稀土MOF发光调色板和高等级防伪条形码材料

<正>MOF(metal-organic framework,金属-有机骨架)是由金属和有机配体组成的骨架材料,是一类新型的多孔材料。简单的来说MOF就是由金属离子或金属和氧原子、羟基、羧酸等组成的团簇与有机配体结合而成的框架材料。而稀土MOF兼具了有机配体与稀土离子的发光特性,增加了发光形式的多样性和可调性,在OLED(Organic Light-Emitting Diode,有机发光半导体)发光材料与器件、化学传感器、生物功能材料、防伪与显示材料等诸多方面有着广     

一个中心对称的(6,3)拓扑二维蜂窝网的Ni-咪唑基三脚架配合物的合成、结构及其介电性

利用水热合成法,以金属盐NiSO4·6H2O与三脚架配体1,3,5-三(1-咪唑基)苯(tib)进行组装,得到了一个结构新颖的有序金属-有机框架(MOFs){[Ni3(tib)2(H2O)12](SO4)3}n(1).利用X-射线单晶衍射仪检测其晶体结构,并进行元素分析,红外光谱射线,粉末衍射等相关表征.配合物1为一个典型的(6,3)拓扑二维蜂窝网结构,由于π-π空间叠加效应和氢键相互作用形成了稳定的三维结构.对配合物1介电性能进行测定,发现其在138℃时达到最大的介电异常值10.08,为典型的介电材料,通过热重分析,表明此材料具有较好的热力学稳定性,对新型多维MOFs及新型介电性能材料的开发具有借鉴和指导意义.     

MOF衍生CoP/C的制备、表征及电化学析氢性能

采用类沸石咪唑酯骨架化合物ZIF-67(zeolitic imidazolate framework-67)和六水合硝酸钴为原料制备金属-有机物框架材料(metalorganicframeworks,MOF),经过高温煅烧及磷化,得到碳包覆磷化钴(CoP/C)粉体。用X射线衍射仪、扫描电镜及透射电镜对CoP/C粉末进行表征与分析,并进行电催化析氢实验。结果表明,高温煅烧后,ZIF-67的有机组分转化为导电炭骨架,钴离子转化为单质钴纳米颗粒嵌于炭骨架中,形成金属有机框架。经进一步磷化后,得到纯相CoP/C粉体。CoP/C粉末表现出良好的电化学析氢性能,其过电位为64 mV,塔菲尔斜率为66 mV/dec,历经15 h电催化析氢后仍保持高催化活性。     

咪唑基四唑Fe~Ⅱ、Co~Ⅱ配合物的[2+3]原位合成、结构及性质研究

采用咪唑基配体MID(1-甲基-1H-咪唑-4,5-二甲腈)和Na N3为[2+3]环加成反应原料,分别在Fe SO4·7H2O和Co SO4·7H2O作为路易斯酸催化剂条件下进行水热反应,原位合成2个结构新颖的单核咪唑基四唑配合物[Fe·(MTIC)·(H2O)](1)和[Co·(MTIC)·(H2O)](2)及1个配体结构[(MTIC)·(H2O)](3).结果表明:在化合物1-3中,只有1个氰基发生生成四唑的Sharpless反应,而另一个氰基未发生变化.X-射线单晶衍射分析表明,配合物1-3均结晶于P-1空间群.此外,还对上述配合物进行了元素分析、红外光谱、差热分析和粉末衍射等表征.研究结果对开发新型有机金属超分子结构材料具有一定的指导和借鉴意义.     

金属有机骨架材料的合成方法及应用进展

金属有机骨架材料(MOFs)是近年来发展迅猛的一种具有三维孔结构的新型高分子材料,由有机配体和金属离子通过配位键自组装形成,具有比表面积大、孔隙率高、微孔结构有序等优良的性能在气体存储、吸附分离等领域受到越来越多的关注。综述了利用包括溶剂(水)热合成法、微波辅助合成法、扩散法、超声法、机械研磨法等合成MOFs的优缺点。对近年来MOFs在吸附挥发性有机物(VOCs)领域的研究进行了综述,对MOFs材料在未来的研究及发展进行了展望。     

