Chemical Physics最新文献_第7页

Unraveling the correlation between complex phase transitions and tunable electrocaloric responses via constructing near polymorphic phase boundaries in multi-parameter phase diagrams 通过在多参数相图中构建近多晶相边界来揭示复杂相变与可调电热响应之间的关系

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-10-28 DOI: 10.1016/j.chemphys.2025.113000

Xiancheng Zhang , Feng Zhang , Jianting Li , Fang Cao , Yimeng Tang , Yaodong Yang , Yang Bai , Wei-Feng Rao

Ferroelectric materials near polymorphic phase boundaries (PPBs) exhibit rich phase transitions, yet the relationship between multi-parameter coupling and electrocaloric (EC) effects remains unclear. Here, the multi-parameter phase diagrams for BaTi_1-xSn_xO₃ incorporating composition, temperature, and electric field orientation are constructed using a Landau phenomenological approach. It is revealed that when the low-temperature phase possesses a higher polarization component along the electric field orientation, the field induces a high-to-low temperature phase transition, resulting in a positive-slope phase boundary in the electric field-temperature phase diagram. Conversely, if the high-temperature phase exhibits a higher polarization component along the field orientation, the field drives a low-to-high temperature phase transition, corresponding to a negative-slope boundary. Transitions across positive-slope boundaries are accompanied by a field-induced reduction in entropy, yielding a positive EC effect, whereas those across negative-slope boundaries involve a field-induced entropy increase, leading to a negative EC effect. Notably, EC behaviors at multiphase critical points (x = 0.11) are identified as synergistic superposition effects of rhombohedral-orthorhombic-tetragonal-cubic multistage phase transitions. This work establishes a multi-parameter thermodynamic framework for deciphering and tailoring tunable EC properties via phase-boundary engineering.

在多晶相边界（PPBs）附近的铁电材料表现出丰富的相变，但多参数耦合与电热效应之间的关系尚不清楚。本文采用朗道现象学方法构建了BaTi1-xSnxO3的含成分、温度和电场取向的多参数相图。结果表明，当低温相沿电场方向具有较高的极化分量时，电场诱发高低温相变，导致电场-温度相图中出现正斜率相边界。相反，如果高温相沿场方向呈现较高的极化分量，则场驱动低温相向高温相转变，对应于负斜率边界。跨越正斜率边界的过渡伴随着场诱导的熵减少，产生正的电导率效应，而跨越负斜率边界的过渡涉及场诱导的熵增加，导致负的电导率效应。值得注意的是，多相临界点（x = 0.11）的EC行为被确定为菱形-正交-四方-立方多级相变的协同叠加效应。这项工作建立了一个多参数热力学框架，用于通过相边界工程来解码和剪裁可调谐的电子传输特性。

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引用次数: 0

Biosorption of Lead (II) and cadmium (II) ions from aqueous solution by buckwheat (Fagopyrum Esculentum) hulls biosorbent: kinetic, equilibrium and thermodynamic studies 荞麦壳生物吸附剂对铅（II）和镉（II）离子的生物吸附：动力学、平衡和热力学研究

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-10-27 DOI: 10.1016/j.chemphys.2025.112997

Tayyab Tahir , Rūta Druteikienė , Zita Žukauskaitė , Jūratė Vaičiūnienė , Aušra Selskienė , Ilja Ignatjev , Muhammad Adnan

In this study buckwheat hull was used as an efficient, cheap and environmentally safe for the removal of Pb(II) and Cd(II) from an aqueous solution through optimizing various experimental parameters such as temperature (25–50 °C), solution pH (2–6 for Pb(II) and 2–7 for Cd(II)), amount of buckwheat hulls (0.1–0.35 g), initial Pb(II) and Cd(II) concentration (5–400 mg L⁻¹) and contact time (30–1440 min). SEM, FTIR, EDX, and pH_pzc measurements were used to analyze buckwheat hulls before and after biosorption. Kinetic data fitted best to the pseudo-second-order model due to higher values of R² (R²_Pb(II) = 0.999 and R²_Cd(II) = 0.999). Equilibrium data matched the Langmuir model, yielding sorption capacities of 87.72 mg·g⁻¹ for Pb(II) and 23.2 mg·g⁻¹ for Cd(II), indicating monolayer adsorption. Analysis of thermodynamic parameters, revealed the non-spontaneous and exothermic characteristics of the removal of Pb(II) and Cd(II) by buckwheat hulls.

