Chinese Chemical Letters最新文献_第9页

Visible-light-promoted multi-component carbene transfer reactions of diazo compounds via ring-opening of cyclic ethers 可见光通过环醚开环促进重氮化合物的多组分碳转移反应

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-13 DOI: 10.1016/j.cclet.2025.111834

Feng Zhao , Hongyu Ding , Ting Sun , Chao Shen , Zu-Li Wang , Wei Wei , Dong Yi

Carbenes as one of the most important class of intermediates have been widely utilized in various organic synthetic transformations. Carbene insertion-initiated ring-opening reactions of cyclic ethers offer a valuable strategy for constructing new carbon-oxygen bonds. In comparison with traditional thermal or metal-mediated carbene transfer reactions, visible-light-promoted multi-component reaction strategy provides a mild and eco-friendly approach to access densely functionalized molecules. Recently, visible-light-induced multi-component carbene transfer reactions of diazo compounds have been rapidly developed and attracted a great deal of research interest of chemists owing to their advantages of simple operation, mild condition, high atom economy and rich structural diversity. This paper summarizes the recent research progress on the visible-light-promoted multi-component carbene transfer reactions of diazo compounds via ring-opening of cyclic ethers with various nucleophiles. The reaction patterns of different nucleophiles and their corresponding mechanism are described in this review. The future research direction and challenges in this area are also discussed.

卡宾是一类重要的中间体，在各种有机合成转化中得到了广泛的应用。由卡宾插入引发的环醚开环反应为构建新的碳氧键提供了一种有价值的策略。与传统的热或金属介导的碳转移反应相比，可见光促进的多组分反应策略提供了一种温和且环保的方法来获得密集功能化分子。近年来，可见光诱导重氮化合物的多组分碳转移反应以其操作简单、反应条件温和、原子经济性高、结构多样性丰富等优点得到了迅速发展，引起了化学家们的广泛研究。本文综述了近年来在可见光促进下环醚与各种亲核试剂开环催化重氮化合物多组分碳转移反应的研究进展。本文综述了不同亲核试剂的反应模式及其反应机理。并对该领域未来的研究方向和面临的挑战进行了讨论。

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引用次数: 0

Pd@PtNiCoRuIr core-shell high-entropy alloys mesoporous nanospheres for temporally decoupled ammonia splitting by a Zn-NH3 battery Pd@PtNiCoRuIr核壳高熵合金介孔纳米球用于Zn-NH3电池暂时解耦氨分裂

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-11 DOI: 10.1016/j.cclet.2025.111826

Cuiping Lin , Chenchen Wang , Shaoqi Li , Qi Shen , Xiaodong Yang , Zengsheng Guo , Haiming Feng , Cuncheng Li , Yiqing Sun , Lifeng Hang

Conversion of ammonia into hydrogen, a crucial pathway for the hydrogen economy, is severely constrained by the intricacy of the required equipment and the low efficiency. Herein, Pd@PtNiCoRuIr core-shell mesoporous bifunctional electrocatalysts were fabricated via a one-step wet-chemical reduction approach. By utilizing the limiting effect of triblock copolymers, gradient distribution control of six metal elements (Pd core and Pt/Ni/Co/Ru/Ir high-entropy alloys shell) was achieved, where the high-entropy alloy shell forms high-density active sites through lattice distortion effect. With the help of lattice distortion and mesoporous-confinement-enabled interfacial coupling effects, Pd@PtNiCoRuIr catalyst exhibited exceptional bifunctional performance in alkaline media: A low hydrogen evolution reaction (HER) overpotential of 30.5 mV at 10 mA/cm² and a high ammonia oxidation reaction (AOR) peak current density of 19.6 mA/cm² at 0.7 V vs. RHE, representing a 3.83-fold enhancement over commercial Pt/C. Moreover, a rechargeable Zn-NH₃ battery system was constructed and achieved 92.3 % Faradaic efficiency (FE) for NH₃-to-H₂ conversion with outstanding stability at 16 mA/cm², thereby providing an innovative solution for efficient ammonia decomposition-based hydrogen production.

