CN108623814A - A kind of copper-based Porous coordination polymer hydrogen storage material and preparation method thereof - Google Patents
A kind of copper-based Porous coordination polymer hydrogen storage material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of copper-based Porous coordination polymer hydrogen storage material, molecular formula Cu3C32H17O16S6, molecular weight 1041g/mol, crystal morphology is light blue octahedron, and crystal structure belongs to cubic system, and space group is Pn 3, cell parameter a=24.225, b=24.225, c=24.225, α=90 °, β=90 °, γ=90 °.The invention also discloses the preparation methods of above-mentioned copper-based Porous coordination polymer hydrogen storage material.Copper-based Porous coordination polymer hydrogen storage material surface polarity and electronegativity prepared by the present invention is enhanced, the H small especially suitable for dipole moment active force2、CH4The absorbing and storing of equal gases, and water stability is good, has a good application prospect.
Description
Technical field
The invention belongs to Porous coordination polymer fields, and in particular to a kind of copper-based Porous coordination polymer hydrogen storage material and
Preparation method.
Background technology
With the aggravation of environmental pollution and energy crisis, people are next there is an urgent need to develop a kind of new renewable and clean energy resource
Instead of traditional fossil fuel.Hydrogen has many advantages, such as that abundance, combustion product are pollution-free, the combustion heat is big, becomes New Energy
Research hotspot in source；And the development of hydrogen storage material is still the bottleneck in hydrogen energy source application.
Metal-organic framework materials（Metal-organic frameworks, MOFs）Also referred to as Porous coordination polymer,
It is to be connected by rigid organoligand coordination by metal ion, forms the class zeolitic material with supermolecule microporous network structure.
Studies have shown that the material has preferable application prospect in hydrogen adsorption technical field of memory.Copper-based Porous coordination polymer is
Principal item in Porous coordination polymer series material, such as HKUST-1（Also referred to as Cu3(BTC)2）It is current a small number of realization quotient
Industry melts one of porous coordination polymer material of hair.HKUST-1 type porous coordination polymer materials have suitable aperture ruler
Very little and larger specific surface area, pore volume, preferable performance is shown during energy gas absorbing and storing.But the material
Expect that hydrothermal stability is to be improved, it is perishable especially to meet the water capacity；In addition, unsatuated metal Cu in HKUST-12+Point with π
The adsorbate of electronics such as CO2、C2H2And C2H4Between there are stronger electrostatic interactions, and for the small H of dipole moment active force2、
CH4Equal gas molecules adsorption is relatively low.Therefore, it is necessary to improve the coordination knot of existing copper base porous coordination polymer material
Structure increases the adsorption effect of hydrogen molecule.
Nadeen Al-Janabi etc.（Chemical Engineering Journal, 281(2015):669-677）It is public
A kind of Cu-BTC is opened（That is HKUST-1）The preparation method of porous coordination polymer material weighs 2mmol trimesic acids, molten
Solution stirs the Gerhardite of addition 3.62mmol after 10min in 24mL ethanol waters, continues to stir 10min, will be blue
Color solution is placed in the stainless steel cauldron of 50mL tetrafluoro liners, and synthesis is crystallized at 100 DEG C.After the completion of synthesis, product is dropped
To room temperature, crystallized product is rinsed to the processing of solution suction filtration, and using 60mL ethanol waters, obtained blue colored crystal is put into very
Empty drying box, dry 16h, obtains HKUST-1 type porous coordination polymer materials at 120 DEG C.The material has preferable BET ratios
Surface area and pore volume, but be easy to deliquesce under water vapour environment, i.e., water-resistant stability is poor, is unfavorable for industrialization gas absorption and deposits
Storage application.
CN104138746A discloses a kind of preparation method and application of copper-based-metal-organic framework materials porous material.
