CN107188241B - 一种Evans-Showell型多酸与碱土金属的化合物及其制备方法与催化应用 - Google Patents
一种Evans-Showell型多酸与碱土金属的化合物及其制备方法与催化应用 Download PDFInfo
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- 229910052784 alkaline earth metal Inorganic materials 0.000 title claims abstract description 17
- 150000001342 alkaline earth metals Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title abstract description 10
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 14
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910001422 barium ion Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 229940125904 compound 1 Drugs 0.000 claims description 5
- 229940125782 compound 2 Drugs 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 229910001427 strontium ion Inorganic materials 0.000 claims description 5
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
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- 238000002156 mixing Methods 0.000 claims description 2
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- 150000002500 ions Chemical class 0.000 claims 2
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- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 21
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- 239000010703 silicon Substances 0.000 abstract description 21
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000001299 aldehydes Chemical class 0.000 description 13
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- 238000007333 cyanation reaction Methods 0.000 description 7
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- 238000000034 method Methods 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- -1 rare earth ion Chemical class 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000003934 aromatic aldehydes Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/66—Cobaltates containing alkaline earth metals, e.g. SrCoO3
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- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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Abstract
一种Evans‑Showell型多酸与碱土金属的化合物及其制备方法与催化应用,属于多酸化学新材料技术领域。3D结构多酸化合物为单斜晶系,空间群为Cc;化合物1晶胞参数为β=125.6870(10)°;化合物2晶胞参数为 β=104.486(2)°;本发明采用(NH4)6[Co2Mo10H4O38]多酸和硝酸锶或硝酸钡为原料,原料价格低廉,合成产率较高,具有较好的催化醛的硅氰化性能;制备工艺简单、产品纯度高,具有潜在催化应用前景。
Description
技术领域