氨转化为氢是氢经济的一个重要途径，但由于所需设备的复杂性和效率低下而受到严重限制。本文采用一步湿法还原法制备了Pd@PtNiCoRuIr核壳双功能电催化剂。利用三嵌段共聚物的限制效应，实现了6种金属元素（Pd核和Pt/Ni/Co/Ru/Ir高熵合金壳）的梯度分布控制，其中高熵合金壳通过晶格畸变效应形成高密度活性位点。借助晶格畸变和介孔-约束界面耦合效应，Pd@PtNiCoRuIr催化剂在碱性介质中表现出优异的双功能性能：在10 mA/cm2时，低析氢反应（HER）过电位为30.5 mV，在0.7 V时，与RHE相比，高氨氧化反应（AOR）峰值电流密度为19.6 mA/cm2，比商用Pt/C提高了3.83倍。此外，构建了一个可充电的Zn-NH3电池系统，其nh3 - h2转化的法拉第效率（FE）为92.3 %，稳定性为16 mA/cm2，从而为基于氨分解的高效制氢提供了创新的解决方案。

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引用次数: 0

High-performance bifunctional electrocatalyst (NiFe-LDH/MoNi4) with enhanced chloride corrosion resistance for achieving seawater overall-splitting at industrial temperature 高性能双功能电催化剂（NiFe-LDH/MoNi4），具有增强的耐氯化物腐蚀性，可在工业温度下实现海水的整体分解

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-11 DOI: 10.1016/j.cclet.2025.111825

Gang Zhao , Wenbo Liao , Lan Mu , Baojie Zhang , Ning Zhao , Tianyong Zhang , Xijin Xu

Nickel-iron double hydroxides are corroded by Cl⁻ during seawater electrolysis, which reduces their catalytic activity and stability. Here, a high-performance bifunctional electrocatalyst (NiFe-LDH/MoNi₄) with enhanced chloride corrosion resistance was synthesized. In the OER process, Mo element in the catalyst was reconstructed to form MoO₄²⁻, which repelled Cl⁻ to prevent the catalyst from being corroded. Besides, the heterostructure of NiFe-LDH/MoNi₄ decreased the reduction of HER active site during HER process (Mo element dissolves easily in alkaline media due to thermodynamic instability). Therefore, based on in-situ self-reconstruction of Mo element and heterostructure in alkaline seawater, NiFe-LDH/MoNi₄ delivered a current density of 10 mA/cm² for the HER (OER) at industrial temperatures (80 °C) with an overpotential of merely 32 mV (139 mV). Additionally, when NiFe-LDH/MoNi₄ is employed as both the anode and cathode, a battery voltage of just 1.39 V (3.13 V) is sufficient to attain a current density of 10 mA/cm² (1 A/cm²). The system is also capable of sustained operation at a high current density of 500 mA/cm² for a period of 50 h.

在海水电解过程中，镍铁双氧水被Cl−腐蚀，导致其催化活性和稳定性降低。本文合成了一种高性能的双功能电催化剂（NiFe-LDH/ mon4），具有增强的耐氯腐蚀性能。在OER过程中，催化剂中的Mo元素重构形成MoO42−，MoO42−排斥Cl−，防止催化剂被腐蚀。此外，NiFe-LDH/ mon4的异质结构降低了HER活性位点的还原（Mo元素在碱性介质中易溶解，热力学不稳定）。因此，基于碱性海水中Mo元素和异质结构的原位自重构，NiFe-LDH/MoNi4在工业温度（80 °C）下为HER （OER）提供了10 mA/cm2的电流密度，过电位仅为32 mV（139 mV）。此外，当镍铁- ldh /MoNi4同时用作阳极和阴极时，仅1.39 V（3.13 V）的电池电压就足以获得10 mA/cm2 （1 a /cm2）的电流密度。该系统还能够在500 mA/cm2的高电流密度下持续工作50 h。

