CN115558121B - Porous coordination polymer and preparation and separation method for isotopologues - Google Patents
Porous coordination polymer and preparation and separation method for isotopologues Download PDFInfo
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- CN115558121B CN115558121B CN202211196018.4A CN202211196018A CN115558121B CN 115558121 B CN115558121 B CN 115558121B CN 202211196018 A CN202211196018 A CN 202211196018A CN 115558121 B CN115558121 B CN 115558121B
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Abstract
The invention discloses a porous coordination polymer and a preparation method and a separation method for isotopologues, wherein the coordination polymer is formed by self-assembling metal ions and organic ligands through coordination bonds, wherein the organic ligands have a general formula in a formula (I) or a formula (II),
the coordination polymer in the invention is provided with a turnover unit capable of turnover movement, the coordination polymer allows the isotopologues of water to pass through and controls the diffusion of the isotopologues, and the diffusion rates of the isotopologues of water in the coordination polymer in the invention are different, so that the separation of the isotopologues of water is realized, and the coordination polymer in the invention is separated from H at 298K 2 O/HDO/D 2 Dynamic separation of H in O ternary mixed system 2 The separation coefficient of O is up to about 210. In addition, the coordination polymer has higher stability in water and organic solvents, thereby ensuring the feasibility of water isotopologue separation.
Description
Technical Field
The invention relates to the technical field of isotopologue separation, in particular to a porous coordination polymer and a preparation method and a separation method for isotopologue thereof.
Background
Isotopologues are substances which differ only in their chemical composition, e.g. hydrogen isotopes D 2 /H 2 Isotopologue D of water 2 O/HDO/H 2 O/H 2 18 O, etc. The development of efficient methods for the identification and isolation of isotopologues is extremely important both in basic research and in industrial applications, but has remained a major challenge in the chemical field to date. In order to apply isotopes widely to industrial, biomedical and scientific research, chemists have attempted to distinguish isotopes by molecular chemistry, for example, capturing one of them using a host material including a cage compound or a rigid porous material. However, since isotopologues have the same chemical structure and dimensions, the thermodynamic properties are very similar, and thus separation of isotopologues from each other is very difficult, with isotopologues of water being the most indistinguishable. Water (H) 2 O) and heavy water (D) 2 O) are very similar as two typical isotopologues of water, their physicochemical properties such as melting point (273.15K vs.276.94K), boiling point (373.15K vs.374.56K), bond energy (458.9 kJ mol-1 bond-1 vs 466.4kJ mol-1 bond-1) and so on, resulting in industrially employed high temperature multistage rectification techniques and electrolyzed water techniquesThe efficiency of separating water isotopologues is extremely low (separation factor 1.02-2.0). In addition, when H 2 O and D 2 When O is mixed, half-weight water (HDO) is rapidly generated by proton exchange chemical equilibrium. At 298K, the equilibrium constant k= [ HDO (liquid)] 2 /{[H 2 O(liquid)]·[D 2 O(liquid)]And 3.85, all three coexist. Therefore, the thermodynamic methods of proton exchange equilibrium such as the Geib-Spovack method adopted industrially are also extremely low in the efficiency of separating isotopologues of water (separation factor 1.2 to 2.0). In addition, H 2 O and D 2 The molecular kinetic diameters of O are very small and identical
This makes it quite difficult to perform adsorptive separation using a host material. Over the last decades, chemists have attempted to exploit the differences in adsorption properties in porous materials to effect isotopologue separation of water, but no success has been reported to date.
On the other hand, the hydrogen isotope can be effectively separated by the kinetic quantum sieving effect at a low temperature of less than 40K because the diffusion rate of the hydrogen isotope at low temperature is slightly different, and the pore diameter of the micropores of the porous material is equal to D by strictly controlling 2 Is of Debroglie wavelength
When this occurs, quantum tunneling effect can be generated, so that this difference can be amplified, and the isotopologue of water does not show a significant difference in diffusion rate even at low temperature, thereby achieving effective separation. Materials that control isotopologue diffusion of water have not been reported to date.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a porous coordination polymer, a preparation method and application thereof, wherein the coordination polymer is provided with a turnover unit capable of turnover movement, the unique pore structure and channel inside the coordination polymer allow the isotopologue of water to pass through and control the diffusion of the isotopologue of water, and the isotopologue of water is in the inventionThe diffusion rates of the coordination polymers are different, thereby realizing the separation of isotopologues of water, and the coordination polymer in the invention is separated from H at 298K 2 O/HDO/D 2 Dynamic separation of H in O ternary mixed system 2 The separation coefficient of O is up to about 210; in addition, the coordination polymer has higher stability in water and organic solvents, thereby ensuring the feasibility of water isotopologue separation.
