杂多酸/离子液体杂化材料催化苯的高选择性羟基化

制备了V取代的磷钼酸H_3+xPMo_12-xV_xO₄₀（x=0,1,2）及1-丁基-3-甲基咪唑溴盐离子液体（[C₄mim]Br）,并采用离子交换的方法制备了系列杂化材料（[C₄mim]3+xPMo_12-xV_xO₄₀,x=0,1,2）;采用X射线衍射（XRD）、傅里叶变换红外光谱（FT-IR）、紫外-可见漫反射光谱（UV-Vis DRS）对所制备样品进行了表征;以H₂O₂为氧化剂,考察了所得样品催化苯羟基化制苯酚的活性。结果表明,和相应的离子液体及杂多酸相比,杂化材料的催化活性得到了很大的提高,尤其是催化剂[C₄mim]₅PMo₁₀V₂O₄₀,在优化后的条件下,苯的转化率可达到21%,苯酚的选择性在99%以上。而且,该催化剂具有很好的可重复使用性,连续使用五次后,苯的转化率和苯酚的选择性没有明显降低。     

A spectroscopic study on the 12-heteropolyacids of molybdenum and tungsten (H3PMo12−nWnO40) combined with cetylpyridinium bromide in the epoxidation of cyclopentene

The epoxidation of cyclopentene with hydrogen peroxide catalyzed by 12-heteropolyacids of molybdenum and tungsten (H₃PMo_12−nW_nO₄₀, n = 1–11), 12-tungstophosphoric acid and 12-molybdophosphoric acid combined with cetylpyridinium bromide as a phase transfer reagent was carried out in acetonitrile. Among 13 heteropolyacids investigated, catalyst of H₃PMo₆W₆O₄₀ showed the highest activity, giving a conversion of 60% and a selectivity of 95% in the epoxidation of cyclopentene. The fresh catalysts and the catalysts under reaction condition were characterized by UV–vis, FT-IR and ³¹P NMR spectroscopy, which has revealed that all of the molybdotungstophosphoric acids were degraded in the presence of hydrogen peroxide to form a considerable amount of phosphorus-containing species. The active species resulted from H₃PMo₆W₆O₄₀ are new kinds of phosphorus-containing species, which is different from {PO₄[WO(O₂)₂]₄}³⁻.     

H3PMo12O40-catalyzed coupling of diarylmethanols with epoxides/ diols/aldehydes toward polyaryl-substituted aldehydes

A versatile heteropoly acid (H₃PMo₁₂O₄₀)-catalyzed coupling of diarylmethanols with epoxides was established for the synthesis of polyaryl-substituted aldehydes. Furthermore, the catalytic system was also suitable for the reaction of diarylmethanols and diols/aldehydes. The application of such an earthabundant, readily accessible, and nontoxic catalyst provides a green approach for the construction of polyaryl-substituted aldehydes.     

基于2-氨基吡啶的两个簇基超分子化合物的合成、 结构及催化性能

以磷钼酸、 2-氨基吡啶、 五氧化二钒、 氯化锌和氯化镍等为主要原料, 采用水热方法合成了2个簇基超分子化合物[H₃PMo₁₂O₄₀]₂[C₅H₆N₂]₆(1)和[H₂PMo₁₂V₂O₄₂][C₅H₆N₂]₅·3H₂O(2)(C₅H₆N₂=2-氨基吡啶). 通过元素分析、 红外光谱、 紫外-可见光谱、 X射线光电子能谱、 热重分析、 X射线单晶衍射及X射线粉末衍射等手段对化合物进行了结构表征. 结构分析显示, 簇单元不同的2个超分子化合物以各自独特的堆积方式形成三维超分子网络. 利用苯乙烯的环氧化反应研究了2个化合物的催化性能.     

Inhibitory effect of H_(3 + x)PMo_(12－x)V_xO_(40)-Ton the self-polymerization of methyl methacrylate

In this work,a series of molybdovanadophosphoric heteropoly acid quaternary ammonium salts H_(3+x)PMo_(12 -x)V_xO40-T were synthesized and employed as a reaction inhibitor in the selfpolymerization of methyl methacrylate(MMA).The polymerization inhibition effect of H_(3+x)PMoPMo_(12 -x)V_xO40-T)with different number of vanadium atoms and reaction dosages was investigated using differential scanning calorimetry(DSC).It shows that the inhibitory effect was improved with the increasing dosages of H_(3+x)PMoPMo_(12 -x)V_xO40-T),and the polymerization inhibition was also affected by the number of vanadium atoms in the H_(3+x)PMo_(12 -x)V_xO40-T .Furthermore,cyclic voltammograms(CV)was used to probe the mechanism of the inhibition reaction with H3+xPMo12xVxO40-T.The result of CV indicates that the inhibition reaction is an oxidation–reduction reaction.H_(3+x)PMo_(12 -x)V_xO40-T can react directly with the MMA monomer radicals,which eliminated the MMA monomers,and therefore the self-polymerization of the MMA can be effectively inhibited by H_(3+x)PMo_(12 -x)V_xO40-T.     