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引用次数: 0

Nonporous cavitand-crosslinked polymers: Harnessing deep cavities for efficient organic micropollutant removal from water 无孔空腔交联聚合物：利用深空腔高效去除水中的有机微污染物

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-11 DOI: 10.1016/j.cclet.2025.111824

Yang Liang , Xiaojuan Zhou , Rui Wang , Julius Rebek Jr. , Yang Yu

Organic pollutants, a pivotal factor in water pollution, have persistently menaced the aquatic ecosystem, as well as the sustainable development of human health, economy, and society. Consequently, there is an urgent need for advanced techniques to efficiently eliminate organic micropollutants from water. Here, we present the synthesis of three nonporous cavitand-crosslinked polymers capable of adsorbing diverse organic pollutants from aqueous solutions. These polymeric adsorbents exhibit outstanding adsorptive performance towards the tested micropollutants, characterized by high apparent adsorption rate constants (k_obs) and maximum adsorption capacities (q_max,e). Notably, Compound NCCP-1 demonstrated a remarkable q_max,e of 459 mg/g for bisphenol A (BPA), ranking among the highest values reported for organic polymer adsorbents. In-depth investigation of the adsorption mechanism of the nonporous polymer revealed that it involves the recognition of pollutants by the deep cavities of the cavitand moieties and the interstitial spaces between them, primarily mediated by the hydrophobic effect. Furthermore, NCCP-1 was applied in situ water purification simulations and was proven to maintain its removal efficiency over more than four cycles, highlighting its potential for practical applications in water treatment.

有机污染物是水体污染的关键因素，一直威胁着水生生态系统，威胁着人类健康、经济和社会的可持续发展。因此，迫切需要先进的技术来有效地去除水中的有机微污染物。在这里，我们提出了三种无孔空腔交联聚合物的合成，能够从水溶液中吸附各种有机污染物。这些高分子吸附剂具有较高的表观吸附速率常数（kobs）和最大吸附容量（qmax,e），对所测微污染物具有优异的吸附性能。值得注意的是，化合物NCCP-1对双酚a （BPA）的qmax为459 mg/g，是有机聚合物吸附剂中最高的。对无孔聚合物吸附机理的深入研究表明，无孔聚合物的吸附主要由疏水作用介导，通过腔体和基团的深空腔及其间隙对污染物进行识别。此外，NCCP-1应用于原位水净化模拟，并被证明在四个以上的循环中保持其去除效率，突出了其在水处理中的实际应用潜力。

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引用次数: 0

Growth of Ce-doped NiCo-LDHs on tin dioxide-modified nickel foam as oxygen evolution reaction catalyst electrode 二氧化锡改性泡沫镍作为析氧反应催化剂电极生长ce掺杂NiCo-LDHs

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-09 DOI: 10.1016/j.cclet.2025.111804

Zhongjie Song , Nannan Zhang , Jun Yu , Huiyu Sun , Zhengying Wu , Yukou Du

Developing catalysts with excellent stability while significantly reducing the overpotential of the oxygen evolution reaction (OER) is crucial for advancing overall water splitting (OWS) systems. In this study, we synthesized the electrode material Ce-NiCo-LDHs@SnO₂/NF through a two-step hydrothermal reaction, where Ce-doped NiCo-LDHs are grown on nickel foam modified by a SnO₂ layer. Ce doping adjusts the internal electronic distribution of NiCo-LDHs, while the introduction of the SnO₂ layer enhances electron transfer capability. Together, these factors contribute to the reduction of the OER energy barrier and experimental evidence confirms that the reaction proceeds via the lattice oxygen evolution mechanism (LOM). Consequently, Ce-NiCo-LDHs@SnO₂/NF exhibits high level electrochemical performance in OER, requiring only 234 mV overpotential to achieve a current density of 10 mA/cm², with a Tafel slope of just 27.39 mV/dec. When paired with Pt/C/NF, an external potential of only 1.54 V is needed to drive OWS to attain a current density amounting to 10 mA/cm². Furthermore, the catalyst demonstrates stability for 100 h during the OWS stability test. This study underscores the feasibility of enhancing the OER performance through Ce doping and the introduction of a conductive SnO₂ layer.

