两个基于八钼酸盐的无机-有机杂化材料的合成、结构和光催化性能

通过水热法成功合成了两个新的基于(β-Mo₈O₂₆)^4-构型的无机-有机杂化材料,分子式分别为{[Ni(β-Mo₈O₂₆)(H₂O)₄](H₂Fbix) 2H₂O}_n(1)和{[Co(β-Mo₈O₂₆)(H₂O)₄](H₂Fbix) 2H₂O}_n(2)(Fbix=2,3,5,6-四氟-二(1,4-咪唑-1-甲基)苯)。利用X-射线单晶衍射、X-射线粉末衍射、红外光谱、热重分析和元素分析等对该化合物的结构和性能进行了表征。晶体结构分析表明：化合物1和2为同构化合物。在化合物1中,扭曲八面体构型的Ni^II与两个β-[Mo₈O₂₆]^4-单...     

锰钒氧无机-有机杂化材料

氧化锰、钒氧簇构筑块经与有机组分组合可形成新型结构的锰钒氧无机-有机杂化材料。人们预测锰钒氧无机-有机杂化材料将兼有金属锰配合物和钒氧无机-有机杂化材料结构的多样性、独特的物理性质和广阔的应用前景。本文综述了近年来锰钒氧无机-有机杂化材料的合成、组成、结构及有关性质的研究与进展。     

坡缕石/聚丙烯酰胺无机-有机杂化絮凝剂的合成、表征与应用

将酸活化坡缕石(PGS)与氯化乙醇胺(EACl)所得氯化乙醇胺改性坡缕石(PGS-EACl)与高价铈盐(Ce⁴⁺)组成氧化还原非均相引发体系,引发丙烯酰胺单体聚合得到了坡缕石/聚丙烯酰胺(PGS/PAM)无机-有机杂化物.用¹HNMR、FTIR、粘度法和电导法对杂化物进行了结构表征,表明杂化物中存在PGS^Θ⊕NH₃R离子键合作用.考察了PGS-EACl用量、聚合反应时间和单体浓度对杂化物特性粘数的影响.由PGS/PAM杂化絮凝剂分别处理高岭土和氧化铁红两种配制废水,发现杂化絮凝剂的絮凝效果明显优于纯PAM絮凝剂.     

两个基于[SMo12O40]2-和冠醚基超分子阳离子的无机-有机杂化晶体的合成及晶体结构

以18-冠-6和4-碘-苯铵盐,二苯并30-冠-10和3-氟-4-氯-苯铵盐为超分子阳离子构建单元,分别引入到Keggin型[SMo₁₂O₄₀]^2-中,使用H管扩散法和溶剂挥发法合成了无机-有机杂化材料[（4-I-Anis）（[18]crown-6）]₂[SMo₁₂O₄₀]·CH₃CN（1）和[（3-F-4-Cl-Anis）₂（DB[30]crown-10）][SMo₁₂O₄₀]·2CH₃CN（2）（4-I-Anis=4-碘-苯铵盐;3-F-4-Cl-Anis=3-氟-4-甲基苯铵盐;DB[30]crown-10=二苯并30-冠-10）。通过红外光谱、元素分析、热重分析、固态漫反射光谱和X射线单晶结构分析对化合物进行了表征。结构分析表明,晶体1和2通过非共价键自组装作用构建而成,冠醚基超分子阳离子是通过N-H…O氢键作用形成。晶体1中,在bc平面,每个[SMo₁₂O₄₀]^2-多酸阴离子被6个超分子阳离子（4-I-Anis）（[18]crown-6）围绕,形成六边形的结构;晶体2中,在bc平面,每个[SMo₁₂O₄₀]^2-多酸阴离子被4个大的超分子阳离子（3-F-4-Cl-Anis）₂（DB[30]crown-10）围绕,形成四边形的结构。热重分析表明,氢键在维持晶体1和2的稳定性上起着主要的作用。固态漫反射光谱表明,[SMo₁₂O₄₀]^2-和冠醚基超分子阳离子之间存在电荷转移作用。     

