有机-无机杂化四核镍取代的夹心型砷钨酸盐的合成与晶体结构

在水热条件下,合成了-种有机-无机杂化四核镍取代的夹心型砷钨酸盐[Ni(detaH)2(H2O)]2[Ni(deta)2][Ni4(H2O)2(B-α-AsW9O34)2]·4H2O(deta=二乙烯三胺),并借助IR光谱和X射线单晶衍射对其结构进行了表征.标题化合物属于正交晶系,Pbca空间群,晶胞参数:a=2.16...     

一种一维超分子链状四核镍夹心砷钨酸盐的合成和表征(英文)

利用水热方法合成了一种一维超分子链状四核镍夹心的砷钨酸盐[enH2][Ni(en)2]4[Ni4(H2O)2(α-AsW9O34)2].10H2O(1)(en=ethylene diamine);借助元素分析、红外光谱和单晶X射线衍射对其进行了表征。结果表明,化合物1的分子结构单元由1个二支撑的四核镍夹心砷钨酸盐多阴离子{[Ni(en)2]2[Ni4(H2O)2(α-AsW9O34)2]}6-,2个游离的[Ni(en)2]2+配离子,1个游离的双质子化[enH2]2+阳离子和10个结晶水分子组成。有趣的是,相邻的四核镍夹心砷钨酸盐多阴离子{[Ni(en)2]2[Ni4(H2O)2(α-AsW9O34)2]}6-借助Ni…O弱相互作用构筑一维超分子链状结构[Ni…O距离分布在0.253 2～0.283 7nm之间]。     

孔道结构H3PW12040／TiO2的制备及其可见光光催化降解水溶性染料的性能

采用溶胶一凝胶方法制备了孔道结构复合材料H3PW12040／TiO2，采用ICP-AES，UV／DRS，^31PMAS NMR，TEM和N2吸附等技术对其组成和结构进行了表征．结果表明，催化剂中活性组分H3PW12O40的基本骨架结构未发生改变，H3PW12O40的担载量为22．29％，催化剂平均粒径为40nm，具有双孔结构，其平均微孔和介孔孔径分别为0．6l和3．06nm．考察了催化剂可见光光催化降解6种水溶性染料的性能．结果表明，6种染料均可不同程度地被降解和矿化．通过对染料中性红的光催化降解实验，比较了H3PW12040／TiO2，Degussa P-25和锐钛矿结构Ti02的可见光光催化活性，其中，H3PW12040／TiO2活性最高，且催化剂最易分离，可循环使用．     

一种硒桥连的四核锰取代的类Dawson硒钨酸盐

在水溶液中合成了一种新型硒桥连的四核锰取代的类Dawson硒钨酸盐[H_2N(CH_3)_2]_4 KH_7[Mn_4(H_2O)_6(SeO)_2(Se_2W_(12)O_(46))_2]·45H_2O (1),并通过红外光谱,热重分析和X射线单晶衍射对其结构进行了表征.1中二聚的[Mn_4(H_2O)_6(SeO)_2(Se_2W_(12)O_(46))_2]~(12-)阴离子由两个六缺位类Dawson的[Se_2W_(12)O_(46)]~(12-)片段通过两个[Mn(H_2O)_2(SeO)]~(4+)和两个[Mn(H_2O)_2]~(2+)离子连接而成.值得注意的是两种不同配位方式的锰原子在连接两个[Se_2W_(12)O_(46)]~(12-)片段时发挥着重要的作用.一类Mn~(2+)离子和Se~(4+)离子结合作为桥占据[Se_2W_(12)O_(46)]~(12-)片段的"极位",另一类Mn~(2+)离子占据了"赤道位".此外,对其磁性进行了研究.     

一种Zn-K取代夹心型锑钨酸盐的制备、晶体结构和光催化活性（英文）

合成了一种Zn-K取代的夹心型锑钨酸盐Na9[Zn_3K_3(H_2O)_9][B-α-SbW_9O_(33)]_2·44 H_2O(1),并借助元素分析、红外光谱和X射线单晶衍射等方法对其进行了表征.标题化合物属于单斜晶系,C2/c空间群,晶胞参数:a=1.399 93(12)nm,b=2.317 6(2)nm,c=3.208 8(3)nm,β=98.804 0(10)°,V=10.288 0(15)nm~3,Z=4,D c=3.930 g/cm~3,GOOF=1.026,R_1=0.043 6,wR_2=0.103 5.X射线单晶衍射结构分析表明,化合物1分子结构由2个三缺位锑钨构筑块[B-α-Sb W9O33]9-通过12个缺位氧原子与1个六边形锌钾簇[Zn_3K_3(H_2O)_9]~(9+)相连而成.光催化结果表明,化合物1在一定程度上可以抑制偶氮荧光桃红的光降解.     

