过渡金属修饰的磷钼氧簇合物的合成及催化活性研究
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摘要
多金属氧酸盐杂化材料具有富氧表面和多样的拓扑结构,在催化科学、磁学研究和材料科学等领域有着广泛的应用前景。利用过渡金属离子修饰多金属氧簇阴离子,进而获得具有独特结构和优异性能的晶体材料是当前多金属氧酸盐研究领域的热点之一。本论文在水热条件下,设计合成了七种过渡金属修饰的磷钼氧酸盐。利用元素分析、红外光谱、紫外-可见漫反射光谱、光电子能谱和X-射线单晶衍射等分析手段对所合成的晶体材料进行了结构表征;研究了晶体材料的热稳定性;以阿司匹林的合成为探针反应,详细研究了合成材料的催化性能。通过研究取得了如下结果:
通过对水热合成反应影响因素的研究,得出过渡金属修饰磷钼氧酸盐的合成工艺为:反应物浓度为0.1~0.5mol·L~(-1);反应温度为180℃;pH值范围为3.5~6.0;反应物中n(Mo): n(Metal)的比值为6.1~6.5。
利用元素分析和X-射线单晶衍射分析确定七种化合物的化学式分别为: (C_2N_2H_(10))_5[(P_4Mo_6O_(25)(OH)_6)_2Co] (1);(Co(H_2O)_6)_2(C_5NH_6)_6 [(P_4Mo_6O_(25_)(OH)_6)_2Co]·10H_2O (2);[H_2en]_3Na_4[Ni(H_2O)_3][H_30(MoV_(16)O_(32))Ni_(14)(PO_4)_(26)O_2(OH)_4(H_2O)_8]·8H_2O (3);(C_2N_2H_(10)) [HCo(H_2O)2P_2MoO_(10)] (4);(C_3N_2H_(12))_4[Co_3 [P_4Mo_6O_(26)(OH)_5]_2]·5H_2O (5);(C_2N_2H_(10))_4{Mn_3 [P_4Mo_6O_(26) (OH)_5]_2}·6H_2O (6);(C_2N_2H_(10))_4{Cd_3 [P_4Mo_6 O_(26) (OH)_5]_2}·6H_2O (7)。
X-射线单晶衍射分析表明:化合物1和2都是由[P_4Mo_6O_(31)]~(12-)与Co~(2+_结合而成的夹心型双聚体簇阴离子零维结构;化合物3是由双缺位轮型簇阴离子[H_(30)P_(26)Ni_(14)Mo_(16)O_(138)(OH)_4(H_2O)_8]~(12-)经[Ni(H_2O)3]~(2+)连接形成一维链状结构;化合物4和5分别是由[CoMoP_2]型和[Co(Mo_6P_4)_2]型簇阴离子形成二维层状结构;化合物6和7是同构化合物,都是由[M(Mo_6P_4)_2]型簇阴离子通过{MO6}八面体(M=Mn~(2+)或Cd~(2+))连接形成三维孔道结构。对七种化合物的晶体结构进行分析后发现,含氮有机配体的种类和过渡金属离子的核外电子构型共同决定着化合物的晶体结构类型。
热稳定性研究表明,七种晶体材料的簇阴离子结构在低于200℃的温度下均能稳定存在。催化合成阿司匹林的结果表明,所有化合物均具有较高的催化活性,均可再生、重复使用,其催化合成阿司匹林的工艺条件分别为:化合物1用量0.09g(质量分数3%),反应温度80℃,反应时间25min;化合物2用量0.06g(质量分数2%),反应温度80℃,反应时间20min;化合物3用量0.12g(质量分数4%),反应温度80℃,反应时间20min;化合物4用量0.06g(质量分数2%),反应温度80℃,反应时间30min;化合物5用量0.12g(质量分数4%),反应温度80℃,反应时间15min;化合物6用量0.09g(质量分数3%),反应温度80℃,反应时间25min;化合物7用量0.09g(质量分数3%),反应温度80℃,反应时间25min。同时,确定了反应的速率方程,计算了反应的表观活化能。通过对催化实验结果分析,发现水杨酸转化率随化合物的比表面积增大而增高;比表面积大的高维高核化合物的催化选择性高、催化活性好。同时,催化反应机理研究发现,过渡金属修饰的磷钼氧簇合物的质子的可流动性是其能够催化合成阿司匹林的主要原因;其簇阴离子表面较大的负电性可以很好地稳定碳正离子反应中间体,从而促进催化反应的进行。
With nucleophiclic oxygen-enriched surfaces and abundant topologies, polyoxometalate hybrid materials have broad applications in many fields such as catalysis, magnetism and materials science. Currently, an important advance is to decorate polyoxoanions with transition metal ions and then to assemble into different dimensional polyoxometalate clusters with unique structures. In this dissertation, seven transition metal-modified molybdenum phosphate oxide clusters have been designed and synthesized by hydrothermal synthesis. These crystalline materials have been structurally characterized by elemental analyses, single-crystal X-ray diffraction, IR spectroscopy, XPS, XRD and UV-vis spectra. By using synthesis of aspirin as a probe reaction, catalytic properties of crystalline materials have been studied in detail. The results as follow:
On the basis of summarizing the law of synthesis, the synthesis conditions for product have been determined: concentration of reactant is between 0.1 mol?L-1 and 0.5mol?L-1, pH=3.5-6.0, T=180℃, nMo:nMetal (mole ratio of atoms of reactants) should be between 6:5 and 6:1.
