Dalton Transactions最新文献_第9页

Bio-reductive hetero-bimetallic Co(III)-Pt(II) complex for tumor-selective platinum release and cytotoxicity 生物还原的异双金属Co(III)-Pt（II）配合物用于肿瘤选择性铂释放和细胞毒性

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-01-20 DOI: 10.1039/d5dt02296g

Sharmila Wahengbam, Neha Masarkar, Himanshi Sharma, Sukhes Mukherjee, Chandi C. Malakar, Mithun Roy

The application of bioreductive metalloprodrugs in cancer therapy has emerged as a promising strategy to achieve site-specific activation of cytotoxic agents by exploiting the reductive microenvironment which is a characteristic of tumors, thereby minimizing off-target effects. In this study, we report the synthesis of a heterobimetallic [Co(III)-Pt(II)] complex designed to harness the tumor-specific redox conditions for selective anticancer activity. The complex was thoroughly characterized using a suite of spectroscopic techniques, and its redox behavior was investigated via electrochemical analysis, which revealed a quasi-reversible one-electron reduction with an E₁/₂ value of -0.52 V vs Ag/AgCl—suggesting the feasible reduction of Co(III) under biologically relevant conditions. Cellular uptake studies, performed using inductively coupled plasma mass spectrometry (ICP-MS), demonstrated efficient internalization of the complex within 12 hours in A549 lung carcinoma cells. Furthermore, binding studies with 5′-guanosine monophosphate (5′-GMP), conducted via electrospray ionization mass spectrometry (ESI-MS), confirmed the reductive release of the Pt(II) fragment and its subsequent coordination with nucleophilic targets. Induction of apoptosis was verified using Annexin V assays, indicating the activation of programmed cell death pathways.The complex exhibited potent cytotoxicity under both normoxic and hypoxic conditions in A549 cells and showed significant activity against a panel of cancer cell lines, including HT-29 (colorectal), MCF-7 (breast), and MDA-MB-231, a highly aggressive triple-negative breast cancer line. These findings highlight the potential of this redox-responsive bimetallic complex as a next-generation anticancer agent capable of overcoming platinum resistance, enhancing tumor selectivity, and reducing systemic toxicity relative to conventional platinum-based therapies.

生物还原性金属前药物在癌症治疗中的应用已经成为一种有前途的策略，通过利用肿瘤的还原性微环境来实现细胞毒性药物的位点特异性激活，从而最大限度地减少脱靶效应。在这项研究中，我们报道了一种杂双金属[Co(III)-Pt(II)]配合物的合成，旨在利用肿瘤特异性氧化还原条件进行选择性抗癌活性。利用一套光谱技术对该配合物进行了彻底的表征，并通过电化学分析对其氧化还原行为进行了研究，结果显示其具有准可逆的单电子还原作用，其E₁/ 2值为-0.52 V vs Ag/ agcl -这表明在生物相关条件下Co（III）的还原是可行的。使用电感耦合等离子体质谱（ICP-MS）进行的细胞摄取研究表明，A549肺癌细胞在12小时内有效地内化了复合物。此外，通过电喷雾电离质谱（ESI-MS）进行的与5 ' -鸟苷单磷酸（5 ' -GMP）的结合研究证实了Pt（II）片段的还原释放及其随后与亲核靶点的配合。通过Annexin V检测证实了细胞凋亡的诱导，表明程序性细胞死亡途径的激活。该复合物在A549细胞常氧和缺氧条件下均表现出强大的细胞毒性，并对一系列癌细胞系，包括HT-29（结直肠癌）、MCF-7（乳腺癌）和MDA-MB-231（一种高度侵袭性的三阴性乳腺癌系）显示出显著的活性。这些发现突出了这种氧化还原反应性双金属配合物作为下一代抗癌药物的潜力，与传统的铂基治疗相比，它能够克服铂耐药性，增强肿瘤选择性，降低全身毒性。