多金属氧酸盐光催化降解有机污染物研究进展

光催化作为一种高级氧化技术在有机污染物的降解方面得到广泛研究。本文概述了多金属氧酸盐光催化降解有机卤化物、染料、农药等有机污染物的研究进展,介绍了多金属氧酸盐与半导体氧化物、层状双氢氧化物、分子筛与介孔材料、离子交换树脂形成的复合材料,以及与半导体氧化物、聚乙烯醇等形成的复合膜材料的相关研究。     

一种锑桥连的四核铥嵌入锑钨酸盐及其发光性质（英文）

在酸性水溶液中Na_9[B-α-SbW_9O_(33)]·19.5H_2O, SbCl_3, Tm(NO_3)_3·6H_2O和盐酸二甲胺反应,合成一例锑桥连的四核铥嵌入四聚锑钨酸盐[H_2N(CH_3)_2]_8Na_6H_8{[Tm_4(H_2O)_6Sb_6O_4](B-α-SbW_(10)O_(37))_2(B-α-SbW_8O_(31))_2}·24H_2O (1).该簇合物的四聚阴离子是由两个二缺位[B-α-SbW_(10)O_(37)]~(11-)片段、两个四缺位[B-α-SbW_8O_(31)]~(11-)片段和两个[Tm_2(H_2O)_3Sb_3O_2]~(11+)簇组成.发光性质研究表明在353 nm紫外光激发下,1的发射光谱在450 nm处显示出一个特征发射峰,该发射峰归属于铥离子~1D_2→~3F_4跃迁.它相关的发光性能参数如色度坐标、色纯度、主波长和色温分别为(0.184 3, 0.135 0)、71.69%、470 nm和4 471 K.这些数据表明1有可能作为蓝色发光体应用于白光发光二极管领域.     

SnⅡ取代的Keggin型多金属氧酸盐的合成及光催化性能

合成了Sn~(Ⅱ)取代的Keggin型钨磷、钨硅多金属氧酸盐,用IR、电子光谱、~(31)P NMR测试技术对样品进行了表征,表征结果显示,合成化合物为纯的Sn~Ⅱ取代多金属氧酸盐,无Sn~Ⅳ取代物存在,其中Sn~(2 )未进入空穴八面体的中心,其阴离子的对称性介于相应的饱和与缺位结构之间。继而研究了此类化合物对于几种水溶性染料的光催化降解性能。结果表明,所制备的Sn~Ⅱ取代的钨硅多金属氧酸盐具有高的光催化活性,活性高于一般常用的PW_(12)、SiW_(12)化合物。特别是Sn~Ⅱ取代的钨硅多金属氧酸盐,即使在室内自然日光下对甲基橙和亚甲基蓝的光降解也呈现出很高的催化活性,反应7 h,降解率可达90％以上。对光催化机理的研究表明, Sn~Ⅱ取代的钨磷、钨硅多金属氧酸盐发生O→W荷移跃迁所需的能量较小,因此低能量的光照就可激发其HOMO能级上的电子,引发光催化反应,大大提高了光能利用率。     

表面活性剂@Weakley型稀土多酸复合催化剂对甲基橙的光催化降解活性

以光催化活性高的多酸阴离子CeW_(10)O_(36)~(9-)、不同结构阳离子表面活性剂为构筑基元,通过水/氯仿两相静电包埋技术制备了一系列表面活性剂@多酸复合物,并利用傅里叶红外光谱(FTIR)、热重分析(TGA)对复合物的组成及结构进行分析;以甲基橙为光催化降解底物分子、表面活性剂@多酸复合物为催化剂,考察不同表面活性剂、催化剂用量、甲基橙浓度、有机染料对光催化降解率的影响;不同表面活性剂@稀土多酸复合催化剂的光催化活性顺序为DTAB(十二烷基三甲基溴化铵)@CeW_(10)TTAB(十四烷基三甲基溴化铵)@CeW_(10)CTAB(十六烷基三甲基溴化铵)@CeW_(10)OTAB(十八烷基三甲基溴化铵)@CeW_(10)DODA(双十八烷基二甲基溴化铵)@CeW_(10)。     

Efficient photocatalytic degradation of rhodamine-B by Fe doped CuS diluted magnetic semiconductor nanoparticles under the simulated sunlight irradiation