氨基醇杂多酸类离子液体催化环酮的Baeyer-Villiger氧化反应

合成了一系列氨基醇杂多酸类离子液体, 并将其用于催化环酮的Baeyer-Villiger氧化反应. 以2-庚基环戊酮为模板底物, H₂O₂为氧化剂, 探究了此类氨基醇杂多酸类离子液体的催化活性, 筛选出催化活性最高的催化剂为[Pro-ps]H₂PW₁₂O₄₀, 最佳反应条件: n(2-庚基环戊酮)∶n(催化剂)∶n(H₂O₂)=1∶0.03∶4, 反应温度40 ℃, 反应时间8 h, 无溶剂. 在最佳条件下, 2-庚基环戊酮的转化率为98.19%, 产物δ-十二内酯的选择性可达82.84%. 水相中的离子液体[Pro-ps]H₂PW₁₂O₄₀经干燥后可以重复使用. 经过5次循环使用后催化活性未见明显下降. [Pro-ps]H₂PW₁₂O₄₀还可用于催化其它多种环酮的Baeyer-Villiger氧化反应, 结果表明, 该催化剂具有良好的重复使用性和底物普适性.     

Design and synthesis of hybrid solids based on the tetravanadate core toward improved catalytic properties

Five inorganic–organic hybrid vanadates based on tetravanadate cores, transition metals and N-donor ligands have been designed and synthesized under hydrothermal conditions, namely, [Zn(eIM)_3]_2V_4O_(12)(1), [Zn(pIM)_3]_2V_4O_(12)H_2O(2), [Zn(ipIM)_3]_2V_4O_(12)(3), [Co(e IM)_3]_2V_4O_(12)H_2O(4), [Cu(eIM)_2(H+2O)]_2V_4O_(12)(_5)(eIM = 1-ethylimidazole, p IM = 1-propylimidazole, ip IM = isopropylimidazole). All compounds were fully characterized by single-crystal XRD, powder XRD, elemental analysis, TGA, and FT-IR spectroscopy.The hybrid zinc vanadates(1–3) and cobalt vanadate(4) exhibit interesting 2D folded structures and the hybrid copper vanadate(5) presents a 1D chain configuration. All compounds can catalyze olefin epoxidation reactions when using TBHP(TBHP = tert-butyl hydroperoxide) as an oxidant in acetonitrile.The introduction of transition metal ions into tetravanadate cores not only improved the catalytic activity but also fulfilled the heterogeneous catalytic behavior. 1–5 all exhibit extraordinary efficiency in converting olefins to the corresponding epoxides with high conversion and selectivity(particularly,conv. up to 97.1%, sele. up to 100% for 1). Leaching test was also carried out to prove the heterogeneous behavior.     

SiO_2负载磷钨钒杂多酸杂化材料的制备及其氧化脱硫性能的研究

利用磷酸氢二钠、偏钒酸纳和钨酸钠为原料,合成了具有Keggin结构的磷钨钒杂多化合物(H5PW10V2O40),并与1-丁基-3-甲基咪唑溴(BmimBr)离子液体反应生成一种杂多酸杂化材料([Bmim]5PW10V2O40)。利用红外光谱(FT-IR)、X射线衍射光谱(XRD)和紫外可见光谱(UV-vis)对所合成的杂多酸杂化材料进行表征。结果表明,[Bmim]5PW10V2O40具有咪唑阳离子基团和Keggin型杂多阴离子基团的结构特征,并且两种基团之间存在相互作用。以SiO_2为载体制备负载型的杂多酸杂化材料催化剂[Bmim]5PW10V2O40/SiO_2,以H2O_2作为氧化剂,考察该催化剂对模拟油中DBT的氧化性能,并优化氧化反应条件,在反应温度40℃,O/S物质的量比为3.0的条件下,反应50min,模拟油品中的DBT的转化率可以达到100%。催化剂可以通过离心法分离,经过干燥之后,可以循环使用至少七次,而对DBT的氧化活性没有降低。     