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引用次数: 0

Synergistic Co-doping and Te-defects Engineering in NiTe₂ Singlecrystals for Enhanced Hydrogen Evolution in Acidic and Alkaline Environments NiTe 2单晶中协同共掺杂和te缺陷工程在酸性和碱性环境下促进析氢

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-01-19 DOI: 10.1039/d5dt02989a

Zilong Xie, Qingyan Li, Jing Fang, Yuhang Yang, Haisen Liu, Bin Liu, Lei Gao, Jianchen Lu

Transition metal dichalcogenides (TMDs) are promising hydrogen evolution reaction (HER) catalysts due to their layered structures and tunable electronic properties. However, NiTe₂ suffers from suboptimal hydrogen adsorption energy (ΔGH*) and low active site density. Here, we propose a synergistic strategy involving Co doping and Te vacancy engineering to optimize HER performance in both acidic and alkaline electrolytes of Ni 1-x CoxTe 2 single crystals. Co 2+ doping induces linear contraction of the a-axis lattice parameter, reducing charge transfer resistance by 80%. The synchronously formed Te vacancies significantly increase active site density, as evidenced by a 31% enhancement in double-layer capacitance.Optimized Ni 0.6 Co 0.4 Te 2 achieves near-ideal ΔGH* (-0.0345 eV), delivering ultralow overpotentials of 419 mV (acidic) and 362 mV (alkaline) at 10 mA cm⁻²-17% and 26% lower than pristine NiTe₂ respectively-with >80 h stability. This work establishes a scalable strategy for designing bifunctional electrocatalysts operable in acidic and alkaline media.

过渡金属二硫族化合物（TMDs）具有层状结构和可调谐的电子特性，是一种很有前途的析氢反应（HER）催化剂。然而，NiTe₂的氢吸附能不理想（ΔGH*），活性位点密度低。本文提出了Co掺杂和Te空位工程的协同策略，以优化Ni 1-x CoxTe 2单晶在酸性和碱性电解质中的HER性能。Co 2+掺杂导致a轴晶格参数线性收缩，使电荷转移电阻降低80%。同步形成的Te空位显著增加了活性位点密度，双层电容提高了31%。优化后的Ni 0.6 Co 0.4 Te 2达到了接近理想的ΔGH* (-0.0345 eV)，在10 mA cm（⁻²）下提供419 mV（酸性）和362 mV（碱性）的超低过电位，比原始Ni 2分别低17%和26%，稳定性为80 h。这项工作建立了一个可扩展的策略，设计双功能电催化剂可操作在酸性和碱性介质。

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引用次数: 0

Cationic Heteroleptic Ni(II) Complexes of Dithiocarbamate and Phosphine Ligands: Synthesis, Characterization and Proton Reduction Study 二硫代氨基甲酸酯和膦配体阳离子异电性Ni（II）配合物的合成、表征和质子还原研究

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-01-19 DOI: 10.1039/d5dt02840j

Sarvesh Kumar Pal, Anjali Mishra, Gaurav Kumar Mishra, Ruben Hansson, Vishal Jaiswal, Ebbe Nordlander, George Lisensky, Amrendra Kumar Singh, Nanhai Singh, Prem Lama, Kamlesh Kumar

Three cationic heteroleptic Ni(II) dithiocarbamate complexes ([Ni(L)(L')n]PF₆, n = 1 or 2) were synthesized and characterized to explore the relationship between diphosphine chelate ring size and their electrocatalytic activity for hydrogen production. These complexes (1-3) feature a common dithiocarbamate ligand (L) and varied diphosphine ligands (L'): dppm (1), dppe (2), and dppp (3). Single-crystal X-ray analysis showed distorted square pyramidal geometry for 1 and square planar geometries for 2 and 3 around NiP₂S₂ core. Electrochemical studies revealed small variation in redox potentials (∆E1/2 ≈ 60 mV) suggesting weak electronic effect of ligands from dppm (1) to dppp (3). However, significant difference in catalytic half-wave potentials (∆Ecat/2 ≈ 200 mV in 4 mM CH3COOH) indicates the strong influence of the P-Ni-P bite angles. The catalytic activity of complexes significantly influenced by chelate ring size and their P-Ni-P bite angles as: 92.07(4)o (3) > 86.84(6)o (2) > 75.24(3)o (1). The enhanced electrocatalytic performance of 3 with low overpotential (~600 mV), high turnover frequency (~706 s⁻¹), and Faradaic efficiency (88%), is attributed to the conformational flexibility of six-membered chelate ring in 3 due to the dppp ligand. Both experimental data and DFT calculations support an ECEC mechanism for HER catalysed by heteroleptic Ni(II) complexes with the formation of Ni(III)–H intermediate species.