咪唑基配体及其金属配合物的合成与应用

咪唑及其衍生物作为一类重要的配体分子，可以通过不同的配位模式与众多主体金属离子作用，形成主体-客体配合物。同时，这些配合物在离子识别、荧光材料、药物设计、磁性材料、自组装、气体吸附和催化剂的研发等领域展现出广阔的应用前景。本文着重综述了咪唑基衍生物配体及其配合物的研究进展，对一些此类新型配合物的合成方法与应用做了详细介绍，并展望了未来发展的方向。     

基于Ag@Co基金属-有机聚合物复合材料及其非酶葡萄糖传感器的制备与性能研究

金属-有机聚合物(MOPs)作为一种新型功能材料,用途广泛,但其导电性差,一定程度上限制了其在电化学传感领域的应用.本工作使用6-(3'-吡啶基)间苯二甲酸(H2PIA)配体,采用溶剂热法合成了一种新的Co基金属-有机聚合物,即[Co(PIA)(H2O)4]n(A),通过沉积还原的方法在其上负载Ag纳米颗粒(NPs),...     

双水杨醛1,6-己二胺希夫碱轻稀土配合物的合成和表征

合成并表征了双水杨醛缩 1,6 己二胺希夫碱配体 (C2 0 H2 4 N2 O2 ,以L表示 )与轻稀土Ln3 的 7种新的固体配合物 [LnL2 ](NO3) 3(Ln =La、Ce、Pr、Nd、Sm、Eu、Gd)。利用元素分析、摩尔电导、红外光谱、电子光谱、X射线衍射物相分析、热分析方法进行表征。中心金属离子Ln3 与希夫碱配体中的亚胺氮和酚羟基中的氧发生配位 ,配位数为 8。     

ZIF-8/ZIF-67衍生钴氮共修饰碳的合成及电催化性能研究

开发并利用高效廉价的电催化剂来代替传统的贵金属铂(Pt)基催化剂,对新能源材料与器件的开发和利用意义重大。以锌/钴基沸石咪唑酯骨架材料(ZIF-8/ZIF-67)为前驱体,通过不同的热解方式,合成表面原位生长碳纳米管的钴氮共修饰碳十二面体(Co@NCD/CNT)和表面光滑的钴氮共修饰碳十二面体(Co@NCD)。采用X射线衍射仪(XRD)、拉曼光谱仪(Raman)、场发射扫描电镜(FESEM)对合成催化剂的组份和形貌进行表征。XRD图谱显示Co@NCD和Co@NCD/CNT为无定型碳结构,并存在Co金属物种。Raman图谱显示Co@NCD/CNT比Co@NCD具有更高的石墨化程度。FESEM图像显示Co@NCD呈表面光滑的十二面体状,Co@NCD/CNT呈十二面体状且表面长有碳纳米管。电化学测试结果显示,Co@NCD/CNT和Co@NCD催化剂在碘电解液体系中的的传荷电阻分别为0.79和0.91Ω·cm²,还原峰值电流密度分别为-6.43和-4.46 mA·cm²。由光伏测试结果可知,Co@NCD/CNT对电极催化剂组装的染料敏化太阳能电池获得...     

2,2’-联吡啶-5,5’-二羧酸CuII 配合物的构筑、结构及性质研究

利用2,2’-联吡啶-5,5’-二羧酸、氧化铜和高氯酸在水热条件下得到了一个有趣的铜配合物[Cu（H₂bpdc）]·ClO₄（1）（H₂bpdc=2,2’-联吡啶-5,5’-二羧酸）.对其进行X射线单晶衍射,利用SHELXTL软件解析其结构,单晶结构分析表明配合物1为零维结构,分子间存在着丰富的氢键,通过氢键和弱的π-π相互作用使得配合物1形成一个三维网状结构.对配合物1和配体的固体荧光对比研究表明,配体与金属CuII离子配位后发生了荧光淬灭现象.利用热重分析研究了配合物1的热稳定性及热分解与晶体结构的关系.对开发新型多维有机金属框架结构及新型荧光材料具有一定的指导和借鉴意义.      