开发具有优异稳定性的催化剂，同时显著降低析氧反应（OER）的过电位，是推进整体水裂解（OWS）体系的关键。在本研究中，我们通过两步水热反应合成了电极材料Ce-NiCo-LDHs@SnO₂/NF，其中ce掺杂的NiCo-LDHs生长在经过SnO2层修饰的泡沫镍上。Ce掺杂调整了NiCo-LDHs的内部电子分布，而SnO₂层的引入提高了电子传递能力。这些因素共同有助于OER能垒的降低，实验证据证实反应是通过晶格析氧机制（LOM）进行的。因此，Ce-NiCo-LDHs@SnO₂/NF在OER中表现出高水平的电化学性能，仅需234 mV过电位即可实现10 mA/cm2的电流密度，塔菲尔斜率仅为27.39 mV/dec。当与Pt/C/NF配对时，仅需要1.54 V的外部电位即可驱动OWS达到10 mA/cm2的电流密度。此外，催化剂在OWS稳定性测试中表现出100 h的稳定性。该研究强调了通过Ce掺杂和引入导电SnO₂层来提高OER性能的可行性。

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引用次数: 0

Environmentally friendly Bpy-COF/PThC all-organic heterojunction for efficient removing antibiotic-resistant bacteria and organic pollutants 环境友好型Bpy-COF/PThC全有机异质结，高效去除耐药细菌和有机污染物

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-09 DOI: 10.1016/j.cclet.2025.111805

Feng Liu , Liaofang Shang , Yao Liu , Xinyue Zhang , Chunbo Liu , Guangbo Che , Haiyong Guo , Yaqian Lan

The extensive use of various antibiotics and organic dyes has led to increasingly severe environmental issues and posed a significant threat to human health. Developing an efficient and safe dual-functional photocatalytic material for degradation and antibacterial purposes is the key to solving environmental pollution problems. Polythiophene and covalent organic frameworks (COFs) possess excellent photophysical properties, high stability, and ease of modification, offering broad application prospects and significant development potential in the removal of organic pollutants and antibiotic-resistant bacteria (ARB). A high-performance conductive polymer PTET-T-COOH (PThC) was prepared via the Stille coupling reaction, and a bipyridine (Bpy) covalent organic framework Bpy-COF was synthesized through acid-catalyzed imine condensation. By utilizing the π-π stacking and hydrogen bonding interactions between Bpy-COF and PThC, a novel Bpy-COF/PThC all-organic heterojunction was successfully fabricated. Compared to Bpy-COF and PThC, the composite exhibits a broadened spectral response range and higher carrier separation efficiency. The 30 % Bpy-COF/PThC demonstrates the best photocatalytic performance, achieving a 99.96 % inactivation rate of methicillin-resistant Staphylococcus aureus (MRSA) with a cell density of 7.23 log and a 95.28 % bactericidal rate of Escherichia coli (E. coli) with a cell density of 7.50 log within 60 min. Under natural light, it not only exhibits good inactivation effects on both MRSA and E. coli, but also shows excellent degradation performance for rhodamine B, methylene blue, and tetracycline. The cytotoxicity experiment demonstrates that the composite exhibits good biocompatibility and potential for practical applications. The research results provide new design ideas for constructing efficient and safe organic photocatalysts, and offer a theoretical basis for the treatment of water pollution.