本研究通过优化温度（25-50℃）、溶液pH （Pb（II）为2-6、Cd（II）为2-7）、荞麦壳用量（0.1-0.35 g）、初始Pb（II）和Cd（II）浓度（5-400 mg L−1）和接触时间（30-1440 min）等实验参数，将荞麦壳作为高效、廉价、环保的水溶液中Pb（II）和Cd（II）的脱除剂。利用扫描电镜（SEM）、红外光谱（FTIR）、EDX和pHpzc等测量方法对生物吸附前后的荞麦壳进行了分析。由于R2较高(R2Pb(II) = 0.999, R2Cd(II) = 0.999)，动力学数据最符合伪二阶模型。平衡数据符合Langmuir模型，Pb（II）的吸附量为87.72 mg·g−1,Cd（II）的吸附量为23.2 mg·g−1，表明其为单层吸附。热力学参数分析揭示了荞麦壳去除Pb（II）和Cd（II）的非自发和放热特性。

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引用次数: 0

First-principles study of ga-doped γ-TiAl intermetallic compound ga掺杂γ-TiAl金属间化合物的第一性原理研究

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-10-25 DOI: 10.1016/j.chemphys.2025.112979

Hongsheng Zhao , Yuhao Chen , Bingyin Feng , Xubiao Wang , Xiliang Zhang , Qian Yang , Jing Zhao , Yinfeng Li , Yanhui Wang

TiAl-based alloys show great potential for aerospace and automotive applications but are limited by room-temperature brittleness and insufficient high-temperature strength. This study employs first-principles calculations to systematically investigate the effects of Ga doping at different sites (Ti substitution, Al substitution, and interstitial positions) on the structural, electronic, thermodynamic, and mechanical properties of γ-TiAl alloys. Results reveal that Ti-site substitution induces in-plane lattice contraction with c-axis expansion, while interstitial doping causes significant volumetric expansion. Electronic structure analysis shows that interstitial doping increases the density of states near the Fermi level, enhancing electron mobility, whereas Ti-site substitution strengthens bonding through enhanced d-d orbital hybridization. Al-site substitution exhibits the lowest thermal expansion coefficient (18 % reduction at 300 K), improving dimensional stability, while Ti-site substitution displays higher work functions (4.05–4.15 eV), suggesting better corrosion resistance. Mechanical properties are optimized at 0.03 % Ga concentration, at which the elastic modulus peaks at 194.48 GPa and the Pugh ratio (B/G = 1.75) indicates improved ductility. However, higher concentrations (≥0.04 %) lead to hardness reduction and increased elastic anisotropy. This work provides theoretical insights for optimizing TiAl alloys through controlled Ga doping strategies.

钛基合金在航空航天和汽车应用方面显示出巨大的潜力，但受到室温脆性和高温强度不足的限制。本研究采用第一性原理计算系统地研究了不同位置（Ti取代、Al取代和间隙位置）Ga掺杂对γ-TiAl合金结构、电子、热力学和力学性能的影响。结果表明，钛位取代引起平面内晶格收缩并伴有c轴膨胀，而间隙掺杂引起明显的体积膨胀。电子结构分析表明，间隙掺杂增加了费米能级附近的态密度，增强了电子迁移率，而钛位取代通过增强d-d轨道杂化增强了键合。al -取代表现出最低的热膨胀系数（在300 K时降低18%），提高了尺寸稳定性，而ti -取代表现出更高的功函数（4.05-4.15 eV），表明具有更好的耐腐蚀性。当Ga浓度为0.03%时，合金的力学性能得到优化，弹性模量峰值为194.48 GPa， Pugh比（B/G = 1.75）表明合金的延性得到改善。然而，较高的浓度（≥0.04%）会导致硬度降低和弹性各向异性增加。这项工作为通过控制Ga掺杂策略优化TiAl合金提供了理论见解。

