CN110229346A - A kind of strontium coordination polymer and its preparation method and application - Google Patents
A kind of strontium coordination polymer and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of strontium coordination polymer and its preparation method and application, the chemical formula of the strontium coordination polymer is { [Sr4(hedpH2)4(μ2‑H2O)2(H2O)4]·4H2O}n, n is positive integer, and hedp is 1-hydroxy ethylidene-1,1-diphosphonic acid organic ligand；The strontium coordination polymer has preferable proton conductivity of phosphoric acid, higher water stability, and the conductivity of strontium coordination polymer of the present invention is 4.9 × 10 under 55 DEG C and 98% relative humidity‑3S/cm can be applied in the proton exchange membrane material of the fuel cell not high to performance requirement；The preparation method raw material of strontium coordination polymer of the present invention is easy to get, cheap, it can be achieved that lower production cost, and the cost of fuel cell is effectively reduced；Simultaneously using water as solvent, environmentally protective, simple production process, reaction condition is mild, and yield is higher, easy to industrialized production.
Description
Technical field
The present invention relates to coordination polymer technical fields, and in particular to a kind of strontium coordination polymer and preparation method thereof, with
And the application in proton exchange membrane material.
Background technique
The energy and environment are the two large problems of face of mankind nowadays.Currently, the master of fossil fuel or human being's production, life
Want the energy, but with the growth of global energy usage amount and not scientifical use, environmental problem caused by fossil fuel is increasingly tight
Weight, this taps a new source of energy with regard to an urgent demand people.Fuel cell is a kind of device that can efficiently convert chemical energy to electric energy,
It is considered as solving one of the most effective approach of energy and environmental problem.In numerous kinds of fuel cells, proton exchange membrane
Fuel cell (PEMFC) most has wide application prospects.And proton-conducting material is one of its core component in PEMFC,
Performance quality directly determines the performance and used life of fuel cell.Nafion membrane is that the proton of successful commercialization passes at present
Lead material, but the problems such as its high production cost and use scope small (high humidity and be lower than 80 DEG C) greatly limits its application.
Therefore the research hotspot that cheap proton exchange membrane material is current fuel cell field is developed.
Coordination polymer or metal organic framework are with organic ligand by metal ion or ion cluster by being self-assembly of
The crystalline material with periodical skeleton structure.In recent years, because its structure has height designability, scientist couple is caused
The research interest of its proton conduction property, while the material of alternative Nafion a kind of is developed into (referring to Shimizu
G.K.H. etc., Science, 2013,341,354；The Chem.Soc.Rev. such as X.Meng, 2017,46,464).
But all there is poor water stability, high production cost, be difficult in the current good coordination polymer of most of proton conductives
The problems such as industrialization, so preparing the coordination that the proton conduction property having had, water stability are high, raw material is cheap and convieniently synthesized
Polymer material is a huge challenge.
Summary of the invention
Water stability in order to solve proton conductive coordination polymer in the prior art is poor, synthesis cost is high and is difficult to work
The problem of industry, and a kind of strontium coordination polymer is provided and preparation method thereof, and the application in proton exchange membrane material.
The invention is realized by the following technical scheme:
A kind of strontium coordination polymer, chemical formula are { [Sr4(hedpH2)4(μ2-H2O)2(H2O)4]·4H2O}n, wherein n
For positive integer, hedp is organic ligand 1-hydroxy ethylidene-1,1-diphosphonic acid in formula, and molecular structural formula is as follows:
Further, the strontium coordination polymer is the crystal structure of anorthic system, P-1 space group, cell parameter are as follows:α=101.879 (3) °, β=91.601 (3) °,
γ=94.329 (3) °.
Further, the strontium coordination polymer has dissymmetrical structure unit, includes in the dissymmetrical structure unit
Four strontium ions (label Sr1, Sr2, Sr3, Sr4), four organic ligand ions, six waters of coordination (match for bridging by two of them
Position water) and four lattice watters.