一个钼钒二聚体簇合物的合成及其性能

以NH₄VO₃, H₃PMo₁₂O₄₀·xH₂O, Cu(NO₃)₂和哌嗪为主要原料,采用水热方法,合成了一个新的钼钒二聚体簇合物--(H₂NC₄H₈NH₂)₆［Mo^VI₁₆V^V₁₂P₂O₈₄］·5H₂O(1),其结构和性能经UV-Vis, IR, X-射线衍射、光电子能谱及热重分析表征。1属单斜晶系,P2(1)/c空间群, 晶胞参数a=20.450(4) , b=24.989(5) , c=20.450(4) , β=93.89 °, V=10 427(4) ³, Fw=4 159.18, Dc=2.650 g·cm^-3, μ=3.018 mm^-1, F(000)=7 952, Gof=1.029。晶体结构解析表明：1由两个单元Keggin型簇核［PMo₈V₆O₄₂］^7-聚合而成一个二聚体簇［P₂Mo_l6V₁₂O₈₄］^14-,该二聚体簇核和有机配体哌嗪之间通过复杂的氢键相互作用,展示三维超分子网络结构。     

Keggin型杂多酸表面和体相的催化活性和选择性之差异的研究

本文以异丙醇脱水、甲醇转化等为模型反应,采用改变12-钨磷酸在载体SiO₂上担载量的办法,对Keggin型杂多酸催化剂进行了研究,结果表明:HPA的表面和体相酸中心,对于极性较大可进入其体相内部的异丙醇分子的脱水反应,在担载量为5×10^-5-1.5×10^-1molHPA/(dm)³SiO₂的范围内,具有相同的转化频率。HPA的表面和体相酸中心具有不同的催化选择性。     

Keggin结构稀土钼钒磷四元杂多配合物的合成、表征及苯酚羟化制苯二酚的催化活性

合成了5种通式为(NH₄)₁₅[RE(PMo₉V₂O₃₉)₂]·xH₂O(RE=La³⁺,Ce³⁺,Gd³⁺,Y³⁺,Yb³⁺)的稀土钼钒磷四元杂多配合物,并用IR,UV,XRD,ICP,TG-DTA和CV等手段对其结构和性能进行了表征.催化活性实验表明,标题化合物对苯酚过氧化氢羟化制苯二酚反应有良好的催化活性.     

Hydration and acetoxylation of dihydromyrcene catalyzed by heteropoly acid

The liquid-phase hydration and acetoxylation of the monoterpene dihydromyrcene (DHM, 3,7-dimethyl-1,6-octadiene) are efficiently catalyzed by Keggin-type heteropoly acid H₃PW₁₂O₄₀ (HPA) at 14–30°C to yield dihydromyrcenol (DHM---OH, 2,6-dimethyl-7-octen-2-ol) and dihydromyrcenyl acetate (DHM---OAc). Homogeneous, biphasic (DHM/AcOH-H₂O-HPA) and heterogeneous (with HPA/SiO₂ catalyst) reactions have been studied. HPA has a much higher catalytic activity than conventional acid catalysts such as H₂SO₄ and Amberlyst-15. A synthetically useful biphasic acetoxylation/hydration of DHM has been developed. The method provides a 90% selectivity to the sum of DHM---OH and DHM---OAc at 21% DHM conversion and allows for easy and clean catalyst recycling without loss of activity.     

Cu-V-O氧化物催化燃烧甲苯的活性和抗硫性

采用溶胶-凝胶法制备一系列不同Cu/V比例的Cu-V-O催化剂,利用XRD、BET、H₂-TPR等手段对催化剂进行了表征,并考察其催化燃烧甲苯的活性和抗硫性。结果表明,适量的Cu掺杂会提高催化剂比表面积,而且Cu-V可以形成Cu₃V₂O₈晶型结构,使V₂O₅晶格氧活动增加,提高催化剂氧化-还原能力。其中,Cu_0.15V_0.85催化剂表现出最佳的活性和抗硫性;通过TiO₂负载可以进一步提高催化剂对甲苯的催化燃烧活性和抗硫性。     

