IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2026-02-01 DOI: 10.1016/j.cjsc.2025.100771

Xiaohan Wang , Xue Guo , Zhuo Song , Chen Guan , Chengyu Yang , Tianyang Li , Yukun Zhu , Yan Xu

Cobalt-based catalysts for peroxymonosulfate (PMS) activation are often hindered by metal leaching and structural instability, limiting their practical application. To address these challenges, we developed a novel Co₉S₈/Ni₃S₂ heterojunction catalyst via a hydrothermal method followed by thermal reduction, employing interface engineering to inhibit metal cation leaching. The resulting Co₉S₈/Ni₃S₂/PMS system achieved complete tylosin degradation within 120 s. Notably, cobalt leaching was reduced by 4.5 times compared to pure Co₉S₈, demonstrating significantly enhanced catalyst stability. Furthermore, this system exhibited high efficiency in degrading a variety of antibiotics, good cyclic stability, and strong tolerance to diverse aqueous environments. The enhanced performance is attributed to the interface-engineered heterojunction, which not only improves the structural stability by suppressing metal cation leaching, but also facilitates PMS adsorption onto the catalyst surface. This improved PMS adsorption, particularly on cobalt active sites, results in substantial electron enrichment, thereby promoting efficient tylosin degradation. This work highlights the importance of interface engineering in designing advanced heterojunction catalysts for stable and efficient antibiotic wastewater treatment.

钴基催化剂在过氧单硫酸盐（PMS）活化中经常受到金属浸出和结构不稳定的阻碍，限制了它们的实际应用。为了解决这些挑战，我们通过水热法和热还原法开发了一种新型Co9S8/Ni3S2异质结催化剂，利用界面工程来抑制金属阳离子的浸出。Co9S8/Ni3S2/PMS体系在120s内完全降解了tylosin。值得注意的是，与纯Co9S8相比，钴的浸出减少了4.5倍，表明催化剂的稳定性显著提高。此外，该体系对多种抗生素的降解效率高，循环稳定性好，对多种水环境的耐受性强。这种增强的性能归功于界面工程异质结，它不仅通过抑制金属阳离子浸出提高了结构稳定性，而且还促进了PMS在催化剂表面的吸附。这种改进的PMS吸附，特别是在钴活性位点，导致大量的电子富集，从而促进有效的泰络菌素降解。这项工作强调了界面工程在设计先进的异质结催化剂以稳定高效地处理抗生素废水中的重要性。

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引用次数: 0

MOF-derived carbon-encapsulated ZnS/MnO porous microspheres for high-performance lithium storage 用于高性能锂存储的mof衍生碳包封ZnS/MnO多孔微球

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2026-02-01 DOI: 10.1016/j.cjsc.2025.100795

Jiamin Xiong , Baiying Huang , Yuling Zhang , Kaixin Zhou , Yuxuan Liu , Shengen Gong , Zhiguang Xu , Yongbo Wu , Akif Zeb , Xiaoming Lin

The advantages of transition metal compounds such as ultrahigh theoretical capacity and abundant active sites make them promising anode materials for high energy density lithium-ion batteries. Unfortunately, problems such as severe volume expansion and poor electrical conductivity seriously hinder their large-scale application. In general, reasonable optimization of composition and structure is an effective strategy for developing anode materials with excellent lithium storage properties. In this paper, ZnS/MnO composites are constructed by solvothermal sulfidation and calcination using Zn–Mn organic frameworks as self-sacrificing templates. From the perspective of material composition, both ZnS and MnO have excellent theoretical specific capacity, and the two-component metal center can provide more abundant active sites. From the perspective of structural optimization, the ZnS/MnO composites inherit the loose porous structure of the calcined metal-organic frameworks, which can not only effectively alleviate the volume expansion during the charge and discharge process, but also help improve the conductivity of composites and promote charge transport. Both experimental results and density functional theory calculations show that the two-component metal center of ZnS/MnO composites can improve the electronic conductivity and reduce the migration energy barrier, thus showing excellent cycle stability and remarkable rate performance. The study provides another idea for the development of high-performance anode materials for lithium-ion batteries.

