CN109593207B - Two-dimensional MOFs material with proton conductivity and preparation method thereof - Google Patents
Two-dimensional MOFs material with proton conductivity and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 14
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 4
- 239000013077 target material Substances 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- MQBIGZBUVUVDKE-UHFFFAOYSA-N [2-(4-phosphonopyridin-2-yl)pyridin-4-yl]phosphonic acid Chemical compound OP(O)(=O)C1=CC=NC(C=2N=CC=C(C=2)P(O)(O)=O)=C1 MQBIGZBUVUVDKE-UHFFFAOYSA-N 0.000 claims description 9
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004020 conductor Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 22
- 239000000446 fuel Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000013299 conductive metal organic framework Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000013212 metal-organic material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical group OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 240000003291 Armoracia rusticana Species 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Fuel Cell (AREA)
- Conductive Materials (AREA)
Abstract
本发明涉及质子导电材料领域，公开了一种具有优良质子导电性能的MOFs材料及其制备方法。该方法以H4L为联接配体，Cu2+，Cl‑为连接点，通过加热制备二维层目标材料。本发明材料具有良好质子导电率，制备方法简单易操作，产率高，热力学和化学性能稳定，易于大面积推广应用。
The invention relates to the field of proton conductive materials, and discloses a MOFs material with excellent proton conductive properties and a preparation method thereof. The method uses H 4 L as the connecting ligand, Cu 2+ , Cl ‑ as the connecting points, and prepares the two-dimensional layer target material by heating. The material of the invention has good proton conductivity, the preparation method is simple and easy to operate, the yield is high, the thermodynamic and chemical properties are stable, and it is easy to be popularized and applied in a large area.
Description
Technical Field
The invention belongs to the technical field of proton conducting materials, and relates to a two-dimensional MOFs material with proton conducting property and a preparation method thereof.
Background
Currently, numerous advanced energy storage and conversion devices are involved in the search for solutions to energy challenges and environmental issues, among which proton transfer membrane Fuel Cells are considered a very promising option, mainly due to their superior properties such as high energy density, low pollutant emissions and mild operating conditions (reference: Barbir F. PEM Fuel Cells: Theory and Practice. (Elsevier Academic Press, New York, 2005)). Although intensive research has been conducted in the field of proton transfer membrane fuel cells, the design and synthesis of electrode materials with high proton conductivity and stability remain a challenge. In addition, the lack of crystallinity of commonly used Nafion membranes in polymers makes it difficult to understand well-defined proton transport pathways at the atomic level. Over the past few decades, metal organic compounds (MOFs) have gained rapid growth with a growing interest, mainly due to their designable and tunable structure and properties, and potential applications in adsorption, separation, sensing and energy related applications (references: Denny m.s.jr, Moreton j.c., Benz L. & Cohen s.m.nat. rev.mater.2016,1,16078; Schoedel a., Ji Z. & Yaghi o.m.nat. energy,2016,1,16034; kren l.e., Leong k., Farha o.k., Allendorf, Van Duyne r.p.and Hupp j.t.chem.rev.2012,112, 1105). Current research indicates that proton conducting metal-organic materials can potentially be applied in proton transfer membrane fuel cells (references: ramasswamy p., Wong N.E. & Shimizu g.k.h.chem.soc.rev.,2014,43,5913; Horike s., Umeyama D. & Kitagawa s.acc.chem.res.,2013,46,2376.). On the other hand, in order to design a better proton conducting material, the metal organic material exhibits its advantages in many aspects, such as its crystalline nature may allow intuitive visualization of proton transport channel models; the regular structure is easy to introduce acidic groups, thereby forming effective proton transport channels and increasing proton conductivity (references: Taylor J.M., Mah R.K., Moudrakovski I.L., Ratcliffe C.I., Vaidhyatahan R., Shimizu G.K.H.J.Am.Chem.Soc.2010,132, 14055; Bao S.S., Shimizu G.K.H., Zheng L.M., coord. chem.Rev.,2019,1, 577-594.). Therefore, researches are explored to introduce bipyridyl-containing diphosphoric acid groups into metal organic materials so as to obtain two-dimensional proton conducting MOFs materials with better performance, which is beneficial to the development of fuel cells, and no relevant report is found at present.