Keggin型P-Mo-V杂多酸的合成

杂多化合物(Ｈｅｔｅｒｏｐｏｌｙｃｏｍｐｏｕｎｄ,简写为ＨＰＣ)的结构、性质特殊:化学计量的ＨＰＣ组成简单、结构确定,既有配合物和金属氧化物的结构特征,又有酸性和氧化还原性质,多数在水和含氧有机溶剂中溶解度甚大,而且相当稳定,固态ＨＰＣ的热稳定性也较好,广泛用于催化领域,在医学领域特别是抗癌及抗病毒领域也有较好的应用前景[1]。具有Ｋｅｇｇｉｎ结构的ＨＰＣ具有三级结构,其一级结构为杂多阴离子(Ｈｅｔｅｒｏｐｏｌｙａｎｉｏｎ,简写成ＨＰＡＮ),表达通式为[ＸＭ12Ｏ40]ｎ-8(ｎ为元素Ｘ的氧化数),结构描述以[ＸＯ4]四面…     

含氮多齿配体构筑的无机-有机杂化材料及其光催化研究进展

综述了金属离子与多齿含氮配体构筑的无机-有机杂化材料,并概述了这些材料在光催化降解亚甲基蓝(MB)方面的研究进展.为此类材料在光催化降解染料方面的研究提供了理论和实验基础.     

亚磷酸锌无机-有机杂化化合物的合成与结构表征

在水热条件下, 以1,6-己二胺为模板剂合成了一个三维(3D)亚磷酸锌无机-有机杂化化合物(C₆N₂H₁₆)_0.5ZnHPO₃(ZnHPO-CJ15), 并对其单晶结构进行了解析. 结果表明, ZnHPO-CJ15晶体属单斜晶系, P2₁/c空间群, a=1.19587(7) nm, b=0.82766(5) nm, c=0.77756(5) nm, α=90.00°, β=95.8370(10)°, γ=90.00°, V=0.76562(8) nm³, Z=1. ZnHPO-CJ15具有层柱状结构, 其骨架结构是由ZnO₃N四面体和HPO₃假四面体连接构成的二维4×8元环网层结构, 层与层之间由1,6-己二胺分子与Zn配位柱撑连接形成三维结构.     

三维多酸基无机-有机杂化化合物[Cu_6~Ⅰ(pyz)_6][(PMo_(12)O_(40))_2]·11H_2O的合成、结构及电化学性质

利用水热方法合成了三维多酸基无机-有机杂化化合物[CuⅠ6(pyz)6][(PMo12O40)2]·11H2O(pyz=吡嗪),并通过单晶X射线衍射、红外光谱、元素分析、热重分析和粉末X射线衍射等方法对其进行了表征.结构分析表明该化合物属于立方晶系,Ia-3d空间群,晶胞参数a=b=c=2.602 66(3)nm,α=β=γ=90°,V=17.630 0(4)nm3,Z=8,R1=0.052 7,wR2=0.137 8.进一步研究了该化合物的电化学性质,结果表明其在电催化氧化葡萄糖反应中具有良好的活性.     

无机-有机杂化光催化剂:合成、机理及应用（英文）

由无机与有机组分组成的无机-有机杂化材料因其优异的性能及良好的物理化学性质在光催化领域得到了广泛的关注.目前,已经开发的单相光催化剂有很多种,但其很难同时满足宽的光激发范围以及高的光吸收能力和强的氧化还原能力等需求,因此,科研人员开发了很多方法去解决上述问题,主要包括以下两大类.第一类,修饰光催化剂扩大光激发范围以及增强可见光吸收.例如构建固溶体、引入表面缺陷、杂质掺杂、染料敏化和表面等离子体共振等策略.第二类,构建半导体异质结,通过界面处的协同作用有效促进光生电子空穴对的转移与分离.例如type II型、直接Z型以及S型异质结等.有机成分与无机成分的杂化是有效解决上述问题的方法之一.大部分有机材料具有成本低、吸光系数高以及比表面积大等优点;但低的强度以及宽的带隙限制了有机材料在光催化上的应用.而大部分无机材料具有高强度、窄带隙以及良好的光学性能.但低韧性和较差的分散性限制了无机材料在光催化上的应用.无机-有机杂化材料不仅保留了无机与有机组分的原有性质,而且界面处组分之间的协同作用会产生新的性质,如高的载流子传输能力和高的光吸收能力等.无机-有机杂化材料是多相材料,其中的一相是纳米材料...     

