CN116023670B - Phosphonic acid group hydrogen bond organic framework material, preparation method thereof and application thereof in proton conduction - Google Patents
Phosphonic acid group hydrogen bond organic framework material, preparation method thereof and application thereof in proton conduction Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 115
- 239000001257 hydrogen Substances 0.000 title claims abstract description 113
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 113
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000013384 organic framework Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000010992 reflux Methods 0.000 claims abstract description 51
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 8
- 238000001953 recrystallisation Methods 0.000 claims abstract description 8
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 6
- 239000010452 phosphate Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- QCTBMLYLENLHLA-UHFFFAOYSA-N aminomethylbenzoic acid Chemical compound NCC1=CC=C(C(O)=O)C=C1 QCTBMLYLENLHLA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 9
- 229920002866 paraformaldehyde Polymers 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 6
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical group COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 9
- 239000013078 crystal Substances 0.000 abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 22
- 238000001914 filtration Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000000634 powder X-ray diffraction Methods 0.000 description 8
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 7
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- MICRDKKVJPDJHX-UHFFFAOYSA-N 4-amino-3-ethylhexan-3-ol Chemical compound CCC(N)C(O)(CC)CC MICRDKKVJPDJHX-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to the technical field of crystal material preparation and proton conduction, in particular to a preparation method of a phosphonic acid group hydrogen bond organic framework material, which comprises the steps of introducing phosphate into an organic building block through a covalent bond, and recrystallizing the organic building block to obtain the phosphonic acid group hydrogen bond organic framework material; wherein the recrystallization comprises: and dissolving the organic building blocks in an acidic aqueous solution, and heating and refluxing to obtain the phosphonic acid group hydrogen bond organic framework material. According to the invention, the proton conductivity can be effectively improved by regulating and controlling the substituent of oxygen on the phosphate group, so that the phosphate hydrogen bond organic framework material with good proton conductivity is obtained.
Description
Technical Field
The invention relates to the technical field of crystal material preparation and proton conduction, in particular to a phosphonic acid group hydrogen bond organic framework material, a preparation method thereof and application thereof in proton conduction.
Background
With the rapid development of modern industrial technology and rapid consumption of energy, humans face serious energy and environmental problems. In recent years, researchers have vigorously developed various novel power generation technologies, and clean energy is utilized to replace traditional fossil energy. Proton exchange membrane fuel cells have been attracting attention over the past decades as an important clean energy platform. The ideal solid state proton conductor as an electrolyte in a proton exchange membrane fuel cell requires not only high conductivity but also high stability and safety under severe operating conditions to accommodate long cycle testing. A commercially used PEM (proton exchange membrane) material is a sulfonated fluoropolymer. However, the disadvantages of higher cost, narrow working conditions, intrinsic amorphous structure and the like exist, so that the corresponding proton conducting material cannot be further optimized and the conduction mechanism cannot be determined. Therefore, developing proton conductive materials with high crystallinity, adjustable structure, good stability and optimizability becomes one of the research hotspots in the field.
The hydrogen bond organic framework material is a novel crystal proton conductive material assembled by organic building blocks through hydrogen bond interaction. The rich hydrogen bonds and high crystallinity of hydrogen bond organic framework materials provide opportunities for optimizing proton conduction pathways, improving proton conductivity, and making them a model for understanding proton conductor conduction mechanisms. These unique characteristics make hydrogen-bonded organic framework materials a potentially tunable platform for building unique solid state proton conductors. However, hydrogen bonded organic framework materials present challenges of poor stability and low controllability. Most hydrogen bond interactions are intrinsically weak, flexible and low directional in terms of bond energy and bond angle compared to covalent and coordination bonds.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a phosphonic acid group hydrogen bond organic framework material, wherein phosphate is introduced into an organic building block through a covalent bond, and the organic building block is recrystallized to obtain the phosphonic acid group hydrogen bond organic framework material.
According to an embodiment of the invention, the recrystallization comprises: and dissolving the organic building blocks in an acidic aqueous solution, and heating and refluxing to obtain the phosphonic acid group hydrogen bond organic framework material.
According to an embodiment of the invention, the organic building block is present in the acidic aqueous solution in an amount of 2-15mg/mL, for example 5-10mg/mL.
