新型V、Ge无机固体材料的合成、结构及性质研究
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摘要
新型无机材料的合成一直是材料化学的研究热点,这些材料在分离,吸附,离子交换,催化和放射性废物处理等领域都有广泛的应用,其中锗酸盐和钒酸盐也因其结构多样性以及在各自领域广泛存在的应用价值受到许多材料合成小组的关注。本文以新型孔道锗酸盐及新颖钒酸盐的合成为目标,利用水热及溶剂热合成技术,通过调控反应条件等因素,成功地合成了11种未见报道的化合物,并通过X-射线衍射技术确定了它们的晶体结构,对它们的结构进行了表征,并利用元素分析(ICP),红外光谱(FI-IR),热重(TG)等分析手段对所合成化合物进行了性质研究。
1.在水热条件下合成了三种新的镍配合物, [Ni(C_3N_2H_4)_6](SO_4)(H_2O)_2 1 ,Ni_3(C_(10)N_2H_8)_2(SO_4)_3(H_2O)_(11) 2和Ni_2V_4O_(12.5) (C_(10)N_2H_8)_4 (H_3O) 3,并且分别通过IR光谱,热重和单晶X射线衍射对其进行了表征。化合物1:三方晶系,空间群P-31c,a = b = 9.0029(9) (?), c = 22.937(4) (?), V = 1610.0(4) (?)~3, Z = 2。化合物2:三斜晶系,空间群P1, a = 11.1737(11) (?), b = 11.1737(11) (?), c = 11.3668(11) (?),α= 72.8220(10)°,β= 73.3880(10)°,γ= 83.6400(10)°, V = 844.09(14) (?)~3, Z = 1。化合物3:三斜晶系,空间群P-1, a = 8.995(4)(?), b = 11.282(5)(?), c = 14.966(7) (?),α= 76.262(6)°,β= 81.595(6)°,γ= 68.378(5)°, V = 1368.6(11) (?)~3, Z = 2.这三种镍配合物具有不同维度的结构,是通过调控水热及溶剂热合成条件而获得的三种简单结构的镍配合物。
2.在溶剂热条件下合成了两种结构相似的钒硫酸盐, (C_2H_(10)N_2)_4 [GaV_3 (SO_4)_8(OH)_4]·4H_2O 4和[C_4H_(12)N_2][V~III (OH)(SO_4)_2]·H_2O 5,并且分别通过IR光谱,粉末X射线衍射,热重和单晶X射线衍射对其进行了表征。化合物4:单斜晶系,空间群P2(1)/c,a = 6.8956(15) (?), b = 10.303(2) (?), c = 15.094(3) (?),β= 90.802(3)°,V = 1073.23 (3) (?)~3, Z = 1。化合物5:单斜晶系,空间群P2(1)/c,a = 9.290(4) (?), b = 18.264(7) (?), c = 7.132(3) (?),β= 98.149(8)°,V= 1197.9(8) (?)~3, Z = 4。化合物4、5的结构都是一维的钒硫酸链的结构,-OH和SO4四面体作为桥连配体连接VO6八面体形成了无限链的骨架结构,链间分别填充的是质子化的乙二胺分子和哌嗪分子,链与模板剂之间通过氢键作用形成了三维超分子结构。
3.在水热、溶剂热条件下合成了三种新的不同拓扑结构的锗酸盐,Ge_(10)O_(20) (H_2O)_3 6,Ge_7O_(12)(OH)_4(C_6NH_(15))_(0.5)(H_2O)_4 7和Ge_7O_(12)(OH)_4(C_3NH_9)_(0.25)(H_2O)_5 8,并且分别通过IR光谱,粉末X射线衍射,热重和单晶X射线衍射对其进行了表征。化合物6:四方晶系,空间群P4/mcc, a = b = 8.7885(18) (?) , c = 14.490(6) (?), V = 1119.2(6) (?)~3, Z = 2。化合物7:立方晶系,空间群是P-43m,a = 7.7187(1) (?), V = 459.87(1) (?)~3, Z = 1。化合物8:立方晶系,空间群是P-43m,a = 7.7198(6) (?), V = 460.06(6) (?)~3, Z = 1。化合物6是与ASU-7具有相同拓扑结构的微孔锗酸盐,沿c轴方向具有一维的12元环孔道。化合物7和8是同构的锗酸盐,它们的骨架由Ge_4(OH)_4立方烷和交替的手性双螺旋Ge-O链组成,结构中包含8元环孔道。
4.以提高孔道锗酸盐的稳定性为目的,在溶剂热条件下合成了三种具有不同分子筛拓扑结构的微孔锗铝酸盐[C_4H_(12)N] [AlGe_3O_8] 9,KAlGe_3O_8 10和KAl_2Ge_2O_7F 11,并且分别通过IR光谱,粉末X射线衍射,热重和单晶X射线衍射对其结构进行了表征。化合物9:四方晶系,空间群I41/a, a = b = 10.7754(8) (?), c = 9.9116(14) (?), V = 1150.8(2) (?)~3, Z = 4。化合物10:正交晶系,空间群Pnma, a = 9.4336(13) (?), b = 8.7068(12) (?), c = 9.8212(14) (?), V = 806. 68 (19) (?)~3, Z = 4。化合物11:四方晶系,空间群I-42d,a = b = 7.3626(4) (?), c = 17.4940(18) (?),V = 948.31(12) (?)~3, Z = 4。化合物9是具有类似GIS分子筛的拓扑结构的有机模板微孔锗铝酸盐,它的结构中包含二维的8元环孔道结构,化合物10是具有para分子筛结构的微孔锗铝酸盐,结构中也包含二维的8元环孔道,但孔道中填充的是金属K离子,化合物11具有MON分子筛拓扑结构,结构中包含8元环孔道和5元环结构,孔道中填有金属离子。其中,化合物9表现出了很好的热稳定性,有机模板被移除后,孔道骨架仍然被保留,这将为微孔锗酸盐的应用拓宽了范围,提供更广泛的应用前景。