In a first aspect of the present invention, there is provided a coordination polymer self-assembled from metal ions and organic ligands through coordination bonds.
According to a first aspect of the invention, in some embodiments of the invention, the organic ligand has the general formula in formula (i) or formula (ii):
in some preferred embodiments of the invention, the R 1 ～R 6 Are independently selected from the group consisting of-H, -O, -CH 3 、-C 2 H 5 、-OCH 3 One of them.
In some preferred embodiments of the invention, the R 7 ～R 14 Are independently selected from the group consisting of-H, -O, -CH 3 、-C 2 H 5 、-OCH 3 One of them.
In some preferred embodiments of the invention, the organic ligand intermediate is substituted in the 5-position with at least one of iminostilbene, iminodibenzyl, 5H-dibenzo [ b, f ] azepin-10 (11H) -one, 10-methoxyiminostilbene.
In some preferred embodiments of the invention, the organic ligand comprises a unit that can be folded for movement.
In some more preferred embodiments of the invention, the organic ligand has a structure in formula (iii) or formula (iv):
in some preferred embodiments of the present invention, the metal ion is selected from one of cobalt, zinc, nickel, copper, sodium, potassium, calcium.
In some more preferred embodiments of the invention, the metal ion is from a soluble metal salt.
In some more preferred embodiments of the present invention, the metal salt is selected from one of cobalt nitrate, zinc nitrate, nickel nitrate, copper nitrate, sodium nitrate, potassium nitrate, calcium nitrate, copper acetate, potassium acetate, cobalt acetate, zinc acetate, copper sulfate, zinc sulfate, sodium sulfate, cobalt sulfate, zinc sulfate, copper chloride, zinc chloride, cobalt chloride, nickel chloride, calcium chloride.
In some preferred embodiments of the invention, the coordination polymer has a coordination number of 2.
In some preferred embodiments of the invention, the coordination polymer is a porous coordination polymer.
In some more preferred embodiments of the present invention, the coordination polymer has a pore size of
And the aperture has dynamic adjustment capability.
In a second aspect of the present invention, there is provided a method for producing a coordination polymer according to the first aspect of the present invention by
The organic ligand obtained by the reaction and the salt containing metal ions are self-assembled through coordination bonds, wherein X is a halogen atom.
According to a second aspect of the invention, in some embodiments of the invention, the metal ion is from a soluble metal salt.
In some preferred embodiments of the present invention, the metal salt is selected from one of cobalt nitrate, zinc nitrate, nickel nitrate, copper nitrate, sodium nitrate, potassium nitrate, calcium nitrate, copper acetate, potassium acetate, cobalt acetate, zinc acetate, copper sulfate, zinc sulfate, sodium sulfate, cobalt sulfate, zinc sulfate, copper chloride, zinc chloride, cobalt chloride, nickel chloride, calcium chloride.
In some more preferred embodiments of the invention, the organic ligand is prepared by the steps of:
s1, will
2-dicyclohexyl phosphorus-2 ',4',6' -triisopropyl biphenyl, cesium carbonate and tris (dibenzylideneacetone) dipalladium (0) are placed in a container, and a solvent is added under the protection of inert gas for reaction;
s2, when
Stopping the reaction when the reaction completely disappears, adding ethyl acetate and diatomite, and filtering out the solid to obtain an organic phase for extraction;
s3, collecting an organic phase, and then performing column chromatography separation and elution to obtain the compound 1
S4, dissolving the compound 1 in an organic solvent, and then adding an NaOH aqueous solution for reflux reaction;
s5, cooling, removing the organic solvent, adjusting the pH value, filtering out the solid, and washing and drying to obtain the organic ligand.
In some preferred embodiments of the present invention, the solvent described in step S1 is ultra-dry toluene.