合成了三种阳离子杂性Ni（II）二硫代氨基甲酸酯配合物([Ni(L)(L')n]PF₆，n = 1或2)，并对其进行了表征，探讨了二膦螯合物环大小与其制氢电催化活性的关系。这些配合物（1-3）具有常见的二硫氨基甲酸酯配体(L)和多种二膦配体（L'）： dppm(1)、dppe(2)和dppp(3)。单晶x射线分析显示，在NiP₂S₂核心周围，1为扭曲的方形锥体几何形状，2和3为方形平面几何形状。电化学研究表明，dppm(1)到dppp(3)的氧化还原电位变化较小（∆E1/2≈60 mV），表明配体的电子效应较弱。然而，催化半波势（4 mM CH3COOH中∆Ecat/2≈200 mV）差异显著，表明P-Ni-P咬角的影响较大。配合物的催化活性受螯合环大小和P-Ni-P咬角的影响显著，分别为：92.07(4)o (3) > 86.84(6)o (2) > 75.24(3)o(1)。3具有低过电位（~600 mV）、高周转率（~706 s⁻¹）和法拉第效率（88%）的电催化性能的增强，是由于dppp配体使3的六元螯合环具有构象灵活性。实验数据和DFT计算均支持异电性Ni（II）配合物催化HER的ECEC机制，并形成Ni(III) -H中间体。

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引用次数: 0

Environmental applications of an ultrasonically synthesized and PEG assisted Yb2O3/ZnFe2O4 nanocomposite for dye and herbicide degradation and electrochemical sensing of catechol 超声合成聚乙二醇辅助Yb2O3/ZnFe2O4纳米复合材料在染料和除草剂降解及儿茶酚电化学传感中的环境应用

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-01-19 DOI: 10.1039/D5DT02596F

Nashra Fatima, Srishti Dwivedi, Pratibha Bansal, Ekhlakh Veg, Vishal Mishra and Tahmeena Khan

This study effectively generated zinc ferrite (ZnFe₂O₄) and ytterbium oxide (Yb₂O₃) nanoparticles (NPs) using the co-precipitation method. Using the synthesized NPs, a binary nanocomposite Yb₂O₃/ZnFe₂O₄@PEG supported by polyethene glycol (PEG) was formed via ultrasonication. The morphological, structural, functional, and optical features of the produced NPs and the binary nanocomposite were examined using scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and UV-visible spectroscopy. The photocatalytic activity of the NPs and the nanocomposite against the pesticide glyphosate and the Brilliant Blue FCF dye was investigated under the influence of visible light. In contrast to the individual NPs, the Yb₂O₃/ZnFe₂O₄@PEG nanocomposite had noticeably better photocatalytic activity. It achieved 86% and 91% degradation of the dye and pesticide, respectively, under 90 minutes, which may be explained on the basis of enhanced charge separation, synergistic interactions, and increased surface activity. Moreover, the Yb₂O₃/ZnFe₂O₄@PEG nanocomposite was tested for catechol sensing through the electrochemical method. The cyclic voltammetry analysis showed that the bare GCE produced a negligible current response, whereas the nanocomposite-modified electrode displayed pronounced redox peaks in the presence of catechol, confirming its strong electrocatalytic activity. The sensor exhibited a linear response for catechol in the concentration range of 40–100 µM, with a sensitivity of 0.367 µA µM⁻¹ cm⁻² and a limit of detection of 11.52 µM, confirming its suitability for sensitive electrochemical monitoring. The resulting binary nanocomposite can be used as a photocatalyst to effectively break down hazardous dyes and pesticides, hence enabling environmental cleanup applications.