It by copper acetate and trimesic acid ball milling after mixing, is washed 2~3 times with ethanol water, impregnates, is centrifugation, dry, being made
Copper-based-metal-organic framework materials porous material.The material has larger specific surface area and high porosity, under equal conditions,
Gas absorption amount is inhaled higher than the conventional adsorbents such as activated carbon, zeolite, about hydrothermal synthesis HKUST-1 types metal-organic framework materials
2 times of attached amount.But the material relies primarily on Cu2+Benzene ring structure in point and material skeleton realizes gas absorption, for
The small gas molecule adsorption effect of the dipole moments active force such as hydrogen is bad.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of copper-based Porous coordination polymer hydrogen storage material and its preparations
Method.Copper-based Porous coordination polymer hydrogen storage material surface polarity and electronegativity prepared by the present invention is enhanced, particularly suitable
In the small H of dipole moment active force2、CH4The absorbing and storing of equal gases, and water stability is good, has a good application prospect.
Copper-based Porous coordination polymer hydrogen storage material provided by the invention, molecular formula Cu3C32H17O16S6, molecular weight is
1041g/mol, crystal morphology are light blue octahedron, and crystal structure belongs to cubic system, space group Pn-3, cell parameter a=
24.225, b=24.225, c=24.225, α=90 °, β=90 °, γ=90 °；In this Porous coordination polymer, six
Copper atom and 8 μ on 2,2'- union II thiophene -5,5'- oxalic acid ligands3- O and 12 2,2'- union II thiophene -5,5'- two
12 carboxyls on acetic acid Hgand are connected, and constitute 12 connection secondary building unit [Cu of six cores6O4(OH)4], this
Secondary building unit connects two level knot by 2,2'- union II thiophene -5,5'- oxalic acid ligands with the 12 of adjacent 12 six cores again
Structure unit is connected, and constitutes the copper-based Porous coordination polymer of a three dimensional skeletal structure.
The angle constructed is connected from skeleton, six copper atoms form the cluster of six cores, logical per three adjacent copper atoms
Cross a μ3- O be connected, each two adjacent copper atom again with the carboxylic on 2,2'- union II thiophene -5,5'- oxalic acid ligand
Two oxygen atoms on base are connected.In this Porous coordination polymer, due to 2,2'- union II thiophene -5,5'- oxalic acid ligands
Nonlinear organization, cause Porous coordination polymer that warp architecture by a small margin is presented, exist simultaneously two kinds of basket structures, one is four
The tetrahedron cage that a adjacent secondary building unit surrounds, another kind are the octahedrons that six adjacent secondary building units surround
Cage.In octahedra cage, six secondary building units occupy octahedral six vertex, per three adjacent secondary building units
Define the face of a triangle；Simultaneously this triangle face be also a tetrahedron cage bottom, then with another two level
Structural unit, which is connected, just constitutes a tetrahedron cage.Due to it is each it is octahedra in there are the face of eight triangles, one
Octahedra cage and eight tetrahedron cages are connected by the face of triangle, have been built into three dimensional skeletal structure.Wherein, octahedra cage and
The port size of tetrahedron cage is 1.06nm and 0.59nm respectively.
The preparation method of the above-mentioned copper-based Porous coordination polymer hydrogen storage material of the present invention uses solvent process for thermosynthesizing：（1）
Weigh a certain amount of nitric hydrate mantoquita, phenyl carboxylic acid and N, N'- dimethylformamide（DMF）, it is ultrasonically treated certain time；
（2）A certain amount of 2,2'- union IIs thiophene -5,5'- oxalic acid is added into reactant again, continues to be ultrasonically treated certain time；（3）It will
Solution shifts in supreme borosilicate tube reactor, heating treatment certain time；（4）Product is rinsed through filtering, organic solvent after cooling
Afterwards, it is dried to obtain copper-based Porous coordination polymer hydrogen storage material through anaerobic dynamic vacuum.
The chemical structural formula of the 2,2'- union II thiophene -5,5'- oxalic acid is：
The 2,2'- union IIs thiophene -5,5'- oxalic acid is made by 2,2'- union II -5,5'-3- methylthiophene carboxylation reactions.Such as
Following method may be used：By 6~10mmol 2,2'- union II -5,5'-3- methylthiophenes and 80~120mL anhydrous tetrahydro furans
Uniformly mixing under nitrogen protection, concentration 1~2mol/L, 30~60mL of n-BuLi are added at 150~200K, wait for reactant
It is to continue to be cooled to 200K after temperature is increased to 273K；1~5g dry ice is added into reaction system, persistently stirs 10~15h, then
60~90mL of hydrochloric acid, the 3~6h of acidification reaction of 1~1.5mol/L of concentration is added, reaction product is filtered, washing, 70-90 DEG C
8~12h of vacuum drying obtains required organic ligand.