In some preferred embodiments of the present invention, the temperature of the reaction in step S1 is 110 to 120 ℃.
In some preferred embodiments of the invention, the reaction time in step S1 is 14 to 18 hours.
In some preferred embodiments of the invention, the reaction is monitored in step S2 using thin layer chromatography.
In some preferred embodiments of the present invention, the extraction sequence in step S2 is 3 times with ethyl acetate and 3 times with saturated saline.
In some preferred embodiments of the invention, the organic phase is subjected to a drying treatment in step S3 prior to column chromatography separation.
In some preferred embodiments of the present invention, the drying treatment may be performed using anhydrous magnesium sulfate.
In some preferred embodiments of the present invention, the eluent eluted in step S3 is ethyl acetate/n-hexane.
In some more preferred embodiments of the present invention, the volume ratio of ethyl acetate to n-hexane is (3 to 6): 1.
in some preferred embodiments of the invention, the yield of compound 1 in step S3 is 55-60%.
In some preferred embodiments of the present invention, the organic solvent in step S4 is a mixture of Tetrahydrofuran (THF) and methanol (MeOH).
In some more preferred embodiments of the invention, the volume ratio of THF to MeOH is 1:1.
in some preferred embodiments of the present invention, the concentration of the aqueous NaOH solution in step S4 is 1 to 3M.
In some preferred embodiments of the present invention, the time of the reflux reaction in step S4 is 14 to 18 hours.
In some preferred embodiments of the present invention, the method for removing the organic solvent in step S5 includes a spin drying method.
In some preferred embodiments of the invention, the pH in step S5 is between 1 and 2.
In some more preferred embodiments of the invention, the pH adjustment is performed using ice-hydrochloric acid.
In some preferred embodiments of the invention, the solid is washed 2-4 times with water in step S5.
In some preferred embodiments of the present invention, the temperature of drying in step S5 is 50 to 70 ℃.
In some preferred embodiments of the present invention, the drying time in step S5 is 10 to 14 hours.
In a third aspect of the invention there is provided the use of a coordination polymer according to the first aspect of the invention in the isotopologue separation of water.
According to a third aspect of the present invention, in some embodiments of the present invention, the coordination polymer is activated prior to use.
In some preferred embodiments of the invention, the method of activation is vacuum-resting at a temperature of 353K to 393K for 8 to 15 hours.
The high temperature is used for sufficiently volatilizing the solvent in the coordination polymer pore canal, so that the adsorption quantity of the coordination polymer to water can be improved, and the isotopologue of the water can be separated more effectively.
In some preferred embodiments of the present invention, the coordination polymer is isolated at a temperature of 278K to 473K.
In some preferred embodiments of the present invention, the coordination polymer has an adsorption amount in water of 50 to 70mL/g.
In some preferred embodiments of the invention, the isotopologue of water comprises D 2 O、HDO、H 2 O、H 2 18 O。
In some preferred embodiments of the invention, the coordination polymer is used to separate isotopologues of two or more waters.
The inventor proposes a low energy-consuming 'diffusion control' strategy to achieve effective separation of isotopologues of water. The essence of this strategy is to control the diffusion of the isotopologues of water with a dynamic "locally flexible" framework material and to amplify the diffusion rate differences of the isotopologues of water. The dynamic "locally flexible" framework material will preferentially adsorb one isotopologue molecule from the isotopologue mixture of water according to the kinetic differences, thereby achieving an efficient kinetic identification of the isotopologue of water. In particular, a method is established by turning over the ligand groupA "locally flexible" porous coordination polymer system that controls the process of isotopologue molecular diffusion of water. The dynamic switch with temperature response is knitted on the cage-shaped pore wall of the Porous Coordination Polymer (PCPs) with a rigid framework to show the adsorption behavior with temperature response, so that the slight difference of diffusion rate among isotopologues of water can be amplified, and H can be realized 2 High selectivity adsorption of O. The coordination polymer in the present invention is prepared from H at 298K 2 O/HDO/D 2 Dynamic separation of H in O ternary mixed system 2 The separation coefficient of O is up to about 210.