本研究采用共沉淀法有效制备了铁酸锌（ZnFe2O4）和氧化镱（Yb2O3）纳米颗粒（NPs）。利用合成的纳米粒子，通过超声法制备了聚乙二醇（PEG）负载的二元纳米复合材料Yb2O3/ZnFe2O4@PEG。利用扫描电镜（SEM）、x射线衍射（XRD）、傅里叶变换红外光谱（FT-IR）和紫外可见光谱（UV-visible spectroscopy）对合成的纳米粒子和二元纳米复合材料的形貌、结构、功能和光学特性进行了表征。在可见光的影响下，研究了NPs和纳米复合材料对农药草甘膦和亮蓝FCF染料的光催化活性。与单个NPs相比，Yb2O3/ZnFe2O4@PEG纳米复合材料具有明显更好的光催化活性。在90分钟内，染料和农药的降解率分别达到86%和91%，这可能是由于电荷分离、协同作用和表面活性的增强。此外，通过电化学方法测试了Yb2O3/ZnFe2O4@PEG纳米复合材料对儿茶酚的传感性能。循环伏安分析表明，裸露的GCE产生的电流响应可以忽略不计，而纳米复合材料修饰的电极在儿茶酚存在下显示出明显的氧化还原峰，证实了其强大的电催化活性。该传感器在40 ~ 100µM浓度范围内对儿茶酚具有良好的线性响应，灵敏度为0.367µaµM-1 cm-2，检出限为11.52µM，适用于电化学敏感监测。由此产生的二元纳米复合材料可以用作光催化剂，有效地分解有害染料和农药，从而实现环境清洁应用。

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引用次数: 0

Hybrid amino/iminopyridines with auxiliary phosphines enhancing their zinc complex catalysts for the ring-opening polymerization of lactide 杂化氨基/亚氨基吡啶与辅助膦增强其锌络合催化剂在丙交酯开环聚合中的应用

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-01-19 DOI: 10.1039/d5dt02857d

Xiaopan Xue, Dongzhi Zhu, Wenjuan Zhang, Tongxin Zheng, Rui Wang, Yanping Ma, Wen Hua Sun

The series of 2-(dipehnylethyl)amino-6-iminopyridines, 2-((Ph2PCH2CH2)N=CMe)-6-(ArN=CMe)C5H3N (Ar=2,6-iPr2C6H3 (L1), 2,6-Et2C6H3 (L2), 2,6-Me2C6H3 (L3), 2,4,6-Me3C6H2 (L4), 2,6-(CHPh2)2−4-MeC6H2 (L5)), and its analogue 2-(n-butyl)amino-6-iminopyridine L6 were synthesized and used to form their dichlorozinc complexes, LZnCl2 (Zn1-Zn6). All organic compounds and zinc complexes were well characterized by 1H/13C/31P NMR spectroscopy and elemental analysis along with the single crystal X-ray diffraction of Zn1 and Zn4 indicating bistrigonal geometry around zinc. By treated with two equivalents of LiN(SiMe3)2, all Zn1-Zn6 performed high activities toward ring-opening polymerization (ROP) of L-lactide (L-LA), indicating the positive influences of substituents as well as auxiliary phosphine. Notably, the excellent activity was achieved even at high temperature; such as, Zn1/2LiN(SiMe3)2 catalyzed 2000 equiv. L-LA with 86% conversion in 10 minutes at 100 ℃, observing its TOF as 10320 h−1. The activities were observed in the order of substituents as: isopropyl > ethyl > methyl, so were higher activities for more alkyl substituents. The auxiliary phosphine enhanced the activities of zinc complexes; all Zn1-Zn5 showed higher activities than Zn6 (with butyl), which formed the PLA with relatively lower molecular weight. The coordination–insertion and ring expansion mechanism has been proposed for the ROP of L-lactide.

