CN1712406A - A novel pore structure vanadium phosphate compound and its synthesis method - Google Patents
A novel pore structure vanadium phosphate compound and its synthesis method Download PDFInfo
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- CN1712406A CN1712406A CN 200410049721 CN200410049721A CN1712406A CN 1712406 A CN1712406 A CN 1712406A CN 200410049721 CN200410049721 CN 200410049721 CN 200410049721 A CN200410049721 A CN 200410049721A CN 1712406 A CN1712406 A CN 1712406A
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- 239000011148 porous material Substances 0.000 title claims description 13
- 239000012002 vanadium phosphate Substances 0.000 title claims description 4
- -1 vanadium phosphate compound Chemical class 0.000 title abstract description 6
- 238000001308 synthesis method Methods 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- 239000007858 starting material Substances 0.000 claims description 3
- 238000002447 crystallographic data Methods 0.000 claims description 2
- 238000006073 displacement reaction Methods 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims 2
- 230000008025 crystallization Effects 0.000 claims 2
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract 2
- 229910000540 VOPO4 Inorganic materials 0.000 abstract 1
- 235000011007 phosphoric acid Nutrition 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
Description
本发明是关于一种新型孔道结构钒磷酸盐化合物及其合成方法。The invention relates to a novel pore structure vanadium phosphate compound and a synthesis method thereof.
孔道结构材料因具有独特的晶体结构和优异的吸附、离子交换、催化等性能而被广泛应用于石油化工、微电子和光学技术等领域。应用最早、最广泛的孔道结构材料是沸石型铝硅酸盐孔道结构材料。随着社会、经济和科学技术的发展，传统的以硅氧四面体为结构骨架的沸石型孔道材料已无法满足需求。孔道结构材料正朝着组成元素及结构多元化和大孔径的方向发展。Pore structure materials are widely used in petrochemical, microelectronics and optical technology fields due to their unique crystal structure and excellent properties of adsorption, ion exchange and catalysis. The earliest and most widely used pore structure material is the zeolite-type aluminosilicate pore structure material. With the development of society, economy and science and technology, the traditional zeolite-type channel materials with silicon-oxygen tetrahedron as the structural framework can no longer meet the demand. Porous structure materials are developing toward the direction of composition elements and structure diversification and large pore size.
V-P-O体系孔道结构化合物是目前除硅酸盐体系外最重要的一类孔道结构材料。这类材料由于钒价态的可变性及其配位体的多样性以及与磷氧四面体灵活的连接，具有结构复杂多变、孔径大、吸附和催化性质优异等特点。在层状结构V-P-O化合物已被广泛用于催化应用的基础上，上世纪90年代初又成功合成了应用潜力更为巨大、具三维孔道结构体系的V-P-O化合物，使这类化合物的合成研究成为目前研究的热点。迄今为止已合成出的该体系孔道化合物达三十余种。本发明合成的孔道结构钒磷酸盐化合物是一种尚未见有报道的新型孔道结构化合物。该化合物为暗绿色透明片状晶体，结构式为：(NH3CH2CH2NH2)[VOPO4]，分子式为：C2H9N2O5PV。晶体学数据如下：a＝0.92108(2)nm，b＝0.72851(1)nm，c＝0.98204(2)nm，β＝101.269(7)°，V＝0.6462(4)nm3，Z＝4，空间群：P21/c，计算密度：2.303g cm-3。通过单晶X-射线获得的该化合物的原子坐标(除H原子以外)及主要键长、键角值分别如表1、表2、表3所示。The VPO system pore structure compound is currently the most important type of pore structure material except the silicate system. Due to the variability of the vanadium valence state, the diversity of its ligands, and the flexible connection with the phosphorus-oxygen tetrahedron, this type of material has the characteristics of complex and changeable structure, large pore size, and excellent adsorption and catalytic properties. Based on the fact that layered structure VPO compounds have been widely used in catalytic applications, in the early 1990s, VPO compounds with even greater application potential and three-dimensional pore structure system were successfully synthesized, making the synthesis of such compounds the current state of the art. research hotspot. More than 30 kinds of channel compounds of this system have been synthesized so far. The pore structure vanadium phosphate compound synthesized by the invention is a novel pore structure compound which has not been reported yet. The compound is dark green transparent flaky crystal, the structural formula is: (NH 3 CH 2 CH 2 NH 2 )[VOPO 4 ], and the molecular formula is: C 2 H 9 N 2 O 5 PV. The crystallographic data are as follows: a=0.92108(2)nm, b=0.72851(1)nm, c=0.98204(2)nm, β=101.269(7)°, V=0.6462(4)nm 3 , Z=4, Space group: P2 1 /c, calculated density: 2.303g cm -3 . The atomic coordinates (except H atom) and main bond lengths and bond angles of the compound obtained by single crystal X-rays are shown in Table 1, Table 2, and Table 3, respectively.