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引用次数: 0

Effects of hydrotropes and temperature on interactions between sodium alginate and cetyltrimethylammonium bromide surfactant: An experimental and theoretical study 水异构物和温度对海藻酸钠与十六烷基三甲基溴化铵表面活性剂相互作用影响的实验和理论研究

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-10-25 DOI: 10.1016/j.chemphys.2025.112992

Maria Akhtar , Sharmin Akhter Maya , Md. Rafikul Islam , Md. Masiur Rahaman , Md Abdul Goni , Dileep Kumar , Md. Anamul Hoque , Mahbub Kabir , Ajamaluddin Malik

This study investigates the self-assembly of cetyltrimethylammonium bromide (CTAB) with sodium alginate (SA) in presence of anionic and nonionic hydrotropes (HYDTs) using conductometric technique. The research focused on determining critical micelle concentration (CMC) and degree of micelle ionization (α) of the CTAB + SA mixture by analyzing conductivity versus CTAB concentration plots. Results indicated that introduction of HYDTs significantly impeded micelle formation compared to aqueous medium. The CMC values also displayed a clear dependency on temperature variation. Notably, spontaneous micelle formation is confirmed by the negative Gibbs free energy (

{ΔG}_{m}^{0}

) values across all solvents examined, suggesting favorable thermodynamic conditions for micellization. Additionally, magnitudes of enthalpy (

{ΔH}_{m}^{0}

) and entropy changes (

{ΔS}_{m}^{0}

) provided significant insights into underlying interaction forces, indicating that hydrophobic and electrostatic interactions play vital roles in the self-assembly process. These findings influence a deeper understanding of surfactant behavior in complex systems and may have expressive implications for industrial formulations, markedly in drug delivery and pharmaceutical design.

采用电导法研究了十六烷基三甲基溴化铵（CTAB）与海藻酸钠（SA）在阴离子和非离子型水异构物（hydt）存在下的自组装反应。研究重点是通过分析电导率与CTAB浓度的关系，确定CTAB + SA混合物的临界胶束浓度（CMC）和胶束电离度（α）。结果表明，与水介质相比，hydt的引入显著阻碍了胶束的形成。CMC值也与温度变化有明显的关系。值得注意的是，所有溶剂的自发胶束形成都被负吉布斯自由能（ΔGm0）值所证实，这表明有利的胶束形成热力学条件。此外，焓（ΔHm0）和熵变化（ΔSm0）的大小为潜在的相互作用力提供了重要的见解，表明疏水和静电相互作用在自组装过程中起着至关重要的作用。这些发现影响了对复杂系统中表面活性剂行为的更深层次的理解，并可能对工业配方，特别是药物输送和药物设计具有表达意义。

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引用次数: 0

Relationship between the morphology and activity of a heterogeneous catalyst: A fractal geometry approach to CO oxidation over Fe2O3 nanoparticles 非均相催化剂的形态和活性之间的关系：用分形几何方法在Fe2O3纳米颗粒上进行CO氧化

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-10-25 DOI: 10.1016/j.chemphys.2025.112983

O.O. Zhokh , A.I. Trypolskyi , K.S. Gavrilenko , V.I. Gritsenko , I.L. Stolyarchuk , P.E. Strizhak

A fractal geometry approach is established to relate a heterogeneous catalyst's performance to its surface morphology. We show that the activation energy of a reaction and the pre-exponential factor are directly connected with the surface fractal dimension of a catalyst. The experimental verification of the approach is achieved using a first-order model reaction, e.g., CO oxidation over Fe₂O₃ nanoparticles of various morphologies. For this reaction, both pre-exponential factor and activation energy increase monotonically with the growth of the surface fractal dimension of Fe₂O₃ catalyst, which is in agreement with theoretical predictions.