本发明属于多酸化学新材料技术领域,具体涉及一种Evans-Showell型多酸与碱土金属形成的3D结构化合物,该化合物的制备方法及其催化应用。
背景技术
多金属氧酸盐简称多酸是由前过渡金属离子(MoⅥ,WⅥ,VⅤ,NbⅤ及TaⅤ等)与氧原子按照一定的结构配位形成的多核配合物。因其具有较高的热稳定性、氧化还原性、溶解性和酸碱性等,这使得人们投入大量的精力研究其在催化、光学、药学等方面的应用(K.Kamata,K.Yonehara,Y.Sumida,K.Yamaguchi,S.Hikichi,N.Mizuno.Science.,2003,300,964-966;J.T.Rhule,C.L.Hill.D.A.Judd.Chem.Rev.,1998,98,327–358)。迄今为止,多酸的合成研究已将近200年的历史,而3D结构多酸的研究则相对较少,尤其是纯无机元素构筑的3D骨架。因此,选择合适的多酸和金属结点来合成3D多酸无机功能材料是一个十分具有挑战性的课题。
Evans-Showell型多酸[Co2Mo10H4O38]6-具有两个端氧,这有利于增强它与金属离子的配位能力,而且基于[Co2Mo10H4O38]6-多酸的3D骨架材料目前只有一例报道[Ln(H2O)7][Ln(H2O)5][Co2Mo10H4O38]·5H2O(Ln=Gd,Tb)。碱土金属离子不仅拥有与稀土离子相近的半径和配位点,而且还在催化、激光和荧光等方面有潜在的应用(B.L.Fei,W.Li,J.H.Wang,Q.B.Liu,J.Y.Long,Y.G.Li,K.Z.Shao,Z.M.Su and W.Y.Sun,Dalton Trans.,2014,T.T.Basiev,A.A.Sobol,Y.K.Voronko.Opt Mater.,2000,15,205-216;S.B.Mikhrin,A.N.Mishin,A.S.Potapov.Nucl Instrum Methods Phys Res,Sect A.,2002,486,295-297;E.Guermen,E.Daniels,J.S.King.J.Chem.Phys.,1971,55,1093–1097)。但由于碱土金属与多酸在溶液中易形成沉淀导致关于碱土金属与多酸结合形成的化合物报道较少。因此,基于[Co2Mo10H4O38]6-多酸与碱土金属离子的3D无机框架材料的合成面临更多的困难与机遇。
多酸作为一类高效的催化剂,在有机合成领域具有诱人的应用前景。氰醇是合成多官能基化合物的重要中间体,而醛的硅腈化反应是获取氰醇最简单有效的途径。多酸化合物催化醛的硅腈化反应方面的应用追溯到2012年Mizuno课题组报道了双核夹心型稀土-多酸化合物[{Y(H2O)2}2(α-SiW10O36)2]10-作为均相催化剂,催化苯甲醛的硅腈化,反应15min后,反应产率高达94%。随后几年人们相继报道了几例具有催化硅腈化反应性质的多酸,如:[{Ln(H2O)2(acetone)}2(α-SiW10O36)2]10-(Ln=Y3+,Nd3+,Eu3+,Gd3+,Tb3+,or Dy3+),{[Cu2(bpy)(H2O)5.5]2[H2W11O38]3H2O·0.5CH3CN}等等(Y.J.Kikukawa,K.Suzuki,M.Sugawa,T.Hirano,K.Kamata,K.Yamaguchi,and N.Mizuno.Angew.Chem.Int.Ed.,2012,51,3686–3690;K.Suzuki,M.Sugawa,Y.Kikukawa,K.Kamata,K.Yamaguchi andN.Mizuno.Inorg.Chem.,2012,51,6953;X.Han,X.P.Sun,J.Li,P.T.Ma and J.Y.Niu,Inorg.Chem.,2014,53,6107;T.P.Hu,Y.Q.Zhao,Z.K.Yu,X.P.Wang,andD.Sun.Inorg.Chem.,2015,54,7415-7423)。目前在多酸催化醛的硅氰化反应的研究方面,主要选用多酸与稀土或过渡金属结合形成的化合物作为催化剂,而采用碱土金属阳离子与多酸结合构筑用于催化醛的硅腈化反应的催化剂至今未见报道。因此,设计合成基于碱土金属离子与Evans-Showell多酸的3D物种,不仅将丰富多酸的结构化学,而且其将具有较好的硅腈化催化作用,是一项挑战性大但具实际应用价值的课题。
发明内容
本发明的目的在于合成一种基于Evans-Showell多酸与碱土金属离子的3D结构化合物,同时提供该化合物的制备方法和催化应用
本发明的技术方案:
一种Evans-Showell型多酸与碱土金属的化合物,所述的化合物包括化合物1和化合物2,其化学式为(C2N2H10)2[Sr(H2O)5][Co2Mo10H4O38]·2H2O或(C2N2H10)2[Ba(H2O)3][Co2Mo10H4O38]·3H2O,该化合物为单斜晶系,空间群为Cc;化合物1的晶胞参数为β=125.6870(10)°;化合物2的晶胞参数为 β=104.486(2)°;