The beneficial effects of the invention are as follows:
(1) The coordination polymer in the invention is provided with a turnover unit capable of turnover movement, the coordination polymer allows the isotopologues of water to pass through and controls the diffusion of the isotopologues, and the diffusion rates of the isotopologues of water in the coordination polymer in the invention are different, so that the separation of the isotopologues of water is realized, and the coordination polymer in the invention is separated from H at 298K 2 O/HDO/D 2 Dynamic separation of H in O ternary mixed system 2 The separation coefficient of O is up to about 210.
(2) The coordination polymer has higher stability in water and various organic solvents, and the powder X-ray diffraction analysis (PXRD) spectrogram of the coordination polymer does not change obviously no matter the coordination polymer is soaked at normal temperature or high temperature, so that the feasibility of water isotopologue separation is ensured.
Drawings
FIG. 1 is a hydrogen spectrum of an organic ligand IDB-ipa in example 2 of the present invention;
FIG. 2 is a carbon spectrum of an organic ligand IDB-ipa in example 2 of the present invention;
FIG. 3 is a mass spectrum of an organic ligand IDB-ipa in example 2 of the present invention;
FIG. 4 is a graph of the turnover kinetic potential energy of the DBAP ring in the organic ligand of example 1 and the IDB ring in the organic ligand of example 2;
FIG. 5 is an optical micrograph of a coordination polymer prepared in an example of the present invention;
FIG. 6 is an activated crystal structure of FDC-1a and FDC-2 a;
FIG. 7 is a graph showing PXRD spectra of coordination polymers prepared in examples of the present invention after 7 days of immersion in different solvents;
FIG. 8 shows the coordination polymer pair H in the example of the present invention at 298K 2 O and D 2 An adsorption-desorption curve and a time-dependent adsorption curve of O;
FIG. 9 shows the adsorption of H by coordination polymer in the examples of the present invention at different temperatures 2 O and D 2 Pressure-diffusion rate-adsorption amount panorama of O;
FIG. 10 is a MeCaibu-Tile diagram of the separation of isotopologues from water at 298K in an embodiment of the present invention;
FIG. 11 shows the H in the adsorption phases of FDC-1a and FDC-2a in the examples of the invention at 298K 2 O separation factor follows H in raw material steam 2 Variation of O content.
Detailed Description
The invention will be further described with reference to specific embodiments, and advantages and features of the invention will become apparent from the description. These examples are merely exemplary and do not limit the scope of the invention in any way. It will be understood by those skilled in the art that various changes and substitutions of details and forms of the technical solution of the present invention may be made without departing from the spirit and scope of the present invention, but these changes and substitutions fall within the scope of the present invention.
EXAMPLE 1 Synthesis of organic ligands
The synthetic route for the organic ligand in example 1 is:
the preparation method comprises the following specific steps:
dimethyl 5-iodoisophthalate (19.20 g,60.0mmol,1.2 eq), iminostilbene (9.66 g,50.0mmol,1.0 eq), 2-dicyclohexylphosphorus-2 ',4',6' -triisopropylbiphenyl (XPhos, 1.19g,2.5mmol,0.05 eq), cesium carbonate (Cs) 2 CO 3 32.58g,100.0mmol,2.5 eq) andtris (dibenzylideneacetone) dipalladium (0) (Pb) 2 (dba) 3 1.37g,1.5mmol,0.03 eq) was placed in a 500mL round bottom flask, the flask was evacuated of air and filled with argon, 200mL of ultra-dry toluene (tolene) was added under argon and stirred at 115℃for 16h. The reaction was monitored by Thin Layer Chromatography (TLC), and when iminostilbene had completely disappeared, the reaction was stopped and cooled to room temperature, 50mL of ethyl acetate and celite were added to the flask, the solid was filtered off after stirring, and the organic phase was extracted with ethyl acetate (200 ml×3 times) and saturated brine (100 ml×3 times). Collecting organic phase, drying with anhydrous magnesium sulfate, spin-drying, separating by column chromatography, eluting with ethyl acetate/n-hexane (volume ratio is (3-6): 1), and vacuum drying at 80deg.C for 12 hr to obtain powder
The mass thereof was 11.18g, and the yield thereof was 58%. Will contain the compound->
A solution of (5.0 g,12.95 mmol) in THF/MeOH (100 mL,1/1 v/v) was added to a 500mL round bottom flask, followed by 2M aqueous NaOH (100 mL,200 mmol) and the reaction was refluxed for 16h. After cooling to room temperature, the organic solvent was removed by rotary evaporation, the pH of the solution was adjusted to 1-2 with 3% ice-HCl, the solid was filtered off and washed three times with deionized water. Vacuum drying at 60deg.C for 12 hr to obtain white powder +.>
The mass of the solution was 9.1g, which was designated DBAP-ipa, and the yield was 98%.