过渡金属化合物具有超高的理论容量和丰富的活性位点等优点，是高能量密度锂离子电池极具前景的负极材料。不幸的是，严重的体积膨胀和导电性差等问题严重阻碍了它们的大规模应用。总的来说，合理优化组成和结构是开发具有优异储锂性能的负极材料的有效策略。本文以Zn-Mn有机骨架为自牺牲模板，采用溶剂热硫化和煅烧法制备了ZnS/MnO复合材料。从材料组成上看，ZnS和MnO均具有优异的理论比容量，双组分金属中心可以提供更丰富的活性位点。从结构优化的角度来看，ZnS/MnO复合材料继承了煅烧金属-有机骨架的松散多孔结构，不仅可以有效缓解充放电过程中的体积膨胀，而且有助于提高复合材料的导电性，促进电荷输运。实验结果和密度泛函理论计算均表明，双组分金属中心可以提高ZnS/MnO复合材料的电子导电性，降低迁移能垒，从而表现出优异的循环稳定性和显著的速率性能。该研究为高性能锂离子电池负极材料的开发提供了另一种思路。

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引用次数: 0

Interface design of S-scheme Co9S8/flower-like g-C3N4 van der Waals heterojunction with enhanced photocatalytic hydrogen production and tetracycline hydrochloride degradation S-scheme Co9S8/花状g-C3N4 van der Waals异质结增强光催化产氢和盐酸四环素降解的界面设计

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2026-02-01 DOI: 10.1016/j.cjsc.2025.100798

Yun Wang , Huage Lin , Jiaxiang Zong , Mengjiao Yu , Guangyu Wu , Weinan Xing

The construction of heterojunctions at phase interfaces represents a crucial strategy for enhancing photocatalytic activity, but developing more cost-effective and higher-performance photocatalysts remains a challenge. Herein, we designed a S-scheme van der Waals heterojunctions (vdWHs) photocatalyst by in situ growth of Co₉S₈ on flower-like graphitic carbon nitride (FCN). The S-scheme heterojunction ensures efficient charge separation and significantly enhances redox capabilities, while the vdWHs specifically overcome the lattice mismatch limitation inherent in conventional S-scheme heterojunctions owing to its interfacial coupling. In situ XPS analysis was used to confirm the direction of interfacial charge transfer. Consequently, the photocatalyst achieved an optimal H₂ evolution of 948.04 μmol h⁻¹ g⁻¹ without Pt cocatalysts. The tetracycline hydrochloride degradation reached 97.90% within 9 min through photocatalytic peroxymonosulfate activation that generated multiple reactive oxygen species. Liquid chromatography-mass spectrometry was employed to identify the possible reaction pathways and investigate the degradation products. This work advanced a rational design of S-scheme Co₉S₈/FCN vdWHs photocatalysts and offered promising solutions for both renewable energy production and wastewater remediation.

在相界面上构建异质结是提高光催化活性的关键策略，但开发更具成本效益和更高性能的光催化剂仍然是一个挑战。在此，我们设计了一种S-scheme范德华异质结（vdWHs）光催化剂，通过在花状石墨氮化碳（FCN）上原位生长Co9S8。s型异质结确保了有效的电荷分离并显著增强了氧化还原能力，而vdwh由于其界面耦合而克服了传统s型异质结固有的晶格失配限制。用原位XPS分析确定了界面电荷转移的方向。结果表明，该光催化剂的最佳析氢速率为948.04 μmol h−1 g−1。通过光催化过氧单硫酸盐活化产生多种活性氧，在9 min内对盐酸四环素的降解达到97.90%。采用液相色谱-质谱联用技术鉴定了可能的反应途径，并对降解产物进行了研究。本研究提出了S-scheme Co9S8/FCN vdWHs光催化剂的合理设计，为可再生能源生产和废水修复提供了有前途的解决方案。