各种抗生素和有机染料的广泛使用导致了日益严重的环境问题，对人类健康构成了重大威胁。开发一种高效、安全的降解和抗菌双功能光催化材料是解决环境污染问题的关键。聚噻吩和共价有机框架材料（COFs）具有优异的光物理性质、高稳定性和易于改性等优点，在有机污染物和耐药菌（ARB）的去除方面具有广阔的应用前景和显著的发展潜力。通过Stille偶联反应制备了高性能导电聚合物PTET-T-COOH (PThC)，并通过酸催化亚胺缩合合成了联吡啶（Bpy）共价有机骨架Bpy- cof。利用Bpy-COF与PThC之间的π-π堆叠和氢键相互作用，成功制备了新型的Bpy-COF/PThC全有机异质结。与Bpy-COF和PThC相比，复合材料具有更宽的光谱响应范围和更高的载流子分离效率。30 % Bpy-COF/PThC表现出最佳的光催化性能，在60 min内，对耐甲氧西林金黄色葡萄球菌（MRSA）在7.23 log细胞密度下的灭活率为99.96 %，对大肠杆菌（E. coli）在7.50 log细胞密度下的杀菌率为95.28 %。在自然光下，它不仅对MRSA和大肠杆菌都表现出良好的灭活效果，而且对罗丹明B、亚甲蓝、四环素也表现出优异的降解性能。细胞毒性实验表明，该复合材料具有良好的生物相容性和实际应用潜力。研究结果为构建高效、安全的有机光催化剂提供了新的设计思路，并为水污染治理提供了理论依据。

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引用次数: 0

Stabilizing the dual electrode interface via a crosslinked gelatin nonwoven separator for durable lithium metal batteries 稳定双电极界面通过交联明胶非织造隔膜耐用锂金属电池

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-09 DOI: 10.1016/j.cclet.2025.111809

Weijie Cai , Xinxin Han , Min Chen , Haoyuan Chen , Hao Wang , Zhixiang Chen , Mengmeng Shao , Ke Zheng , Wenlong Wang , Rui Hong , Xiaodong Shi

The uncontrollable dendrite growth of lithium anode and active material dissolution of transition metal oxides cathodes severely hinder the development of lithium metal batteries. An effective strategy to address these issues is optimizing the separator to regulate ion transport and trap the lost active component. Herein, a crosslinked gelatin nonwoven (CGN) separator is elaborately fabricated through electrospinning and in-situ vapor phase crosslinking process to manipulate the dual electrode interface. Benefitting from the characteristic composition of gelatin, and porous structure of electrospun nonwoven, the CGN separator exhibits excellent interface wettability and low interface resistance, featuring a high Li⁺ transference number of 0.70 and high ionic conductivity of 3.75 mS/cm. As expected, the symmetrical Li/Li cells present stable cycling behavior for 1900 h at 0.5 mA/cm² with low overpotential of 20 mV. The optimized LiMn₂O₄/Li cells deliver high reversible capacity of 103 mAh/g as well as high capacity-retention ratio of 83.7 % after 100 cycles at 0.3 C, which can be effectively attributed to the strong interaction between CGN separator and Mn ions to prevent the loss of active Mn component. This study indicates the application potential of protein-based electrospun membrane for high-performance lithium metal batteries.

锂阳极枝晶生长不可控和过渡金属氧化物阴极活性物质溶解严重阻碍了锂金属电池的发展。解决这些问题的有效策略是优化分离器以调节离子传输并捕获丢失的活性成分。本文通过静电纺丝和原位气相交联工艺制备了一种交联明胶非织造布（CGN）分离器，以操纵双电极界面。得益于明胶的特性组成和静电纺非织造布的多孔结构，CGN隔膜具有优异的界面润湿性和低界面阻力，具有0.70的高Li+转移数和3.75 mS/cm的高离子电导率。正如预期的那样，对称锂/锂电池在0.5 mA/cm2下表现出1900 h的稳定循环行为，过电位低至20 mV。优化后的LiMn2O4/Li电池在0.3℃下循环100次后可获得103 mAh/g的高可逆容量和83.7 %的高容量保持率，这可有效归功于CGN分离器与Mn离子之间的强相互作用，防止了活性Mn组分的损失。该研究表明了蛋白基电纺丝膜在高性能锂金属电池中的应用潜力。

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引用次数: 0

F/N interface engineering of nonflammable polymer electrolyte for wide-temperature quasi-solid-state Li metal batteries 宽温准固态锂金属电池用不燃聚合物电解质的F/N界面工程

