固体杂多酸盐的催化性能Ⅲ．钼磷、钼硅杂多酸碱金属盐的合成、表征和催化酯化反应

合成了Ｈ３ＰＭｏ１２、Ｈ４ＳｉＭｏ１２杂多酸的一系列铯盐：ＣｓｘＨ３－ｘＰＭｏ１２Ｏ４０·ｍＨ２Ｏ（ｘ＝０￣３，ｍ＝４￣７），ＣｓｘＨ４－ｘＳｉＭｏ１２Ｏ４０·ｍＨ２Ｏ（ｘ＝０￣４，ｍ＝４￣７）。测定了它们的酸强度、ｐＨ滴定曲线、ＮＨ３－ＴＰＤ、ＩＲ光谱和比表面积。以乙酸和正丁醇的酯化为探针反应，考察了催化剂的酸催化活性。实验结果表明，杂多酸铯盐对乙酸和正丁醇的催化酯化活性只与总酸量有关，与表面积     

固体杂多酸盐的催化性能Ⅲ．钼磷、钼硅杂多酸碱金属盐的合成、表征和催化酯化反应

合成了Ｈ３ＰＭｏ１２、Ｈ４ＳｉＭｏ１２杂多酸的一系列铯盐：ＣｓｘＨ３－ｘＰＭｏ１２Ｏ４０·ｍＨ２Ｏ（ｘ＝０～３，ｍ＝４～７），ＣｓｘＨ４－ｘＳｉＭｏ１２Ｏ４０·ｍＨ２Ｏ（ｘ＝０～４，ｍ＝４～７）。测定了它们的酸强度、ｐＨ滴定曲线、ＮＨ３－ＴＰＤ、ＩＲ光谱和比表面积。以乙酸和正丁醇的酯化为探针反应，考察了催化剂的酸催化活性。实验结果表明，杂多酸铯盐对乙酸和正丁醇的催化酯化活性只与总酸量有关，与表面积无关，属假液相反应     

固体杂多酸盐催化性能 Ⅰ．钨磷、钨硅杂多酸碱金属盐的合成、表征和催化酯化反应

合成了ＨＰＷ１２、ＨＳｉＷ１２杂多酸的一系列铯盐：ＣｓｘＨ３－ｘＰＷ１２（ｘ＝０～３），ＣｓｘＨ４－ｘＳｉＷ１２（ｘ＝０～４）．测定了它们的酸强度、ｐＨ滴定曲线、ＮＨ３－ＴＰＤ、ＩＲ光谱和比表面积．以乙酸和正丁醇的酯化为探针反应，考察了催化剂的酸催化活性．实验发现，碱金属取代后，ＰＷ１２系列的多数催化剂的酸强度提高，而ＳｉＷ１２系列的则降低，但对同一系列来说，由ＮＨ３－ＴＰＤ测得的酸强度和酸量均随取代量增加而减小，ｐＨ滴定的结果与此类似，当ｘ＝２．５时，两系列催化剂的比表面积均存在一个极值．对乙酸和正丁醇的催化酯化活性只与总酸量有关，与表面积无关，属假液相反应．     

Cs_yP_（1．33）－kMo_（12）SblCu_mV_nAs_kO_x催化剂的研究

以共沉淀方法制备了杂多酸盐催化剂ＣｓｙＰ１．３３－ｋＭｏ１２ＳｂｌＣｕｍＶｎＡｓｋＯｘ．利用ＩＲ及ＳＥＭ研究了催化剂的结构，ＤＳＣ研究了催化剂的稳定性，ＥＳＲ研究了催化剂的氧化还原性，及ＮＨ３－ＴＰＤ研究了催化剂的酸性．同时考察了催化剂对异丁醛一步氧化制甲基丙烯酸的催化性能，并与催化剂的氧化还原性进行了关联．发现Ｃｓ１．５Ｐ１．１３Ｍｏ１２Ｓｂ０．２５Ｃｕ０．２５Ｖ０．２５Ａｓ０．２０Ｏｘ催化剂使异丁醛氧化的目的产物甲基丙烯酸收率最高，达７０．１％．     