建立了一种分形几何方法，将多相催化剂的性能与其表面形貌联系起来。结果表明，反应活化能和指数前因子与催化剂的表面分形维数直接相关。该方法的实验验证是通过一级模型反应实现的，例如，不同形态的Fe2O3纳米颗粒上的CO氧化。该反应的指前因子和活化能随着Fe2O3催化剂表面分形维数的增加而单调增加，这与理论预测一致。

引用次数: 0

Study on the action mechanism of two typical binders on the thermal decomposition process of HMX 研究了两种典型粘结剂对HMX热分解过程的作用机理

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-10-25 DOI: 10.1016/j.chemphys.2025.112993

Xiyao Yun , Wanxiao Guo , Shaokang Tian , Weiyi Li , Hui Fu , Yilin Fang , Zexin Jiang , Jintao Wang , Tao Wang

In this study, a ReaxFF force field was developed for the composite system comprising 1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), 1,4-polybutadiene rubber (BR), and fluoropolymer (F₂₆₀₄). Based on this force field, molecular dynamics (MD) simulations were employed to investigate the mechanisms by which BR and F₂₆₀₄ influence the thermal decomposition of HMX. The results indicate that the presence of BR and F₂₆₀₄ binders generally extends the decomposition duration of HMX. Throughout the reaction process, these binders facilitate the conversion of HMX decomposition intermediates into stable end products, thereby preventing the excessive accumulation of intermediates and mitigating intense interactions among them during the middle stage of decomposition. This research elucidates the role of binders in the thermal decomposition of high-energy explosives, offering novel insights and methodological approaches for future studies in this field.

本研究建立了由1,3,5,7-四硝基-1,3,5,7-四氮辛（HMX）、1,4-聚丁二烯橡胶（BR）和含氟聚合物（F2604）组成的复合体系的ReaxFF力场。在此力场基础上，采用分子动力学（MD）模拟研究了BR和F2604对HMX热分解的影响机理。结果表明，BR和F2604粘结剂的存在普遍延长了HMX的分解时间。在整个反应过程中，这些结合剂促进了HMX分解中间体转化为稳定的终产物，从而防止了中间体的过度积累，减轻了分解中期中间体之间强烈的相互作用。本研究阐明了粘合剂在高能炸药热分解中的作用，为该领域的未来研究提供了新的见解和方法途径。

引用次数: 0

Indium-doped 2D ZnO quantum dots for NO2 and NH3 detection: A first-principles and machine learning study 用于NO2和NH3检测的铟掺杂二维ZnO量子点：第一性原理和机器学习研究

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-10-24 DOI: 10.1016/j.chemphys.2025.112978

Hoang Van Ngoc , Trieu Quynh Trang

This work explores indium-doped two-dimensional zinc oxide quantum dots (2D InZnO QDs) as potential candidates for gas sensing, focusing on their interaction with NO₂ and NH₃. Structural, electronic, magnetic, and optical properties of pristine and adsorbed systems were investigated using Density Functional Theory (DFT) combined with machine learning approaches. Gas adsorption was found to strongly influence the physical properties, particularly in the NO₂ case. NO₂ adsorption reduces the bulk modulus, modifies electronic states, and introduces new features in the dielectric function and absorption spectrum, mainly in the ultraviolet-visible region. By contrast, NH₃ adsorption induces only minor perturbations, reflecting weak binding. Joint density of states (JDOS) analysis indicates dominant electron–hole transitions near 13 eV, with NO₂ adsorption leading to broader transitions and anisotropic optical responses. These results highlight the tunability of optoelectronic properties in 2D InZnO QDs through gas adsorption, supporting their potential in nanoscale sensing applications.

