Chinese Chemical Letters最新文献_第5页

Salt-assisted synthesis of WTe2 contact electrodes for efficient MoS2-based hydrogen evolution reaction 盐辅助合成基于mos2的高效析氢反应的WTe2接触电极

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-29 DOI: 10.1016/j.cclet.2025.111917

Zhuojun Duan , Peiyue Jin , Houying Xing , Jian Chen , Yueting Yang , Yawen Tan , Song Liu

The hydrogen evolution reaction (HER) is crucial for hydrogen production and sustainable energy storage. Molybdenum disulfide (MoS₂), a representative transition metal dichalcogenides (TMDs), shows potential as an HER catalyst but suffers from limited performance due to poor charge transfer and interfacial effects. Here, we report a salt-assisted chemical vapor deposition (CVD) method for synthesizing high-quality tungsten ditelluride (WTe₂) with tunable morphologies using alkali halides (NaCl, KCl and LiCl). The prepared WTe₂ nanoribbons and hexagonal nanosheets exhibit morphology-dependent electrical conductivity, with nanosheets showing superior performance. To evaluate WTe₂ as a contact electrode, WTe₂−MoS₂ heterostructures were fabricated and compared with graphene-MoS₂ counterparts. The WTe₂−MoS₂ heterostructure exhibits a superior Tafel slope of 111.57 mV/dec and an overpotential of 298 mV at -10 mA/cm², significantly outperforming graphene-based electrodes. This improvement is attributed to the excellent conductivity of WTe₂ and reduced interfacial Schottky barriers. Moreover, we systematically investigate the influence of WTe₂ thickness on HER performance and assess the electrochemical durability and structural stability of the heterostructure, further confirming the effectiveness of WTe₂ as a contact electrode for enhancing the HER activity of MoS₂. This study offers a novel approach for enhancing the HER performance of MoS₂ through controlled WTe₂ growth and application as a contact electrode. Our findings provide valuable insights into the synthesis of high-quality WTe₂ and broaden the potential applications of two-dimensional materials in energy catalysis.

析氢反应（HER）对制氢和可持续储能至关重要。二硫化钼（MoS2）是典型的过渡金属二硫族化合物（TMDs），具有作为HER催化剂的潜力，但由于电荷转移和界面效应较差，其性能受到限制。在这里，我们报道了一种盐辅助化学气相沉积（CVD）方法，以碱卤化物（NaCl， KCl和LiCl）合成具有可调形貌的高质量二碲化钨（WTe2）。制备的WTe2纳米带和六角形纳米片的电导率具有形态依赖性，其中纳米片表现出优异的导电性能。为了评价WTe2作为接触电极的性能，制备了WTe2−MoS2异质结构，并与石墨烯-MoS2异质结构进行了比较。WTe2−MoS2异质结构的Tafel斜率为111.57 mV/dec，在-10 mA/cm2时过电位为298 mV，明显优于石墨烯基电极。这种改善是由于WTe2的优异导电性和减少的界面肖特基势垒。此外，我们系统地研究了WTe2厚度对HER性能的影响，并评估了异质结构的电化学耐久性和结构稳定性，进一步证实了WTe2作为接触电极对提高MoS2的HER活性的有效性。该研究为通过控制WTe2的生长和作为接触电极的应用来提高MoS2的HER性能提供了一种新的方法。我们的发现为高质量WTe2的合成提供了有价值的见解，并拓宽了二维材料在能量催化方面的潜在应用。

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引用次数: 0

Interface challenges of solid-state electrolytes/lithium metal anode: From origin analysis, failure mechanism to interface optimization strategies 固态电解质/锂金属阳极的界面挑战：从起源分析、失效机制到界面优化策略

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-29 DOI: 10.1016/j.cclet.2025.111905

Dongfan Li , Jinlong Lv , Jian-Cang Wang , Jiaxiang Liu , Huizhe Niu , Lu Yang , Hao Luo , Du Lv , Lichun Niu , Zemin He , Zongcheng Miao

The advent of all-solid-state lithium metal batteries (ASSLMBs) holds promise for overcoming the safety hazards and energy density limitations faced by traditional lithium-ion batteries, thereby advancing the industrialization of next-generation energy storage technologies with high safety and specific energy. However, during practical application, three core challenges persist at the interface between the solid-state electrolytes (SSEs) and the lithium metal anode (LMA): Poor physical contact, interfacial side reactions, and growth of lithium dendrites. These interfacial issues constrain the overall performance of ASSLMBs and impede the commercialization process of this battery system. This review begins by examining the underlying mechanisms responsible for the interfacial problems between SSEs and LMA. Building on this foundation, optimization strategies and recent research progress are systematically introduced, classified according to the interfacial components: SSE-side optimizations, interface engineering, and LMA-side treatments. Finally, future research directions, strategies, and optimization schemes addressing the interfacial challenges between SSEs and LMA are prospected. This analysis aims to facilitate critical breakthroughs in the stability, cycling lifespan, and energy density of ASSLMBs, promoting their transition from laboratory innovation to commercial application.