Another aspect of the present invention provides a kind of preparation method of above-mentioned strontium coordination polymer,
The preparation method is that the synthesis of strontium coordination polymer monocrystalline: organic ligand and strontium salt are dissolved in water, are uniformly mixed,
PH=3~5 are adjusted, are reacted 24~36 hours at 80~100 DEG C under confined conditions, then cooled to room temperature, obtains strontium
Coordination polymer monocrystalline.The culture of monocrystalline to the water of reaction, pH, temperature and time it is more demanding.Hypervolia then produces
Amount is too low, can then generate powder very little；PH < 3 will lead to monocrystalline low output and generate even without product, and pH > 5 can be generated largely
Powder and have impurity generation；Temperature is too high, and crystal growth is too fast, crystallizes bad while can generate with powder, too low to cause
It can not react；Reaction 24 hours to 36 hours, can obtain preferable crystal, and time short crystal is small and low yield, spend 36 hours,
Yield does not have significant change.
Further, the strontium salt is strontium nitrate or strontium chloride, and the organic ligand is 1-hydroxy ethylidene-1,1-diphosphonic acid；It is organic to match
The molar ratio of body, strontium salt and water is (0.5~1): 1:(2000-4000).
The preparation method is that the synthesis of strontium coordination polymer powder: organic ligand and alkali is soluble in water, it is uniformly mixed,
Then the aqueous solution of strontium salt is added dropwise, stirs 0.5~1 hour, filters, washes, it is dry, obtain strontium coordination polymer powder.It is described
By organic ligand and the alkali concentration soluble in water for not requiring organic ligand and alkali, as long as guaranteeing organic ligand and alkali soluble
Solution；The aqueous solution of the strontium salt does not have concentration requirement, as long as guaranteeing to dissolve strontium salt.
Further, the strontium salt is strontium nitrate or strontium chloride, and the organic ligand is 1-hydroxy ethylidene-1,1-diphosphonic acid；It is described to have
The molar ratio of machine ligand, strontium salt and alkali is (0.5~1): 1:(1~2)；The alkali is sodium hydroxide or potassium hydroxide.
The present invention finally provides a kind of application of above-mentioned strontium coordination polymer in proton exchange membrane material.
Advantageous effects: the present invention relates to a kind of strontium coordination polymer and its preparation method and application, strontiums of the invention
Coordination polymer has preferable proton conductivity of phosphoric acid, higher water stability, the strontium of the present invention under 55 DEG C and 98% relative humidity
The conductivity of coordination polymer is 4.9 × 10-3S/cm can be applied to the proton exchange membrane of the fuel cell not high to performance requirement
In material；The preparation method raw material of strontium coordination polymer of the present invention is easy to get, cheap, it can be achieved that lower production cost, and
The cost of fuel cell is effectively reduced；Simultaneously using water as solvent, environmentally protective, simple production process, reaction condition is mild,
Yield is higher, easy to industrialized production.
Detailed description of the invention
Fig. 1 is powder x-ray diffraction (PXRD) map of strontium coordination polymer made from embodiment 1 and embodiment 3.
Fig. 2 is infrared spectroscopy (FT-IR) figure of the strontium coordination polymer of embodiment 2 and embodiment 3.
Fig. 3 is the asymmetric cell figure (hydrogen atom omission) of strontium coordination polymer of the present invention.
Fig. 4 is the coordination context diagram (hydrogen atom omission) of four strontium ions in strontium coordination polymer of the present invention.
Fig. 5 is the strontium coordination polymer of embodiment 1 and embodiment 3 in 25 DEG C, 50%~98% relative humidity and conductivity
Relational graph.
Specific embodiment
The present invention is further described below in conjunction with drawings and the specific embodiments, but does not limit the scope of the invention.
Embodiment 1
1-hydroxy ethylidene-1,1-diphosphonic acid (2.06g, 0.01mol) and potassium hydroxide (0.56g, 0.01mol) are dissolved in 10mL water, mixed
It closes uniformly, instills the 10mL aqueous solution of strontium nitrate (2.12g, 0.01mol), stir 0.5 hour, filter, distill water washing, air
It is dry, obtain the powder 2.5g of strontium coordination polymer, yield 74%.
Embodiment 2
1-hydroxy ethylidene-1,1-diphosphonic acid (1.03g, 0.005mol) and sodium hydroxide (0.8g, 0.02mol) are dissolved in 15mL water, mixed
It closes uniformly, instills the 5mL aqueous solution of Strontium dichloride hexahydrate (2.66g, 0.01mol), stir 1 hour, filter, distill water washing,
It is air-dried, obtains the powder 1.4g of strontium coordination polymer, yield 85%.