这项工作探索了铟掺杂二维氧化锌量子点（2D InZnO量子点）作为气体传感的潜在候选者，重点研究了它们与NO2和NH3的相互作用。利用密度泛函理论（DFT）结合机器学习方法研究了原始系统和吸附系统的结构、电子、磁性和光学性质。发现气体吸附对物理性质有很大影响，特别是在NO2的情况下。NO2吸附降低了体积模量，改变了电子态，并在介电函数和吸收光谱中引入了新的特征，主要是在紫外可见区。相比之下，NH3吸附只引起轻微的扰动，反映了弱结合。联合态密度（JDOS）分析表明，在13 eV附近的电子-空穴跃迁占主导地位，NO2吸附导致更宽的跃迁和各向异性光学响应。这些结果强调了二维InZnO量子点通过气体吸附的光电特性的可调性，支持了它们在纳米级传感应用中的潜力。

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引用次数: 0

Luminescence and thermometric performance of Tb(III) activated Mg3WO6 double perovskite phosphor Tb（III）活化Mg3WO6双钙钛矿荧光粉的发光和测温性能

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-10-24 DOI: 10.1016/j.chemphys.2025.112985

Naresh Degda , Nimesh Patel , Yashesh Gandhi , K.V.R. Murthy , M. Srinivas

Luminescence and thermoresponsive properties of Mg₃WO₆:Tb³⁺ double perovskites were investigated for optical thermometry. Rietveld refinement of X-ray diffraction (XRD) data confirmed the formation of monoclinic crystallites. Photoluminescence (PL) response under various excitation wavelengths revealed a tunable color emission, ascribed to host emission and characteristic Tb³⁺ transitions. The optimal PL intensity was achieved with 0.4 mol% Tb³⁺ doping, beyond which concentration quenching occurred due to dipole-dipole interactions. The temperature-dependent PL (TDPL) spectra demonstrated that the ⁵D₄–⁷F₆ and ⁵D₄–⁷F₅ transitions of Tb³⁺ displaying different responses to temperature, exhibiting thermal dependence. Utilizing the fluorescence intensity ratio (FIR) from the TDPL spectra within 303–513 K, the temperature reading properties of the Mg₃WO₆:0.4 % Tb³⁺ phosphor was examined. Subsequently, highest relative sensitivity S_R (0.62 % K⁻¹) was obtained at 303 K. Furthermore, the FIR calculated from the TDPL spectra obtained during heating and cooling processes, along with repeatability cycles, confirmed the reliability and repeatability of the temperature sensor.

用光学测温法研究了Mg3WO6:Tb3+双钙钛矿的发光和热响应特性。x射线衍射（XRD）数据的Rietveld细化证实了单斜晶的形成。不同激发波长下的光致发光（PL）响应显示出可调谐的颜色发射，归因于宿主发射和Tb3+跃迁的特征。当Tb3+掺杂量为0.4 mol%时，发光强度达到最佳，超过该浓度时，由于偶极子-偶极子相互作用而发生浓度猝灭。温度相关的PL （TDPL）光谱表明，Tb3+的5D4-7F6和5D4-7F5跃迁对温度的响应不同，表现出热依赖性。利用TDPL光谱在303 ~ 513 K范围内的荧光强度比（FIR），考察了mg3wo6: 0.4% Tb3+荧光粉的读温性能。随后，在303 K下获得了最高的相对灵敏度SR （0.62% K−1）。此外，根据加热和冷却过程中获得的TDPL光谱计算的FIR以及可重复性循环，证实了温度传感器的可靠性和可重复性。

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引用次数: 0

Planar pentacoordinate beryllium in neutral Be©Al5H5 species: Alkaline-earth aromaticity and covalent bonds 平面五坐标铍中性Be©Al5H5种：碱土芳香性和共价键

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-10-23 DOI: 10.1016/j.chemphys.2025.112984

Hong-Lang Yu , Qiao-Qiao Yan , Wen-Xing Zhang , Yu Chen , Yang-Miao Ou , En-Dong Huang , Shao-Jie Li , Yi-Ran Li