全固态锂金属电池（asslmb）的出现有望克服传统锂离子电池面临的安全隐患和能量密度限制，从而推进具有高安全性和比能量的下一代储能技术的产业化。然而，在实际应用中，固态电解质（sse）与锂金属阳极（LMA）之间的界面存在三个核心挑战：物理接触不良、界面副反应和锂枝晶的生长。这些接口问题限制了asslmb的整体性能，并阻碍了该电池系统的商业化进程。本文首先探讨了导致sse和LMA之间的接口问题的潜在机制。在此基础上，系统地介绍了优化策略和最新研究进展，并根据界面组件进行了分类：sse侧优化、界面工程和lma侧处理。最后，展望了未来的研究方向、策略和优化方案，以解决sse和LMA之间的接口挑战。该分析旨在促进asslmb在稳定性、循环寿命和能量密度方面的关键突破，促进其从实验室创新向商业应用的过渡。

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引用次数: 0

An optical pressure sensing phosphor of high-sensitivity by soft structure 一种软结构的高灵敏度光学压敏荧光粉

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-29 DOI: 10.1016/j.cclet.2025.111916

Ruijing Fu , Bin Xiao , Haoyuan Weng , Pan Wang , Guangxia Wang , Qingguang Zeng , Dawei Wen , Guanjun Xiao

Luminescent materials function as optical pressure sensors based on pressure-dependent emission. Optical pressure sensors offer a broad measurement range and non-contact operation but face limitations in sensitivity. In this study, we establish a selection principle based on low-dimensional structures and conduct a high-pressure evaluation of xCr³⁺-doped Sr₉Ga_1-_x(PO₄)₇ (x = 0.2, 0.5, and 0.8) phosphor, demonstrating its exceptional pressure sensitivity. Upon excitation at 488 nm, Sr₉Ga_0.5(PO₄)₇:0.5Cr³⁺ displays a broad near-infrared emission peak centered at 840 nm. Specifically, the phosphor maintains its structural integrity under pressures up to 10.0 GPa, with a continuous blue shift. The fluorescence peak shifts from 839.5 nm to 757.9 nm, demonstrating a high-pressure sensitivity of 8.11 nm/GPa. These findings establish Sr₉Ga_0.5(PO₄)₇:0.5Cr³⁺ as a viable candidate for optical pressure sensor, thereby offering valuable insights into advancing optical sensor development through host selection.

发光材料是基于压力相关发射的光学压力传感器。光学压力传感器具有广泛的测量范围和非接触式操作，但在灵敏度上存在局限性。在本研究中，我们建立了基于低维结构的选择原则，并对xCr3+掺杂的Sr9Ga1-x(PO4)7 （x = 0.2,0.5和0.8）荧光粉进行了高压评价，证明了其优异的压力敏感性。在488 nm激发下，Sr9Ga0.5(PO4)7:0.5Cr3+显示出以840 nm为中心的宽近红外发射峰。具体来说，荧光粉在高达10.0 GPa的压力下保持其结构完整性，并具有连续的蓝移。荧光峰从839.5 nm位移到757.9 nm，高压灵敏度为8.11 nm/GPa。这些发现确立了Sr9Ga0.5(PO4)7:0.5Cr3+作为光学压力传感器的可行候选材料，从而为通过宿主选择推进光学传感器的发展提供了有价值的见解。

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引用次数: 0

The 5th Xihua Chemistry and Biomedicine Forum 第五届西华化学与生物医药论坛

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-29 DOI: 10.1016/j.cclet.2025.111925

Dongfang Liu , Zhouyu Wang , Junli Wang , Leyong Wang

引用次数: 0

Cl-adsorbed Cu(111)/H2O interface selectively realizes electrochemical CO2 reduction towards C2H4 product: Mechanistic understanding cl -吸附Cu(111)/H2O界面选择性实现电化学CO2还原C2H4产物的机理认识

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-29 DOI: 10.1016/j.cclet.2025.111920