EXAMPLE 2 Synthesis of organic ligands
The synthetic route for the organic ligand in example 2 is similar to example 1, except that the compound
Replaced by->
The specific synthetic route is as follows:
the resulting organic ligand was designated IDB-ipa, 9.1g in mass and 98% in yield.
Fig. 1 to 3 show the hydrogen spectrum, the carbon spectrum and the mass spectrum of the organic ligand IDB-ipa of the turnover movement, respectively, and it can be seen from the figures that the organic ligand IDB-ipa of the turnover movement is prepared in the embodiment of the invention, and the turnover energy barrier and dihedral angle (C 1 N 1 C 2 C 3 ) Wherein dihedral angle (C) 1 N 1 C 2 C 3 ) Ranging from 100 ° -160 ° (10 ° interval), as shown in fig. 4, wherein fig. 4a is the turndown energy barrier and dihedral angle C of the DBAP ring in the organic ligand DBAP-ipa 1 N 1 C 2 C 3 FIG. 4b shows the turnover energy barrier and dihedral angle C of the IDB ring in the organic ligand IDB-ipa 1 N 1 C 2 C 3 Is a relationship of (3). As can be seen from FIG. 4, the energy change (ΔE) of the turning motion is small for both DBAP ring and IDB ring, and the change ΔE with respect to the dihedral angle of 20 DEG is less than 20kJ mol -1 . The above results indicate that the energy change of the DBAP ring or IDB ring in the organic ligand in the embodiment of the present invention is small, the folding can effectively occur at very low temperature, and the amplitude of the folding motion is increased with the increase of temperature.
EXAMPLE 3 Synthesis of coordination Polymer
500mg (1.40 mmol) of DBAP-ipa from example 1 was dissolved in 50mL of Dimethylacetamide (DMA) at 30℃and 676mg (2.80 mmol) of Cu (NO) was then added 3 ) 2 ·3H 2 O aqueous solution (50 mL). The mixture was heated in an oven at 80℃for 24 hours to give a dark green bulk single crystal having a size of approximately 1mm, and as shown in FIG. 5a, the crystal was filtered, washed three times with DMA and water, and dried at 30℃to give Cu (DBAP) (noted FDC-1, 538mg, yield 78%).
EXAMPLE 4 Synthesis of coordination Polymer
500mg (1.40 mmol) of IDB-ipa from example 2 was dissolved in 50mL of DMA at 30℃and 676mg (2.80 mmol) of Cu (NO) was added 3 ) 2 ·3H 2 O aqueous solution (50 mL). The mixture was heated in an oven at 80℃for 24 hours to give a dark green bulk single crystal having a size of approximately 1mm, and as shown in FIG. 5b, the crystal was filtered, washed three times with DMA and water, and dried at 30℃to give Cu (IDB) (designated as FDC-2, 538mg, yield 80%).
Of course, a person skilled in the art can synthesize other organic ligands according to the above steps and self-assemble with different metal ions through coordination bonds to prepare other coordination polymers.
Use of FDC-1 and FDC-2 in water isotopologue separation
1. Experimental procedure
1. Sample loading and activation: the coordination polymer (0.40 g) of example 3 or 4 was loaded into a cylindrical cuvette (diameter 8 mm), vacuum dried at 393K for activation for 10 hours, then the cuvette was mounted on a BEL-CAT II instrument and activated in situ on the instrument for 1 hour, and helium gas was purged at a constant rate of 10sccm for 1 hour during activation; the activation process should ensure complete removal of the adsorbed solvent from the sample, and the activated samples were designated FDC-1a and FDC-2a, respectively.