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-09 DOI: 10.1016/j.cclet.2025.111815

Lisi Xu , Maosheng Li , Anqi He , Haijiao Xie , Kuirong Deng

Polymer-electrolyte-based solid-state Li metal batteries with high-voltage Ni-rich cathodes are promising energy storage technologies owing to their favorable security and high energy densities. However, operating in wide temperature range and at high voltage is a tough challenge for them. Herein, F/N donating fluorinated-amide-based plasticizers regulated polymer electrolyte capable of enabling high-voltage Li||LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) batteries with excellent performance in wide temperature range is developed. F/N donating fluorinated-amide-based plasticizers significantly improve ionic conductivity (1.52 mS/cm at 30 °C), enhance oxidation stability (5.0 V vs. Li⁺/Li) and fabricate robust LiF/Li₃N-rich electrode-electrolyte interphases, which significantly improve the interface stability of Li metal anode and NCM811 cathode. The designed polymer electrolyte is nonflammable and has excellent dimensional stability at 200 °C. Capitalizing on these advantageous attributes, the Li||NCM811 cells show excellent cycle stability and rate capability from −20 °C to 60 °C at high voltages (∼4.6 V), and under high-loading full cell condition, which display impressive capacity retention of 84.4 % after 1000 cycles and ultrahigh capacity of 154.8 mAh/g at 10 C. This work provides a rational design strategy of polymer electrolytes for wide-temperature high-energy solid-state Li metal batteries.

具有高电压富镍阴极的聚合物电解质固态锂金属电池具有良好的安全性和高能量密度，是一种很有前途的储能技术。然而，在宽温度范围和高电压下工作对他们来说是一个艰巨的挑战。本文研制了F/N供氟化酰胺基增塑剂调控聚合物电解质，可使高压Li||LiNi0.8Co0.1Mn0.1O2 （NCM811）电池在宽温度范围内具有优异的性能。F/N给体氟酰胺基增塑剂显著提高了离子电导率（30 °C时为1.52 mS/cm），增强了氧化稳定性（5.0 V vs. Li+/Li），制备了坚固的富LiF/ li3n电极-电解质界面，显著提高了Li金属阳极和NCM811阴极的界面稳定性。所设计的聚合物电解质不易燃，在200 °C时具有优异的尺寸稳定性。利用这些优势，Li||NCM811电池在高电压（~ 4.6 V）和高负载满电池条件下，在- 20 °C至60 °C范围内表现出优异的循环稳定性和倍率能力，在1000次循环后的容量保持率为84.4 %，在10℃时的超高容量为154.8 mAh/g。这项工作为宽温高能固态锂金属电池的聚合物电解质设计提供了合理的策略。

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引用次数: 0

Ligand-bridged nanoassemblies boost the peroxidase-mimicking activity of gold nanoclusters 配体桥接纳米组件提高了金纳米团簇的过氧化物酶模拟活性

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-09 DOI: 10.1016/j.cclet.2025.111806

Jin-Ao Li , Nana Pan , Li Lu , Yifan Wei , Wenchang Hu , Zhiyang Zhang , Houda Amrani , Fang Huang , Xiaojuan Wang

Rational design of nanozymes with enhanced catalytic efficiency remains a central challenge in the development of artificial enzymes. Herein, we report the construction of ultrasmall gold nanocluster-based nanoassemblies (Dp-AuNCs@Fe²⁺) through the coordination of Fe²⁺ ions by a dopa-containing peptidomimetic ligand (DpCDp). This nanoarchitecture simultaneously integrates catalytically active gold cores and redox-active Fe²⁺ centers, bridged by DpCDp to facilitate directional electron transfer. Comprehensive spectroscopic and kinetic analyses reveal that DpCDp promotes efficient charge migration from the Au core to surface-bound Fe²⁺, significantly enhancing H₂O₂-mediated peroxidase-like activity. Compared to bare Dp-AuNCs, Dp-AuNCs@Fe²⁺ display a 4.3-fold improvement in detection sensitivity, a 6.7-fold increase in catalytic efficiency, and markedly stronger hydroxyl radical generation. Mechanistically, this activity stems from a synergistic triad: direct H₂O₂ oxidation at gold surfaces, radical generation at Fe²⁺ sites, and DpCDp-facilitated electron shuttling. This work presents a robust strategy for nanozyme enhancement via electronic and structural co-engineering, offering valuable insights for the future design of bioinspired catalytic systems.