所述的化合物的结构:在不对称单元中存在一个晶体学独立的[Co2Mo10H4O38]6-多酸阴离子、两个质子化的乙二胺和一个碱土金属锶离子或钡离子;所述的锶离子采用八配位的双帽三棱柱构型,所述的钡离子采用七配位的单帽三棱柱构型;首先[Co2Mo10H4O38]6-多酸阴离子通过Sr-O-Mo或Ba-O-Mo形成1D链状结构,1D链状结构间通过Sr-O-Mo或Ba-O-Mo形成2D网状结构,2D网状结构又通过Sr-O-Mo或Ba-O-Mo形成3D框架结构;从拓扑学角度来看每一个[Co2Mo10H4O38]6-与三个锶或钡相连,每一个锶或钡也同时与三个[Co2Mo10H4O38]6-结构单元相连,整个化合物结构看做是具有103拓扑的网络结构,进一步沿b轴观察拓扑结构,该化合物是由左手与右手两种1D螺旋手性链构成。
一种Evans-Showell型多酸与碱土金属的化合物的制备方法,采用常规水溶液的制备方法,步骤如下:
将(NH4)6[Co2Mo10H4O38]和硝酸锶混合,待溶解,先加入乙二胺,再用HCl调节PH=2.5-4.0,其中,(NH4)6[Co2Mo10H4O38]、硝酸锶和乙二胺的物质的量之比为1:2-1.5:0.015,室温搅拌,然后在75-85℃条件下回流8-14h,溶液冷却后过滤,放置至晶体生成,晶体经洗涤和干燥,即得多酸材料。
所述的硝酸锶由硝酸钡替换。
一种Evans-Showell多酸与碱土金属的3D材料在催化醛的硅腈化反应中的应用,利用气相色谱仪,在无溶剂条件下测定本发明的3D多酸材料催化芳香醛与脂肪醛的硅氰化反应性能。结果表明,本发明利用碱土金属离子的Lewis酸和多酸阴离子的Lewis碱的协同作用较好地催化了各种醛的硅氰化反应,在催化苯甲醛的实验中,反应6小时,产率达到99%。因此,本发明Evans-Showell型多酸与碱土金属形成的3D结构化合物可以用作醛的硅氰化反应的催化材料。
本发明的有益效果:
(1)本发明提供的3D多酸化合物结构明确,为首例基于Evans-Showell多酸[Co2Mo10H4O38]6-和碱土金属的3D物种,同时该类物种显示出较好的催化芳香醛与脂肪醛的硅氰化反应性能,而这也是首例由多酸与碱土金属形成的化合物进行的硅氰化催化性质研究。基于本发明的3D多酸材料能较好地催化醛的硅氰化反应,因此本发明在催化方面有潜在的应用前景。
(2)本发明的3D多酸材料在硅氰化反应中作为多相催化剂,具有易回收和多次重复利用的优点。以催化反应结束后,过滤得到的固体粉末为催化剂,进行多次重复催化实验,催化结果表明反应产率无明显的降低。对重复利用的催化剂进行IR和XRD的表征,结果表明催化前后IR和XRD特征峰无明显变化,均证实该多酸材料为多相催化剂。
(3)本发明提供的3D多酸材料的方法策略为常规水溶液法,操作安全简单,原料成本较低,收率为62%。
附图说明
图1为本发明3D结构多酸化合物的不对称单元图,当连结点是锶离子为化合物1,当连结点是钡离子为化合物2。
图2为本发明多酸阴离子与碱土金属离子的3D结构图。
图3本发明实施例1所得的3D结构多酸化合物的拓扑结构图。
图4为本发明实施例1所得的3D结构多酸化合物的红外光谱图。
图5为本发明实施例1所得的3D结构多酸化合物的固体紫外图。
图6为本发明实施例1所得的3D结构多酸化合物的催化前后的红外对比图,a为实施例1的红外图,b为实施例1催化反应后的红外图。
图7为本发明实施例1所得的3D结构化合物的催化前后的X射线粉末衍射谱图。
具体实施方式
以下将通过具体实施例对本发明作进一步的详细说明,但此处只为解释本发明而非用于限定本发明。
实施例1 3D结构多酸化合物的制备包括以下步骤:
将0.0423g硝酸锶和0.2g(NH4)6[Co2Mo10H4O38]·7H2O溶于15ml水中搅拌,一滴乙二胺加入上述溶液,并用HCl调节PH=3.0,然后80℃回流12小时,冷却即得所需化合物。
将0.0523g硝酸钡和0.2g(NH4)6[Co2Mo10H4O38]·7H2O溶于15ml水中搅拌,一滴乙二胺加入上述溶液,并用HCl调节PH=3.0,然后80℃回流12小时,冷却即得所需化合物。
实施例2 3D结构多酸化合物的制备包括以下步骤:
将0.0423g,硝酸锶和0.2g(NH4)6[Co2Mo10H4O38]·7H2O溶于15ml水中搅拌,一滴乙二胺加入上述溶液,并用HCl调节PH=2.5,然后80℃回流12小时,冷却即得所需化合物。
将0.0523g硝酸钡和0.2g(NH4)6[Co2Mo10H4O38]·7H2O溶于15ml水中搅拌,一滴乙二胺加入上述溶液,并用HCl调节PH=2.5,然后80℃回流12小时,冷却即得所需化合物。
实施例3 3D结构多酸化合物的制备包括以下步骤:
将0.0317g,硝酸锶和0.2g(NH4)6[Co2Mo10H4O38]·7H2O溶于15ml水中搅拌,一滴乙二胺加入上述溶液,并用HCl调节PH=3.0,然后80℃回流12小时,冷却即得所需化合物。
将0.0392g硝酸钡和0.2g(NH4)6[Co2Mo10H4O38]·7H2O溶于15ml水中搅拌,一滴乙二胺加入上述溶液,并用HCl调节PH=3.0,然后80℃回流12小时,冷却即得所需化合物。
对上述实施例中的产物进行检测,得到化合物的化学式为(C2N2H10)2[Sr(H2O)5][Co2Mo10H4O38]·2H2O和(C2N2H10)2[Ba(H2O)3][Co2Mo10H4O38]·3H2O,本发明3D多酸化合物的晶体结构如图1,2和3。
利用红外光谱对实施例1中的产物进行检测,图4即为本发明3D多酸化合物的红外光谱图,显示出Mo-Ot、Mo-Ob和Mo-Oc及水分子和N-H的特征振动吸收峰。