2. Adsorption process: at 10K min -1 The temperature was reduced from 393K to 298K, and when the temperature reached the specified temperature, mixed steam was blown through the sample at a rate of 10sccm (mixed steam flow rate was controlled by a mass flow meter) and the temperature was maintained at 298K throughout the adsorption process.
3. And discharging unadsorbed steam in the sample cell: helium was continuously purged at a flow rate of 10sccm for 1 hour at 298K to vent excess vapor from the sample cell and tubing.
4. And (3) desorption and separation detection of adsorption gas: at 10K min -1 The temperature of the sample cell was raised to 393K at which time the adsorbed vapors within the sample were desorbed while helium was continuously purged at 10sccm to deliver the desorbed vapors to the detector and the desorbed vapors were detected by mass spectrometry. By integrating the area of the current signal after the base line is deductedCalculation of liberated H 2 O, HDO and D 2 Ratio of O.
Those skilled in the art may also select different activation temperatures according to actual needs and is not limited to 393K.
The temperature of adsorption may be selected by those skilled in the art according to actual needs, for example, the temperature of adsorption may be 278K, 288K, 308K, 323K or 393K.
Wherein H is 2 The O separation factor is defined as:
wherein X is H2O Representing H in the adsorption phase 2 The concentration of O; y is Y H2O Indicating H in the raw material steam 2 The concentration of O; x is X HDO Represents the concentration of HDO in the adsorption phase; y is Y HDO Representing the concentration of HDO in the raw material steam; x is X D2O Representing D in the adsorption phase 2 The concentration of O; y is Y D2O Represents D in raw material steam 2 O concentration.
2. Experimental results
1. Crystal structure of activated FDC-1a and FDC-2a
The crystal structures of the FDC-1a and FDC-2a in the activated state are shown in FIG. 6, wherein FIG. 6a is a structure diagram of the activated crystals of the FDC-1a and FDC-2a, FIG. 6b is a structure of the pores in the FDC-1a and FDC-2a, FIG. 6c is a diffusion channel and structure of the FDC-1a, and FIG. 6d is a diffusion channel and structure of the FDC-2a. As can be seen in FIG. 6, the FDC-1a and FDC-2a are composed of a plurality of nano Kong Long and extremely narrow diffusion channels of the same size, and 6 identical diffusion channels are provided from one pore cage to the adjacent pore cage. One of all diffusion channels in FDC-1a
Is surrounded by two benzene rings in two isophthalic acids and DBAP. Similarly, the "gate" in FDC-2a is surrounded by two benzene rings in two isophthalic acids and IDB, and has a size +.>
Slightly smaller than FDC-1a. It follows that fine tuning of the ligand structure brings about a change in the size of the diffusion channel which, although slight, has a very small molecular dynamics diameter +.>
Is of critical importance for the water isotopologue molecules of (a).
2. Crystal stability of activated FDC-1a and FDC-2a
FDC-1a and FDC-2a were immersed in water (298K or 363K), methanol (298K or 333K) and N, N-Dimethylformamide (DMF) (298K or 393K), respectively, for 7 days. FIG. 7 shows PXRD spectra of FDC-1a and FDC-2a after 7 days of immersion in different solvents, wherein FIG. 7a shows PXRD spectra of FDC-1a after 7 days of immersion in different solvents, and FIG. 7b shows PXRD spectra of FDC-2a after 7 days of immersion in different solvents, and it can be seen from FIG. 7 that the PXRD curves of FDC-1a and FDC-2a after immersion in water, methanol and DMF are substantially unchanged, indicating that FDC-1a and FDC-2a exhibit excellent hydrothermal and solvent stability.