Lihui Ou , Zhancheng Liu , Dai-Huo Liu , Zhi Zhang

Cu electrocatalysts have been demonstrated to have unique ability to reduce CO₂ to various high value-added C₂ products like ethylene and alcohols. However, realizing high selectivity of C₂ products are still a main challenge due to complex CO₂ electroreduction pathways and small opportunity of CC coupling reactions. Here, we found the origin of enhanced CO₂ electroreduction reaction activity and product selectivity towards C₂ products and CC coupling mechanism at halogen atoms-adsorbed Cu/H₂O interfaces, the corresponding CO₂ electroreduction evolution mechanisms at the halogen atoms-modified Cu/H₂O interfaces are systematically studied via theoretical modeling and calculations. The calculated results indicate that halide anions modifications are beneficial to CO dimerization into OCCO dimer, especially Cl⁻-adsorbed Cu(111)/H₂O interface has the optimum activity and selectivity towards OCCO dimer, subsequent Cl-adsorbed Cu(111)/H₂O interface can selectively reduce CO₂ into C₂H₄ product. The function relationship between adsorption free energy of Cl atom and electrode potential explain why the adsorption of Cl⁻ can enhance selectivity of C₂H₄ product. The determinations of onset potentials indicate that electroreduction pathways of CO₂ towards C₂H₄ product are facile to take place and further explain the origin of the significantly enhanced CO production activity and C₂H₄ product selectivity. This work on selective realization of CO₂ electroreduction towards C₂H₄ product via Cl⁻-modified Cu(111)/H₂O interface provide a theoretical guideline for how to selectively realize other high value-added C₂ products.

铜电催化剂已被证明具有独特的能力，可以将二氧化碳还原为各种高附加值的C2产品，如乙烯和醇。然而，由于CO2电还原途径复杂，CC偶联反应机会小，实现C2产物的高选择性仍然是一个主要挑战。本研究发现了CO2电还原反应活性和产物对C2选择性增强的原因以及卤素原子吸附Cu/H2O界面上的CC耦合机理，并通过理论建模和计算系统地研究了卤素原子修饰Cu/H2O界面上相应的CO2电还原演化机理。计算结果表明，卤化物阴离子改性有利于CO二聚成OCCO二聚体，特别是Cl−吸附的Cu(111)/H2O界面对OCCO二聚体具有最佳的活性和选择性，后续Cl−吸附的Cu(111)/H2O界面可以选择性地将CO2还原成C2H4产物。Cl原子的吸附自由能与电极电位之间的函数关系解释了吸附Cl−可以提高C2H4产物选择性的原因。起始电位的测定表明，CO2对C2H4产物的电还原途径很容易发生，并进一步解释了CO生产活性和C2H4产物选择性显著增强的原因。通过Cl−修饰Cu(111)/H2O界面选择性实现CO2电还原C2H4产品，为选择性实现其他高附加值C2产品提供了理论指导。

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引用次数: 0

Stereoselective in situ assembled hydrofunctionalization and cascade 立体选择性原位组装氢化和级联

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-29 DOI: 10.1016/j.cclet.2025.111921

Li-Hong Xiong , Liang Chen , Zhi-Tao He

Hydrofunctionalization of unsaturated hydrocarbons via transition metal catalysis is a powerful route to prepare allyl skeletons, but is limited to mono- and two-component transformation models. Here we describe a novel protocol for the unprecedented three-component hydrofunctionalization via in situ formed diene species. Both amines and stabilized carbon nucleophiles undergo the assembled hydrofunctionalization with various olefins and alkenyl bromides through Pd-catalyzed tandem Heck coupling and outer-sphere allylation, generating allylic C–N and C–C bonds in reasonable yields and with excellent regioselectivities. In particular, the combination of assembled hydrofunctionalization and following derivatizations enables new access to a series of valuable substituted cyclic skeletons. Preliminary mechanistic studies support the in situ formation of critical conjugated diene intermediate for sequential hydrofunctionalization

过渡金属催化不饱和烃的加氢功能化是制备烯丙基骨架的有效途径，但仅限于单组分和双组分转化模型。在这里，我们描述了一种新的方案，前所未有的三组分氢化通过原位形成的二烯物种。胺和稳定碳亲核试剂都通过pd催化的串联Heck偶联和外球烯丙基化与各种烯烃和烯基溴进行组装的加氢功能化，以合理的产率和优异的区域选择性生成烯丙基C-N和C-C键。特别是，组合的氢功能化和随后的衍生化相结合，可以获得一系列有价值的取代环骨架。初步的机制研究支持原位形成的关键共轭二烯中间体的顺序加氢功能化

引用次数: 0

Enantioselective synthesis of α‑aryl ketones via cross-hydroacylation of two distinct alkenes 通过两种不同烯烃的交叉氢酰化，对映选择性合成α -芳基酮

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-25 DOI: 10.1016/j.cclet.2025.111893