利用固体紫外对实施例1中的产物进行检测,图5即为本发明3D多酸化合物的固体紫外光谱图,表明在紫外区224nm和305nm处有吸收峰可归属于O→Mo的电荷转移,可见光区441nm和607nm处吸收峰可归属于多酸阴离子中低自旋八面体配位的Co3+的1A1g→1T2g和1A1g→1T1g电子跃迁。
利用红外对实施例1中的化合物催化反应前后进行检测,图6即为本发明3D多酸化合物的催化反应前后的红外对比,特征峰位无明显变化表明实施例1为多相催化剂。
利用XRD对实施例1中的化合物催化反应前后进行检测,图7即为本发明3D多酸化合物的实验与拟合及反应后的XRD对比,表明实施例1为多相催化剂。
利用气相色谱仪,在无溶剂条件下测定本发明的3D多酸化合物催化芳香醛与脂肪醛的硅氰化反应性能。表1表明,本发明利用碱土金属离子的Lewis酸和多酸阴离子的Lewis碱的协同作用较好地催化了各种醛的硅氰化反应,在催化苯甲醛的实验中,反应6小时,产率达到99%。因此,本发明Evans-Showell型多酸与碱土金属形成的3D结构化合物可以用作醛的硅氰化反应的催化材料。表2表明,本发明的催化剂进行催化反应后,可通过过滤回收该固体粉末催化剂,再进行两次重复催化实验后,催化结果表明反应产率无明显的降低,说明其为稳定的多相催化剂。
表1化合物1和2催化醛的硅腈化反应产率表
实验方法如下:无溶剂条件下,催化剂2mol%,醛0.5mmol,三甲基硅腈1.5mmol,氮气保护,室温(25℃)反应,气相色谱确定反应产率(萘内标)。
表2化合物1多相催化苯甲醛硅腈化反应重复利用三次效率表
Claims (4)
1.一种Evans-Showell型多酸与碱土金属的化合物,其特征在于,所述的化合物包括化合物1和化合物2,其化学式为(C2N2H10)2[Sr(H2O)5][Co2Mo10H4O38]·2H2O和(C2N2H10)2[Ba(H2O)3][Co2Mo10H4O38]·3H2O,该化合物为单斜晶系,空间群为Cc;化合物1的晶胞参数为β=125.6870(10)°;化合物2的晶胞参数为 β=104.486(2)°;
所述的化合物的结构:在不对称单元中存在一个晶体学独立的[Co2Mo10H4O38]6-多酸阴离子、两个质子化的乙二胺和一个碱土金属锶离子或钡离子;所述的锶离子采用八配位的双帽三棱柱构型,所述的钡离子采用七配位的单帽三棱柱构型;首先[Co2Mo10H4O38]6-多酸阴离子通过Sr-O-Mo或Ba-O-Mo形成1D链状结构,1D链状结构间通过Sr-O-Mo或Ba-O-Mo形成2D网状结构,2D网状结构又通过Sr-O-Mo或Ba-O-Mo形成3D框架结构;从拓扑学角度来看每一个[Co2Mo10H4O38]6-与三个锶或钡相连,每一个锶或钡也同时与三个[Co2Mo10H4O38]6-结构单元相连,整个化合物结构看做是具有103拓扑的网络结构,进一步沿b轴观察拓扑结构,该化合物是由左手与右手两种1D螺旋手性链构成。
2.一种Evans-Showell型多酸与碱土金属的化合物的制备方法,其特征在于,采用常规水溶液的制备方法,步骤如下:
将(NH4)6[Co2Mo10H4O38]和硝酸锶混合,待溶解,先加入乙二胺,再用HCl调节PH=2.5-4.0,其中,(NH4)6[Co2Mo10H4O38]、硝酸锶和乙二胺的物质的量之比为1:2-1.5:0.015,室温搅拌,然后在75-85℃条件下回流8-14h,溶液冷却后过滤,放置至晶体生成,晶体经洗涤和干燥,即得多酸材料。
3.根据权利要求2所述的制备方法,其特征在于,所述的硝酸锶由硝酸钡替换。
4.一种权利要求1所述的Evans-Showell型多酸与碱土金属的化合物在催化醛的硅氰化反应中的应用。
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Non-Patent Citations (3)
Title |
---|
3D Racemic Microporous Frameworks and 3D Chiral Supramolecular Architectures Based on Evans-Showell-Type Polyoxometalates Controlled by the Temperature;Haiyan An, et al.;《Crystal Growth & Design》;20141205;第15卷;164-175 * |
A new BEDT-TTF salt and polypyrrole films containing the chiral polyoxometalate [H4Co2Mo10O38]6-;E. Coronado, et al.;《Synthetic Metals》;20051231;第154卷;241-244 * |
Investigation of spillover effect in hydrotreating catalysts based on Co2Mo10-heteropolyanion and cobalt sulphide species;Al. A. Pimerzin, et al.;《Applied Catalysis B: Environmental》;20150109;第168-169卷;396-407 * |
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