Embodiment 3
1-hydroxy ethylidene-1,1-diphosphonic acid (0.0103g, 0.05mmol) and strontium nitrate (0.0106g, 0.05mmol) are dissolved in 2mL
Water is added ammonium hydroxide and adjusts pH=3 after mixing, under confined conditions, reacting 36 hours at 90 DEG C, then natural cooling
To room temperature, the colorless and transparent rectangle flat crystal of strontium coordination polymer is obtained, monocrystalline yield is 45%.
Embodiment 4
1-hydroxy ethylidene-1,1-diphosphonic acid (0.0103g, 0.05mmol) and strontium nitrate (0.0212g, 0.1mmol) are dissolved in 7mL water,
After mixing, ammonium hydroxide adjusting pH=5 is added to react 30 hours at 100 DEG C, then naturally cool under confined conditions
Room temperature, obtains the colorless and transparent rectangle flat crystal of strontium coordination polymer, and monocrystalline yield is 43%.
The strontium coordination polymer of above embodiments is prepared in water at high temperature, and prepared strontium coordination polymer has
Preferable water stability.
X-ray single crystal diffraction, the crystallography measured are carried out to colorless and transparent rectangle flat crystal obtained by embodiment 3
Data are shown in Table 1.
The crystallographic data of 1 embodiment of table, 3 gained coordination polymer monocrystalline
It is known that strontium coordination polymer crystallization belongs to anorthic system, P-1 space group, cell parameter from table 1
Forα=101.879 °, β=91.601 (3) °,
γ=94.329 °.
Powder x-ray diffraction is carried out to strontium coordination polymer made from embodiment 1 and embodiment 3, PXRD schemes such as Fig. 1 institute
Show, it can be seen that powder obtained by embodiment 1 and embodiment 3 and monocrystalline are consistent with the analogue value, product is pure phase.
FTIR spectrum (FT-IR) test, spectrogram such as Fig. 2 are carried out to strontium coordination polymer made from embodiment 2 and 3
It is shown, it can be seen that embodiment 2 is identical with the product of embodiment 3,3421cm-1The strong peak of width should be in hydrone, ligand
Hydroxyl stretching vibration absworption peak in hydroxyl and the phosphonic functional groups of non-deprotonation；1579cm-1The peak at place is attributed to O-H in hydroxyl
The bending vibration absorption peak of key, 1427cm-1The peak of left and right is the asymmetric angle absorption peak of methyl, in 1143~883cm-1Area
The absorption peak in domain should be attributed to the stretching vibration peak of P=O and P-O in phosphoric acid function figure.
As shown in figure 3,01W~010W represents water in figure, 01-06 is the asymmetric cell figure of strontium coordination polymer of the present invention
Water of coordination, 07-010 are lattice watter, in the asymmetric cell of strontium coordination polymer comprising four strontium ions be respectively Sr1, Sr2,
Sr3, Sr4, four organic ligand H2hedp2-Ion, six waters of coordination (two of them are bridging water of coordination) and four lattice watters.
The coordination context diagrams of four strontium ions in strontium coordination polymerization of the present invention is as shown in figure 4, as seen from the figure, Sr1 and four
The six phosphoric acid oxygen and two water molecule coordinations of a hedp ligand form the anti-prism configuration in four directions；Sr2 and four hedp ligand
Seven oxygen atoms (six of them phosphoric acid oxygen and a hydroxyl oxygen) and two water molecule coordinations form nine coordination steamed sponge cake configurations；Sr3
Also with eight oxygen atom ligands, six of them is from the phosphoric acid oxygen with four hedp ligands, and remaining two from water of coordination
Molecule forms double cap trigone column configurations；Sr4 also forms steamed sponge cake configurations with nine oxygen atom ligands, and six of them is phosphoric acid oxygen, and one
A is hydroxyl oxygen, and two come from water of coordination.