The synthesis of novel inorganic materials has been receiving great attention due to their widespread applications in separation, absorption, ion-exchange, catalysis and remediation of radioactive waste. Recent decades, many groups have commit themselves to the synthesis of novel germanates and vanadates because of not only the diversity of the structures but also the potential applications in different fields. In this thesis, in order to improve the thermal stability of germanates and obtain novel vanadates, eleven novel compounds have been reported, which were synthesized under hydrothermal and sovlothermal conditions by changing and adjusting different factors including the materials, solvents, temperature, concentration and so on. All of the structures were characterized by single crystal X-ray diffraction and their properties were studied by Elemental Analysis, IR, TG .
1. Three new nickel complexes [Ni(C_3N_2H_4)_6](SO_4)(H_2O)_2 1 ,Ni_3(C_(10)N_2H_8)_2(SO_4)_3(H_2O)_(11) 2 and Ni_2V_4O_(12.5) (C_(10)N_2H_8)_4 (H_3O) 3 have been synthesized under hydrothermal conditions and characterized by IR spectroscopy, powder XRD, TG and single crystal X-ray diffraction. Compound 1 crystallizes in the Trigonal space group P-31c with a = b= 9.0029(9) (?), c = 22.937(4) (?), V = 1610.0(4) (?)~3, Z = 2. Compound 2:Triclinic,space group P1, a = 11.1737(11) (?), b = 11.1737(11) (?), c = 11.3668(11) (?),α= 72.8220(10)°,β= 73.3880(10)°,γ= 83.6400(10)°, V = 844.09(14) (?)~3, Z = 1. Compound 3:Triclinic,space group P-1, a = 8.995(4) (?), b = 11.282(5) (?), c = 14.966(7) (?),α= 76.262(6)°,β= 81.595(6)°,γ= 68.378(5)°, V = 1368.6(11) (?)~3, Z = 2. These three nickel complexes were new and obtained by adjusting the reaction conditions during experiments, which keep different dimensional strctures.
2. Two new organic templated 1-D linear vanadium sulfates (C_2H_(10)N_2)_4 [GaV_3 (SO_4)_8(OH)_4]·4H_2O 4 and [C_4H_(12)N_2][V~III (OH)(SO_4)_2]·H_2O 5 have been synthesized under solvothermal conditions and characterized by IR spectroscopy, TG and single crystal X-ray diffraction. Compound 4 crystallizes in the Monoclinic space group P2(1)/c, a = 6.8956(15) (?), b = 10.303(2) (?), c = 15.094(3) (?),β= 90.802(3)°,V = 1073.23 (3) (?)~3, Z = 1. Compound 5:Monoclinic, P2(1)/c,a = 9.290(4) (?), b = 18.264(7) (?), c = 7.132(3) (?),β= 98.149(8)°, V = 1197.9(8) (?)~3, Z = 4. In the structure of compound 4 and 5, the OH and SO4 tetrahedra as bridging ligands connected the VO6 octahedra to generate an infinite chain, and protonated organic amines exist between the chains and involve in the hydrogen bonding interaction to generate a 3D supermolecule structure.