新型Brnsted-Lewis酸性催化剂LaPW_(12)O_(40)/SiO_2制备及其在催化酯化反应合成生物柴油中的应用

以十二磷钨杂多酸(Tungstophosphoric acid,H_3PW_(12)O_(40))为基体,分别通过普通浸渍法、溶胶凝胶法和超声浸渍法进行了La3+改性作用,合成了三种固体酸催化剂A-LaPW_(12)O_(40)、B-LaPW_(12)O_(40)/Si O2和C-LaPW_(12)O_(40)。采用X射线荧光光谱(XRF)、孔径比表面积测定、X射线粉末衍射(XRD)、透射电镜(TEM)、红外光谱(FT-IR)、热重(TG)、N2吸附-脱附、NH3程序升温脱附(NH3-TPD)、吡啶吸附红外光谱(Py-FTIR)、X射线光电子能谱(XPS)等方法对合成的催化剂进行了表征,并比较了以上催化剂在用于催化以油酸和甲醇为反应物经酯化反应合成生物柴油时的活性和稳定性。结果表明,B-LaPW_(12)O_(40)/Si O2具有最高催化活性,当甲醇与油酸的物质的量比为8∶1,催化剂用量为反应物总质量的2%,反应温度为65℃,反应1 h后,油酸的转化率即高达93%。循环使用B-LaPW_(12)O_(40)/Si O2催化剂六次后,油酸的转化率仍高达86.4%。B-LaPW_(12)O_(40)/Si O2的高催化活性和稳定性可归因于在溶胶凝胶的转化过程中,作为硅源材料的四乙氧基硅(TEOS)易在酸性条件下发生水解反应形成Si O2网络,进而Si O2网络中的硅醇键与H_3PW_(12)O_(40)中的H+发生配位作用,生成具有强静电吸附力的(≡Si-OH2+)(H2PW12O-40)络合物。随着该络合物的形成,促进了La3+在Si O2表面的吸附而堵塞了H_3PW_(12)O_(40)的孔道结构,抑制了H_3PW_(12)O_(40)颗粒在焙烧过程中进一步聚集长大。Si O2将作为载体并以干凝胶状态存在于B-LaPW_(12)O_(40)/Si O2催化剂中,由于Si O2凝胶的高比表面积而使B-LaPW_(12)O_(40)/Si O2具有了较大的比表面积,从H_3PW_(12)O_(40)的1.4 m2/g增加至31.3 m2/g。并且,通过吡啶吸附红外光谱确定B-LaPW_(12)O_(40)/Si O2为Br9nsted-Lewis酸型固体酸,由于Br9nsted酸位易与酯化反应过程中生成的水发生水合反应而失活,因而Lewis酸位的形成有助于减少催化剂的失活现象发生。Lewis酸位的出现可归因于(≡Si-OH2+)(H2PW12O-40)与吸附在其表面的具有强吸电子作用的La3+发生键合作用后生成了LaPW_(12)O_(40)/Si O2。     

Anaerobic oxidation of isobutane: Catalytic properties of MgV2O6 and Mg2V2O7 prepared by the molten method

The catalytic activity of MV₂O₆ and M₂V₂O₇ type oxides prepared by the molten method (MM) for anaerobic oxidation of isobutane was studied in order to construct a system for the selective oxidation of isobutene using a thin layer reactor. Isobutene, CO and CO₂ were formed by every catalyst tested. The activities for isobutene formation were CuV₂O₆ > ZnV₂O₆, NiV₂O₆, CoV₂O₆ > MgV₂O₆ > MnV₂O₆  CaV₂O₆. Isobutene was a major product over M₂V₂O₇ (MM). Co₂V₂O₇ showed the highest activity and high isobutene selectivity exceeded 90%, demonstrating that Co₂V₂O₇ is a suitable oxide for a thin layer reactor for anaerobic oxidation of isobutane. Partial substitution of Mg by Cu in Mg₂V₂O₇ (MM) improved the activity. It is shown by the oxidation at low O₂ concentration as 2–3% that two types of oxidations occurred simultaneously: isobutene formation by the lattice oxygen ions diffused from the bulk, and CO and CO₂ formation by the oxygen species derived from molecular oxygen in the gas phase.     

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.     