According to an embodiment of the present invention, the acidic aqueous solution may be selected from one, a mixture of two or more aqueous solutions of hydrochloric acid, formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, phenylphosphonic acid, and the concentration of the acidic aqueous solution is 0.1 to 1mol/L, for example, 0.4 to 0.5mol/L, and exemplary is an aqueous solution of hydrochloric acid having a concentration of 0.4 mol/L.
According to an embodiment of the invention, the temperature of the heated reflux is 80-120 ℃, preferably the temperature of the recrystallization is 95-105 ℃, for example 100 ℃.
According to an embodiment of the invention, the time of the heating reflux is 2-10 hours, preferably the time of the recrystallization is 4-6 hours.
According to the embodiment of the invention, the method further comprises the steps of filtering, washing and airing after heating and refluxing.
According to an embodiment of the invention, the organic building blocks include semi-hydrolyzed organic building blocks and fully hydrolyzed organic building blocks.
According to an embodiment of the invention, the method for preparing a semi-hydrolyzed organic building block comprises the steps of:
1) Heating and refluxing triethylamine, 4- (aminomethyl) benzoic acid, paraformaldehyde and trialkyl phosphite in methanol to obtain a reflux solution;
2) Adding an alkaline aqueous solution into the reflux solution for reflux to obtain a reflux product;
3) And acidifying and semi-hydrolyzing the reflux product to obtain the semi-hydrolyzed organic building block.
Preferably, the trialkyl phosphite is selected from trimethyl phosphite or triethyl phosphite.
According to an embodiment of the invention, step 1) comprises the steps of: firstly, mixing triethylamine and methanol, heating to 80-85 ℃, then sequentially adding 4- (aminomethyl) benzoic acid, trialkyl phosphite and paraformaldehyde, and refluxing.
According to an embodiment of the present invention, in step 1), the molar ratio of 4- (aminomethyl) benzoic acid to trialkyl phosphite is (1-2): (1-3), preferably, the molar ratio of 4- (aminomethyl) benzoic acid to trialkyl phosphite is (1-1.5): (1-2).
According to an embodiment of the present invention, in step 1), the molar ratio of 4- (aminomethyl) benzoic acid to paraformaldehyde is (1-3): (0.3-2), preferably (1-2): (0.8-1).
According to an embodiment of the present invention, in step 1), the molar ratio of 4- (aminomethyl) benzoic acid to triethylamine is (1-3): (2-6), preferably (1-2.5): (3-5).
According to an embodiment of the invention, in step 1), the temperature of the heated reflux is 60-120 ℃, preferably the temperature of the heated reflux is 85-95 ℃.
According to an embodiment of the present invention, in step 1), the time of the heating reflux is 2 to 10 hours, preferably, the time of the heating reflux is 3 to 5 hours.
As an example, in step 1), the heating and refluxing includes heating and refluxing until the solution becomes clear, and refluxing for 3 to 6 hours, preferably, 4 to 5 hours after the clarification.
According to an embodiment of the present invention, in step 2), the alkaline aqueous solution may be selected from one, two or more mixed aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate, and the concentration of the alkaline aqueous solution is 2 to 10mol/L, preferably 5 to 7mol/L.
According to an embodiment of the invention, in step 2), the time of the reflux is 1 to 5 hours, preferably the time of the reflux is 1 to 3 hours.
Preferably, after refluxing in step 2), a step of obtaining a refluxed product by cooling, filtering and evaporating is further included.
According to an embodiment of the invention, the acidification in step 3) is performed in an aqueous hydrochloric acid solution having a concentration of 1-10mol/L, preferably having a concentration of 5-7mol/L.
According to an embodiment of the invention, the acid hydrolysis of the reflux product described in step 3) comprises the steps of: and adding an aqueous solution of hydrochloric acid into the reflux product for semi-hydrolysis until powder is separated out, thus obtaining the semi-hydrolyzed organic building block.
According to an embodiment of the invention, the method further comprises the steps of filtering and drying the powder after precipitation of the powder to obtain the semi-hydrolyzed organic building block.