Disclosure of Invention
The invention aims to provide a two-dimensional proton conductive MOFs material with good thermal stability, chemical stability and proton conductivity; another object is to provide a process for the preparation thereof.
In order to achieve the purpose, the invention constructs the metal organic compound based on 2,2 '-bipyridine-4, 4' -diphosphonic acid and tests the proton conductivity of the metal organic compound. The two-dimensional proton conductive MOFs material takes 2,2 '-bipyridine-4, 4' -diphosphonic acid as a ligand (H)4L)，Cu2+，Cl-And a two-dimensional layer structure is constructed as the connection point. Cu2+，Cl-One-dimensional chains are formed in the c-direction and then through H in the b-direction3L-The ligands link the copper atoms of the upper and lower chains to form a two-dimensional layer. Unit cell parameters: belongs to monoclinic system, C2/C space group,
β＝100.391°,F(000)＝1656.0,
and Z is 8. The molecular formula is C10H9ClCuN2O6P2The molecular structure is schematically shown in figure 1.
The synthesis method comprises the following steps: 2,2 '-bipyridine-4, 4' -diphosphonic acid and CuCl2Adding the mixture into a mixed solution of water and concentrated hydrochloric acid, heating the mixture at 200-250 ℃ for reaction, and naturally cooling the mixture after the reaction is finished to obtain green crystals, thus obtaining the target material.
CuCl2The mol ratio of the 2,2 '-bipyridine-4, 4' -diphosphonic acid is selected from: 1.0-2.0: 1.0;
the concentrated hydrochloric acid: selecting 1 part of water by mass: 5-8.
The synthetic route is as follows:
CuCl2+H4L→Cu-Cl-H3L
the invention has the advantages that: the diphosphoric acid group is introduced, the synthesized two-dimensional proton conductive MOFs material has good crystallization capacity, higher thermal stability and chemical stability, good proton conductivity at medium and low temperature, and insolubility in various solvents provides possibility for material application, and shows attractive application prospect in the aspect of proton conductivity. The invention adopts one-step synthesis, has simple preparation and easily controlled conditions, and is easy for industrialized popularization and production.
Drawings
FIG. 1 is a schematic diagram of the structure of a compound of the present invention;
FIG. 2 is an infrared spectrum of a compound of the present invention;
FIG. 3 is a thermogram of a compound of the present invention;
FIG. 4 is an XRD pattern of a compound of the present invention, in which A-single crystal simulation, B-before conductivity test, and C-after conductivity test);
FIG. 5 is a graph of proton conductivity as a function of humidity for compounds of the present invention at 25 ℃ and 100 ℃;
FIG. 6 is an Arrhenius diagram showing proton conductivity at a temperature of 25 to 100 ℃ and a relative humidity of 98% for the compound of the present invention.
Detailed Description
To better illustrate the invention, the following examples are given:
example 1
0.05mmol of 2,2 '-bipyridine-4, 4' -diphosphonic acid and CuCl20.05mmol was placed in a bottle, and then concentrated hydrochloric acid: water (mass ratio) 1: adding 1.5ml of mixed solution into a bottle, heating at 200 ℃ for 5 hours, and naturally cooling to obtain green crystals. The infrared spectrum is shown in figure 2.
Unit cell parameters: the compound crystallizes in the monoclinic system, C2/C space group,
β＝100.391°,F(000)＝1656.0,
Z＝8。
example 2
0.05mmol of 2,2 '-bipyridine-4, 4' -diphosphonic acid and CuCl20.1mmol was placed in a bottle, and then concentrated hydrochloric acid: water (mass ratio) 1: 5 total 1.5ml of the mixed solution is added into a bottle, heated for 3 hours at 240 ℃, and naturally cooled to obtain green crystals. The infrared spectrum is shown in figure 2.
The proton conductivity of the resulting compound was tested: at a Relative Humidity (RH) of 98%, the proton conductivity of the compound increased with increasing temperature in a linear relationship, and was 1.97X 10 at 25 ℃ and 100 ℃ respectively-4And 4.32X 10-3S·cm-1. Under these conditions, the activation energy of the compound was 0.41 eV. The powder proton conductivity of the compound at 25 ℃ does not change much with increasing humidity (1.64X 10 from RH 35%)-41.96X 10 to RH 98%-4S·cm-1). The powder proton conductivity of the compound at 100 ℃ increased with increasing humidity (1.97X 10 from RH 35%)-34.32X 10 to RH 98%-3S·cm-1) See fig. 5. The compound has good proton conductivity, so that the compound can be used as a proton conductive material in the field of fuel cellsPotential candidate solid materials for the material.