合成了2-（二苯乙基）氨基-6-亚氨基吡啶，2-((Ph2PCH2CH2)N=CMe)-6-(ArN=CMe)C5H3N (Ar=2,6- ipr2c6h3 (L1), 2,6- et2c6h3 (L2), 2,6- me2c6h3 (L3), 2,4,6- me3c6h2 (L4), 2,6-(CHPh2)2−4- mec6h2 (L5))及其类似物2-（正丁基）氨基-6-亚氨基吡啶L6，并用于形成它们的二氯锌配合物LZnCl2 （Zn1-Zn6）。所有有机化合物和锌配合物均通过1H/13C/31P核磁共振谱和元素分析进行了很好的表征，Zn1和Zn4的单晶x射线衍射表明锌周围呈双方几何结构。经两种等量的LiN(SiMe3)2处理后，Zn1-Zn6对l -丙交酯（L-LA）的开环聚合（ROP）均表现出较高的活性，表明取代基和辅助膦的积极影响。值得注意的是，即使在高温下也能保持良好的活性；在100℃条件下，Zn1/2LiN(SiMe3)2在10分钟内催化了2000等量L-LA，转化率为86%，TOF为10320 h−1。取代基的活性依次为：异丙基>；乙基>；甲基，烷基取代基越多，活性越高。辅助膦增强了锌配合物的活性；Zn1-Zn5的活性均高于Zn6（含丁基），形成相对较低分子量的聚乳酸。提出了l -丙交酯ROP的配位插入和扩环机理。

{"title":"Hybrid amino/iminopyridines with auxiliary phosphines enhancing their zinc complex catalysts for the ring-opening polymerization of lactide","authors":"Xiaopan Xue, Dongzhi Zhu, Wenjuan Zhang, Tongxin Zheng, Rui Wang, Yanping Ma, Wen Hua Sun","doi":"10.1039/d5dt02857d","DOIUrl":"https://doi.org/10.1039/d5dt02857d","url":null,"abstract":"The series of 2-(dipehnylethyl)amino-6-iminopyridines, 2-((Ph2PCH2CH2)N=CMe)-6-(ArN=CMe)C5H3N (Ar=2,6-iPr2C6H3 (L1), 2,6-Et2C6H3 (L2), 2,6-Me2C6H3 (L3), 2,4,6-Me3C6H2 (L4), 2,6-(CHPh2)2−4-MeC6H2 (L5)), and its analogue 2-(n-butyl)amino-6-iminopyridine L6 were synthesized and used to form their dichlorozinc complexes, LZnCl2 (Zn1-Zn6). All organic compounds and zinc complexes were well characterized by 1H/13C/31P NMR spectroscopy and elemental analysis along with the single crystal X-ray diffraction of Zn1 and Zn4 indicating bistrigonal geometry around zinc. By treated with two equivalents of LiN(SiMe3)2, all Zn1-Zn6 performed high activities toward ring-opening polymerization (ROP) of L-lactide (L-LA), indicating the positive influences of substituents as well as auxiliary phosphine. Notably, the excellent activity was achieved even at high temperature; such as, Zn1/2LiN(SiMe3)2 catalyzed 2000 equiv. L-LA with 86% conversion in 10 minutes at 100 ℃, observing its TOF as 10320 h−1. The activities were observed in the order of substituents as: isopropyl > ethyl > methyl, so were higher activities for more alkyl substituents. The auxiliary phosphine enhanced the activities of zinc complexes; all Zn1-Zn5 showed higher activities than Zn6 (with butyl), which formed the PLA with relatively lower molecular weight. The coordination–insertion and ring expansion mechanism has been proposed for the ROP of L-lactide.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"272 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995935","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis of CeMnOδ/3DOM Ti1−xWxOy catalysts: catalytic performance and reaction mechanism for the simultaneous removal of soot and NOx CeMnOδ/3DOM Ti1-xWxOy催化剂的合成：同时脱除烟尘和NOx的催化性能和反应机理