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引用次数: 0

Hydrogen migration induced magnetic phase transition in two-dimensional Fe-porphyrinoid metal-organic frameworks 二维类铁卟啉金属-有机骨架中氢迁移诱导的磁相变

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2026-02-01 DOI: 10.1016/j.cjsc.2025.100801

Chao Jia , Min Ren , Yingdi Jin , Xingxing Li

The control of magnetic state is crucial for spintronic applications but remains a significant challenge. Traditionally, controlling magnetic state relies on physical approaches, such as applying external magnetic fields or utilizing spin-orbit coupling. In our previous work, we proposed a novel chemical approach to manipulate the magnetic state of a system through lactim-lactam tautomerization. Here, by first principles calculations, we extend the type of tautomerization to intramolecular hydrogen migration, and reveal that hydrogen migration can modulate magnetic coupling and lead to distinct magnetic configurations in two-dimensional (2D) metal-organic frameworks (MOFs) composed of diradical porphyrinoid and Fe. The migration of hydrogen atoms within porphyrinoid results in four isometric MOFs with notable changes in spin density distribution on organic linkers, which subsequently alters the magnetic coupling between the metal node and organic linkers, leading to ferromagnetic-ferrimagnetic (FM-FiM) transition in the framework. The magnetic coupling strength also changes significantly, with the Curie temperature enhanced from 5.2 to 100.1 K. Furthermore, accompanied with the magnetic transition, the MOFs experience an electronic transition from normal half semiconductors (with band gaps of 0.11 and 0.03 eV), where the valence band (VB) and conduction band (CB) share the same spin channel, to bipolar magnetic semiconductors (with band gaps of 0.06 and 0.13 eV), where the VB and CB become fully spin-polarized in opposite directions.

磁态的控制是自旋电子应用的关键，但仍然是一个重大的挑战。传统上，控制磁态依赖于物理方法，如施加外磁场或利用自旋轨道耦合。在我们之前的工作中，我们提出了一种新的化学方法，通过内酰胺-内酰胺互变异构来操纵系统的磁态。通过第一性原理计算，我们将变异构化的类型扩展到分子内的氢迁移，并揭示了氢迁移可以调节磁耦合并导致由双自由基卟啉类和铁组成的二维金属有机框架（mof）的不同磁构型。类卟啉内氢原子的迁移产生了四个等距mof，有机连接体上的自旋密度分布发生了显著变化，从而改变了金属节点与有机连接体之间的磁耦合，导致框架中铁磁-铁磁（FM-FiM）跃迁。磁耦合强度也发生了显著变化，居里温度从5.2 K提高到100.1 K。此外，伴随着磁跃迁，mof经历了从普通半半导体（带隙为0.11和0.03 eV）到双极磁性半导体（带隙为0.06和0.13 eV）的电子跃迁，其中价带（VB）和导带（CB）共享相同的自旋通道，其中VB和CB在相反方向上完全自旋极化。

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引用次数: 0

MOF derived Co–Mo2C heterojunctions with interfacial electronic modulation for oxygen reduction reaction and zinc-air batteries MOF衍生的Co-Mo2C异质结与界面电子调制用于氧还原反应和锌-空气电池

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2026-02-01 DOI: 10.1016/j.cjsc.2025.100796

Desheng Li , Qin Li , Peng Xu , Xingyu Guo , Heng Wu , Rui Liu , Fei Tan

Zinc-air batteries (ZABs) have emerged as promising candidates for next-generation energy storage systems due to their high energy density, safety, and environmental benignity. However, their efficiency is hindered by sluggish oxygen reduction reaction (ORR) kinetics. Constructing heterojunction with optimized interfacial electronic structure has emerged as a promising approach to enhance ORR activity. Herein, we report a Co–Mo₂C heterojunction encapsulated within nitrogen-doped carbon (Co–Mo₂C@NC) derived from a ZnCoMo-based metal-organic framework (ZnCoMo–HZIF). The intimate interface between Co and Mo₂C enables the strong electronic coupling, which induces the interfacial charge redistribution and optimizes the d-band center of Co active sites. This electronic modulation significantly enhances the oxygen intermediate adsorption and lowers the energy barrier. As a result, Co–Mo₂C@NC delivers outstanding ORR performance with a high half-wave potential (E_1/2) of 0.85 V, a low Tafel slope of 94.7 mV dec⁻¹, and a good long-term stability. Additionally, Co–Mo₂C@NC as the air cathode in a ZAB exhibits superior power performance and outstanding cycling stability.