By elemental analyses and single-crystal X-ray diffraction analyses, the chemical formulas of seven compounds have been determined. Chemical formulas are as follows: (C_2N_2H_(10))_5[(P_4Mo_6O_(25)(OH)_6)_2Co] (1), (Co(H_2O)_6)_2(C_5NH_6)_6 [(P_4Mo_6 O_(25)(OH)_6)_2Co]·10H_2O (2), [H_2en]_3Na_4[Ni(H_2O)_3][H_(30)(MoV_(16)O_(32))Ni14(PO4)_(26)O_2 (OH)_4(H_2O)_8]·8H_2O (3), (C_2N_2H_(10))[HCo(H_2O)_2P_2MoO_(10)] (4), (C_3N_2H_(12))_4[Co_3 [P_4Mo_6 O_(26)(OH)_5]_2]·5H_2O (5), (C_2N_2H_(10))4{Mn3 [P_4Mo_6O_(26) (OH)_5]2}·6H_2O (6), (C_2N_2H_(10))4 {Cd3 [P_4Mo_6O_(26) (OH)_5]2}·6H_2O (7).
Single-crystal X-ray diffraction analyses reveal that both structures of compound 1 and 2 are zero-dimensional units consisting of sandwich-shaped dimers formed by [P_4Mo_6O31]12-and Co~(2+). Compound 3 represents a one-dimension chainlike structure which is constructed from unusual divacant wheel-type polyoxoanions [H30P_26Ni14Mo16O138(OH)_4(H_2O)8]12- and the [Ni(H_2O)3]~(2+) linkers. The vacant sites of the wheels are occupied by the H_2en ligands via H-bonds. Both anions of compound 4 and 5 possess two-dimensional layered structure. The layered structure of compound 4 is composed of [CoMoP_2] cluster anions that consist of {MoO6} octahedra, {CoO6} octahedra and {PO4} tetrahedra through sharing vertices. Compound 5 represents two-dimensional structure constructed from sandwich-shaped anions Co [P_4Mo_6O_(26)(OH)_5]2 2- and [CoO4]6- linkers. Compound 6 and 7 are isomorphic and represent three-dimension framework based on sandwich-shaped [M(P_4Mo_6)_2] cluster anions linked with {MO6} octahedra (M=Mn or Cd). By comparative analysis of results, we found that the structural types of the polyoxoanions depend on types of organic ligands with nitrogen and electron configuration of transition metal ions.
The thermal stabilities show that polyoxoanions of all compounds are stable below 200℃. Catalytic results show that all compounds have catalytic activities for preparation of aspirin, and these catalysts can be recovered, reactivated and reused several times. The best experimental condition is: For compound 1, catalyst dose is 0.09g (mass fraction 3%), temperature is 80℃, time is 25min; For compound 2, catalyst dose is 0.06g (mass fraction 2%), temperature is 80℃, time is 20min; For compound 3, catalyst dose is 0.12g (mass fraction 4%), temperature is 80℃, time is 20min; For compound 4, catalyst dose is 0.09g (mass fraction 3%), temperature is 80℃, time is 15min; For compound 5, catalyst dose is 0.12g (mass fraction 4%), temperature is 80℃, time is 25min; For compound 6, catalyst dose is 0.09g (mass fraction 3%), temperature is 80℃, time is 25min; For compound 7, catalyst dose is 0.09g (mass fraction 3%), temperature is 80℃, time is 25min, respectively. The chemical reaction kinetics was studied and the apparent activation energy was calculated. By comparative analysis of the results of experimentation, the relationships between structures and catalytic properties of the compounds have been summarized: The conversion of salicylic acid increases with the surface area of compound; High nuclear structure of high dimensional compounds with large surface area show high catalytic selectivities and high activities. Furthermore, the reaction mechanisms have been inferred. Surface proton migration of transition metal-modified molybdenum phosphate oxide cluster anions were crucial to the catalytic synthesis of asprin. Meanwhile, we found that larger negative charge density on the surface of the cluster anions could stabilize the carbocation intermediates and then accelerate the reaction.