The present work is planned for a simple, inexpensive and efficient approach for the synthesis of Cu_1-xFe_xS (x = 0.00, 0.01, 0.03, 0.05 and 0.07) nanoparticles via simplistic chemical co-precipitation route by using ethylene diamine tetra acetic acid (EDTA) as a capping molecules. As synthesized nanoparticles were used as competent catalysts for degradation of rhodamine-B organic dye pollutant. The properties of prepared samples were analyzed with energy dispersive analysis of X-rays (EDAX), X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-visible optical absorption spectroscopy, Fourier transform infrared (FTIR) spectra, Raman spectra and vibrating sample magnetometer (VSM). EDAX spectra corroborated the existence of Fe in prepared nanoparticles within close proximity to stoichiometric ratio. XRD, FTIR and Raman patterns affirmed that configuration of single phase hexagonal crystal structure as that of (P6₃/mmc) CuS, without impurity crystals. The average particle size estimated by TEM scrutiny is in the assortment of 5–10 nm. UV-visible optical absorption measurements showed that band gap narrowing with increasing the Fe doping concentration. VSM measurements revealed that 3% Fe doped CuS nanoparticles exhibited strong ferromagnetism at room temperature and changeover of magnetic signs from ferromagnetic to the paramagnetic nature with increasing the Fe doping concentration in CuS host lattice. Among all Fe doped CuS nanoparticles, 3% Fe inclusion CuS sample shows better photocatalytic performance in decomposition of RhB compared with the pristine CuS. Thus as synthesized Cu_0·97Fe_0·03S nanocatalysts are tremendously realistic compounds for photocatalytic fictionalization in the direction of organic dye degradation under visible light.     

Ultrasound-assisted nanoscaled supramolecular coordination polymer as an efficient recyclable catalyst for photocatalytic degradation of dye pollutants

An ultrasound-assisted nanoscaled supramolecular coordination polymer (nanosized 1′ ) has been synthesized using a self-assembly reaction of K₃[Cu (CN)₄] and hexamethylenetetramine in the presence of Me₃SnCl under ambient conditions. Nanosized 1′ was examined using elemental analysis, Fourier transform–infrared, transmission electron microscopy, scanning electron microscopy and X-ray powder diffractions. It was structurally compared with the single crystal supramolecular coordination polymer ^∞₃[Cu₆(CN)₇(C₆H₁₂N₄)₂(OH₃)]; SCP 1. The photocatalytic activities of nanosized 1′ and SCP 1 toward different hazardous organic dyes were determined under ambient, UV-light irradiation and ultrasonic conditions. SCP 1 and nanosized 1′ as heterogeneous nanoparticles catalysts exhibited high catalytic activity for degradation of Congo Red, Methyl Violet 2B and Methylene Blue dyes. The effects of operational parameters on catalytic degradation process, identification of the degradation products and recycling of the catalyst were also investigated. SCP 1 and nanosized 1′ are recyclable heterogeneous catalysts and can be reused with efficient activities. The mechanism of degradation using different scavenger techniques iss proposed and discussed. The catalytic oxidation process is mainly caused by ^•OH radicals.     

Facile synthesis and characterization of Fe2O3 nanoparticles using L-lysine and L-serine for efficient photocatalytic degradation of methylene blue dye

In this work, Fe₂O₃ nanoparticles, abbreviated as OL and OS, were facilely synthesized by the combustion procedure using L-lysine and L-serine as organic fuels, respectively. Also, the OL and OS samples were identified using different instruments such as Raman spectrometer, FT-IR spectrophotometer, UV–Vis spectrophotometer, XRD, HR-TEM, BET surface area, and FE-SEM. The XRD confirmed that the mean grain size of OL and OS samples is 42.23 and 33.16 nm, respectively. The HR-TEM images confirmed that irregular, hexagonal, and spherical shapes, have an average diameter of 39.13 and 34.28 nm, were observed in the OL and OS samples, respectively. The BET surface area of the OL and OS samples is 16.20 and 28.34 m²/g, respectively. Additionally, the OL and OS samples were accomplished for the photocatalytic degradation of methylene blue dye in the absence and presence of hydrogen peroxide. The % degradation of 45 mL of 25 mg/L of methylene blue dye in the case of using OL and OS samples in the absence of hydrogen peroxide is 55.23 and 63.64 % after 120 min, respectively. Also, in the presence of hydrogen peroxide, the % degradation in the case of using OL and OS samples is 100 % after 35 and 25 min, respectively.     

三维Cu-MOF对亚甲蓝的吸附和光催化降解及其机理

本文报道了[Cu₃(ppda)₃(tib)₂(H₂O)₄]·6H₂O(Cu-MOF)的合成、结构、吸附和光催化降解性能。在Cu-MOF中,1,4-苯二乙酸(H₂ppda)和1,3,5-三(1-咪唑基)苯(tib)配体交替连接Cu离子形成二维层,层与层之间通过trans-ppda^2-相互穿插形成稳定的三维结构。Cu-MOF对亚甲蓝(MB)的催化效率为97%,最高反应速率常数为0.019 7 min^-1。光催化降解机理：在光的激发下,催化剂表面的光生电子和空穴对发生分离,并与O₂、H₂O、H₂O₂反应生成活性物质,将染料降解为CO₂和H₂O。在MB溶液中加入NaCl(200 g·L^-1)后,Cu-MOF的吸附量有所提升(87.23 mg·g     