合理设计具有高催化效率的纳米酶仍然是人工酶发展的核心挑战。在此，我们报道了通过含多巴的拟肽配体（DpCDp）配位Fe2+离子构建超小金纳米团簇纳米组件（Dp-AuNCs@Fe2+）。这种纳米结构同时集成了催化活性金核和氧化还原活性Fe2+中心，由DpCDp桥接以促进定向电子转移。综合光谱和动力学分析表明，DpCDp促进了电荷从Au核向表面结合的Fe2+的有效迁移，显著增强了h2o2介导的过氧化物酶样活性。与裸Dp-AuNCs相比，Dp-AuNCs@Fe2+的检测灵敏度提高了4.3倍，催化效率提高了6.7倍，羟基自由基的生成明显增强。从机制上讲，这种活性源于三个协同作用：H2O2在金表面的直接氧化，Fe2+位点的自由基生成，以及dpcdp促进的电子穿梭。这项工作提出了一种通过电子和结构协同工程增强纳米酶的强大策略，为未来设计生物激发催化系统提供了有价值的见解。

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引用次数: 0

Metallocene-based molecule junctions: Electron transport across Au||Au and Au||graphene electrodes 茂金属基分子结：Au||Au和Au b| |石墨烯电极上的电子传输

IF 8.9 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chinese Chemical Letters

Pub Date : 2025-09-09 DOI: 10.1016/j.cclet.2025.111811

Chang Liu , Jianbo Li , Yijia Wang , Chenguang Liu , Sylvain Pitie , Mahamadou Seydou , Chun Zhao , Paul J. Low , Yannick J. Dappe , Li Yang

Metallocenes are a wide family of organometallic compounds, in which two cyclopentadienyl ligands ‘sandwich’ a metal ion, M(η⁵-C₅R₅)₂, and have considerable potential for use as components in molecular electronics applications. Here we have studied the electronic transport properties of the matallocenes MCp₂ (M = V, Cr, Mn, Fe, Co, Ni, Ru; Cp = η⁵-C₅H₅) and MCp*₂ (M =  Mn, Fe, Co; Cp* = η⁵-C₅Me₅). Molecular junctions have been fabricated using either two gold, or one gold and one graphene electrode(s), giving rise to single-molecule conductance values of the order of -4 to -3 log(G/G₀)) depending on both the nature of the metallocene and the electrode materials. Calculations on model junctions at the density functional theory level of theory reveal significant charge transfer from the metallocene to the junction electrodes and changes in the nature of the primary charge transport pathways in response to the nature of the metal, supporting ligands, molecular oxidation state and electrode composition.

茂金属化合物是一类广泛的有机金属化合物，其中两个环戊二烯基配体“夹心”一个金属离子M(η5-C5R5)2，在分子电子学应用中作为组分具有相当大的潜力。本文研究了matalocene MCp2 （M = V, Cr, Mn, Fe, Co, Ni, Ru; Cp = η5-C5H5）和MCp*2 （M = Mn, Fe, Co; Cp* = η5-C5Me5）的电子输运性质。分子结可以使用两个金电极或一个金电极和一个石墨烯电极制造，根据茂金属和电极材料的性质，产生-4到-3 log(G/G0))量级的单分子电导值。在密度泛函理论水平上对模型结的计算揭示了从茂金属到结电极的显著电荷转移，以及根据金属的性质、支持配体、分子氧化态和电极组成的变化，主要电荷传输途径的性质发生了变化。

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