According to an exemplary embodiment of the present invention, when the trialkyl phosphite is trimethyl phosphite, the semi-hydrolyzed organic building block is prepared as L-CH 3 。
According to an exemplary embodiment of the present invention, when the trialkyl phosphite is triethyl phosphite, the semi-hydrolyzed organic building block prepared is designated L-Et.
According to an embodiment of the invention, the method for preparing the fully hydrolyzed organic building block comprises the steps of: adding the semi-hydrolyzed organic building blocks into a hydrochloric acid aqueous solution for reflux full hydrolysis to obtain full-hydrolyzed organic building blocks;
according to an embodiment of the invention, the aqueous hydrochloric acid solution has a concentration of 4-12mol/L, preferably 5-7mol/L, for example 6mol/L.
According to an embodiment of the invention, the time for which the semi-hydrolyzed organic building block is refluxed in aqueous hydrochloric acid is from 6 to 12 hours, preferably the time for which the semi-hydrolyzed organic building block is refluxed in aqueous hydrochloric acid is from 8 to 10 hours.
According to an embodiment of the invention, the fully hydrolyzed organic building block is designated L-H.
The invention also provides a phosphonic acid group hydrogen bond organic framework material which is prepared by the method.
According to an embodiment of the invention, the phosphonic acid based hydrogen bonding organic framework material is a rod-like structure having a length of 1-200 μm, preferably 20-150 μm, e.g. 60-100 μm.
According to an embodiment of the invention, the phosphonic acid based hydrogen bonding organic framework material is a crystalline compound.
According to an embodiment of the invention, the phosphonic acid based hydrogen bond organic framework material is selected from phosphonic acid based hydrogen bond organic framework materials L-CH 3 Organic framework material L-Et and organic framework material L-H.H 2 O。
According to an embodiment of the invention, the phosphonic acid based hydrogen bonding organic framework material L-CH 3 Has the molecular formula of C 10 H 14 NO 5 P, belonging to monoclinic system, the space group is P2 1 /n，
According to an embodiment of the invention, the phosphonic acid based hydrogen bonding organic framework material L-Et has the formula C 11 H 16 NO 5 P, belonging to monoclinic system, the space group is P2 1 /n，
According to an embodiment of the invention, the phosphonic acid based hydrogen bonding organic framework material L-H.H 2 O has the molecular formula of C 9 H 14 NO 6 P, belonging to orthorhombic system, the space group is P2 1 2 1 2 1 ，
In the preparation process of the phosphonic acid group hydrogen bond organic framework material, the unit cell parameters of the obtained crystalline compound have slight differences due to the slight torsion of the organic building blocks.
According to an embodiment of the invention, the phosphonic acid based hydrogen bonding organic framework material L-CH 3 Has a crystal structure diagram basically shown in figure 1, a one-dimensional hydrogen bond chain and a three-dimensional space structure diagram.
According to an embodiment of the present invention, the phosphonic acid based hydrogen bonding organic framework material L-Et has a crystal structure schematic, one-dimensional hydrogen bonding chain and three-dimensional space structure diagram substantially as shown in fig. 2.
According to an embodiment of the invention, the phosphonic acid based hydrogen bonding organic framework material L-H.H 2 O has a crystal structure schematic diagram substantially as shown in FIG. 3, a one-dimensional hydrogen bond chain and a three-dimensional space structure diagram.
According to an embodiment of the present invention, the phosphonic acid based hydrogen bonding organic framework material has substantially the X-ray powder diffraction pattern as shown in fig. 4.
According to an embodiment of the present invention, the phosphonic acid based hydrogen bonding organic framework material has substantially the scanning electron microscope picture as shown in fig. 5.
According to an embodiment of the present invention, the phosphonic acid based hydrogen bonding organic framework material has substantially the crystal diagram as shown in fig. 6.
According to an embodiment of the present invention, the phosphonic acid based hydrogen bonding organic framework material has substantially the thermogravimetric profile as shown in fig. 7.
According to an embodiment of the present invention, the phosphonic acid based hydrogen bonding organic framework material has substantially the infrared profile as shown in fig. 8.
According to an embodiment of the invention, the phosphonic acid based hydrogen bonding organic framework material also has water stability and acid-base stability. The material had an X-ray powder diffraction pattern substantially as shown in figures 9-11 after thirty days of immersion in water, acidic solution and alkaline solution, with no change in structure compared to the material prior to immersion.