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-01-19 DOI: 10.1039/D5DT02813B

Ruidan Wang, Lanyi Wang, Xinyu Chen, Di Yu, Chunlei Zhang, Siyu Gao, Xiaoqiang Fan, Xuehua Yu and Zhen Zhao

The reduction and elimination of soot particles (PM) and nitrogen oxides (NO_x) emitted by diesel engines are of paramount importance and urgent necessity. Herein, a family of novel CeMnO_δ/3DOM Ti_1−xW_xO_y catalysts was prepared using the colloidal crystal template method and incipient-wetness impregnation method. The catalytic performance of the CeMnO_δ/3DOM Ti_1−xW_xO_y catalysts for the simultaneous abatement of soot and NO_x was investigated by adjusting the molar ratio of Ti and W in the 3DOM Ti_1−xW_xO_y carriers. The results show that when the Ti : W molar ratio is 7 : 3, the temperature corresponding to the highest soot oxidation activity is 488 °C, and at this ratio, the catalyst not only exhibits the highest NO conversion rate of 99.2% but also has the widest NO conversion window (216–377 °C) over a 90% conversion rate among the as-prepared catalysts; at the same time, it also demonstrates excellent stability. Moreover, the selectivity for N₂ is improved by the component of W in the support. The enhanced catalytic activity of the CeMnO_δ/3DOM Ti₇W₃O_y catalyst can be ascribed to its macroporous structure, sufficient surface acid sites and oxygen vacancies, and the synergistic effects between different elements. This study also proposes the potential reaction mechanisms of CeMnO_δ/3DOM Ti_1−xW_xO_y catalysts and offers valuable insights into the design and synthesis of high-efficiency catalysts for the purification of soot and NO_x.

减少和消除柴油机排放的烟尘颗粒（PM）和氮氧化物（NOx）是至关重要和迫切需要的。本文采用胶体晶体模板法和初湿浸渍法制备了一系列新型CeMnOδ/3DOM Ti1-xWxOy催化剂。通过调整3DOM Ti1-xWxOy载体中Ti和W的摩尔比，研究了CeMnOδ/3DOM Ti1-xWxOy催化剂同时减排烟灰和NOx的催化性能。结果表明：当Ti: W摩尔比为7:3时，烟尘氧化活性最高的温度为488℃，在此温度下，NO转化率最高，达到99.2%，且转化率在90%以上时，NO转化窗口最宽（216 ~ 377℃）；同时，它也表现出优异的稳定性。此外，载体中W的加入提高了对N2的选择性。CeMnOδ/3DOM Ti7W3Oy催化剂的催化活性增强主要归因于其大孔结构、充足的表面酸位和氧空位以及不同元素之间的协同作用。本研究还提出了CeMnOδ/3DOM Ti1-xWxOy催化剂的潜在反应机理，并为设计和合成高效的烟尘和NOx净化催化剂提供了有价值的见解。

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引用次数: 0

Interface enhancement through electrostatic self-assembly for synergistically stabilized silicon anodes in lithium-ion batteries 通过静电自组装增强协同稳定锂离子电池硅阳极的界面

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-01-19 DOI: 10.1039/d5dt02736e

Junfeng Shi, Siqi Hou, Weiyan Li, Dafang He, Maolei Huang, Jiawei Xia, Xingyue Qian, Haiqun Chen