铌和过氧铌取代Dawson结构钨磷杂多配合物的氧化还原性质研究

本文用电化学方法研究了铌和过氧铌一、三取代Ｄｗｓｏｎ结构杂多配合物：ａ２－ＭａＨｂＰ２Ｗ１５ＮｂＯ６２．ｘＨ２Ｏ，ａ－１，２，３－ＭａＨｂＰ２Ｗ１５Ｎｂ３Ｏ６２．ｘＨ２Ｏ，ａ２－ＭａＨｂＰ２Ｗ１７（ＮｂＯ２）Ｏ６１．ｘＨ２Ｏ，ａ－１，２，３－ＭａＨｂＰ２Ｗ１５（ＮｂＯ２）３Ｏ５９．ｘＨ２Ｏ（Ｍ＝Ｋ，ＴＭＡ，ＴＥＡ和ＴＢＡ）共十六种盐的氧化还原性质。     

金属键有机化合物的研究──非对称型η~5－取代环戊二烯基三羰基钼（钨）金属单键化合物的合成及表征

通过η５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭＮａ与η~５－Ｒ~２Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭＮａ（Ｍ＝Ｍｏ，Ｗ）以及η~５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭｏＮａ与η~５－Ｒ~２Ｃ＿５Ｈ＿４（ＣＯ）＿３ＷＮａ在Ｆｅ＿２（ＳＯ＿４）＿３醋酸水溶液作用下的交叉氧化偶联反应，合成了７个新的非对称型金属单键化合物η~５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）－３Ｍｏ─Ｍｏ（ＣＯ）＿３Ｃ＿５Ｈ＿４Ｒ~２－η~５（Ｒ~１，Ｒ~２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ），η５－Ｒ１Ｃ５Ｎ４（ＣＯ）３Ｗ─Ｗ（ＣＯ）３Ｃ５Ｈ４Ｒ２－η５（Ｒ１，Ｒ２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ；Ｈ，ＣＯ２Ｅｔ）和η５－Ｒ１Ｃ５Ｈ４（ＣＯ）３Ｍｏ─Ｗ（ＣＯ）３Ｃ５Ｈ４Ｒ２－η５（Ｒ１，Ｒ２：Ｃ（Ｏ）Ｍｅ，Ｈ；Ｅｔ，Ｃ（Ｏ）Ｍｅ；Ｃ（Ｏ）Ｍｅ，ｎ－Ｂｕ；ＣＯ２Ｍｅ，ｎ－Ｂｕ）．用Ｃ／Ｎ分析、ＩＲ、１ＨＮＭＲ和ＭＳ表征了它们的结构，并对该氧化偶联反应的特点进行了讨论．     

H3PMoxW12-xO40·nH2O和N-甲基吡咯烷酮电荷转移盐的合成、表征和非线性光学性质

由Ｈ３ＰＭｏｘＷ１２－ｘＯ４０．ｎＨ２Ｏ（ｘ＝０,１,３,９,１１,１２）和Ｎ－甲基吡咯烷酮合成了一系列分子组成为「ＮＭＰＨ」３ＰＭｏｘＷ１２－ｘＯ４０．ＣＨ３ＣＮ的电荷转移化合物,用元素分析,红外光谱进行了表征。结果表明,该系列化合物固体中阴离子和阳离子间存在强的相互作用;化合物在光照发生分子内电荷转移,导致阳离子氧化和阴离子还原;ＥＳＲ结果表明,阴离子还原处于单电子阶段,非线性光学性质研究表明,随化合物分子内钨取代数增多,化合物倍频效应增强;三阶非线性系数增大。     

THE REACTION OF（μ_3－CPh）Co_3（CO）_9 WITH TRANSITION METAL CARBONYL ANION M（CO）_3（RCOCp）AND CHARACTERIZATION OF CLUSTERS（μ_3－CPh）CO_2M（CO）_8（RCOCPp）（M＝Mo，W；R＝H，CH_3．C_2H_5O）