锌基金属-有机框架材料CO_2吸附性能研究进展

本文概述近几年国内外Zn-MOFs材料吸附CO_2的研究进展,综述Zn-MOFs材料的特性、制备方法及其CO_2吸附的研究,最后展望该材料的研究方向和发展前景。     

Catalytic thermal decomposition of ammonium perchlorate by a series of lanthanide EMOFs

Given their unique and excellent properties,metal-organic frameworks(MOFs) materials have been used in many scientific fields.EMOFs use energetic materials as ligands,which can provide part of the energy for the system while catalyzing ammonium perchlorate.The energetic material 1.1’-dihydroxyazotetrazole(H₂AzTO),as a high-energy nitrogen-rich material,was selected as a ligand.Five kinds of La³⁺,Ce³⁺,Pr³⁺,Nd³⁺,and Sm³⁺ lanthanide ...     

一种高效双功能电催化剂CoP/Co@NPC@rGO的制备

简单的热处理和热处理磷化ZIF-67/氧化石墨烯（GO）前驱体得到具有典型的多孔碳结构特征的CoP/Co@NPC@rGO纳米复合材料电催化剂。通过扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线衍射（XRD）、X射线光电子能谱（XPS）、拉曼光谱（Raman）和N₂等温吸脱附曲线等对其形貌、成分和结构进行分析和表征。采用线性扫描伏安法、电化学阻抗谱和计时电位法探讨了CoP/Co@NPC@rGO纳米复合电催化剂对氢气析出反应（HER）和氧气析出反应（OER）的电催化活性和稳定性。结果表明,CoP/Co@NPC@rGO?350在1.0 mol·L–1 KOH溶液中达到10 mA·cm?2电流密度的析氢过电位仅127 mV;同时,在1.0 mol·L–1 KOH溶液中显示出优于贵金属RuO₂的析氧性能,达到10 mA·cm?2电流密度的过电位为276 mV,塔菲尔斜率仅为42 mV·dec?1。这种高析氢和析氧电催化活性主要归因于高度石墨化的N掺杂多孔碳与N掺杂石墨烯之间的协同效应。CoP/Co@NPC@rGO是电催化全解水电催化剂的候选材料,且为基于金属有机骨架（MOFs）/氧化石墨烯复合材料的高效电催化剂的设计开辟了一条新的途径。      

Synthesis of rare earth metal-organic frameworks （Ln-MOFs） and their properties of adsorption desulfurization

The rare earth metal-organic frameworks(Ln-MOFs) materials,Ln(BTC)(H2O)·(DMF),were synthesized using the rare earth metal(Ln=Sm,Eu,Tb,Y) and 1,3,5-trimesic acid(BTC) as a metal ion center and ligand,respectively.X-ray diffraction(XRD) and infrared spectroscopy(FT-IR) were employed to characterize the Ln-MOFs structural features.The property of adsorption desulfurization of Ln-MOFs materials was evaluated with thiophene/n-octane as model oil.The results showed that Ln-MOFs with rare earth metals Sm,Eu,Tb and Y had perfect crystalline and good adsorption desulfurization ability.Y(BTC)(H2O)·(DMF) material had a comparatively better activity for the adsorption desulfurization with desulfurization rate up to 80.7% and the sulfur adsorption capacity was found 30.7 mgS/g(Y-MOFs).The Ln-MOFs materials had excellent reusability.     

Solvent extraction of heavy metals contained in phosphoric acid solutions by 7-(4-ethyl-1-methyloctyl)-8-hydroxyquinoline in kerosene diluent

The solvent extraction of zinc, cadmium and chromium contained in 5.5 mol/L phosphoric acid solutions (30% P₂O₅) was investigated using 7-(4-ethyl-1-methyloctyl)-8-hydroxyquinoline-Kelex 100® as extractant and treated kerosene as diluent. At organic-to-aqueous phase ratio (1/1) and at room temperature, 58% of zinc, 34% of chromium and 15% of cadmium were recovered in 240 min. In order to improve the kinetics of extraction, a modifier reagent was added to the organic phase. The addition of n-decanol (10 vol.%) increased the rate metals extraction by reducing the equilibrium time from 240 min to 30 min, along with 60% recovery of metals. Extraction of metal ions increased with increasing aqueous phase pH. The pH_0.5 values difference of 0.1 M with Kelex 100® indicates the possible separation of cadmium, zinc and chromium. Increasing the concentration of Kelex 100® increased the percentage extraction of metal ions. The loading capacity values were found to be 83%, 80% and 71% for zinc, chromium and cadmium, respectively, at 0.4 M Kelex 100® concentration, indicating that the extractant is highly selective for the metal ions considered.     