Due to its high theoretical specific capacity and abundant natural reserves, silicon (Si) is regarded as one of the most promising candidates for the next generation of lithium-ion batteries (LIBs). However, the poor conductivity and significant volume expansion of Si during the lithiation/delithiation process seriously hinder the commercialization of Si anode for LIBs. Herein, polydiallyl dimethylammonium chloride (PDDA) was introduced to modify the surface charge of Si nanoparticles (NPs) and then encapsulated with a graphene framework, followed by covering them with a carbon layer to form the Si-C composite (Si@PDDA@RGO/C). Specially, the pyrolytic carbon not only mitigates the large volume change of Si but also ensures good contact with graphene, thereby preserving the structural integrity of the electrode during cycling. The flexible lamellar structure of graphene provides ample space for the dispersion of Si NPs, improving the conductivity of the composite while also suppressing the volume change of Si. The results demonstrate that the double-layer carbon-coated Si NPs improves the cycling stability of the anode material with the initial charge-discharge capacity of 783.48/1292.24 mAh g -1 , a coulombic efficiency of 60.63%, and a discharge capacity of approximately 620.13 mAh g -1 after 100 cycles at 0.2 A g -1 , as well as excellent rate performance and electrochemical reaction kinetics.

由于其较高的理论比容量和丰富的自然储量，硅（Si）被认为是下一代锂离子电池（LIBs）最有前途的候选者之一。然而，硅在锂化/去气过程中的导电性差和体积膨胀严重阻碍了锂离子电池硅阳极的商业化。本文采用聚二烯丙基二甲基氯化铵（PDDA）修饰Si纳米颗粒（NPs）的表面电荷，然后用石墨烯框架封装，再用碳层覆盖，形成Si-C复合材料（Si@PDDA@RGO/C）。特别是，热解碳不仅减轻了Si的体积变化，而且保证了与石墨烯的良好接触，从而保持了电极在循环过程中的结构完整性。石墨烯的柔性层状结构为Si NPs的分散提供了充足的空间，提高了复合材料的导电性，同时也抑制了Si的体积变化。结果表明，双层碳包覆的Si NPs提高了负极材料的循环稳定性，初始充放电容量为783.48/1292.24 mAh g -1，库仑效率为60.63%，在0.2 a g -1下循环100次后放电容量约为620.13 mAh g -1，具有优异的倍率性能和电化学反应动力学。

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引用次数: 0

Aliovalent Solid Solutions of Metal-Organic Frameworks 金属-有机骨架的共价固溶体

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-01-19 DOI: 10.1039/d5dt02764k

Marco Taddei

Metal-organic frameworks (MOFs) are amenable to the formation of solid solutions by isomorphous substitution of the organic linker and/or the metal ion. In the case of metal substitution, the incorporation of aliovalent species, i.e., having a different oxidation state from the original ion, leads to the generation of excess charges in the framework, which must be compensated. Depending on the charge compensation mechanism, new properties can emerge. Despite limited work has been done so far in this area of research, aliovalent substitution has the potential to become an important tool to fine tune the physico-chemical properties in MOFs and should be investigated more systematically. Here, the available literature on aliovalent solid solutions of MOFs is critically analysed under the lens of inorganic solid-state chemistry.

金属-有机骨架（mof）可以通过有机连接剂和/或金属离子的同构取代形成固溶体。在金属取代的情况下，同价离子的加入，即与原始离子具有不同的氧化态，导致在框架中产生多余的电荷，这必须得到补偿。根据电荷补偿机制，可以产生新的性质。尽管迄今为止在这一领域的研究工作有限，但共价取代有可能成为微调mof的物理化学性质的重要工具，应该进行更系统的研究。本文从无机固体化学的角度对mof的共价固溶体进行了批判性的分析。

引用次数: 0

A Stable Yttrium-Based Metal-Organic Framework Built on Ladder Building Units for Size-Exclusion Separation of Hexane Isomers 基于阶梯结构单元的稳定钇基金属-有机骨架用于己烷异构体的尺寸不相容分离

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-01-19 DOI: 10.1039/d5dt02828k