Step（1）Nitric hydrate mantoquita, phenyl carboxylic acid and the N, N'- dimethylformamides（DMF）Molar ratio be
1：（40~80）：（350~900）, preferably 1：（60~75）：（500~700）.
Step（1）The nitric hydrate mantoquita is in nitrate trihydrate copper, Copper nitrate hexahydrate and nine water copper nitrates etc.
One or more, preferably nitrate trihydrate copper.Phenyl carboxylic acid is selected from benzoic acid, phenylacetic acid, 1- phenyl-cyclohexane-carboxylic acids and 1- phenyl
One or more of cyclopentane-carboxylic acid etc., preferably phenylacetic acid.Be ultrasonically treated temperature be 25 DEG C~80 DEG C, preferably 40 DEG C~60
℃；Sonication treatment time is 5min~50min, preferably 20min~40min.
Step（2）The molar ratio of organic ligand 2,2'- the union II thiophene -5,5'- oxalic acid and nitric hydrate mantoquita
For（0.1~1）：1, preferably（0.3~0.7）：1.Continue to be ultrasonically treated temperature to be 15 DEG C~50 DEG C, preferably 20 DEG C~30 DEG C；
Sonication treatment time is 5min~50min, preferably 20min~40min.
Step（3）After shifting supreme borosilicate tube reactor, reaction temperature is 75 DEG C~150 DEG C, preferably 100 DEG C~130 DEG C；
Reaction time is 40h~150h, preferably 90h~120h.
Step（4）The organic solvent is in methanol, ethyl alcohol, chloroform, dichloromethane, DMF and deionized water etc.
It is one or more of.It is preferred that using DMF and dichloromethane, it is first DMF, then dichloromethane more preferably to rinse order.
Step（4）The anaerobic dynamic vacuum drying is different from conventional vacuum and dries, i.e., remarkable to improve vacuum degree
As promotion processing means.It is that heat transfer media reaches heat using material itself residual moisture under the low situation of pressure
Convection current with pass to, solve the problems, such as when pressure is low that material is difficult to obtain heat, realize that efficient cryogenic anaerobic dynamic is dry.From behaviour
Make to say in technique, also not simply vacuumizes realization anaerobic.Its vacuum system is by conventional water ring vacuum pump and Roots vaccum pump
Composition.It is controlled using PLC technology, anaerobic dynamic vacuum is dried due to the control ratio to pressure, temperature, time technological parameter
Relatively frequently, manual operation inevitably malfunctions, and pressure, temperature, time technological parameter can be carried out by different material using PLC technology
Setting, and be dried.Control device vacuum degree is in 450Pa~850Pa, preferably 550Pa~630Pa；Drying temperature 10
DEG C~50 DEG C, preferably 20 DEG C~30 DEG C；Drying time 10h~60h, preferably 20h~35h.
The present invention also provides the applications of above-mentioned copper-based Porous coordination polymer hydrogen storage material, are used for absorbing and storing H2、CH4
Etc. the small micro-molecular gas of dipole moments active force.In a mild condition, adsorption effect is good, and water stability is good.Adsorption conditions are：It inhales
Enclosure pressure 1bar~5bar, adsorption temp are generally room temperature, usually 200K~233K.
The copper-based Porous coordination polymer hydrogen storage material and preparation method thereof of the present invention, has the following advantages that：
（1）Select 2,2'- union II thiophene -5,5'- oxalic acid as organic ligand, on the one hand by the non-linear knot of organic ligand
Structure and small distortion pattern overcome conventional copper-based porous coordination polymer material（Such as HKUST-1）Meet the perishable problem of the water capacity；
On the other hand, S hetero atoms are contained in ligand, is conducive to enhance porous coordination polymer material surface polarity and electronegativity, improve
Material is for the small H of dipole moment active force2、CH4The suction-operated of equal gas molecules.