We unveiled an unprecedented Be©Al₅H₅ motif featuring a planar pentacoordinate beryllium atom. This molecule exhibits robust electronic, thermodynamic, and dynamic stability up to 500 K. Our analysis confirmed that Be©Al₅H₅ exhibits σ/π double aromaticity. Both this aromaticity and the five outermost hydrogen atoms were indispensable for maintaining its molecular planarity. We further explored the substitution chemistry of Be©Al₅H₅ by replacing the outer hydrogen atoms with strong electron-withdrawing groups (-COOH). DFT and MP2(full) calculations confirmed that both the mono- and penta-substituted derivatives maintain rigid ppBe structures. The computed solvation free energies showed that the ppBe Be©Al₅H₅, Be©Al₅H₄(COOH) and Be©Al₅(COOH)₅ dissolve more readily in polar solvents. Calculations indicated that these compounds can be readily extracted from benzene or cyclohexane into the aqueous phase. Given its unique solubility in polar solvents and a strong potential for generating derivatives, we suggest that Be©Al₅H₅ could serve as a promising building block for aluminum‑beryllium covalent compounds.

我们推出了一个前所未有的以平面五坐标铍原子为特征的Be©Al5H5基序。该分子表现出强大的电子，热力学和动态稳定性高达500k。结果表明，Be©Al5H5具有σ/π双芳构性。这种芳香性和最外层的五个氢原子对于保持分子的平面性是必不可少的。我们进一步探索了Be©Al5H5的取代化学，用强吸电子基团（-COOH）取代外层氢原子。DFT和MP2（全）计算证实，单取代和五取代衍生物都保持刚性ppBe结构。计算的溶剂化自由能表明，ppBe Be©Al5H5、Be©Al5H4（COOH）和Be©Al5(COOH)5更容易在极性溶剂中溶解。计算表明，这些化合物可以很容易地从苯或环己烷中提取到水相中。鉴于其在极性溶剂中的独特溶解度和生成衍生物的强大潜力，我们认为Be©Al5H5可以作为铝铍共价化合物的有希望的构建块。

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引用次数: 0

Research on strain-responsive Arsenene/SnSeS heterojunction for digital media technology: A first-principles calculations 数字媒体技术中应变响应的Arsenene/SnSeS异质结研究：第一性原理计算

IF 2.4 3区化学 Q4 CHEMISTRY, PHYSICAL

Chemical Physics

Pub Date : 2025-10-23 DOI: 10.1016/j.chemphys.2025.112982

Zhaopeng Zhou , Anqi Jiang

The rapid advancement of artificial intelligence and big data has led to a significant increase in global demand for data storage and information transmission, raising concerns regarding capacity and efficiency. Consequently, the development of novel stimulus-responsive materials has emerged as a critical area of research. This study presents the construction of a new Arsenene/SnSeS heterojunction and employs first-principles methods to manipulate its electronic and optical properties through the application of strain. The computational findings reveal that the Arsenene/SnSeS heterojunction demonstrates remarkable stability and favorable electronic characteristics. Notably, the bandgap of the heterojunction is smaller than that of both the Arsenene monolayer and the SnSeS monolayer, thereby facilitating enhanced charge transfer. Furthermore, the electronic properties of the Arsenene/SnSeS heterojunction can be effectively modulated by strain, which induces redshift or blueshift in the optical absorption peaks. These research outcomes offer valuable insights for the advancement of intelligent stimulus-responsive materials.

人工智能和大数据的快速发展，导致全球对数据存储和信息传输的需求大幅增加，引发了对容量和效率的担忧。因此，新型刺激反应材料的开发已成为一个关键的研究领域。本研究提出了一种新的砷/SnSeS异质结的构建，并采用第一性原理方法通过施加应变来操纵其电子和光学性质。计算结果表明，砷/ snse异质结具有良好的稳定性和良好的电子特性。值得注意的是，该异质结的带隙比Arsenene单层和snse单层的带隙都小，从而促进了电荷转移的增强。此外，应变可以有效地调制Arsenene/ snse异质结的电子特性，引起光学吸收峰的红移或蓝移。这些研究成果为智能刺激响应材料的发展提供了有价值的见解。

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引用次数: 0