三维Cu-MOF对亚甲蓝的吸附和光催化降解及其机理

本文报道了[Cu₃(ppda)₃(tib)₂(H₂O)₄]·6H₂O (Cu-MOF)的合成、结构、吸附和光催化降解性能。在Cu-MOF中,1,4-苯二乙酸(H₂ppda)和1,3,5-三(1-咪唑基)苯(tib)配体交替连接Cu离子形成二维层,层与层之间通过trans-ppda^2-相互穿插形成稳定的三维结构。Cu-MOF对亚甲蓝(MB)的催化效率为97%,最高反应速率常数为0.019 7 min^-1。光催化降解机理：在光的激发下,催化剂表面的光生电子和空穴对发生分离,并与O₂、H₂O、H₂O₂反应生成活性物质,将染料降解为CO₂和H₂O。在MB溶液中加入NaCl (200 g·L^-1)后,Cu-MOF的吸附量有所提升(87.23 mg·g^-1),准二级动力学模型和Langmuir等温线模型的实验数据拟合程度较好,该吸附的主要过程为单层化学吸附。     

Analytical control of photocatalytic treatments: degradation of a sulfonated azo dye

The degradation of Methyl Orange (C₁₄H₁₄N₃SO₃Na), chosen as a model sulfonated azo dye, was investigated in aqueous solutions containing suspended polycrystalline TiO₂ particles under irradiation with simulated sunlight. The dye disappearance and the formation of the mineralization end products were monitored; the formation of the main transient intermediates was also examined in detail. Particular attention was devoted to the identification and to the evolution of fragments retaining the chromophoric group. The comparison of data coming from various analytical techniques led to a possible reaction mechanism for the degradation process, giving insight into an aspect of the treatment which has not been considered in previous studies.     

纳米TiO2光催化分解罗丹明B的动力学分析

锐钛矿型TiO2禁带宽度为3 2eV,在波长小于387nm的紫外辐射激发下,价带电子跃迁到导带,光生电子和空穴分离,与表面接触组分可发生一系列氧化还原反应,可将有机污染物降解为简单的无机化合物[1]。TiO2微粒粒径的降低(几十纳米),吸收光谱发生蓝移,催化活性随粒径的减小而增强[2,3]。纳米TiO2对罗丹明B的光催化分解过程与罗丹明B在TiO2表面的吸附有关[4]。本文采用自制纳米TiO2在4W紫外灯直接照射下,光分解罗丹明B为表观一级反应,反应速率与罗丹明B起始浓度及催化剂用量有关。1　实验部分纳米TiO2 采用sol gel法制备。分别配制不同…     

4-氯酚在TiO2纳米膜上光催化降解及反应动力学特征

氯酚(ＣＰ)化合物被广泛应用于木材防腐、金属防锈及杀虫剂等,因其毒性大、难降解,对环境造成严重污染[1,2]。目前用于ＣＰ的光催化降解的ＴｉＯ2粉体悬浮体系,催化剂不易回收利用。本文采用Ｓｏｌ Ｇｅｌ法制备的负载型ＴｉＯ2纳米粒子膜作为光催化剂,对4 ＣＰ进行了降解实验研究。同时应用ＸＲＤ法表征了不同实验条件下薄膜中ＴｉＯ2的晶相结构和粒度,考察了不同层数ＴｉＯ2膜的光催化活性,并对4 ＣＰ的降解条件及反应动力学特征进行了探讨。1　实验部分1.1　玻璃负载ＴｉＯ2膜的制备与表征[3-5]按照钛酸四丁酯∶无水乙醇∶水=3∶12∶…     

Heterojunction of BiPO4/BiOBr photocatalysts for Rhodamine B dye degradation under visible LED light irradiation

BiOBr synthesized by alcoholysis precipitation is used in the preparation of BiPO₄/BiOBr composites by adding H₃PO₄. Pristine BiOBr and a series of BiPO₄/BiOBr composites have been successfully synthesized using an entirely room-temperature production process. X-ray powder diffraction, scanning electron microscopy, High-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, UV–vis absorption spectroscopy were used to investigated the bulk structure, surface morphology, element composition and optical properties of the samples. The degradation effect of different proportions of BiPO₄/BiOBr composites, BiOBr and BiPO₄ on Rhodamine B (RhB) was evaluated under visible LED light irradiation. Compared to pure BiOBr and BiPO₄, the as-synthesized BiPO₄/BiOBr composites showed enhanced performance, with 30% BiPO₄/BiOBr composite showing the best performance, as it could degrade 95.66% of RhB (100 ml, 15 mg/L) within 120 min. The enhanced photocatalytic activity of BiPO₄/BiOBr was attributed to the heterojunction formation between BiOBr and BiPO₄ and efficient charge separation.