Yongli Liu , Dan Xu , Yuanyuan Ping , Nengzhong Wang , Wangqing Kong

Chiral α-aryl ketone moieties are privileged structural motifs that are widely present in various biologically active natural products and pharmaceuticals. However, traditional carbonylation methods typically rely on the use of noble-metal catalysts and toxic and flammable CO gas as the carbonyl source. To overcomes these challenges, we disclose here a nickel-catalyzed enantioselective cross-hydroacylation of aryl alkenes with unactivated alkenes using isobutyl chloroformate as a safe CO source and electron acceptor. Two distinct alkenes and chloroformates are assembled efficiently in a chemo-, regio- and enantioselective manner, providing a scalable, environmentally friendly alternative for the enantioselective synthesis of α-aryl ketones. The approach proceeds under mild reaction conditions, uses abundant and readily available starting materials, and avoids the use of either toxic CO or metal carbonyl reagents. Mechanistic studies show that in situ generated nickel hydride complexes first undergoes hydrometalation/chain walking with aryl alkenes, followed by sequential migratory insertion of CO and unactivated alkenes, and finally cross-hydroacylated products are obtained through reductive elimination.

手性α-芳基酮是广泛存在于各种具有生物活性的天然产物和药物中的特殊结构基序。然而，传统的羰基化方法通常依赖于使用贵金属催化剂和有毒易燃的CO气体作为羰基源。为了克服这些挑战，我们在这里揭示了镍催化芳基烯烃与非活化烯烃的对映选择性交叉氢化反应，使用氯甲酸异丁酯作为安全的CO源和电子受体。两种不同的烯烃和氯甲酸酯以化学、区域和对映选择性的方式有效地组装，为α-芳基酮的对映选择性合成提供了一种可扩展的、环境友好的替代方法。该方法在温和的反应条件下进行，使用丰富且容易获得的起始材料，避免使用有毒的CO或金属羰基试剂。机理研究表明，原位生成的氢化镍配合物首先与芳基烯烃发生金属氢化反应/走链，随后CO和未活化的烯烃依次迁移插入，最后通过还原消除得到交叉氢化产物。

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引用次数: 0

Interlocked covalent organic cages: Design, synthesis, and self-assembly 联锁共价有机笼：设计、合成和自组装

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-25 DOI: 10.1016/j.cclet.2025.111894

Bin Yao , Yao Bu , Hongfei Sun , Guowang Li , Xianying Wu , Wei Wang

Interlocked covalent organic cages have aesthetic skeletons endowed with structural and topological complexity. Their self-assembly provides a unique possibility to mimic the hierarchical self-assembly of biomacromolecules. In recent years, significant progresses in interlocked covalent organic cages have been witnessed. Different topological structures have been fabricated via various non-template induced methods, and diverse weak interactions are demonstrated to play critical roles in guiding the formation of interlocked structures. Therefore, this article systematically summarizes the recent advances in interlocked covalent organic cages, especially their design, synthesis, and self-assembly properties. Depending on different types of chemical reactions, irreversible and reversible reactions are separately introduced. In each section, proper monomer selection, critical topology design, key driving forces as well as detailed interlocked mechanisms for the formation of interlocked structures, and their self-assembly behaviors in single crystals are discussed detailedly. Finally, the challenge and future development of interlocked covalent organic cages are briefly prospected.

互锁共价有机笼具有结构和拓扑复杂性的美学骨架。它们的自组装为模拟生物大分子的分层自组装提供了独特的可能性。近年来，联锁共价有机笼的研究取得了重大进展。通过各种非模板诱导方法制备了不同的拓扑结构，并证明了不同的弱相互作用在指导互锁结构的形成中起着关键作用。因此，本文系统地综述了近年来连锁共价有机笼的研究进展，重点介绍了连锁共价有机笼的设计、合成和自组装性能。根据化学反应类型的不同，分别介绍了不可逆反应和可逆反应。在每一节中，详细讨论了单体选择、关键拓扑设计、关键驱动力以及形成联锁结构的详细联锁机制及其在单晶中的自组装行为。最后，对连锁共价有机网箱面临的挑战和未来的发展进行了简要展望。

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引用次数: 0

Recent development in radical cycloaddition reactions for the synthesis of carbo- and heterocycles 羰基环加成反应与杂环合成的新进展

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-25 DOI: 10.1016/j.cclet.2025.111886

Saima Perveen , Lulu Qin , Min Zhao , Zhengwei Ding , Yingying Wang , Zaicheng Nie , Pengfei Li