3. Adsorption behavior of FDC-1a and FDC-2a and kinetic study of adsorption process:
FDC-1a and FDC-2a were first studied for H at different relative pressures (P/Ps) of 298K 2 O and D 2 O adsorption-desorption curves, the results of which are shown in FIG. 8a and FIG. 8b, wherein the abscissa represents pressure and the ordinate represents adsorption amount, and it can be seen from FIG. 8a and FIG. 8b that FDC-1a and FDC-2a vs. H at a temperature of 298K when P/Ps is 0.98 2 O/D 2 The O adsorption rates were 1.39 and 1.64, respectively, indicating that FDC-1a and FDC-2a preferentially adsorb H in the isotopologues of water 2 O. Further study on the H of FDC-1a and FDC-2a at different exposure times 2 O and D 2 As shown in FIGS. 8c and 8d, the adsorption and desorption curves of O show that FDC-1a vs. H with prolonged exposure time 2 O and D 2 The O adsorption amount is obviously increased to about 60mL g -1 FDC-2a vs H 2 O and D 2 The O adsorption amount is increased to about 55mL g -1 Illustrating the diffusion kinetics of FDC-1a and FDC-2a fromThe diffusion time is determined. FIG. 9 shows the adsorption of H by coordination polymer in the examples of the present invention at different temperatures 2 O and D 2 Pressure-diffusion rate-adsorption amount panorama of O, wherein x-axis is pressure, y-axis is diffusion rate, z-axis is adsorption amount, temperature is sequentially increased from 278K to 323K along the arrow direction, wherein FIG. 9a is FDC-1a adsorbing H 2 Pressure-diffusion rate-adsorption amount panorama of O, FIG. 9b shows FDC-1a adsorption D 2 Pressure-diffusion rate-adsorption amount panorama of O, FIG. 9c shows adsorption of H by FDC-2a 2 Pressure-diffusion rate-adsorption amount panorama of O, FIG. 9D shows FDC-2a adsorption D 2 As can be seen from FIG. 9, FDC-1a vs. H as the temperature increases from 278K to 323K 2 The adsorption amount of O was 1.7mL g -1 Significantly increased to 32.6mL g -1 FDC-2a vs H 2 The adsorption amount of O was 1.3mL g -1 Increase to 15.1mL g -1 FDC-1a vs D 2 The adsorption amount of O was 0.6mL g -1 Increasing to 24.4mL g -1 The adsorption amount of FDC-2a to D2O is from 0.5mL g -1 Increasing to 11.8mL g -1 . As the temperature increases, FDC-1a and FDC-2a pair H 2 O and D 2 The adsorption amount of O is obviously increased, which indicates that the adsorption behavior is controlled by temperature. Unlike conventional porous materials, where the gas/vapor adsorption decreases with increasing temperature, the reverse adsorption behavior of the system is characteristic of typical diffusion-controlled systems.
4. H at different temperatures 2 O and D 2 Rate of O diffusion
Further study of H at different temperatures 2 O and D 2 The diffusion rate of O in the coordination polymer in the embodiment of the invention (the method for measuring the isotopologue diffusion rate of water is to measure the adsorption curve of the isotopologue diffusion rate of water at a certain temperature, record the original data of the pressure of each measuring point changing along with time, and finally obtain the diffusion rate (Ds) of the isotopologue of water at different temperatures through the solution of a Crank equation). H at different temperatures 2 O and D 2 The diffusion rate of O is shown in FIG. 9, and it can be seen from FIG. 9 that FDC-1a and FDC-2a vs. H at low temperature 2 O or D 2 The diffusion rate of O is very small, with temperature and pressureElevated, FDC-1a and FDC-2a vs H 2 O or D 2 The diffusion rate of O gradually increases. At 298K, H in FDC-1a and FDC-2a 2 The diffusion rates Ds of O are 1.56X10 respectively -2 And 1.11X10.times.10 -2 R 2 s -1 D in FDC-1a and FDC-2a 2 The diffusion rates Ds of O are respectively 2.05X10 -3 And 1.37X10 -3 R 2 s -1 It is evident that in FDC-1a and FDC-2a, H 2 The diffusion rate of O is far greater than D 2 O is D respectively 2 7.6 and 8.1 times O. On the other hand, at 298K, H in FDC-1a 2 O and D 2 The diffusion rate of O was 1.4 times and 1.5 times that of FDC-2a, indicating that the diffusion kinetics of FDC-1a were faster, FDC-2a had smaller diffusion channels and lower diffusion rates than FDC-1a.