The invention also provides application of the phosphonic acid group hydrogen bond organic framework material in proton conduction, such as application in proton exchange membrane fuel cells.
Advantageous effects
According to the hydrogen bond organic framework material, the phosphate is introduced into the organic building block through the covalent bond, and then the phosphonic acid group hydrogen bond organic framework material with stable and adjustable structure is synthesized through a simple recrystallization process. The phosphonic acid group hydrogen bond organic framework material contains rich phosphoric acid groups, can provide more hydrogen bond acceptors and donors, and has higher thermal stability, water stability and acid-base stability. The invention can effectively improve proton conductivity by regulating and controlling the substituent of oxygen on the phosphate group, and obtain the phosphate hydrogen bond organic framework material (L-CH in the material) with good proton conductivity 3 Proton conductivity can be higher than 10 -3 Scm -1 ) Has great application prospect in the aspect of proton exchange membrane fuel cells.
The synthesis method of the phosphonic acid group hydrogen bond organic framework material is simple, short in operation period, easy to process, low in cost and suitable for large-scale industrial production.
Drawings
FIG. 1 is a L-CH prepared in example 1 3 A crystal structure diagram of the crystalline product, a one-dimensional hydrogen bond chain and a three-dimensional space structure diagram;
FIG. 2 is a schematic diagram of the crystal structure, one-dimensional hydrogen bond chain and three-dimensional space structure of the crystalline L-Et product prepared in example 2;
FIG. 3 is L-H.H prepared in example 3 2 A crystal structure diagram of the O crystalline product, a one-dimensional hydrogen bond chain and a three-dimensional space structure diagram;
FIG. 4 shows the L-CH obtained by the preparation of examples 1, 2 and 3 3 ，L-Et，L-H·H 2 X-ray powder diffraction pattern of O;
FIG. 5 is the L-CH prepared in examples 1, 2 and 3 3 ，L-Et，L-H·H 2 O scanning electron microscope image;
FIG. 6 is the L-CH prepared in examples 1, 2 and 3 3 ，L-Et，L-H·H 2 A crystal photograph of the O crystalline product;
FIG. 7 is the L-CH prepared in examples 1, 2 and 3 3 ，L-Et，L-H·H 2 Thermal gravimetric graph of O crystalline product;
FIG. 8 is the L-CH prepared in examples 1, 2 and 3 3 ，L-Et，L-H·H 2 Infrared plot of O crystalline product;
FIG. 9 is a L-CH prepared in example 1 3 X-ray powder diffraction pattern after soaking in water, aqueous hydrochloric acid solution at ph=1, aqueous sodium hydroxide solution at ph=11, respectively, for thirty days;
FIG. 10 is an X-ray powder diffraction pattern of L-Et prepared in example 2 after soaking in water, aqueous hydrochloric acid solution of pH=1, aqueous sodium hydroxide solution of pH=11, respectively, for thirty days;
FIG. 11 is L-H.H prepared in example 3 2 X-ray powder diffraction pattern after soaking O in water, aqueous hydrochloric acid solution at ph=1, aqueous sodium hydroxide solution at ph=11, respectively, for thirty days;
FIG. 12 is a L-CH prepared in example 1 3 Impedance and proton conductivity maps;
FIG. 13 is an impedance plot and proton conductivity plot of the L-Et prepared in example 2;
FIG. 14 is L-H.H prepared in example 3 2 O-impedance and proton conductivity.
Detailed Description
The organic framework material of the present invention, and the method for preparing and using it, will be described in further detail below with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
In this example, the phosphonic acid based organic building block is denoted as L-CH 3 L-Et, L-H; which represents the phosphonic acid group hydrogen bond organic framework material L-CH 3 ，L-Et，L-H·H 2 O is based on L-CH respectively 3 The L-Et and L-H organic building blocks are prepared by reflux recrystallization; for example: phosphonic acid group hydrogen bond organic framework material L-CH 3 Represented by organic building blocks L-CH 3 And (3) carrying out reflux recrystallization at 100 degrees to obtain the product.
In the examples below, the phosphonic acid group hydrogen bond organic framework material (L-CH 3 ，L-Et，L-H·H 2 O) the building block, the one-dimensional hydrogen bond chain and the three-dimensional structure schematic diagram are characterized by a single crystal diffractometer.