Catalysis by hetropoly compounds. Part XXVI. Gas phase synthesis of methyl tert-butyl ether over heteropolyacids

Gas phase synthesis of methyl tert-butyl ether (MTBE) from methanol and isobutylene has been studied with several heteropolyacids at 303–383 K. It was found that a Dawson-type heteropolyacid, H₆P₂W₁₈O₆₂, was much active than Keggin-type heteropolyacids, H_nXW₁₂O₄₀ (X = P, Si, Ge, B, and Co), and other solid acids such as SO²⁻₄/ZrO₂, SiO---Al₂O₃ and H-ZSM-5 at 323 K. Since the acid strength of H₆P₂W₁₈O₆₂ was weaker than H₃PW₁₂O₄₀ and H₄SiW₁₂O₄₀, factors other than the acid strength are important for the catalytic activity. Pseudoliquid phase behavior was demonstrated for H₆P₂W₁₈O₆₂ and H₃PW₁₂O₄₀ by the measurements of the absorption of methanol during the reaction and by the unique pressure dependencies of the rate of synthesis. From the absorption data (the amount and rate), it is concluded that the high catalytic activity of H₆P₂W₁₈O₆₂ is brought about by a high-activity state of the pseudoliquid phase in which controlled amounts of molecule are absorbed and the absorption-desorption is rapid. On the other hand, the pseudoliquid phase of H₃PW₁₂O₄₀ is in a low-activity state absorbing excessive amounts of molecule.     

钒取代的Dawson型磷钼酸对酪氨酸酶的抑制作用

采用酶动力学方法研究了5种钒取代的Dawson型磷钼酸H₇[P₂Mo₁₇VO₆₂]、H₈[P₂Mo₁₆V₂O₆₂]、H₉[P₂Mo₁₅V₃O₆₂]、H₈[P₂Mo₁₄V₄O₆₂H₂]和H₉[P₂Mo₁₃V₅O₆₂H₂](分别简写为P₂Mo₁₇V、P₂Mo₁₆V₂、P₂Mo₁₅V₃、P₂Mo₁₄V₄和P₂Mo₁₃V₅)对蘑菇酪氨酸酶二酚酶的抑制作用,结果表明,效应物P₂Mo₁₇V、P₂Mo₁₆V₂和P₂Mo₁₅V₃能够明显地抑制酪氨酸酶的活性,其半抑制浓度(IC₅₀)值分别为0.409、0.386和0.386 mmol/L,且均表现为可逆的竞争型抑制,效应物P₂Mo₁₇V、P₂Mo₁₆V₂和P₂Mo₁₅V₃对游离酶的抑制常数K_I分别为0.234、0.391和0.249 mmol/L。 而效应物P₂Mo₁₄V₄在0~1.0 mmol/L浓度范围内,对酪氨酸酶二酚酶无明显抑制作用,效应物P₂Mo₁₃V₅对酪氨酸酶二酚酶表现为激活作用。     

具有吸附-分解NOx功能的多酸催化新体系研究

采用乙醚萃取法、浸渍法制备了具有吸附-分解NO_x功能的多酸催化新体系,并对其进行了IR、XRD、TEM表征,在固定床催化反应器中考察了体系对NO_x的吸附与分解性能。结果表明,钨系杂多酸优于钼系,H₃PMo_12-xW_xO₄₀（x=1、3、6、12）随着取代钼的钨原子数目增多,对NO_x的吸附能力增强;二氧化钛、碳纳米管均为磷钨酸（HPW）的优良载体,后者对体系有明显的增效作用;TiO₂经500℃煅烧后,以磷钨酸水溶液为浸渍剂,HPW负载量为20%时,制得的HPW/TiO₂体系的脱硝性能最佳,对NO_x的吸附率可达62.8%;混酸（V_HNO3∶ V_H2SO4=1∶3）能在碳纳米管上引入含氧基团使其在水中的分散性能增强,以水为浸渍溶剂、混酸改性后的碳纳米管为载体制得的HPW/CNT催化体系优于乙醇为浸渍溶剂制备的该催化体系,当HPW负载量为70%时,前者对NO_x的吸附率可达73.5%。通过GC-MS检测确认了吸附质催化分解为N₂的有效性。     

室温固相反应制备Keggin结构杂多酸铵盐纳米粒子

纳米材料由于其量子尺寸效应及表面效应而在磁、光、电等方面显示出许多常规粒子所不具有的特性[1] .纳米材料成功应用的实例及潜在应用前景推动了各种纳米粉末的合成及合成方法的发展 [2～ 4 ] .利用低温固相反应制备纳米粒子尚不多见 ,但已有报道 [5,6] .多金属氧酸盐因其独特的结构而具有较高的催化活性、导电性、磁性、光电致变色性以及抗病毒活性 ,因而有着广阔的应用前景 ,这些方面的研究已越来越引起人们的兴趣 [7～ 10 ] .本文采用室温固相反应首次制备了多金属氧酸盐纳米粒子 (NH4 ) 3PMo12 O4 0 · 9H2 O(1 )和 (NH4 ) 3PW12…