By strontium obtained by the embodiment of the present invention 1 and embodiment 3 cooperate mixed with polymers and with mortar it is finely ground, use tablet press machine
It is pressed into disk, folder between two electrodes, measures its different humidity environment (relative humidity at 25 DEG C using electrochemical workstation
50%~98%) ac impedance spectroscopy under ac impedance spectroscopy and 55 DEG C and 98% relative humidity under.It is obtained by being fitted semicircle
To its resistance, conductivity is calculated by formula σ=L/ (SR) (L is the thickness of sample, and S is the area of sample, and R is resistance)
σ.25 DEG C, the conductivity of strontium coordination polymer under 50%~98% relative humidity as shown in figure 5, as shown in Figure 5, strontium polycomplexation
The proton conductivity of object is closed as the increase of humidity dramatically increases, by 9.1 × 10 under 50% humidity-7It is wet that S/cm increases to 98%
2.3 × 10 under degree-3S/cm, conductivity increase four orders of magnitude.The strong correlation of its proton conductivity and humidity shows to make
What it is for proton conductive medium is that strontium cooperates hydrone in polymer, and hydrone number and humidity in coordination polymer exist flat
Weighing apparatus.Hydrone is more under high humility, and proton conductive is good；Moisture is few under low humidity, and proton conductive is poor.It can also be sent out from crystal structure
Existing, strontium cooperates in polymer and is connected between hydrone by hydrogen bond, forms a big hydrogen bond network, and proton passes through this hydrogen
The transmitting of key network, moisture tail off, and hydrogen bond network is difficult to be formed, and proton transfer is difficult.
By electrochemical workstation test and the Fitting Calculation, the strontium coordination polymer under 55 DEG C and 98% relative humidity is obtained
Conductivity be 4.9 × 10-3S/cm。
The existing every square meter production cost of Nafion membrane is up to 10,000 yuan, greatly limits its large-scale production, and uses this
Strontium coordination polymer per kilogram production cost made from inventive method is can be controlled within 100 yuan, the method for the present invention using water as
Solvent, environmentally protective, simple production process, reaction condition is mild, and yield is higher, is suitable for scale of mass production, and production cost is very
Low, resulting strontium coordination polymer can be applied in the fuel cell not high to performance requirement.
Claims (9)
1. a kind of strontium coordination polymer, which is characterized in that the chemical formula of the strontium coordination polymer is { [Sr4(hedpH2)4(μ2-
H2O)2(H2O)4]·4H2O}n, wherein n is positive integer, and hedp is organic ligand 1-hydroxy ethylidene-1,1-diphosphonic acid in formula, the strontium coordination
The molecular structural formula of polymer is as follows:
2. a kind of strontium coordination polymer according to claim 1, which is characterized in that the strontium coordination polymer is three tiltedly brilliant
The crystal structure of system, P-1 space group, cell parameter are as follows: α=101.879 (3) °, β=91.601 (3) °, γ=94.329 (3) °.
3. a kind of strontium coordination polymer according to claim 1, which is characterized in that it is not right that the strontium coordination polymer has
Claim structural unit, includes four strontium ions, four organic ligand ions, six waters of coordination and four in the dissymmetrical structure unit
A lattice watter.
4. a kind of preparation method of strontium coordination polymer according to claim 1, which is characterized in that the preparation method is that
The synthesis of strontium coordination polymer monocrystalline: being dissolved in water for organic ligand and strontium salt, is uniformly mixed, and adjusts pH=3~5, confined condition
Under reacted at 80~100 DEG C 24~36 hours, then cooled to room temperature, obtains strontium coordination polymer monocrystalline.
5. a kind of preparation method of strontium coordination polymer according to claim 4, which is characterized in that the strontium salt is nitric acid
Strontium or strontium chloride, the organic ligand are 1-hydroxy ethylidene-1,1-diphosphonic acid；The organic ligand, strontium salt, the molar ratio of water be (0.5~
1):1:(2000-4000)。
6. a kind of preparation method of strontium coordination polymer according to claim 1, which is characterized in that the preparation method is that
The synthesis of strontium coordination polymer powder: organic ligand and alkali is soluble in water, it is uniformly mixed, the aqueous solution of strontium salt is then added dropwise,
Stirring 0.5~1 hour filters, and washes, dry, obtains strontium coordination polymer powder.
7. a kind of preparation method of strontium coordination polymer according to claim 6, which is characterized in that the strontium salt is nitric acid
Strontium or strontium chloride, the organic ligand are 1-hydroxy ethylidene-1,1-diphosphonic acid；The organic ligand, strontium salt, the molar ratio of alkali be (0.5~
1): 1:(1~2).
8. a kind of preparation method of strontium coordination polymer according to claim 6, which is characterized in that the alkali is hydroxide
Sodium or potassium hydroxide.
9. a kind of application of strontium coordination polymers described in any item according to claim 1~3 in proton exchange membrane material.
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