In the examples below, the phosphonic acid group hydrogen bond organic framework material (L-CH 3 ，L-Et，L-H·H 2 The X-ray powder diffraction pattern of O) was characterized by a MiniFlex type II powder diffractometer.
In the examples below, the phosphonic acid group hydrogen bond organic framework material (L-CH 3 ，L-Et，L-H·H 2 The morphology of O) was characterized by a Zeiss sigma300 scanning electron microscope.
In the following examples, phosphonic acid based hydrogen bond organicFrame material (L-CH) 3 ，L-Et，L-H·H 2 The crystal pictures of O) are characterized by optical electron microscopy.
In the examples below, the phosphonic acid group hydrogen bond organic framework material (L-CH 3 ，L-Et，L-H·H 2 O) is characterized by a STA449F3 thermogravimetric analyzer.
In the examples below, the phosphonic acid group hydrogen bond organic framework material (L-CH 3 ，L-Et，L-H·H 2 The infrared curve of O) was characterized by a Spectrum one infrared analyzer.
In the examples below, the phosphonic acid group hydrogen bond organic framework material (L-CH 3 ，L-Et，L-H·H 2 O) is detected by a Solartron1260 impedance/gain-phase analyzer and is derived from the debye semicircle in the Nyquist plot.
EXAMPLE 1 phosphonic acid based Hydrogen bonding organic framework Material L-CH 3 And a method for preparing the same
200mL of methanol and 20mL of triethylamine are added into a 250mL two-neck flask, heated to 85 ℃, 5g of 4- (aminomethyl) benzoic acid is then added, 5.7mL of trimethyl phosphite is then added dropwise, 0.96g of paraformaldehyde is added, heating and refluxing are continued for a while, the solution becomes clear, 4 hours of refluxing is carried out, 24mL of 6mol/L aqueous sodium hydroxide solution is added, refluxing is carried out for 2 hours, cooling, filtering and rotary evaporation are carried out, the obtained product is acidified by 30mL of 6mol/L aqueous hydrochloric acid solution, the aqueous hydrochloric acid solution is added dropwise while shaking until white powder is precipitated, filtering and 60 ℃ drying are carried out, and a semi-hydrolyzed organic building block is obtained and is marked as L-CH 3 . 100g of L-CH was taken in a 100mL round bottom flask 3 Adding 10mL of 0.4mol/L hydrochloric acid aqueous solution, refluxing and recrystallizing at 100 ℃, filtering and washing to obtain L-CH 3 And (5) a crystal.
FIG. 1 is a phosphonic acid group hydrogen bond organic framework material L-CH prepared in example 1 3 A structural schematic diagram of the crystal, a one-dimensional hydrogen bond chain and a three-dimensional space structure diagram.
FIG. 4 is a phosphonic acid based hydrogen bonding organic framework material L-CH prepared in example 1 3 Powder diffraction pattern of (2).
The left-hand diagram in FIG. 5 shows the phosphonic acid based hydrogen prepared in example 1Bonded organic framework material L-CH 3 The scanning electron microscope image of (2) shows that the crystal prepared in this example has a rod-like structure.
The left-hand diagram in FIG. 6 shows the phosphonic acid based hydrogen bonding organic framework material L-CH prepared in example 1 3 The crystal prepared in this example had a rod-like structure as can be seen from the figure.
Example 2: phosphonic acid group hydrogen bond organic framework material L-Et and preparation method thereof
200mL of methanol and 20mL of triethylamine are added into a 250mL two-neck flask, the mixture is heated to 85 ℃, 5g of 4- (aminomethyl) benzoic acid is then added, 8.8mL of triethyl phosphite is then added dropwise, 0.96g of paraformaldehyde is added, heating reflux is continued for a while, the solution becomes clear, 4 hours of reflux is carried out, 24mL of 6mol/L aqueous sodium hydroxide solution is added, reflux is carried out for 2 hours, cooling and filtration are carried out, the obtained product is acidified by 30mL of 6mol/L aqueous hydrochloric acid solution, the aqueous hydrochloric acid solution is added dropwise while shaking until white powder is precipitated, filtration is carried out, and 60 ℃ drying is carried out to obtain a semi-hydrolyzed organic building block which is marked as L-Et. 100g of L-Et was taken in a 100mL round-bottomed flask, 10mL of a 0.4mol/L aqueous hydrochloric acid solution was added, and the mixture was recrystallized at 100℃under reflux, filtered and washed to obtain crystals of L-Et.