锌空气电池（ZABs）因其高能量密度、安全性和环境友好性而成为下一代储能系统的有希望的候选者。然而，它们的效率受到缓慢的氧还原反应（ORR）动力学的阻碍。构建具有优化界面电子结构的异质结是提高ORR活性的一种很有前途的方法。在此，我们报道了一种由ZnCoMo-HZIF金属有机骨架（ZnCoMo-HZIF）包裹在氮掺杂碳（Co - Mo2C@NC）内的Co - mo2c异质结。Co与Mo2C之间的紧密界面使得Co与Mo2C之间存在强电子耦合，导致了界面电荷的重新分配，优化了Co活性位点的d波段中心。这种电子调制显著提高了氧中间体的吸附，降低了能垒。因此，Co - Mo2C@NC具有出色的ORR性能，具有0.85 V的高半波电位（E1/2）， 94.7 mV dec−1的低Tafel斜率，以及良好的长期稳定性。此外，Co - Mo2C@NC作为空气阴极在ZAB中表现出优异的功率性能和出色的循环稳定性。

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引用次数: 0

Crystalline porous organic frameworks: Emerging platforms for enzyme immobilization in biomedical applications 晶体多孔有机框架：生物医学应用中酶固定的新兴平台

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2026-02-01 DOI: 10.1016/j.cjsc.2025.100793

Xueting Hu, Lijia Zhao, Tingting Liao, Cheng-Peng Li

Crystalline porous organic frameworks (CPOFs), with their highly ordered pores and tunable organic structures, have shown immense promise as platforms for enzyme immobilization. However, research on enzyme@CPOF composites, particularly for biomedical applications, is still in its early stages and lacks comprehensive and systematic review. This article provides a thorough overview of recent advances in the rational design, synthesis, and application of enzyme@CPOF biocomposites. Emphasis is placed on immobilization strategies and the structure-performance relationships revealed through molecular-level investigations. Furthermore, we highlight emerging applications in biocatalysis and biomedical engineering, and discuss persistent challenges and future directions to advance CPOFs as versatile, high-performance substrates for enzyme immobilization.

晶体多孔有机框架（CPOFs）具有高度有序的孔隙和可调节的有机结构，作为酶固定化平台具有巨大的前景。然而，enzyme@CPOF复合材料的研究，特别是生物医学应用，仍处于早期阶段，缺乏全面和系统的审查。本文全面概述了enzyme@CPOF生物复合材料在合理设计、合成和应用方面的最新进展。重点放在固定策略和结构-性能的关系揭示了通过分子水平的调查。此外，我们强调了在生物催化和生物医学工程中的新兴应用，并讨论了将cpfs作为多功能、高性能酶固定化底物的持续挑战和未来方向。

引用次数: 0

Flat and fabulous: Squeezing elemental metals into the 2D realm 平面和神话：压缩元素金属到二维领域

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2026-02-01 DOI: 10.1016/j.cjsc.2025.100794

Jinbo Pang , Shuye Zhang , Mark H. Rummeli , Hong Liu , Yufeng Hao , Weijia Zhou , Rafael G. Mendes

引用次数: 0

TMO-based SERS: Dual enhancement mechanisms and multi-functional analytical applications 基于tmo的SERS：双重增强机制和多功能分析应用

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2026-02-01 DOI: 10.1016/j.cjsc.2025.100797

Xiaoyu Song , Lei Xu , Xiangyu Meng , Yuening Wang , Mingjian Zhang , Aochi Liu , Jie Lin , Xiaotian Wang