ＴＨＥＲＥＡＣＴＩＯＮＯＦ（μ_３－ＣＰｈ）Ｃｏ_３（ＣＯ）_９ＷＩＴＨ　ＴＲＡＮＳＩＴＩＯＮＭＥＴＡＬＣＡＲＢＯＮＹＬＡＮＩＯＮＭ（ＣＯ）_３（ＲＣＯＣｐ）ＡＮＤＣＨＡＲＡＣＴＥＲＩＺＡＴＩＯＮＯＦＣＬＵＳＴＥＲＳ（μ_３－ＣＰｈ）ＣＯ_２Ｍ（ＣＯ）_８（ＲＣＯＣＰｐ）（Ｍ＝Ｍｏ，Ｗ；Ｒ＝Ｈ，ＣＨ_３．Ｃ_２Ｈ_５Ｏ）Ａｕｔｈｏｒｔｏｗｈｏｍｃｏｒｍｓｐｏｎｄｅｎｃｅｓｈｏｕｌｄａｄｄｒｅｓｓｅｄ．ＥｘｐｅｒｉｍｅｎｔａｌｓｅｃｔｉｏｎＧｅｎｅｒａｌｐｒｏｃｅｄｕｒｅａｎｄｍａｔｅｒｉａｌＡｌｌｏｐｅｒａｔｉｏｎｗａｓｃａｒｒｉｅｄｏｕｔｕｎｄｅｒｈｉｇｈｌｙｐｕｒｅｎｉｔｒｏｇｅｎａｔｍｏｓｐｈｅｒｅｕｓｉｎｇｓｈａｄａｒｄＳｃｈｌｅｎｌｃａｎｄｖａｃｕｕｍｔｅｃｈｎｉｑｕｅｓ．Ｈｅ－ｃａｎｅ，ｂｅｎｚｅｎｅａｎｄｔｅｔｒａｈｙｄｒｏｆｕｒａｎｗｅｒｅｐｒｅｄｒｉｅｄｏｖｅｒｓｏｄｉｕｍｗｉｒｅａｎｄｄｉｓｔｉｌｌｅｄｆｒｏｍｓｏｄｉｕｍ－ｂｅｎｚｏｐｈｅｎｏｎｅｕｎｄｅｒｎｉｔｒｏｇｅｎ．ＮａＭ（ＣＯ）３（ＲＣＯＣＰ）ａｎｄＰｈＣＣｏ３（ＣＯ），ｗｅｒｅｐｒｅｐａｒｅｄａｃｃｏｒｄｉｎｇｔｏｌｉｔｅｒａｔＵｒｅ     

ADDITIVE EFFECT ON THE MI CELLE－CATAL TIC HYDROLYSIS OF CARBOXYLIC ACID ESTERS

ＡＤＤＩＴＩＶＥＥＦＦＥＣＴＯＮＴＨＥＭＩＣＥＬＬＥ－ＣＡＴＡＬＴＩＣＨＹＤＲＯＬＹＳＩＳＯＦＣＡＲＢＯＸＹＬＩＣＡＣＩＤＥＳＴＥＲＳｋＷａｎｄｈｏ：ｒａｔｅｃｏｎｓｔａｎｔｓｆｏｒｓｏｌｕｔｉｏｎｓｆｉｔｈａｎｄｆｉｔｈｏｕｔＣＴＡＢ（０．００４３８ｍｏｌｄｉｎ－．）．ＦＩｇ．Ｉｋｅｇｖｓ．ＣＯＴ￣ｎｆｏｒＮＰＰｉｎＦｉｇ．２ＥｆｆｅｃｔｏｆＮＨ３－ｂｕｆｆｅｒｕｐｏｎＮａＺＣＯ．－ＮａＨＣＯ３ｂｕｆｆｅｒｓｏｌｕｔｉｏｎｔｈｅｈｙｄｒｏｌｙｓｉｓｒａｔｅＯｆＮＰＰＴＩｐａｑｕｅｏｕｓｓｎｉｎｔｉｎｎｏｆ０．００４３８ｍｏ１ｄｉｎ－－３ＣＴＡＢｗａｓｕｓｅｄａｓｔｈｅｍｌｃｅｌＩａｒｓｏＩｌ］ｔＩｏｎｂｅｃａｕｓｅｉｔｉｓｔｈｅｓｉｔＩｕｔｉ（ＩｎｏｆｏｐｔｉｍｕｍｃａｔａｌｙｉＩｃｅｆｆｅｃｔｉｎｔｈｅＮａＺＣＯｇ－ＮａＨＣＯ３ｂｕｆｆｅｒ，ａｓｓｈｏｗｎｉｎＦｉｇ．１．Ｆｏｒｔｈｅｓａｍｅｅｓｔｅｒ．ＮＰＰ，ｋ．１＜ｋ．．ａｎｄＰＨ，ｒｅｐＨＺｗｌｏ，ａｎｄｋｏＺ＝Ｋｏ３ｂｕｔＰＨ：＞ｐｌｌ．．Ｔｈｅｓｅｕｎ－ｒｅａｓｏｎａｂｌｅｒｅｓｕｌｉｓｍａｙｂｅｄｌｌｅｔｏｔｈｅｓｌｍｌＪＩｔａｎｅｏｕｓａｍ     