Inorganic-organic hybrid polyoxometalate: Preparation, characterization and electrochemistry properties

The solid hybrid material (H_3/4pbpy)₄[PMo₁₂O₄₀]·1.25H₂O (1) (pbpy=5-phenyl-2-(4-pyridinyl)pyridine) has been prepared and characterized. A structural feature of compound 1 is that the polyoxometalate anions exhibit a one-dimensional inorganic double chain-like structure via weak interactions of O…O. The organic moiety exhibits regular packing with offset aromatic-aromatic interactions between the pbpys, leading to a compact supramolecular framework structure to accommodate the inorganic chains. Compound 1 was employed to fabricate the three-dimensional bulk-modified carbon paste electrode (1-CPE) to research on its electrochemistry properties. The results indicate that 1 retained Keggin molybdate anion electrocatalytic activities toward the reduction of chlorate, hydrogen peroxide and nitrite.     

New Inorganic-organic Hybrid Compound Containing One Dimensional Keggin Polyoxometalate[SiW11O39Co]6- Chains:Preparation,Characterization and Application in Chemically Bulk-modified Electrode

A new inorganic-organic hybrid compound based on polyoxometalate and organic ligand formulated as （H2bpp）3[SiWlIO39Co]-2H20（1）[bpp=l,3-bis（4-pyridyl）propane] was hydrothermally synthesized and structurally characterized by elemental analysis, single-crystal X-ray diffraction, IR, TG, and cyclic voltammetry. Single-crystal X-ray diffraction analysis reveals that compound 1 consists of interesting cobalt-monosubstituted POMs one dimensional chain together with protonated bpp ligands. Additionally, the polyoxoanions combined with the discrete organic substrates by hydrogen bond interactions to afford a supramolecular 3D network structure. The hybrid compound 1 was used as a bulk modifier to fabricate a three-dimensional chemically modified carbon paste electrode（1-CPE） by direct mixing. The electrochemical behavior and electrocatalysis of 1-CPE were studied in detail. The results indicate that 1-CPE has good electrocatalytic activities toward the reduction of nitrite or bromate in 1 mol/L 1-12SO4 aqueous solution. 1-CPE shows remarkable stability that can be ascribed to the insolubility of compound 1 and the supramolecular interactions existed between 1D POM anion chains and organic ligand bpp, which is very important for practical applications in electrode modification.     

Two New Inorganic-organic Hybrid Compounds Constructed from Different Polymolybdates and Transition Metal-amine Subunits

Two new polyoxometalate(POM)-based hybrid compounds, [Cu(en)][H₄Mo₄O₁₆]_0.5(1)(en=ethylene- diamine) and [Ag(3-C₅H₆N₂)₂][H₂PMo₁₂O₄₀](2)(3-C₅H₆N₂=3-aminopyridine), containing different transition metal-amine subunits were hydrothermally synthesized and characterized by elemental analyses, infrared spectroscopy and single-crystal X^-ray diffraction. For compound 1, each [H₄Mo₄O₁₆]^4-(Mo₄O₁₆) cluster was linked to four neighboring Mo₄O₁₆ clusters through four [Cu(en)]²⁺ subunits to yield a (2,4)-connected 2D layer, which was further extended to a 3D supramolecular network via hydrogen bonding interactions. For compound 2, the adjacent [H₂PMo₁₂O₄₀]^- clusters were bridged by [Ag(3-C₅H₆N₂)₂]⁺ subunits to generate a 1D chain. The electrochemical behaviors and the photocatalytic activities of compounds 1 and 2 were studied in detail.     

Two new Keggin-type polyoxometalate-based organic-inorganic hybrid compounds with metal ions and chelate ligands

Two new hybrid compounds with chemical formulas [Co(L₁)₂(H₂O)₂]₂[SiW₁₂O₄₀]·6H₂O (1) and [Cu₂(C₉H₂₂ N)₂(L₂)₂][SiW₁₂O₄₀]·2H₂O (2) (L₁ = 3,3′-diamino-5,5′-bis(1H-1,2,4-triazole), L₂ = 1,2-bis(3-(2-pyridyl)pyrazole-1-ylmethyl)benzene, C₉H₂₂ N = tripropylamine) were prepared in a hydrothermal reaction system containing Keggin-type polyoxometalates (POMs), transition metal (TM) salts (cobalt salts and copper salts), and chelate L₁/L₂ ligands. X-ray structural analysis reveals that 1 and 2 possess 3-D supramolecular host frameworks with large cavities and the polyoxoanions SiW₁₂ reside in these cavities as the guest templates. The photocatalytic activities of 1 and 2 were investigated. Both compounds show efficient catalytic activity for degradation of RhB with 1 > 2. The loading amount of the POM units and the structural features of these POM-based organic-inorganic hybrid compounds may be necessary factors that affect the activity of catalysts in the photocatalytic degradation.     