Catalytic oxidation of vinyl chloride over Co–Ce composite oxides derived from ZIF-67 template: Effect of cerium incorporation

Transition metal oxides are regarded as an economical and efficient catalytic alternate for catalytic oxidation of volatile organic compounds (VOCs) emissions. The morphological decoration and the incorporation of extrinsic metals were demonstrated to be effective strategies for achieving noticeable catalytic improvement. In this work, a novel Co–Ce composite oxides catalyst was obtained by the pyrolysis of ZIF-67 template with the impregnation of certain cerium cations (denoted as ZIF-CoCe). Compared with the reference Co–Ce composite oxides by the sol-gel (denoted as SG-CoCe) and physical mixing (denoted as MIX-CoCe) methods, ZIF-CoCe delivers significantly higher catalytic activity for vinyl chloride oxidation, which are demonstrated to be closely related with its superior redox capacity, more abundance of surface active Co³⁺ sites and adsorbed active oxygen species from oxygen vacancies. In addition, the unique cage-like morphological feature of the Co-based catalysts derived from ZIF-67 template plays a crucial function in kinetically facilitating the mass transfer of catalytic reaction and promoting the catalytic VC oxidation activity. With regard to in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) analysis, enol and carboxylic acid species are identified to be the key organic intermediates during catalytic vinyl chloride oxidation.     

Surface-effect on detection ability of fluorescent Eu(btc) metal-organic frameworks to metal ions

Eu(btc)metal organic frameworks(MOFs)were prepared by co-precipitation method via 1,2,4-benzenetricarboxylic acids(H3btc)connecting with Eu³⁺ions,and the morphology was controlled from compact spherical to irregular honeycomb by adjusting the pH of reaction solutions.The luminescence properties of Eu(btc)MOFs are found to be related to the surface morphology of products,and the compact spherical one performs stronger emission intensity.The sensing ability of Eu(btc)MOFs to 11 kinds of metal ions was investigated and a prominent quenching effect occurrs in Fe³⁺,or Ni²⁺solutions.Based on UV—vis absorption analysis,an“ion-fence”model presents the competition to absorb exciting light between Eu(btc)MOFs and adsorbed metal ions.Based on Stern-Volmer equation,the Eu(btc)detection is found with higher Ksv value and a lower detection limit.Meanwhile,a higher sensing efficiency is confirmed in the Eu(btc)MOFs with loose honeycomb due to aggravating porous surface offering much more sites for metal ions.     

Extraction of Zinc‐Cobalt from Sulphate Solution of Cobalt Cake by D2EHPA in the Processing of Indian Ocean Nodules

During the processing of Indian ocean nodules, cobalt cake containing zinc in equal proportion is produced. In order to get pure cobalt and zinc from the sulphate leach solution of cake, a solvent extraction process has been considered using an organic extractant, di‐(2‐ethylhexyl) phosphoric acid (D2EHPA). Separation of cobalt and zinc has been carried out by mixing aqueous and organic phases in a rectangular vessel and separating the phases after equilibration in a glass funnel. The analysis of the metal from the aqueous phase was made by atomic absorption spectrometer to compute the metal transfer. The extraction and separation studies carried out under the different operating conditions indicated favourable zinc extraction at the lower pH (~ 2) with partially saponified D2EHPA. The small amount of cobalt co‐extracted with zinc was scrubbed with dilute sulphuric acid. With completely saponified D2EHPA, a high degree of cobalt extraction (99.8%) was achieved at aqueous feed pH of 5.0. The flow sheet developed could be used for the selective extraction and separation of zinc and cobalt from the leach liquor of cobalt cake.