Surface-enhanced Raman scattering (SERS) spectroscopy based on transition metal oxide (TMO) substrates has emerged as a frontier research area, offering distinctive advantages in chemical stability, cost-effectiveness, and tunable optoelectronic properties compared to conventional noble metal substrates. This review systematically clarifies the dual enhancement mechanisms of TMO-based SERS including charge transfer (CT) resonance at the molecule-semiconductor interface and electromagnetic field amplification induced by localized surface plasmon resonance (LSPR); the two work synergistically to achieve signal amplification. In practical applications, TMO enable multi-scenario analysis via the controllable defect engineering-interfacial CT synergistic mechanism in SERS technology. These scenarios include ultrasensitive detection of biomarkers, dynamic tracking of cellular metabolism, real-time monitoring of environmental pollutants, and mechanistic analysis of catalytic reaction pathways. Nevertheless, critical challenges persist, particularly regarding quantitative reproducibility and long-term stability under operational conditions. This review focuses on discussing the SERS enhancement mechanisms of TMO, summarizing their diverse analytical applications across multiple fields, and briefly addressing existing limitations, aiming to provide insights for further advancement in TMO-based SERS research.

基于过渡金属氧化物（TMO）衬底的表面增强拉曼散射（SERS）光谱已经成为一个前沿研究领域，与传统的贵金属衬底相比，它在化学稳定性、成本效益和可调谐光电性能方面具有独特的优势。本文系统地阐述了基于tmo的SERS的双重增强机制，包括分子-半导体界面的电荷转移（CT）共振和局域表面等离子体共振（LSPR）引起的电磁场放大；两者协同工作以实现信号放大。在实际应用中，TMO通过SERS技术中可控缺陷工程-界面CT协同机制实现多场景分析。这些场景包括生物标志物的超灵敏检测、细胞代谢的动态跟踪、环境污染物的实时监测以及催化反应途径的机理分析。然而，关键的挑战仍然存在，特别是在操作条件下的定量可重复性和长期稳定性方面。本文重点讨论了TMO的SERS增强机制，总结了其在多个领域的不同分析应用，并简要介绍了现有的局限性，旨在为进一步推进基于TMO的SERS研究提供见解。

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引用次数: 0

Excitation-dependent tunable photoluminescence in CsCdCl3 all-inorganic perovskite for anti-counterfeiting CsCdCl3全无机钙钛矿的激发依赖可调谐光致发光防伪研究

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2026-02-01 DOI: 10.1016/j.cjsc.2025.100774

Guojun Zhou , Qiqiong Ren , Yanting Wang , Nan Zhang , Yilin Mao , Pei Wang , Xian-Ming Zhang

Developing single-component all-inorganic perovskites with excitation-dependent multicolor emission remains a considerable challenge for next-generation anti-counterfeiting technologies. Herein, we report an excitation-dependent tunable photoluminescence (PL) switching behavior in all-inorganic CsCdCl₃ perovskite, which arises from its unique structural asymmetry featuring both isolated [CdCl₆]⁴⁻ octahedra (D_3d symmetry) and face-sharing [Cd₂Cl₉]⁵⁻ dimers (C_3v symmetry). This dual-coordination environment facilitates the dual-band emissions at 500 and 590 nm, attributed to free exciton (FE) recombination in [CdCl₆]⁴⁻ octahedra and self-trapped exciton (STE) emission from [Cd₂Cl₉]⁵⁻ dimers, respectively. The competitive excitation pathways between FE and STE enable the reversible color switching between green and orange emission via excitation-wavelength modulation. The excitation-wavelength sensitivity is governed by the emission intensity ratio, where 254 nm excitation favors the dimer-associated STE emission at 590 nm while 365 nm excitation selectively strengthens the octahedral FE emission at 500 nm. Density functional theory (DFT) calculations confirm the direct bandgap of CsCdCl₃ (2.62 eV), and elucidate the electronic transition mechanism. The excitation-dependent color-switching capability of CsCdCl₃ offers promising potential for advanced applications in anti-counterfeiting and information encryption technologies. This work establishes a paradigm for designing single-component emitters with excitation-controlled multicolor PL, thereby unlocking possibilities for developing high-security anti-counterfeiting technologies.