FIG. 2 is a schematic diagram of the crystal structure of the phosphonic acid based hydrogen bond organic framework material L-Et prepared in example 2, a one-dimensional hydrogen bond chain and a three-dimensional space structure diagram.
FIG. 4 is a powder diffraction pattern of the phosphonic acid based hydrogen bonding organic framework material L-Et prepared in example 2.
The middle diagram of FIG. 5 is a scanning electron microscope image of the phosphonic acid group hydrogen bonding organic framework material L-Et prepared in example 2, and it is clear from the image that the organic framework material prepared in this example has a rod-like structure with the same or different lengths.
The middle diagram of FIG. 6 is a photograph of crystals of the phosphonic acid based hydrogen bonding organic framework material L-Et prepared in example 2, from which the crystals prepared in this example are seen to have a linear structure.
Example 3: phosphonic acid group hydrogen bond organic frame material L-H.H 2 O and preparation method thereof
200mL of methanol and 20mL of triethylethanolAmine is added into a 250mL two-neck flask, heated to 85 ℃, then 5g of 4- (aminomethyl) benzoic acid is added, then 8.8mL of triethyl phosphite is added dropwise, 0.96g of paraformaldehyde is added, heating reflux is continued for a while, the solution becomes clear, reflux is carried out for 4 hours, 24mL of 6mol/L aqueous sodium hydroxide solution is added, reflux is carried out for 2 hours, cooling, filtration and rotary evaporation are carried out, the obtained product is acidified by 30mL of 6mol/L aqueous hydrochloric acid solution, the aqueous hydrochloric acid solution is added dropwise, shaking is carried out while adding until white powder is precipitated, filtration and 60 ℃ drying are carried out to obtain a semi-hydrolyzed organic building block which is marked as L-Et. A100 mL round bottom flask was used to obtain 6.5g of L-Et, 20mL of 6mol/L hydrochloric acid aqueous solution was added thereto, the mixture was refluxed for 9 hours to hydrolyze the L-Et to obtain fully hydrolyzed L-H, the mixture was distilled, filtered and dried in a 60 ℃ oven to obtain a powdery L-H organic building block, which was designated as L-H. Taking 100g of L-H, adding 10mL of 0.4mol/L hydrochloric acid aqueous solution, refluxing and recrystallizing at 100 ℃, filtering and washing to obtain L-H.H 2 And O crystal.
FIG. 3 is a phosphonic acid based hydrogen bonding organic framework material L-H.H prepared in example 3 2 O crystal structure diagram, one-dimensional hydrogen bond chain and three-dimensional space structure diagram.
FIG. 4 is a phosphonic acid based hydrogen bonding organic framework material L-H.H prepared in example 3 2 Powder diffraction pattern of O.
The right-hand graph of FIG. 5 shows the phosphonic acid based hydrogen bonding organic framework material L-H.H prepared in example 3 2 In the scanning electron microscope image of O, the organic frame materials prepared in this example are rod-like structures with the same or different lengths.
The right-hand graph of FIG. 6 shows the phosphonic acid based hydrogen bonding organic framework material L-H.H prepared in example 3 2 The crystal photograph of O shows that the crystal prepared in this example has a rod-like structure.
The thermogravimetric plot as shown in fig. 7 illustrates that the phosphonic acid based hydrogen bonding organic framework materials of examples 1-3 have good thermal stability.
The infrared plot shown in fig. 8 illustrates the successful preparation of the phosphonic acid based hydrogen bonding organic framework materials of examples 1-3.