3. Three new germanates Ge_(10)O_(20) (H_2O)_3 6,Ge_7O_(12)(OH)_4(C_6NH_(15))_(0.5)(H_2O)_4 7 and Ge_7O_(12)(OH)_4(C_3NH_9)_(0.25)(H_2O)_5 8 with different topology structures have been synthesized under hydrothermal and solvothermal conditions, and characterized by IR spectroscopy, powder XRD, TG and single crystal X-ray diffraction. Compound 6 crystallizes in the tetragonal space group P4/mcc, a = b = 8.7885(18) (?) , c = 14.490(6) (?), V = 1119.2(6) (?)~3, Z = 2. Compound 7: cubic, P-43m,a = 7.7187(1) (?), V = 459.87(1) (?)~3, Z = 1. Compound 8: cubic, P-43m, a = 7.7198(6) (?), V = 460.06(6) (?)~3, Z = 1. Compound 6 has the same framework as ASU-7, which presents 12-membered-ring channels along the c axis. Compounds 7 and 8 are the same structure and templated by two different organic amines, which are composed of Ge4(OH)4 cubanes and chiral intertwined Ge-O double helices, moreover, 2-D 8-membered-ring channels can be observed in the structure.
4. In order to enhance the thermal stability of the germanates, three new microporous aluminogermanates [C_4H_(12)N] [AlGe_3O_8] 9,KAlGe_3O_8 10和KAl_2Ge_2O_7F 11 with different zeolite topologies have been synthesized under solvothermal condition and characterized by IR spectroscopy, powder XRD, TG and single crystal X-ray diffraction. Compound 9 crystallizes in the tetragonal space group I41/a, a = b = 10.7754(8) (?), c = 9.9116(14) (?), V = 1150.8(2) (?)~3, Z = 4. Compound 10: Orthorhombic, Pnma, a = 9.4336(13) (?), b = 8.7068(12) (?), c = 9.8212(14) (?), V = 806. 68 (19) (?)~3, Z = 4. Compound 11: tetragonal, I-42d,a = b = 7.3626(4) (?), c = 17.4940(18) (?),V = 948.31(12) (?)~3, Z = 4. Compound 9 as an organic templated microporous aluminogermanates has the same topology as GIS zeolite. Compound 10 has the same topology as para zeolite, while compound 11 has the same structure as MON zeolite. Specially, compound 9 shows good thermal stability by calcinations, the structure of inorganic framework is retained when the organic amine is removed by calcinations, which provides potential applications for the zeolite.
1.在水热条件下合成了三种新的镍配合物, [Ni(C_3N_2H_4)_6](SO_4)(H_2O)_2 1 ,Ni_3(C_(10)N_2H_8)_2(SO_4)_3(H_2O)_(11) 2和Ni_2V_4O_(12.5) (C_(10)N_2H_8)_4 (H_3O) 3,并且分别通过IR光谱,热重和单晶X射线衍射对其进行了表征。化合物1:三方晶系,空间群P-31c,a = b = 9.0029(9) (?), c = 22.937(4) (?), V = 1610.0(4) (?)~3, Z = 2。化合物2:三斜晶系,空间群P1, a = 11.1737(11) (?), b = 11.1737(11) (?), c = 11.3668(11) (?),α= 72.8220(10)°,β= 73.3880(10)°,γ= 83.6400(10)°, V = 844.09(14) (?)~3, Z = 1。化合物3:三斜晶系,空间群P-1, a = 8.995(4)(?), b = 11.282(5)(?), c = 14.966(7) (?),α= 76.262(6)°,β= 81.595(6)°,γ= 68.378(5)°, V = 1368.6(11) (?)~3, Z = 2.这三种镍配合物具有不同维度的结构,是通过调控水热及溶剂热合成条件而获得的三种简单结构的镍配合物。