Synthesis, Structure, and Photoluminescence Property of a Novel One-dimensional Inorganic-organic Hybrid Gallophosphate JGP-2

A novel one-dimensional inorganic-organic hybrid gallophosphate compound, Ga(2,2′-bipy)(HPO4)· (H2PO4)(denoted JGP-2) was synthesized hydrothermally with 2,2′-bipyridine as a ligand and characterized by X-ray powder diffraction (XRD), elemental analysis, inductively coupled plasma(ICP), TGA analysis, solid-state 31P NMR, and luminescence spectra and structurally determined by single-crystal X-ray diffraction analysis. JGP-2 crystallized in the triclinic system, space group Pī(No.2), with a=0.7818(1) nm, b=0...     

Synthesis and Structure of a Novel Chain-like Inorganic-organic Hybrid Constructed from Isopolyanion and Oxalato-bridged Dinuclear Copper Complex

A novel inorganic-organic hybrid based on isopolyanion,{[Cu2(phen)2(μ-ox)][H2Mo8O26]}·4EtOH·Et2O(1) (phen=phenanthroline,ox=oxalate),was synthesized under open-air mild reaction conditions,and characterized by elemental analysis,IR,ICP,TG and single crystal X-ray diffraction analysis.The crystal structure belongs to triclinic system with space group Pī and cell parameters:a=1.1075(5) nm,b=1.1608(5) nm,c=1.3333(5) nm,α=91.683(5)o,β=113.996(5)o,γ=112.170(5)o,V=1.4159(10) nm3,Mr=2017.44,Z=1,Dc=2.366 g/cm3 and F(000)=980.0.The structure of hybrid 1 is a 1D chain constructed of alternating octamolybdate isopolyanions [β-(Mo8O26)4-] and oxalato-bridged dinuclear copper complex cations [Cu2(phen)2(μ-ox)]2+.Ultimately,a 3D supramolecular network was formed by hydrogen bond interactions among the adjacent chains.The result shows that hybrid 1 is the first example of inorganic-organic hybrid constructed from isopolyanion and oxalato-bridged dinuclear copper complex fragment (CCDC No.665101).     

An ionic 2D inorganic–organic hybrid of tris[((1H-tetrazol-5-yl)methyl) morpholine] dodecatungstophosphate(V) pentahydrate: Synthesis X-ray crystal structure, and spectroscopic characterizations

A unique ionic hybrid material [C6H12N5O]3[(PO4)W12O36]•5H2O has been synthesized from the reaction of ((1H-tetrazole-5-yl)methyl)morpholine and α-H3[(PO4)W12O36].21H2O. It has successfully been characterized by elemental analysis, IR and 1H NMR spectroscopies, TGA and single-crystal X-ray diffraction method. The title compound is constructed from the three [C6H12N5O]+ cations and α-Keggin [(PO4)W12O36]3- polyoxoanion. The most remarkable structural feature of this hybrid can be described as two-dimensional inorganic infinite plane-like (2D/∞[(PO4)W12O36]3-) which forming via van der Waals interactions along the x axis.     

磷钨酸均相光催化还原降解水中偶氮染料酸性大红3R

以磷钨酸(H3PW12O4记为PW12)作为光催化剂,在异丙醇作为电子给体的条件下对偶氮染料酸性大红3R（记为AR3R）进行光催化均相还原脱色研究。循环伏安法、暗反应、O2竞争抑制等实验表明杂多蓝（PW12O404-）对AR3R 具有明显的还原脱色作用。实验研究了催化剂PW12用量、异丙醇浓度、染料浓度、盐浓度对PW12/异丙醇光催化还原降解酸性大红3R的影响。结果表明：AR3R的光催化脱色速率随催化剂PW12、异丙醇浓度的增加而增加,最后趋于恒定;随染料初始浓度增加,初始光解速率增大,且符合Langmuir-Hinshelwood动力学方程;随盐浓度增加,染料脱色速率减小,表现为负的盐效应。由此推测AR3R与光反应生成的杂多蓝预先进行复合,然后发生电子转移引起偶氮染料还原脱色,杂多蓝氧化复原。本研究结果表明磷钨酸/异丙醇/UV绿色光催化还原体系能够有效用于偶氮染料废水的还原脱色处理。