【无机化学学报】doi: 10.11862/CJIC.20230351
设计并合成了Cd基金属有机骨架(MOF)[Cd (BDC)(BPZ)(H2O)]n(1),其中BPZ=3,3′,5,5′-四甲基-1H,1′H-4,4′-联吡唑,H2BDC=对苯二甲酸)。化合物1具有三维孔道,其孔壁内有多个—CH3基团和自由的羧基氧原子,甲基基团的存在显著提高了MOF的疏水性和稳定性。另外,甲基和未配位的羧基氧原子可通过氢键或范德瓦耳斯作用力增强与多巴胺(DA)分子作用。1对DA具有灵敏的电化学传感性能。制备的1/GCE电极的差分脉冲伏安(DPV)测试结果显示其检测DA的线性范围为0.4~764.7 μmol·L-1,检出限为56.8 nmol·L-1。在常见干扰物的存在下,电极的DPV响应电流无明显变化。电极用于实际样品检测时的回收率在95.23%~100.90%之间。
【无机化学学报】doi: 10.11862/CJIC.20230301
Based on the 5-(3, 4-dicarboxyphenoxy) isophthalic acid (H4dppa) ligand, two lanthanide metal-organic frameworks (Ln-MOFs) were designed and synthesized by hydrothermal synthesis: {(dima)[Dy(dppa)(H2O)2]·2.5H2O}n (Dy - MOF) and {(dima) [Eu(dppa) (H2O)2]·1.5H2O}n (Eu - MOF) (dima=dimethylamine cation). The structures were characterized by elemental analysis, infrared spectroscopy, single-crystal X-ray diffraction, etc. Dy-MOF and Eu- MOF are hetero-isomorphic 2D network structures, and adjacent 2D networks further form 3D supramolecular network structures through hydrogen bonding. Fluorescence analysis shows that Dy-MOF and Eu-MOF have excellent fluorescence properties at room temperature, and Dy-MOF has excellent fluorescence sensing properties, which can efficiently and high-sensitively detect a variety of pollutants in water: aniline (ANI), nitrobenzene (NB), tetracycline (TC), pyrimethanil (PTH), and tryptophan (Trp). The fluorescence quenching mechanism of Dy-MOF in detecting pollutants was also investigated.
【无机化学学报】doi: 10.11862/CJIC.20240287
A coordination polymer {[Cd(H2dpa)(bpy)]·3H2O}n (Cd-CP) was designed and hydrothermal synthesized based on 4-(2, 4-dicarboxyphenoxy) phthalic acid (H4dpa), 2, 2′-bipyridine (bpy) and Cd(NO3)2·4H2O. The structure was characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, and infrared spectroscopy. Cd-CP belongs to the monoclinic crystal system with the P21/c space group and performs in a 1D double-chain structure. The adjacent double chains further form a 3D supramolecular network structure through hydrogen bonding. Thermogravimetric analysis shows that Cd-CP has good thermal stability. Fluorescence analysis showed that Cd-CP had good choosing selectively and was sensitive to metal ions (Fe3+ and Zn2+), 2, 4, 6-trinitrophenylhydrazine (TRI), and pyrimethanil (Pth). Interestingly, when Cd-CP was used for fluorescence detection of metal ions, it was found to have a fluorescence quenching effect on Fe3+ but had an obvious enhancement effect on Zn2+. Therefore, we designed an "on-off-on" logic gate. In addition, the mechanism of fluorescence sensing has been deeply explored.
【无机化学学报】doi: 10.11862/CJIC.20230310
A unique 3D luminescent metal-organic framework, namely [Cd(L)(H2O)0.5]·DMF·2.5H2O (1), where H2L=3-(tetrazol-5-yl)triazole, has been successfully prepared and characterized. The framework has demonstrated excellent luminescence properties and structural stability in the water system. Notably, the luminescence intensity of 1 was significantly quenched by Cr(Ⅵ) (1 mL of Cr2O72- or 150 μL of CrO42-, 1 mmol·L-1), leading to the formation of an "on-off" luminescence silencing system (Cr2O72-@1), which was capable of accurately detecting Cr(Ⅵ) in the water system. The primary mechanism responsible for luminescence quenching was the Forster resonance energy transfer (FRET) process. Additionally, by removing the involvement of the FRET process, the luminescence intensity of the Cr2O72-@1 system could be restored, allowing for the highly selective and sensitive detection of ascorbic acid (AA) in water systems. Moreover, it has been demonstrated that 1 can successfully detect AA in vitamin C tablets, yielding recovery rates ranging from 98.20% to 103.33% and relative standard deviations (RSDs) ranging from 1.78% to 3.42%. Based on the findings of this experiment, a luminescent "IMPLICATION" molecular logic gate has been constructed utilizing AA and Cr(Ⅵ) as the chemical inputs, respectively.
【无机化学学报】doi: 10.11862/CJIC.20230414
为设计高稳定性且高灵敏度的纯金属有机骨架(MOF)电化学传感器以检测多巴胺(DA),我们选用铟基MOF [In(2-NH3-BDC)(2-NH2-BDC)]·1.5H2O(RSMOF-1,RSMOF=resistance switchable metal-organic framework,2-NH2-H2BDC=2-氨基对苯二甲酸)修饰玻碳电极(RSMOF-1/GCE)。制备的电极RSMOF-1/GCE的DPV测试结果显示其线性范围为0.990~663 μmol·L-1、检出限为0.770 μmol·L-1。在多种干扰物质如尿酸、尿素、葡萄糖和对乙酰氨基酚存在的条件下,RSMOF-1/GCE对DA仍具有高的选择性。理论模拟结果显示,在RSMOF-1孔道内壁的—NH2可通过氢键增强与DA分子的相互作用,使RSMOF-1/GCE具有灵敏的电化学传感DA的性能。
【无机化学学报】doi: 10.11862/CJIC.20240120
In this work, p-phenylenediamine and L-cysteine were used as raw materials, and water-soluble N, S co-doped carbon dots (N, S-CDs) with excellent performance were prepared through a one-step solvothermal method. The morphology and structure of N, S-CDs were characterized by transmission electron microscope, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy, and the basic photophysical properties were investigated via UV-Vis absorption spectra and fluorescence spectra. Meanwhile, the N, S-CDs have excellent luminescence stability with pH, ionic strength, radiation time, and storage time. Experimental results illustrated the present sensor platform exhibited high sensitivity and selectivity in response to baicalein with a detection limit of 85 nmol·L-1. The quenching mechanism is proved to be the inner filter effect. In addition, this sensor can also detect baicalein in biofluids (serum and urine) with good accuracy and reproducibility.