5. Results of water isotopologue separation
The dynamic separation performance of the mixed steam of FDC-1a and FDC-2a on water isotopologues at 298K was studied using a programmed temperature desorption (TPD) -mass spectrometer. FIG. 10 is a schematic diagram showing the decomposition of water isotopologue by coordination polymer at 298K, wherein the horizontal axis shows the steam content ratio of water isotopologue raw material, the vertical axis shows the adsorption ratio of water isotopologue in adsorption phase, FIG. 10a shows the decomposition of FDC-1a by water isotopologue, FIG. 10b shows the decomposition of FDC-2a by water isotopologue, and it is apparent from FIGS. 10a and 10b that H is the decomposition of water isotopologue by coordination polymer 2 O/HDO/D 2 In the ternary blending steam of O, FDC-1a and FDC-2a are selectively purged from H in the process of 0.5H 2 O/HDO/D 2 Adsorption of H in O mixture 2 O, generate obvious H 2 And (3) enriching O. Even at H 2 O：HDO：D 2 O=0.3: 9.3: 90.4H of FDC-1a and FDC-2a in a mixed vapor 2 The O adsorption ratio still reaches 26.8% and 38.6%, respectively, corresponding to H 2 The O separation factors are 124 and 212, respectively, as shown in FIG. 11, FIG. 11 shows H in the adsorbed phase of the coordination polymer of the present invention at 298K 2 O separation factor follows H in raw material steam 2 The condition of the variation of O content, wherein the abscissa is H 2 O in water isotopologue raw materialIn (2), the ordinate is H 2 Separation factor of O. As can be seen from the figure, FDC-2a vs. H 2 Adsorption ratio of O and H 2 The O separation factor is higher than FDC-1a due to the stricter diffusion control of the water isotopologue by FDC-2a, further amplifying the small differences in the diffusion rates of the water isotopologues.
As can be seen from the above-mentioned studies, the fact that the coordination polymer of the embodiment of the present invention can separate isotopologues of water in the range of 278-473K is because the coordination polymer of the embodiment of the present invention can allow isotopologues of water to pass through and control diffusion thereof, can amplify the fine difference of diffusion rates between isotopologues of water, and realizes H-separation 2 High selectivity adsorption and separation of O.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. A coordination polymer, characterized in that the coordination polymer is self-assembled by a metal ion and an organic ligand through coordination bonds, wherein the organic ligand has a general formula in formula (i) or formula (ii):
wherein the R is 1 ~R 6 Are independently selected from-H, -CH 3 、-C 2 H 5 、-OCH 3 One of the R 7 ~R 14 Are independently selected from-H, -CH 3 、-C 2 H 5 、-OCH 3 One of the following; the metal ion is copper; the pore diameter of the coordination polymer is 2.55-2.65A.
2. The coordination polymer of claim 1 wherein said organic ligand intermediate phthalic acid is substituted in the 5-position with at least one of iminostilbene, iminodibenzyl, 10-methoxyiminostilbene.
3. The coordination polymer of claim 1 wherein the organic ligand has a structure in formula (iii) or formula (iv):
4. the coordination polymer of claim 1 wherein the coordination polymer has a coordination number of 2.
5. A method for producing a coordination polymer according to any one of claims 1 to 4, wherein the coordination polymer is produced by
And->
Or (b)
The organic ligand obtained by the reaction and the salt containing metal ions are self-assembled through coordination bonds, wherein X is a halogen atom.
6. The use of the coordination polymer according to any one of claims 1 to 4 for isotopologue separation of water.
7. The use according to claim 6, wherein the coordination polymer is isolated at a temperature of 278K-473K.
8. The use of claim 6, wherein the isotopologue of water comprises D 2 O、HDO、H 2 O、H 2 18 O。
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| WO1999048586A1 (en) * | 1998-03-25 | 1999-09-30 | Patterson James A | Apparatus and method for separating oxides of heavy isotopes of hydrogen from water |
| CN107344096A (en) * | 2016-05-06 | 2017-11-14 | 北京化工大学 | A kind of gas-chromatography filler that can divide analysis of variance hydrogen isotope and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1999048586A1 (en) * | 1998-03-25 | 1999-09-30 | Patterson James A | Apparatus and method for separating oxides of heavy isotopes of hydrogen from water |
| CN107344096A (en) * | 2016-05-06 | 2017-11-14 | 北京化工大学 | A kind of gas-chromatography filler that can divide analysis of variance hydrogen isotope and preparation method thereof |
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| Title |
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| "金属有机骨架材料用于吸附分离CH4和N2的研究进展";马蕾等;《化工进展》;第40卷(第9期);第5107-5117页 * |
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