2.在溶剂热条件下合成了两种结构相似的钒硫酸盐, (C_2H_(10)N_2)_4 [GaV_3 (SO_4)_8(OH)_4]·4H_2O 4和[C_4H_(12)N_2][V~III (OH)(SO_4)_2]·H_2O 5,并且分别通过IR光谱,粉末X射线衍射,热重和单晶X射线衍射对其进行了表征。化合物4:单斜晶系,空间群P2(1)/c,a = 6.8956(15) (?), b = 10.303(2) (?), c = 15.094(3) (?),β= 90.802(3)°,V = 1073.23 (3) (?)~3, Z = 1。化合物5:单斜晶系,空间群P2(1)/c,a = 9.290(4) (?), b = 18.264(7) (?), c = 7.132(3) (?),β= 98.149(8)°,V= 1197.9(8) (?)~3, Z = 4。化合物4、5的结构都是一维的钒硫酸链的结构,-OH和SO4四面体作为桥连配体连接VO6八面体形成了无限链的骨架结构,链间分别填充的是质子化的乙二胺分子和哌嗪分子,链与模板剂之间通过氢键作用形成了三维超分子结构。
3.在水热、溶剂热条件下合成了三种新的不同拓扑结构的锗酸盐,Ge_(10)O_(20) (H_2O)_3 6,Ge_7O_(12)(OH)_4(C_6NH_(15))_(0.5)(H_2O)_4 7和Ge_7O_(12)(OH)_4(C_3NH_9)_(0.25)(H_2O)_5 8,并且分别通过IR光谱,粉末X射线衍射,热重和单晶X射线衍射对其进行了表征。化合物6:四方晶系,空间群P4/mcc, a = b = 8.7885(18) (?) , c = 14.490(6) (?), V = 1119.2(6) (?)~3, Z = 2。化合物7:立方晶系,空间群是P-43m,a = 7.7187(1) (?), V = 459.87(1) (?)~3, Z = 1。化合物8:立方晶系,空间群是P-43m,a = 7.7198(6) (?), V = 460.06(6) (?)~3, Z = 1。化合物6是与ASU-7具有相同拓扑结构的微孔锗酸盐,沿c轴方向具有一维的12元环孔道。化合物7和8是同构的锗酸盐,它们的骨架由Ge_4(OH)_4立方烷和交替的手性双螺旋Ge-O链组成,结构中包含8元环孔道。
4.以提高孔道锗酸盐的稳定性为目的,在溶剂热条件下合成了三种具有不同分子筛拓扑结构的微孔锗铝酸盐[C_4H_(12)N] [AlGe_3O_8] 9,KAlGe_3O_8 10和KAl_2Ge_2O_7F 11,并且分别通过IR光谱,粉末X射线衍射,热重和单晶X射线衍射对其结构进行了表征。化合物9:四方晶系,空间群I41/a, a = b = 10.7754(8) (?), c = 9.9116(14) (?), V = 1150.8(2) (?)~3, Z = 4。化合物10:正交晶系,空间群Pnma, a = 9.4336(13) (?), b = 8.7068(12) (?), c = 9.8212(14) (?), V = 806. 68 (19) (?)~3, Z = 4。化合物11:四方晶系,空间群I-42d,a = b = 7.3626(4) (?), c = 17.4940(18) (?),V = 948.31(12) (?)~3, Z = 4。化合物9是具有类似GIS分子筛的拓扑结构的有机模板微孔锗铝酸盐,它的结构中包含二维的8元环孔道结构,化合物10是具有para分子筛结构的微孔锗铝酸盐,结构中也包含二维的8元环孔道,但孔道中填充的是金属K离子,化合物11具有MON分子筛拓扑结构,结构中包含8元环孔道和5元环结构,孔道中填有金属离子。其中,化合物9表现出了很好的热稳定性,有机模板被移除后,孔道骨架仍然被保留,这将为微孔锗酸盐的应用拓宽了范围,提供更广泛的应用前景。
The synthesis of novel inorganic materials has been receiving great attention due to their widespread applications in separation, absorption, ion-exchange, catalysis and remediation of radioactive waste. Recent decades, many groups have commit themselves to the synthesis of novel germanates and vanadates because of not only the diversity of the structures but also the potential applications in different fields. In this thesis, in order to improve the thermal stability of germanates and obtain novel vanadates, eleven novel compounds have been reported, which were synthesized under hydrothermal and sovlothermal conditions by changing and adjusting different factors including the materials, solvents, temperature, concentration and so on. All of the structures were characterized by single crystal X-ray diffraction and their properties were studied by Elemental Analysis, IR, TG .