BaCe1—xRExO3—0.5x的溶胶—凝胶法合成及离子导电性

用溶胶－凝胶法合成了系列钙钛矿结构的ＢａＣｅ１－ｘＲＥｘＯ３－０．５ｘ（ＲＥ＝Ｌａ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｄｙ，Ｈｏ，Ｅｒ和Ｙ）复合氧化物，通过ＸＲＤ和热分析对样品结构及生成过程进行了研究．测定了不同温度下样品的交流阻抗谱，讨论了稀土离子掺杂对ＢａＣｅＯ３电性质的影响．溶胶－凝胶法比固相反应法合成温度降低了６００～８００℃，稀土掺杂使ＢａＣｅＯ３离子导电率提高了１０～４０倍．     

Effects of support pore size on new Cs_(2.5)H_(0.5)PW_(12)O_(40)/SiO_2 catalysts for the ring-opening polymerization of tetrahydrofuran

Mesoporous silica supported Cs_(2.5)H_(0.5)PW_(12)O_(40) catalysts were prepared by impregnation method,and several silica supports with different pore size were utilized.N_2 adsorption,XRD and ICP-AES techniques were utilized to characterize the silica supports and catalysts.XRD results showed that the dispersion of Cs_(2.5)H_(0.5)PW_(12) was better for the silica support with larger pore size.The catalytic activity results showed that the pore size played important role on the catalyst activity and the...     

GaxCs2.5-3xH0.5PW12O40的固相法制备及其催化正丁烷异构化反应的活性

利用室温固相法制备了一系列掺镓的钨磷酸铯盐催化剂GaxCs2.5-3xH0.5PW12O40(x=0.05,0.1,0.15).与钨磷酸铯盐相比,掺镓的钨磷酸铯盐催化剂的结构未产生变化,但其酸强度提高,在正丁烷异构化反应中催化活性增强,其中以Ga0.1Cs2.2H0.5PW12O40和Ga0.15Cs2.05H0.5P...     

12-Tungstophosphates I-mmobilized on Chemically Modified Mesoporous Silica SBA-15

A functionalized material. PW/SBA-15m, was prepared successfully in diluted H2SO4 aqueous solutions by immobilizing 12-tungstophosphates on chemically modified mesoporous silica SBA-15 and characterized by elemental analysis, FTIR, ^31p MAS NMR, XRD and TEM. The results indicate that the framework of SBA-15 and the Keggin structure of PW12O40^3- were retained, and that 23%-33% (mass fraction) of PW12O40^3- wasimmobilized; the PW12O40^3- anions were finely dispersed on the pore wall of SBA-15. Having been leached in ethanol at 60 ℃ for 7 h, the loss of PW12O40^3- anions was not found.     

Selective conversion of cellobiose and cellulose into gluconic acid in water in the presence of oxygen, catalyzed by polyoxometalate-supported gold nanoparticles

Gold nanoparticles loaded onto Keggin-type insoluble polyoxometalates (Cs(x)H(3-x)PW(12)O(40)) showed superior catalytic performances for the direct conversion of cellobiose into gluconic acid in water in the presence of O(2). The selectivity of Au/Cs(x)H(3-x)PW(12)O(40) for gluconic acid was significantly higher than those of Au catalysts loaded onto typical metal oxides (e.g., SiO(2), Al(2)O(3), and TiO(2)), carbon nanotubes, and zeolites (H-ZSM-5 and HY). The acidity of polyoxometalates and the mean-size of the Au nanoparticles were the key factors in the catalytic conversion of cellobiose into gluconic acid. The stronger acidity of polyoxometalates not only favored the conversion of cellobiose but also resulted in higher selectivity of gluconic acid by facilitating desorption and inhibiting its further degradation. On the other hand, the smaller Au nanoparticles accelerated the oxidation of glucose (an intermediate) into gluconic acid, thereby leading to increases both in the conversion of cellobiose and in the selectivity of gluconic acid. The Au/Cs(x)H(3-x)PW(12)O(40) system also catalyzed the conversion of cellulose into gluconic acid with good efficiency, but it could not be used repeatedly owing to the leaching of a H(+)-rich hydrophilic moiety over long-term hydrothermal reactions. We have demonstrated that the combination of H(3)PW(12)O(40) and Au/Cs(3.0)PW(12)O(40) afforded excellent yields of gluconic acid (about 85%, 418 K, 11 h), and the deactivation of the recovered H(3)PW(12)O(40)-Au/Cs(3.0)PW(12)O(40) catalyst was not serious during repeated use.     

孔道结构H3PW12O40/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-凝胶方法制备了孔道结构复合材料H3PW12O40/TiO2,采用ICP-AES,UV/DRS,31P MAS 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40 nm,具有双孔结构,其平均微孔和介孔孔径分别为0.61和3.06 nm. 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H3PW12O40/TiO2,Degussa P-25和锐钛矿结构TiO2的可见光光催化活性,其中,H3PW12O40/TiO2活性最高,且催化剂最易分离,可循环使用.     