Test example 1: crystal parameter testing
By single crystal X-ray analysisL-CH prepared in examples 1-3 3 ，L-Et，L-H·H 2 Crystal parameters of O, see table 1:
TABLE 1L-CH 3 ，L-Et，L-H·H 2 Crystal parameters of O
Test example 2: phosphonic acid group hydrogen bond organic framework material has water stability and acid-base stability test
The phosphonic acid group hydrogen bond organic framework materials prepared in examples 1-3 (L-CH 3 ，L-Et，L-H·H 2 O) were soaked in water, aqueous hydrochloric acid solution at ph=1, aqueous sodium hydroxide solution at ph=11 for thirty days, filtered after thirty days, washed with water, dried in air, and tested for X-ray powder diffraction and observed for changes in their structure. Referring to fig. 9 to 11, it can be seen that: the phosphonic acid group hydrogen bond organic framework material has good water stability and acid-base stability.
Test example 3: proton conductivity test
Proton conductivity measurements were made using an ac impedance technique and a Solartron1260 impedance/gain phase analyzer. The crystalline powder samples prepared in examples 1-3 were compressed into discs at a pressure of 101 MPa. The two sides of the wafer are connected to the gold wire by gold glue. At a temperature of from 30 ℃ to 80 ℃ and a Relative Humidity (RH) of from 40 to 98% at a different temperature of from 1 to 10 6 Sample particles were measured at a frequency of Hz. The conductivity of the samples was deduced from the debye semicircle in the Nyquist plot.
As can be seen from fig. 12 to 14: phosphonic acid group hydrogen bond organic framework material L-CH prepared in examples 1-3 of the invention 3 、L-Et、L-H·H 2 Proton conductivities of O are 4.2X10 respectively -3 Scm -1 ，3.33×10 -4 Scm -1 ，6.03×10 -5 Scm -1 。
According to the results, the phosphonic acid group hydrogen bond organic framework material prepared in the embodiment of the invention has higher proton conductivity and L-CH 3 Proton conductivity can be higher than10 -3 Scm -1 The proton conductivity of the material is obviously higher than that of most hydrogen bond organic frame materials, and the material can be applied to the technical field of proton exchange membrane fuel cells.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (23)
1. A preparation method of a phosphonic acid group hydrogen bond organic framework material is characterized in that phosphate is introduced into an organic building block through a covalent bond, and then the organic building block is recrystallized to obtain the phosphonic acid group hydrogen bond organic framework material;
the recrystallization includes: dissolving the organic building blocks in an acidic aqueous solution, and heating and refluxing to obtain the phosphonic acid group hydrogen bond organic framework material;
the organic building blocks comprise semi-hydrolysis organic building blocks and full-hydrolysis organic building blocks;
the preparation method of the semi-hydrolyzed organic building block comprises the following steps:
1) Heating and refluxing triethylamine, 4- (aminomethyl) benzoic acid, paraformaldehyde and trialkyl phosphite in methanol to obtain a reflux solution;
2) Adding an alkaline aqueous solution into the reflux solution for reflux to obtain a reflux product;
3) Acidifying and semi-hydrolyzing the reflux product to obtain a semi-hydrolyzed organic building block;
the preparation method of the fully hydrolyzed organic building block comprises the following steps: and adding the semi-hydrolyzed organic building blocks into a hydrochloric acid aqueous solution to reflux and fully hydrolyze to obtain the fully hydrolyzed organic building blocks.
2. The method for producing a phosphonic acid based hydrogen bonding organic framework material according to claim 1, characterized in that the content of the organic building block in an acidic aqueous solution is 2-15 mg/mL.
3. The method for preparing a phosphonic acid based hydrogen bond organic framework material according to claim 1, wherein the trialkyl phosphite is selected from trimethyl phosphite or triethyl phosphite.
4. The method for preparing a phosphonic acid based hydrogen bonding organic framework material according to claim 1, wherein the step 1) in the method for preparing the semi-hydrolyzed organic building block comprises the following steps: firstly, mixing triethylamine and methanol, heating to 80-85 ℃, then sequentially adding 4- (aminomethyl) benzoic acid, trialkyl phosphite and paraformaldehyde, and refluxing.
5. The method for producing a phosphonic acid based hydrogen bonding organic framework material according to any one of claims 1 to 4, characterized in that in step 1), the molar ratio of 4- (aminomethyl) benzoic acid to trialkyl phosphite is (1-2): (1-3).
6. The method for producing a phosphonic acid based hydrogen bonding organic framework material according to any one of claims 1 to 4, characterized in that in step 1), the molar ratio of 4- (aminomethyl) benzoic acid to paraformaldehyde is (1 to 3): (0.3-2).