通过对水热合成反应影响因素的研究,得出过渡金属修饰磷钼氧酸盐的合成工艺为:反应物浓度为0.1~0.5mol·L~(-1);反应温度为180℃;pH值范围为3.5~6.0;反应物中n(Mo): n(Metal)的比值为6.1~6.5。
利用元素分析和X-射线单晶衍射分析确定七种化合物的化学式分别为: (C_2N_2H_(10))_5[(P_4Mo_6O_(25)(OH)_6)_2Co] (1);(Co(H_2O)_6)_2(C_5NH_6)_6 [(P_4Mo_6O_(25_)(OH)_6)_2Co]·10H_2O (2);[H_2en]_3Na_4[Ni(H_2O)_3][H_30(MoV_(16)O_(32))Ni_(14)(PO_4)_(26)O_2(OH)_4(H_2O)_8]·8H_2O (3);(C_2N_2H_(10)) [HCo(H_2O)2P_2MoO_(10)] (4);(C_3N_2H_(12))_4[Co_3 [P_4Mo_6O_(26)(OH)_5]_2]·5H_2O (5);(C_2N_2H_(10))_4{Mn_3 [P_4Mo_6O_(26) (OH)_5]_2}·6H_2O (6);(C_2N_2H_(10))_4{Cd_3 [P_4Mo_6 O_(26) (OH)_5]_2}·6H_2O (7)。
X-射线单晶衍射分析表明:化合物1和2都是由[P_4Mo_6O_(31)]~(12-)与Co~(2+_结合而成的夹心型双聚体簇阴离子零维结构;化合物3是由双缺位轮型簇阴离子[H_(30)P_(26)Ni_(14)Mo_(16)O_(138)(OH)_4(H_2O)_8]~(12-)经[Ni(H_2O)3]~(2+)连接形成一维链状结构;化合物4和5分别是由[CoMoP_2]型和[Co(Mo_6P_4)_2]型簇阴离子形成二维层状结构;化合物6和7是同构化合物,都是由[M(Mo_6P_4)_2]型簇阴离子通过{MO6}八面体(M=Mn~(2+)或Cd~(2+))连接形成三维孔道结构。对七种化合物的晶体结构进行分析后发现,含氮有机配体的种类和过渡金属离子的核外电子构型共同决定着化合物的晶体结构类型。
热稳定性研究表明,七种晶体材料的簇阴离子结构在低于200℃的温度下均能稳定存在。催化合成阿司匹林的结果表明,所有化合物均具有较高的催化活性,均可再生、重复使用,其催化合成阿司匹林的工艺条件分别为:化合物1用量0.09g(质量分数3%),反应温度80℃,反应时间25min;化合物2用量0.06g(质量分数2%),反应温度80℃,反应时间20min;化合物3用量0.12g(质量分数4%),反应温度80℃,反应时间20min;化合物4用量0.06g(质量分数2%),反应温度80℃,反应时间30min;化合物5用量0.12g(质量分数4%),反应温度80℃,反应时间15min;化合物6用量0.09g(质量分数3%),反应温度80℃,反应时间25min;化合物7用量0.09g(质量分数3%),反应温度80℃,反应时间25min。同时,确定了反应的速率方程,计算了反应的表观活化能。通过对催化实验结果分析,发现水杨酸转化率随化合物的比表面积增大而增高;比表面积大的高维高核化合物的催化选择性高、催化活性好。同时,催化反应机理研究发现,过渡金属修饰的磷钼氧簇合物的质子的可流动性是其能够催化合成阿司匹林的主要原因;其簇阴离子表面较大的负电性可以很好地稳定碳正离子反应中间体,从而促进催化反应的进行。
With nucleophiclic oxygen-enriched surfaces and abundant topologies, polyoxometalate hybrid materials have broad applications in many fields such as catalysis, magnetism and materials science. Currently, an important advance is to decorate polyoxoanions with transition metal ions and then to assemble into different dimensional polyoxometalate clusters with unique structures. In this dissertation, seven transition metal-modified molybdenum phosphate oxide clusters have been designed and synthesized by hydrothermal synthesis. These crystalline materials have been structurally characterized by elemental analyses, single-crystal X-ray diffraction, IR spectroscopy, XPS, XRD and UV-vis spectra. By using synthesis of aspirin as a probe reaction, catalytic properties of crystalline materials have been studied in detail. The results as follow:
On the basis of summarizing the law of synthesis, the synthesis conditions for product have been determined: concentration of reactant is between 0.1 mol?L-1 and 0.5mol?L-1, pH=3.5-6.0, T=180℃, nMo:nMetal (mole ratio of atoms of reactants) should be between 6:5 and 6:1.