在温和条件下合成金属有机骨架与多酸复合材料及其性能研究

本文利用机械球磨法成功将三种多金属氧簇H3PW12O40、H4SiW12O40和H3PMo12O40负载入ZIF-8纳米晶材料中,并采用粉末衍射(PXRD)、紫外可见吸收光谱(UV-Vis)、傅里叶-红外光谱(FT-IR)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等测试方法对复合材料进行了一系列表征.结果表明,复合材料结构稳定,合成方法具有操作简单、反应时间短、产量高等特点.此外,得到的复合材料对重金属离子Cu2+、Pd2+和Cd2+等均表现出良好的吸附性能.     

孔结构对活性炭吸附水溶液中铅离子的影响

选取三种表面化学性质相近的活性炭(AC),通过等温吸附实验考察活性炭对水溶液中铅离子的吸附性能,利用扫描电子显微镜(SEM)观察活性炭的表面微观形貌,通过低温(77 K)液氮吸附测定活性炭的比表面积和孔容,并分别以密度泛函理论(DFT)和Barrett-Joyner-Halenda (BJH)法计算微孔和中孔的孔径分布.结果表明:选用的三种活性炭AC1、AC2、AC3在比表面积和总孔容上呈依次下降的趋势,但表面开放孔均匀分布的AC2,具有最高的饱和吸附量,孔结构类似颗粒堆积孔的AC3,具有与表面开放孔分布集中的AC1相近的饱和吸附量;通过对孔结构与吸附量的关联分析可知,在活性炭吸附铅离子的过程中, 0.4-0.6 nm的孔是有效吸附孔, 10.5-20.6 nm、20.6-55.6 nm、5.2-10.5 nm三个区间的孔则会对吸附产生阻碍作用.     

Phenylimido Functionalization of alpha-[PW12O40]3-

A synthetic route of potentially wide scope is reported herein for the organoimido functionalization of polyoxotungstates. This report focuses on the reaction between the monovacant lacunary polyoxotungstate, alpha-((n-C4H9)4N)4H3[PW11O39], and W(NC6H5)Cl4 in anhydrous acetonitrile. Evidence from 1H, 31P, 183W, and 1H-183W HMQC NMR spectroscopy, as well as cyclic voltammetry, electronic absorption, and elemental analysis, is presented for the formation of alpha-[PW12O39(NC6H5)]3- (2) of Cs symmetry, which is structurally related to Td alpha-[PW12O40]3- (3) by formal oxide substitution. The electronic structure of 2 is significantly perturbed from 3 with significant arylimido-->tungsten charge transfer, primarily localized to the W(NC6H5) fragment with secondary charge delocalization onto the remaining W and corner-shared bridging O atoms. This is consistent with the approximately 800 ppm downfield 183W NMR shift for the phenylimido-tungsten, modest cathodic shifts in reversible redox potentials, electronic and IR spectra, and density functional theory calculations.     

Synthesis and Some Properties of Tungstophosphatozincates and Their Thermolysis Products

Russian Journal of General Chemistry - Tungstophosphatozincates with the Keggin anion structure Kt5[PW11O39Zn(H2O)]?nH2O, Kt = Rb+, Cs+, (CH3)4N+; (C2H5)4N+ were synthesized. Their...     

微孔多酸CsxH5-xPW10V2O40/SiO2的制备及氧化催化作用

Keggin结构杂多酸在固相体系中的催化作用引起了人们的极大兴趣[1～3].性能稳定的杂多酸铯盐催化剂在非均相催化体系中已有广泛的应用,然而由于其在液固体系中通常呈现牛奶状,难以分离和重新使用,尽管化学家们以各种材料作为这些催化剂的载体进行了许多固载化尝试[4～6],但至今尚未从根本上解决这一难题.因此,开发高比表面的耐水微孔固体杂多酸催化剂是多酸催化化学领域中具有理论和实际意义的课题.本文采用Sol-Gel技术,以正硅酸乙酯(TEOS)为硅源,水解产生的具有网络结构的SiO2凝胶为载体,在钒取代型Keggin结构杂多酸CsxH5-xPW10V2O40存在下,制得通式为CsxH5-xPW10V2O40/SiO2的固体双功能微孔杂多酸; 以30%H2O2为氧化剂,以苯甲醇氧化为模型反应,研究其液-固体系中的催化作用.