Ying Wang, Yanli Gai, Xin Zhou, Hao Wang, Kecai Xiong

The separation of hexane isomers represents a critical industrial process, which remains challenging due to their similar physicochemical properties. In this study, we report a three-dimensional (3D) Y-based metal-organic framework (MOF), [Y2(μ3-F)2(TBTC)(2-FBA)·1.5DMF]{denoted as HIAM-320, H3TBTC=1,3,5-tris[4-(carboxyphenyl)oxymethyl]-2,4,6-trimethylbenzene}, which features one-dimensional (1D) channels with appropriate pore size for size-sieving of hexane isomers. The compound is constructed from unique double-chain ladder-like {Y(μ3-F)} 2-n inorganic building units, rendering it exceptionally high structural stability. HIAM-320 adsorbs linear n-hexane (nHEX) and mono-branched 3-methylpentane (3MP), while effectively excluding di-branched 2,2-dimethylbutane (22DMB). The separation capability has been confirmed by multicomponent breakthrough experiments. Density functional theory (DFT) calculations validate the size-sieving separation mechanism and reveal the domains of guest-host interactions.

己烷异构体的分离是一个关键的工业过程，由于它们相似的物理化学性质，这仍然具有挑战性。在这项研究中，我们报道了一个基于三维（3D）的金属有机骨架（MOF）， [Y2(μ3-F)2(TBTC)（2- fba）·1.5DMF]{表示为HIAM-320， H3TBTC=1,3,5-tris[4-（羧基苯基）氧甲基]-2,4,6-三甲基}，它具有一维（1D）通道，具有合适的孔径用于己烷异构体的筛分。该化合物由独特的双链阶梯状{Y(μ3-F)} 2-n无机结构单元构成，具有极高的结构稳定性。HIAM-320吸附线性正己烷（nHEX）和单支3-甲基戊烷（3MP），同时有效排除双支2,2-二甲基丁烷（22DMB）。通过多组分突破实验验证了其分离性能。密度泛函理论（DFT）计算验证了筛分分离机制，揭示了主客相互作用的域。

引用次数: 0

Construction of three-dimensional hierarchical flower-like M(OH)(OCH 3 ) (M=Co, Cu) microspheres for high efficiency electrocatalytic oxygen evolution 三维分层花状M(OH)(OCH 3)（M=Co, Cu）微球高效电催化析氧的构建

IF 4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions

Pub Date : 2026-01-19 DOI: 10.1039/d5dt02687c

Yang Pan, Cong-Min Fan, Tiancheng Feng, Haoyang Peng, Xiaolian Xu, guiqi gao

The slow kinetics of the oxygen evolution reaction hinders the efficiency of water decomposition, so it is crucial to develop noble metal-free electrocatalysts for the efficient decomposition of water via oxygen evolution reaction (OER) in alkaline electrolytes. In this study, flower-like structured hydroxides grown in situ consisting of ultrathin nanosheets stacked on Fe Foam (FF) were prepared by a one-step hydrothermal method for efficient electrocatalytic oxygen evolution reaction. M(OH)(OCH 3 ) (M=Co, Cu) requires only a low overpotential of 270 mV and 379 mV of the OER, to provide 20 mA⋅cm -2 and 100 mA⋅cm -2 current densities respectively. With the synergistic effect of Co 2+ and Cu 2+ , the adsorption capacity of the intermediate OH* and the conductivity are improved, and the structural surface reconstruction are promoted by methoxide. In this work, the structure of FF-based electrocatalysts was modulated by Co 2+ and Cu 2+ introducing and synthesizing methoxy anions, which improved the catalytic activity of the catalysts.

析氧反应的缓慢动力学影响了析氧反应对水的高效分解，因此开发无贵金属电催化剂是实现析氧反应对碱性电解质中水高效分解的关键。在本研究中，采用一步水热法制备了由超薄纳米片堆叠在Fe Foam （FF）上的原位生长的花状结构氢氧化物，用于高效的电催化析氧反应。M(OH)(OCH 3)（M=Co, Cu）仅需270 mV和379 mV的过电位，即可分别提供20 mA⋅cm -2和100 mA⋅cm -2电流密度。在Co 2+和Cu 2+的协同作用下，提高了中间体OH*的吸附能力和电导率，并促进了甲氧基的结构表面重构。本文通过Co 2+和Cu 2+的引入和合成甲氧阴离子来调控ff基电催化剂的结构，提高了催化剂的催化活性。

引用次数: 0