1. Three new nickel complexes [Ni(C_3N_2H_4)_6](SO_4)(H_2O)_2 1 ,Ni_3(C_(10)N_2H_8)_2(SO_4)_3(H_2O)_(11) 2 and Ni_2V_4O_(12.5) (C_(10)N_2H_8)_4 (H_3O) 3 have been synthesized under hydrothermal conditions and characterized by IR spectroscopy, powder XRD, TG and single crystal X-ray diffraction. Compound 1 crystallizes in the Trigonal space group P-31c with a = b= 9.0029(9) (?), c = 22.937(4) (?), V = 1610.0(4) (?)~3, Z = 2. Compound 2:Triclinic,space group P1, a = 11.1737(11) (?), b = 11.1737(11) (?), c = 11.3668(11) (?),α= 72.8220(10)°,β= 73.3880(10)°,γ= 83.6400(10)°, V = 844.09(14) (?)~3, Z = 1. Compound 3:Triclinic,space group P-1, a = 8.995(4) (?), b = 11.282(5) (?), c = 14.966(7) (?),α= 76.262(6)°,β= 81.595(6)°,γ= 68.378(5)°, V = 1368.6(11) (?)~3, Z = 2. These three nickel complexes were new and obtained by adjusting the reaction conditions during experiments, which keep different dimensional strctures.
2. Two new organic templated 1-D linear vanadium sulfates (C_2H_(10)N_2)_4 [GaV_3 (SO_4)_8(OH)_4]·4H_2O 4 and [C_4H_(12)N_2][V~III (OH)(SO_4)_2]·H_2O 5 have been synthesized under solvothermal conditions and characterized by IR spectroscopy, TG and single crystal X-ray diffraction. Compound 4 crystallizes in the Monoclinic space group P2(1)/c, a = 6.8956(15) (?), b = 10.303(2) (?), c = 15.094(3) (?),β= 90.802(3)°,V = 1073.23 (3) (?)~3, Z = 1. Compound 5:Monoclinic, P2(1)/c,a = 9.290(4) (?), b = 18.264(7) (?), c = 7.132(3) (?),β= 98.149(8)°, V = 1197.9(8) (?)~3, Z = 4. In the structure of compound 4 and 5, the OH and SO4 tetrahedra as bridging ligands connected the VO6 octahedra to generate an infinite chain, and protonated organic amines exist between the chains and involve in the hydrogen bonding interaction to generate a 3D supermolecule structure.
3. Three new germanates Ge_(10)O_(20) (H_2O)_3 6,Ge_7O_(12)(OH)_4(C_6NH_(15))_(0.5)(H_2O)_4 7 and Ge_7O_(12)(OH)_4(C_3NH_9)_(0.25)(H_2O)_5 8 with different topology structures have been synthesized under hydrothermal and solvothermal conditions, and characterized by IR spectroscopy, powder XRD, TG and single crystal X-ray diffraction. Compound 6 crystallizes in the tetragonal space group P4/mcc, a = b = 8.7885(18) (?) , c = 14.490(6) (?), V = 1119.2(6) (?)~3, Z = 2. Compound 7: cubic, P-43m,a = 7.7187(1) (?), V = 459.87(1) (?)~3, Z = 1. Compound 8: cubic, P-43m, a = 7.7198(6) (?), V = 460.06(6) (?)~3, Z = 1. Compound 6 has the same framework as ASU-7, which presents 12-membered-ring channels along the c axis. Compounds 7 and 8 are the same structure and templated by two different organic amines, which are composed of Ge4(OH)4 cubanes and chiral intertwined Ge-O double helices, moreover, 2-D 8-membered-ring channels can be observed in the structure.
4. In order to enhance the thermal stability of the germanates, three new microporous aluminogermanates [C_4H_(12)N] [AlGe_3O_8] 9,KAlGe_3O_8 10和KAl_2Ge_2O_7F 11 with different zeolite topologies have been synthesized under solvothermal condition and characterized by IR spectroscopy, powder XRD, TG and single crystal X-ray diffraction. Compound 9 crystallizes in the tetragonal space group I41/a, a = b = 10.7754(8) (?), c = 9.9116(14) (?), V = 1150.8(2) (?)~3, Z = 4. Compound 10: Orthorhombic, Pnma, a = 9.4336(13) (?), b = 8.7068(12) (?), c = 9.8212(14) (?), V = 806. 68 (19) (?)~3, Z = 4. Compound 11: tetragonal, I-42d,a = b = 7.3626(4) (?), c = 17.4940(18) (?),V = 948.31(12) (?)~3, Z = 4. Compound 9 as an organic templated microporous aluminogermanates has the same topology as GIS zeolite. Compound 10 has the same topology as para zeolite, while compound 11 has the same structure as MON zeolite. Specially, compound 9 shows good thermal stability by calcinations, the structure of inorganic framework is retained when the organic amine is removed by calcinations, which provides potential applications for the zeolite.
引文
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