致。这在富w的BCC先前枝晶之间以及较小的孤立沉淀之间形成了一个连续的区域。先前的枝晶区由富W的BCC相组成，其组成为84.10±0.41 W, 13.94±0.73Ti和1.94±0.73Fe （at.%）。利用CALPHAD进行热力学计算，初步预测了富W的BCC相和富Ti和Fe的液相的形成，这与实验结果不一致。修正后的计算降低了μ相在高温下的稳定性，从而改进了预测结果，与实验结果一致。为了研究C14相的力学影响，采用连续刚度测量（CSM）纳米压痕和高速纳米压痕映射相结合的方法测量了基体和析出相的比较硬度，结果表明C14相相对于富w基体相具有很高的硬度。在深度为1.5 μm时，CSM纳米压痕的平均纳米硬度为6.25±0.03 GPa，高于同类B2增强WTiFe合金。

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引用次数: 0

In-situ Self-polymerization PDA@MXene/MB Ratio Electrochemical Sensing for the Detection of Kaempferol 原位自聚合PDA@MXene/MB比电化学传感检测山奈酚

IF 6.2 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Journal of Alloys and Compounds

Pub Date : 2026-01-12 DOI: 10.1016/j.jallcom.2026.186147

Jing Chen, Wenjing Liu, Rongfang Ma, Jingjing Nan, Shuai Wang

Kaempferol (KA) is an important natural flavonoid compound, and its sensitive detection is of great significance in food science and pharmacological analysis. To address the problems of traditional electrochemical sensors being susceptible to environmental interference and having poor stability in complex samples, this study successfully prepared a polydopamine-modified MXene/methylene blue composite material (PDA@MXene/MB), and constructed a novel ratio electrochemical sensor for the highly selective and sensitive detection of kaempferol. This sensor utilizes the high conductivity and large specific surface area of MXene as an ideal base, and through the in-situ polymerization of polydopamine, effectively prevents the stacking of MXene layers and simultaneously fixes methylene blue (MB) as a stable and reliable internal reference signal. During the detection process, the ratio of IKA/IMB is used for quantitative analysis, effectively eliminating the interference of background current fluctuations and environmental factors. Experimental results show that this sensor exhibits excellent analytical performance for kaempferol, presenting a good linear relationship within the concentration range of 0.4-36µM, with a detection limit of 49nM. Moreover, the sensor demonstrates good selectivity, reproducibility and stability, and it was also successfully used to determine kaempferol in actual tablet sample, yielding satisfactory recovery rates.

山奈酚（KA）是一种重要的天然类黄酮化合物，其灵敏检测在食品科学和药理分析中具有重要意义。针对传统电化学传感器易受环境干扰、在复杂样品中稳定性差的问题，本研究成功制备了一种聚多巴胺修饰的MXene/亚甲基蓝复合材料（PDA@MXene/MB），构建了一种高选择性、高灵敏度检测山奈酚的新型比例电化学传感器。该传感器利用MXene的高电导率和大比表面积作为理想基，通过聚多巴胺的原位聚合，有效防止MXene层的堆积，同时固定亚甲基蓝（MB）作为稳定可靠的内部参考信号。在检测过程中，采用IKA/IMB的比值进行定量分析，有效地消除了背景电流波动和环境因素的干扰。实验结果表明，该传感器对山奈酚具有良好的分析性能，在0.4 ~ 36µM的浓度范围内呈良好的线性关系，检出限为49nM。该传感器具有良好的选择性、重现性和稳定性，可用于山奈酚实际片剂样品的测定，回收率令人满意。

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引用次数: 0

Hierarchical 3D honeycomb-inspired nanoarchitecture integrating silicon nanoparticles with high-entropy alloy matrix for ultrahigh-capacity lithium-ion battery anodes 集成硅纳米粒子与高熵合金基体的层叠三维蜂窝状纳米结构用于超高容量锂离子电池阳极

IF 6.3 2区材料科学 Q2 CHEMISTRY, PHYSICAL

Journal of Alloys and Compounds

Pub Date : 2026-01-12 DOI: 10.1016/j.jallcom.2026.186157

Jun Du , XinYi Shen , Binbin Jin , Liwei Liao , Zhe Mei , Qingcheng Du , Liying Liang , Xinyong Tao

Silicon (Si) is regarded as an ideal anode material for next-generation high–energy-density batteries owing to its ultrahigh theoretical capacity. However, its practical application is severely hindered by drastic volume expansion during cycling, interfacial instability, and intrinsically low electrical conductivity. Herein, a Si@HE@C composite was successfully fabricated via an in situ synthesis strategy by embedding silicon nanoparticles (Si NPs) and high-entropy metallic elements (HE) into a three-dimensional (3D) honeycomb carbon framework. The introduction of HE elements promotes the graphitization of the carbon scaffold and enhances electrical conductivity. Meanwhile, the honeycomb-like channels provide sufficient buffering space to accommodate the volume variation of Si NPs, effectively alleviating stress concentration, and offer fast transport pathways for Li⁺ diffusion. Finite element simulations further confirm that the 3D honeycomb porous architecture markedly mitigates stress localization during Si lithiation. Benefiting from the synergistic effects of the rational architecture and composition, Si@HE@C delivers an initial specific capacity of 1473.89 mAh g⁻¹ at 0.1 A g⁻¹ and retains 1203.53 mAh g⁻¹ after 100 cycles (capacity retention of 81.66 %); at 0.5 A g⁻¹, it still maintains 856.78 mAh g⁻¹ after 200 cycles. This work highlights the pronounced advantages of 3D honeycomb porous frameworks in stress accommodation, conductivity enhancement, and cycling stability, and provides a new strategy for developing high-entropy Si-based composite anodes.

硅（Si）具有超高的理论容量，被认为是下一代高能量密度电池的理想负极材料。然而，它的实际应用受到循环过程中剧烈的体积膨胀、界面不稳定和本质上低导电性的严重阻碍。本文通过原位合成策略，将硅纳米颗粒（Si NPs）和高熵金属元素（HE）嵌入三维（3D）蜂窝碳框架中，成功制备了Si@HE@C复合材料。HE元素的引入促进了碳支架的石墨化，提高了导电性。同时，蜂窝状通道为Si NPs的体积变化提供了足够的缓冲空间，有效缓解应力集中，为Li+扩散提供了快速的转运途径。有限元模拟进一步证实，三维蜂窝多孔结构显著减轻了硅锂化过程中的应力局部化。得益于合理的结构和组成的协同效应，Si@HE@C在0.1 A g-1时提供了1473.89 mAh g-1的初始比容量，并在100次循环后保持1203.53 mAh g-1（容量保持率为81.66%）；在0.5 A g-1时，它在200次循环后仍然保持856.78 mAh g-1。这项工作强调了3D蜂窝多孔框架在应力调节、电导率增强和循环稳定性方面的显著优势，并为开发高熵硅基复合阳极提供了一种新的策略。

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引用次数: 0