7. The method for producing a phosphonic acid based hydrogen bonding organic framework material according to any one of claims 1 to 4, characterized in that in step 1), the molar ratio of 4- (aminomethyl) benzoic acid to triethylamine is (1 to 3): (2-6).
8. The method for producing a phosphonic acid based hydrogen bonding organic framework material according to any one of claims 1 to 4, characterized in that in step 2), the alkaline aqueous solution is selected from one, two or more mixed aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the concentration of the alkaline aqueous solution is 2 to 10 mol/L.
9. The method for producing a phosphonic acid based hydrogen bonding organic framework material according to any one of claims 1 to 4, characterized in that in step 2), the time of the reflow is 1 to 5 hours.
10. The method for preparing a phosphonic acid based hydrogen bonding organic framework material according to any one of claims 1 to 4, characterized in that the acidification and semi-hydrolysis of the reflux product in step 3) comprises the following steps: and adding an acidic aqueous solution into the reflux product for semi-hydrolysis until powder is separated out, and obtaining the semi-hydrolyzed organic building block.
11. The method for producing a phosphonic acid based hydrogen bonding organic framework material according to any one of claims 1 to 4, characterized in that when the trialkyl phosphite is trimethyl phosphite, the semi-hydrolyzed organic building block produced is denoted as L-CH 3 。
12. The method for producing a phosphonic acid based hydrogen bonding organic framework material according to any one of claims 1 to 4, characterized in that when the trialkyl phosphite is triethyl phosphite, the semi-hydrolyzed organic building block produced is denoted as L-Et.
13. The method for producing a phosphonic acid based hydrogen bonding organic framework material according to any one of claims 1 to 4, characterized in that the concentration of the aqueous hydrochloric acid solution is 4 to 12 mol/L.
14. The method for preparing a phosphonic acid based hydrogen bonding organic framework material according to any of claims 1-4, characterized in that the time of refluxing the semi-hydrolyzed organic building block in the aqueous hydrochloric acid solution is 6-12 hours.
15. The method for preparing a phosphonic acid based hydrogen bonding organic framework material according to any of claims 1-4, characterized in that the fully hydrolyzed organic building block is denoted as L-H.
16. A phosphonic acid based hydrogen bonded organic framework material prepared by the method of any one of claims 1 to 15.
17. The phosphonic acid based hydrogen bond organic framework material of claim 16 characterized in that the phosphonic acid based hydrogen bond organic framework material is a rod-like structure having a length of 1-200 μιη.
18. The phosphonic acid based hydrogen bond organic framework material of claim 16 or 17, wherein the phosphonic acid based hydrogen bond organic framework material is selected from phosphonic acid based hydrogen bond organic framework materials L-CH 3 Organic framework material L-Et and organic framework material L-H.H 2 O。
19. The phosphonic acid based hydrogen bond organic framework material of claim 18, wherein the phosphonic acid based hydrogen bond organic framework material is L-CH 3 Has the molecular formula of C 10 H 14 NO 5 P belongs to monoclinic system, and the space group isP2 1 /n，a=4.983±0.02 Å，b=10.866±0.02 Å，c =22.041±0.02 Å。
20. The phosphonic acid based hydrogen bonded organic framework material of claim 18 having a molecular formula C 11 H 16 NO 5 P belongs to monoclinic system, and the space group isP2 1 /n，a =4.9868±0.02 Å ，b =10.9257±0.02 Å，c =22.6929±0.02 Å。
21. The phosphonic acid based hydrogen bond organic framework material of claim 18 wherein the phosphonic acid based hydrogen bond organic framework material L-H 2 O has the molecular formula of C 9 H 14 NO 6 P belongs to an orthorhombic system, and the space group isP2 1 2 1 2 1 ，a =5.1358±0.02 Å，b=10.9727±0.02 Å，c =20.9412±0.02 Å。
22. Use of a phosphonic acid based hydrogen bonding organic framework material as claimed in any of claims 16 to 21 for proton conduction.
23. The use according to claim 22, wherein the phosphonic acid based hydrogen bonding organic framework material is used in a proton exchange membrane fuel cell.
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