表1原子坐标参数(×104)和等效各向同性位移因子(nm2×10)
表2选择键长(nm×10-1)
表3选择键角(°)
等效原子的对称变换：#1-x+1，y+1/2，-z+1/2；#2-x+1，-y，-z；#3x，-y+1/2，z-1/2；Symmetric transformations of equivalent atoms: #1-x+1, y+1/2, -z+1/2; #2-x+1, -y, -z; #3x, -y+1/2, z-1/2;
#4-x+1，y-1/2，-z+1/2；#5x，-y+1/2，z+1/2#4-x+1, y-1/2, -z+1/2; #5x, -y+1/2, z+1/2
化合物(NH3CH2CH2NH2)[VOPO4]的最小不对称单元中含一个钒原子，一个磷原子，八个氧原子，两个氮原子和两个碳原子，如图1所示。V呈不规则的八面体配位[VO5N]，其配位体由一个键长较短的钒氧基及其对位氧，三个分别来自三个磷氧四面体的氧，以及一个乙二胺分子的N组成。钒氧基键长V(1)＝O(2)#1为0.1633nm，对位氧键长V(1)-O(2)为0.2202nm，其余四个键(V-O、V-N)的键长介于上述其间。P呈近规则的四面体配位，P-O键长相近(1.5262-1.5360)。[PO4]的四个氧中，有三个分别与不同的钒八面体共用，其余一个氧(O3)为不与其它原子共用的端氧。钒八面体共用角顶的氧形成平行于b轴的“之”字型1D链，链中钒氧基氧和对位氧呈{V＝O...V＝O...}长短键的交替组合。相邻的钒八面体链间由[PO4]共角顶连接成层，链间端氧交替指向层面的上下方，如图2所示。乙二胺分子与层面斜交，伸向层间，相邻层的乙二胺分子链呈“穿插式”分布，以满足最大程度的形成氢键，如图3所示。层间的氢键将结构层连接起来。The smallest asymmetric unit of the compound (NH 3 CH 2 CH 2 NH 2 )[VOPO 4 ] contains one vanadium atom, one phosphorus atom, eight oxygen atoms, two nitrogen atoms and two carbon atoms, as shown in Figure 1 . V is an irregular octahedral coordination [VO 5 N], and its ligand consists of a vanadium oxide with a short bond length and its para-oxygen, three oxygens from three phosphorus-oxygen tetrahedrons, and a N composition of ethylenediamine molecule. The vanadium oxide bond length V(1)=O(2)#1 is 0.1633nm, the para-oxygen bond length V(1)-O(2) is 0.2202nm, and the bond lengths of the remaining four bonds (VO, VN) between the above. P is nearly regular tetrahedral coordination, PO bond length is similar (1.5262-1.5360). Among the four oxygens in [PO 4 ], three are shared with different vanadium octahedrons, and the remaining oxygen (O 3 ) is a terminal oxygen that is not shared with other atoms. The oxygen at the shared corner of the vanadium octahedron forms a "zigzag" 1D chain parallel to the b-axis, and the vanadyl oxygen and the para-oxygen in the chain are in the form of {V=O...V=O...} long and short bonds Alternate combinations. Adjacent vanadium octahedral chains are connected by [PO 4 ]-shared corner tops to form a layer, and the terminal oxygen between the chains points alternately up and down the layer, as shown in Figure 2. The ethylenediamine molecules are obliquely intersected with the layers, extending to the interlayer, and the ethylenediamine molecular chains of the adjacent layers are distributed in an "interspersed" manner to meet the maximum degree of hydrogen bond formation, as shown in Figure 3. Interlayer hydrogen bonds connect the structural layers.
(NH3CH2CH2NH2)[VOPO4]是以V2O5、H3PO4、H2NCH2CH2NH2、H2O为合成起始物，用水热法合成的。实验所用原料为：V2O5(A.R)，H3PO4(85％)(A.R)，乙二胺(A.R)，去离子水。各反应物间的摩尔比V2O5∶H3PO4∶en∶H2O＝0.55∶4∶3.6∶265。将计量磷酸和去离子水混合，然后再依次加入V2O5、en，强烈搅拌，将形成的溶胶移入40mL内衬聚四氟乙烯的压力釜中(充填率40％)，在175℃加热5天，自然冷却至室温。所得产物水洗，自然干燥。产物为单相，产率85％(以钒的量计算)。(NH 3 CH 2 CH 2 NH 2 )[VOPO 4 ] was synthesized by hydrothermal method using V 2 O 5 , H 3 PO 4 , H 2 NCH 2 CH 2 NH 2 , and H 2 O as synthetic starting materials. The raw materials used in the experiment are: V 2 O 5 (AR), H 3 PO 4 (85%) (AR), ethylenediamine (AR), and deionized water. The molar ratio V 2 O 5 :H 3 PO 4 :en: H 2 O=0.55:4:3.6:265 among the reactants. Mix metered phosphoric acid and deionized water, then add V 2 O 5 and en in sequence, stir vigorously, transfer the formed sol into a 40mL autoclave lined with polytetrafluoroethylene (filling rate 40%), and heat at 175°C 5 days, naturally cooled to room temperature. The resulting product was washed with water and dried naturally. The product is a single phase with a yield of 85% (calculated based on the amount of vanadium).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108394881A (en) * | 2018-02-09 | 2018-08-14 | 清华大学 | A kind of preparation method of lithium ion anode material nm delta-VOPO4 |
| CN108408707A (en) * | 2018-02-09 | 2018-08-17 | 清华大学 | A kind of lithium ion anode material nanometer ω-VOPO4Preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108394881A (en) * | 2018-02-09 | 2018-08-14 | 清华大学 | A kind of preparation method of lithium ion anode material nm delta-VOPO4 |
| CN108408707A (en) * | 2018-02-09 | 2018-08-17 | 清华大学 | A kind of lithium ion anode material nanometer ω-VOPO4Preparation method |
| CN108394881B (en) * | 2018-02-09 | 2019-10-22 | 河南理工大学 | A kind of preparation method of lithium ion cathode material nanometer δ-VOPO4 |
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