The structure of the compound shows that the compound is an anhydrous system, and the thermogravimetry shows that the compound does not lose weight below 100 ℃. See fig. 3. Therefore, the proton conductivity of the compound is derived from a hydrogen bond layer formed between the compound layer and the interlayer by a hydroxyl group and an oxygen atom on phosphoric acid. XRD of the compound before and after testing is basically unchanged, which shows that the skeleton of the compound is unchanged, and shows that the compound has good stability to water and good thermal stability, and is shown in figure 4.
Claims (3)
1. The two-dimensional MOFs material with proton conductivity is characterized in that 2,2 '-bipyridine-4, 4' -diphosphonic acid H is used4L is a ligand, Cu2+、Cl-Two-dimensional layer structure constructed as connection point, Cu2+、Cl-In thatcOne-dimensional chains are formed in the direction, thenbIn the direction of H3L-The ligand is connected with copper atoms of the upper chain and the lower chain to form a two-dimensional layer; the molecular formula is C10H9ClCuN2O6P2The unit cell parameters are as follows: belongs to a monoclinic system and is characterized in that,C2/cthe space group is formed by the space group,a=22.9382 Å, b=7.9268 Å, c=14.9860 Å , β= 100.391°, F(000)=1656.0, V= 2680.1(5) Å3, Z=8。
2. a method for preparing two-dimensional MOFs materials with proton conducting properties according to claim 1, characterized by the following steps:
2,2 '-bipyridine-4, 4' -diphosphonic acid and CuCl2Adding into the mixture of water and concentrated hydrochloric acid at 200-250 deg.CoC, heating for reaction, and naturally cooling after the reaction is finished to obtain green crystals, so as to obtain the target material.
3. The method of preparing two-dimensional MOFs materials having proton conducting properties according to claim 2, wherein CuCl2The mol ratio of the 2,2 '-bipyridine-4, 4' -diphosphonic acid is selected from: 1.0-2.0: 1.0; concentrated hydrochloric acid: selecting 1 part of water by mass: 5-8.
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Citations (4)
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| CN106905352A (en) * | 2017-02-28 | 2017-06-30 | 河南省科学院化学研究所有限公司 | A kind of copper organic inorganic hybridization compound and its synthetic method |
| CN106967220A (en) * | 2017-03-31 | 2017-07-21 | 西京学院 | A kind of polyacid Base Metal organic frame proton conductor material of acid molecule functionalization and preparation method thereof |
| CN108084452A (en) * | 2018-01-09 | 2018-05-29 | 武汉理工大学 | A kind of metal-organic framework type proton conductor material being applicable under high temperature, low humidity conditions and preparation method thereof |
| CN108841008A (en) * | 2018-06-27 | 2018-11-20 | 首都师范大学 | A kind of preparation of the Solid-State proton conductive material with wide operating temperature range |
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| CN106905352A (en) * | 2017-02-28 | 2017-06-30 | 河南省科学院化学研究所有限公司 | A kind of copper organic inorganic hybridization compound and its synthetic method |
| CN106967220A (en) * | 2017-03-31 | 2017-07-21 | 西京学院 | A kind of polyacid Base Metal organic frame proton conductor material of acid molecule functionalization and preparation method thereof |
| CN108084452A (en) * | 2018-01-09 | 2018-05-29 | 武汉理工大学 | A kind of metal-organic framework type proton conductor material being applicable under high temperature, low humidity conditions and preparation method thereof |
| CN108841008A (en) * | 2018-06-27 | 2018-11-20 | 首都师范大学 | A kind of preparation of the Solid-State proton conductive material with wide operating temperature range |
Non-Patent Citations (1)
| Title |
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| Synthesis, Structure and Proton Conductivity of a Complex Based on Decorated Keggin-Type Cluster: {[Cu(dmbipy)(H2O)(2)Cl-0.5](2)[PW12O40]}center dot 7H(2)O (dmbipy=4,4"-dimethyl-2,2"-bipyridine);Xi Wang et al.;《JOURNAL OF CLUSTER SCIENCE》;20160107;第27卷;第645-656页 * |
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