开发具有激发依赖性多色发射的单组分全无机钙钛矿仍然是下一代防伪技术的一个相当大的挑战。在此，我们报道了全无机CsCdCl3钙钛矿的激发依赖性可调谐光致发光（PL）开关行为，这是由于其独特的结构不对称，具有分离的[CdCl6]4−八面体（D3d对称）和面共享的[Cd2Cl9]5−二聚体（C3v对称）。这种双配位环境促进了500 nm和590 nm的双频发射，分别归因于[cd2cl6]4 -八面体中的自由激子（FE）重组和[Cd2Cl9]5 -二聚体的自捕获激子（STE）发射。FE和STE之间的竞争激发通路通过激发波长调制实现了绿色和橙色发射之间的可逆颜色切换。激发波长的灵敏度受发射强度比的影响，其中254 nm激发有利于二聚体相关的STE在590 nm的发射，而365 nm激发选择性地增强了500 nm的八面体FE发射。密度泛函理论（DFT）计算证实了CsCdCl3 （2.62 eV）的直接带隙，并阐明了电子跃迁机理。CsCdCl3在防伪和信息加密技术方面的先进应用前景广阔。这项工作为设计具有激励控制的多色PL的单组分发射器建立了范例，从而解锁了开发高安全性防伪技术的可能性。

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引用次数: 0

Two-dimensional atomic crystals for third-order nonlinear optical modulation 用于三阶非线性光学调制的二维原子晶体

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2026-02-01 DOI: 10.1016/j.cjsc.2025.100772

Li Zhou , Fengyu Li , Zhou Lu , Yingwei Wang , Jun He

In the application of nonlinear optical components, ideal nonlinear optical media typically need to possess high nonlinear absorption coefficients and large modulation depths, among other characteristics. The extreme thinness of two-dimensional (2D) materials, typically at the atomic scale, offers significant advantages in miniaturized optoelectronic devices. However, this also reduces the effective light-matter interaction length, ultimately limiting the achievable interaction intensity. To enhance their nonlinear optical response and unlock their full potential in nanophotonics, current research primarily focuses on two directions: one is to develop novel 2D quantum-confined material systems with enhanced intrinsic nonlinear optical responses; the other is to design effective performance modulation strategies based on nonlinear optical theory to enable precise regulation of nonlinear optical properties. Here, recent progress in tailoring third-order nonlinear optical responses of 2D materials is systematically reviewed. Various strategies for modulating and enhancing third-order nonlinear optical responses in 2D materials are comprehensively discussed, which can be systematically classified into intrinsic regulation and light-matter interaction modulation. Moreover, the remaining challenges in modulating third-order nonlinear optical responses of 2D materials and perspectives on future research directions are discussed.

在非线性光学元件的应用中，理想的非线性光学介质通常需要具有高的非线性吸收系数和大的调制深度等特点。二维（2D）材料的极薄，通常在原子尺度上，为小型化光电器件提供了显着的优势。然而，这也减少了有效的光-物质相互作用长度，最终限制了可实现的相互作用强度。为了增强其非线性光学响应，充分发挥其在纳米光子学中的潜力，目前的研究主要集中在两个方向：一是开发具有增强本征非线性光学响应的新型二维量子受限材料系统；二是基于非线性光学理论设计有效的性能调制策略，实现非线性光学特性的精确调节。本文系统综述了二维材料三阶非线性光学响应裁剪的最新进展。全面讨论了二维材料中调制和增强三阶非线性光学响应的各种策略，系统地将其分为本征调节和光物质相互作用调制。最后讨论了二维材料三阶非线性光学响应调制中存在的问题，并对未来的研究方向进行了展望。

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引用次数: 0

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