Radical cycloaddition reactions (RCRs) are highly effective methods for constructing complex carbo- and heterocycles, which are frequently encountered in natural products that exhibit intriguing biological properties and hold significant potential for applications in medicinal chemistry. Radical-mediated cycloaddition strategies, which recycle radical character, are particularly appealing because they require only a catalytic amount of reagent and promise reactions with theoretically high atom economy. This review focuses on recent developments and synthetic applications in RCRs, with an emphasis on visible light-induced radical photocycloaddition reactions (RPCRs), transition metal-catalyzed approaches, and small molecule-catalyzed methods. By highlighting some outstanding innovations and addressing current challenges, this review aims to identify potential areas for improvement. These advancements will provide more efficient pathways for the synthesis of natural product molecules and offer valuable insights for the development of new synthetic methodologies.

自由基环加成反应（RCRs）是构建复杂碳环和杂环的有效方法，在天然产物中经常遇到，具有有趣的生物学特性，在药物化学中具有重要的应用潜力。自由基介导的环加成策略具有回收自由基的特点，因为它只需要催化量的试剂，并且理论上具有很高的原子经济性。本文综述了可见光诱导自由基光环加成反应（RCRs）、过渡金属催化方法和小分子催化方法等方面的研究进展和应用。通过突出一些杰出的创新和解决当前的挑战，本审查旨在确定潜在的改进领域。这些进展将为天然产物分子的合成提供更有效的途径，并为新的合成方法的发展提供有价值的见解。

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引用次数: 0

Carbon dots-embedded hydrogel ratiometric fluorescent platform for portable determination of doxorubicin in clinical samples 碳点包埋水凝胶比例荧光平台用于临床样品中阿霉素的便携式测定

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-24 DOI: 10.1016/j.cclet.2025.111891

Xin Liu , Haoran Zhu , Yi Wang , Haili Zhang , Yujie Li , Hongcheng Gao , Yi Han , Dejin Wang , Yunsheng Xia

Portable ratiometric fluorescent platforms have emerged as promising tools for multifarious detection, yet remain unexplored for point-of-care monitoring doxorubicin (DOX), one of clinically antineoplastic drugs. To this end, we herein develop a portable self-calibrating platform namely carbon dots (C-dots)-embedded hydrogel sensors with a smartphone-assisted high-throughput imaging device, for DOX sensing. The prepared green-emitting (λ_em = 508 nm) and negatively-charged C-dots (−11.40 ± 1.21 mV), which have sufficient spectral overlap with the absorption band of DOX (∼500 nm), can strongly bind with positively-charged DOX molecules by electrostatic attraction effects. As a result, DOX molecules are selectively and rapid (20 s) determined with a detection limit of 10.26 nmol/L via Förster resonance energy transfer processes, demonstrating a remarkably chromatic shift from green to red. Further integrated with a 3D-printed smartphone-assisted device, the platform enabled high-throughput quantification, achieving recoveries of 96.40%–101.85% in human urine/serum (RSDs < 2.94%, n = 3). Notably, the dual linear detection ranges of the platform align with the reported clinical DOX concentrations in urine and plasma (0–4 h post-administration), validating their capability for direct quantification of DOX in clinical samples without special pre-treatment processes. By virtue of attractive analytical performances and robust feasibility, this platform bridges laboratory precision and point-of-care testing needs, offering promising potential for personalized chemotherapy and multiplexed analyte screening.

便携式比例荧光平台已成为多种检测的有前途的工具，但对于临床抗肿瘤药物之一阿霉素（DOX）的即时监测仍未探索。为此，我们在此开发了一种便携式自校准平台，即碳点（C-dots）嵌入式水凝胶传感器，具有智能手机辅助的高通量成像设备，用于DOX传感。制备的绿色发光（λem = 508 nm）和带负电荷的c点（- 11.40±1.21 mV）与DOX的吸收带（~ 500 nm）有足够的光谱重叠，可以通过静电吸引作用与带正电的DOX分子强结合。因此，通过Förster共振能量转移过程，DOX分子被选择性地快速测定（20 s），检测限为10.26 nmol/L，显示出明显的从绿色到红色的色移。该平台进一步集成了3d打印智能手机辅助设备，实现了高通量定量，在人尿/血清中实现了96.40%-101.85%的回收率（rsd < 2.94%, n = 3）。值得注意的是，该平台的双线性检测范围与报告的临床尿液和血浆中DOX浓度（给药后0-4小时）一致，验证了其直接定量临床样品中DOX的能力，无需特殊的预处理过程。凭借具有吸引力的分析性能和强大的可行性，该平台连接了实验室精度和护理点测试需求，为个性化化疗和多路分析物筛选提供了有希望的潜力。

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引用次数: 0