By elemental analyses and single-crystal X-ray diffraction analyses, the chemical formulas of seven compounds have been determined. Chemical formulas are as follows: (C_2N_2H_(10))_5[(P_4Mo_6O_(25)(OH)_6)_2Co] (1), (Co(H_2O)_6)_2(C_5NH_6)_6 [(P_4Mo_6 O_(25)(OH)_6)_2Co]·10H_2O (2), [H_2en]_3Na_4[Ni(H_2O)_3][H_(30)(MoV_(16)O_(32))Ni14(PO4)_(26)O_2 (OH)_4(H_2O)_8]·8H_2O (3), (C_2N_2H_(10))[HCo(H_2O)_2P_2MoO_(10)] (4), (C_3N_2H_(12))_4[Co_3 [P_4Mo_6 O_(26)(OH)_5]_2]·5H_2O (5), (C_2N_2H_(10))4{Mn3 [P_4Mo_6O_(26) (OH)_5]2}·6H_2O (6), (C_2N_2H_(10))4 {Cd3 [P_4Mo_6O_(26) (OH)_5]2}·6H_2O (7).
Single-crystal X-ray diffraction analyses reveal that both structures of compound 1 and 2 are zero-dimensional units consisting of sandwich-shaped dimers formed by [P_4Mo_6O31]12-and Co~(2+). Compound 3 represents a one-dimension chainlike structure which is constructed from unusual divacant wheel-type polyoxoanions [H30P_26Ni14Mo16O138(OH)_4(H_2O)8]12- and the [Ni(H_2O)3]~(2+) linkers. The vacant sites of the wheels are occupied by the H_2en ligands via H-bonds. Both anions of compound 4 and 5 possess two-dimensional layered structure. The layered structure of compound 4 is composed of [CoMoP_2] cluster anions that consist of {MoO6} octahedra, {CoO6} octahedra and {PO4} tetrahedra through sharing vertices. Compound 5 represents two-dimensional structure constructed from sandwich-shaped anions Co [P_4Mo_6O_(26)(OH)_5]2 2- and [CoO4]6- linkers. Compound 6 and 7 are isomorphic and represent three-dimension framework based on sandwich-shaped [M(P_4Mo_6)_2] cluster anions linked with {MO6} octahedra (M=Mn or Cd). By comparative analysis of results, we found that the structural types of the polyoxoanions depend on types of organic ligands with nitrogen and electron configuration of transition metal ions.
The thermal stabilities show that polyoxoanions of all compounds are stable below 200℃. Catalytic results show that all compounds have catalytic activities for preparation of aspirin, and these catalysts can be recovered, reactivated and reused several times. The best experimental condition is: For compound 1, catalyst dose is 0.09g (mass fraction 3%), temperature is 80℃, time is 25min; For compound 2, catalyst dose is 0.06g (mass fraction 2%), temperature is 80℃, time is 20min; For compound 3, catalyst dose is 0.12g (mass fraction 4%), temperature is 80℃, time is 20min; For compound 4, catalyst dose is 0.09g (mass fraction 3%), temperature is 80℃, time is 15min; For compound 5, catalyst dose is 0.12g (mass fraction 4%), temperature is 80℃, time is 25min; For compound 6, catalyst dose is 0.09g (mass fraction 3%), temperature is 80℃, time is 25min; For compound 7, catalyst dose is 0.09g (mass fraction 3%), temperature is 80℃, time is 25min, respectively. The chemical reaction kinetics was studied and the apparent activation energy was calculated. By comparative analysis of the results of experimentation, the relationships between structures and catalytic properties of the compounds have been summarized: The conversion of salicylic acid increases with the surface area of compound; High nuclear structure of high dimensional compounds with large surface area show high catalytic selectivities and high activities. Furthermore, the reaction mechanisms have been inferred. Surface proton migration of transition metal-modified molybdenum phosphate oxide cluster anions were crucial to the catalytic synthesis of asprin. Meanwhile, we found that larger negative charge density on the surface of the cluster anions could stabilize the carbocation intermediates and then accelerate the reaction.
引文
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