Green synthesis of MIL-101/Au composite particles and their sensitivity to Raman detection of thiram
【无机化学学报】doi: 10.11862/CJIC.20240059
Metal-organic framework (MOF) MIL-101 and surface plasmon polariton (SPP) supported gold nanoparticles (Au NPs) hybrid systems were developed as a highly sensitive and reproducible surface-enhanced Raman scattering (SERS) detection platform, in which a green electrostatic self-assembly technology was adopted to construct the substrate. In an aqueous solution, the electronegativity of the particles can be used to prepare the composite substrate without any surface modifier. Due to the enrichment capacity of MIL-101 and the electromagnetic enhancement from Au NPs, the well-designed MIL-101/Au composites possessed ultrahigh sensitivity with the detection limit of Rhodamine 6G (R6G) as low as 10-10 mol·L-1. Meanwhile, the substrate exhibits high stability, excellent reproducibility, and recyclability. Additionally, the novel substrate can be explored for direct capture, and sensitively detect pesticide residues such as thiram.
【无机化学学报】doi: 10.11862/CJIC.20240240
以单芳环多羧酸苯六甲酸(H6BHC)为配体,与Eu (NO3)3·6H2O进行水热反应,成功得到了一个新的铕金属有机骨架(H3O)6[Eu (BHC)(H2O)]2·H2O (1)。单晶X射线衍射分析表明:在1中,相邻的2个Eu (Ⅲ)离子通过BHC6-桥联成二聚单元并作为一个结点,结点之间通过BHC6-桥沿a轴和c轴相连形成二维层状结构,最后沿着b轴通过氢键的交联作用形成三维网络结构。光致发光测试表明1可以在水体系中实现对Pb2+的选择性和灵敏性传感且检测限(LOD)低至0.42 μmol·L-1。
【物理化学学报】doi: 10.1016/j.actphy.2025.100144
光催化燃料电池光阳极活性材料的合理设计对开发高灵敏自供能电化学传感器至关重要。实现光阳极中电荷定向迁移和缩短传输路径是提升光催化燃料电池析氧反应性能的挑战。本文设计了一种具有N–W–O共价键的钨原子分散富碳石墨相氮化碳(W-CN-C)光阳极,用于构建对重金属铜离子检测的自供能光催化燃料电池传感器。通过自组装、剥离和热诱导相结合制备W-CN-C。N–W–O共价键作为界面电荷传输通道,促进电荷载流子分离与迁移。形成的富碳结构增加碳含量,进而增强W-CN-C的π-电子离域,从而显著拓宽太阳光响应范围。原子分散的钨提供活性位点,增强W-CN-C光阳极与电解质界面间的析氧反应动力学。这些协同效应显著提高可见光吸收能力和电荷分离与转移效率,增强W-CN-C光阳极的光电转换效率,表现出优异的析氧反应性能。基于Pt@C电催化剂阴极优异的氧还原反应性能,所构建的光催化燃料电池平台展现出增强的开路电位。在W-CN-C光阳极表面锚定对铜离子特异性识别的探针,构建了自供能光催化燃料电池传感平台,用于检测铜离子。铜离子与探针形成的复合物阻碍W-CN-C光阳极的电子传输,改变光催化燃料电池的输出检测信号。所构筑的传感器表现出跨越五个数量级的宽检测范围(2.0 × 10−2–9.2 × 102 nmol L−1)、低检测限(7.0 pmol L−1)、对常见干扰物的高选择性,以及对水生环境中重金属铜离子检测的可行性。此外,以万用表作为信号输出装置,传感平台实现对铜离子的自供能和便携式检测,检测范围为0.25–1.3 × 102 nmol L−1,检测限为84 pmol L−1。这项工作利用原子分散级金属引入的共价键作为电荷转移通道设计高性能光阳极,为构筑对环境检测的高灵敏自供能电化学传感器提供了思路。
【无机化学学报】doi: 10.11862/CJIC.20250219
In this study, using 3, 5-di(3′, 5′-dicarboxylphenyl)-1H-1, 2, 4-triazole (H4L) as ligands, a gadolinia-based organic framework complex {[GdNa(L)(H2O)3]·2H2O}n (Gd-Na-MOF) was successfully designed and synthesized by hydrothermal method. The structure and properties were systematically characterized and tested by techniques such as single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and fluorescence spectroscopy. The results indicate that this complex has a unique 3D structure, excellent thermal stability, and outstanding luminescent performance. Based on its luminescent properties, a polymer-embedding method was employed to fabricate the Gd-Na-MOF into a flexible, washable composite fluorescent film, Gd-Na-MOF@PMMA/BMA (PMMA=polymethyl methacrylate, BMA=butyl methacrylate). This fluorescent film exhibited highly sensitive recognition capability for tyramine, with a low detection limit of 1.66 μmol·L-1. It was used for the detection of tyramine in bananas, with a recovery rate of 96.92%-100.26%.
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