（2）Due to the nonlinear organization of 2,2'- union II thiophene -5,5'- oxalic acid ligands, the Porous coordination polymer is caused to be in
Now warp architecture by a small margin, compared with similar copper-based Porous coordination polymer, effective aperture moderately narrows, and is conducive to H2It inhales
It is attached.
（3）It is different from and S atom is simply carried on material surface, the S of the copper-based porous coordination polymer material of the present invention is former
Son gos deep into cage type pore passage structure, can significantly improve material surface polarity, reinforcing material is for the small H of dipole moment active force2、
CH4The suction-operated of equal gas molecules.
（4）Using anaerobic dynamic vacuum Drying Treatment Technology, effectively avoid in usual drying processes because caused by oxygen-containing
Readily oxidizable substance is rotten in skeleton component and crystalline form is exceeded, the problems such as influencing product quality stability.
Description of the drawings
Fig. 1 is the structural schematic diagram of the copper-based porous coordination polymer material tetrahedron cage of embodiment 1；
Fig. 2 is the structural schematic diagram of the copper-based porous coordination polymer material octahedron cage of embodiment 1；
Fig. 3 is the copper-based porous coordination polymer material three dimensional structure diagram of embodiment 1；
Fig. 4 is that embodiment 1, embodiment 2, comparative example 1 and 2 porous coordination polymer material of comparative example are bent for hydrogen adsorption enthalpy
Line.
Specific implementation mode
Copper-based Porous coordination polymer hydrogen storage material and its preparation side are further illustrated the present invention below by embodiment
Method and application, but do not answer therefore, it is considered that present invention is limited only by following embodiment.
Embodiment 1
（1）Organic ligand 2,2'- union II thiophene -5,5'- oxalic acid is synthesized first.By 8mmol 2,2'- union II -5,5'-3- first
Base thiophene and 100mL anhydrous tetrahydro furans are uniformly mixed in 250mL round-bottomed flasks under nitrogen protection, are added at 200K dense
Degree is 1.5mol/L n-BuLi 50mL, continues to be cooled to 200K after temperature of reaction system is increased to 273K；To reaction system
Middle addition 2g dry ice, persistently stirs 12h, adds the hydrochloric acid 80mL that concentration is 1mol/L, acidification reaction 5h, to reaction product
Suction filtration processing, is rinsed with ethyl acetate, deionized water and diethyl ether respectively, and 75 DEG C of vacuum drying 10h obtain required organic ligand.
（2）Weigh 0.242g Cu (NO3)2·3H2O and 8.97g phenylacetic acids are dissolved in 47.4g DMF solvents, 50 DEG C of items
Solution Under Ultrasound Treatment 30min under part.0.17g organic ligands 2 are added, 2'- union II thiophene -5,5'- oxalic acid, 25 DEG C are continued to surpass
Sonication solution 30min.Solution is transferred in 1mL high borosilicate pipe reactors, 120 DEG C of synthesis 100h are warming up to.Wait for that product drops
It to room temperature, filters, is rinsed respectively with DMF and dichloromethane, obtained material is in the case where vacuum degree is 610Pa and 25 DEG C, by nothing
Oxygen dynamic vacuum is dried 25h, obtains copper-based Porous coordination polymer hydrogen storage material A.
The copper-based porous coordination polymer material tetrahedron cage of embodiment 1 and octahedra cage is set forth in Fig. 1 and Fig. 2
Structural schematic diagram and copper-based porous coordination polymer material three dimensional structure diagram.It can be seen that the copper-based porous coordination
Polymer material has complete spatial coordination system and can be used for the space site of the micro-molecular gas absorbing and storing such as hydrogen.
Embodiment 2
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.By 0.24g Cu (NO3)2·
3H2O is changed to 0.30g Cu (NO3)2·6H2O, other reaction conditions and material composition are constant, obtain copper-based porous coordination polymerization
Object hydrogen storage material B.
Embodiment 3
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.By 0.24g Cu (NO3)2·
3H2O is changed to 0.35g Cu (NO3)2·9H2O, other reaction conditions and material composition are constant, obtain copper-based porous coordination polymerization
Object hydrogen storage material C.
Embodiment 4
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.8.97g phenylacetic acids are changed to
8.05g benzoic acid, other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage material D.
Embodiment 5
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.8.97g phenylacetic acids are changed to
13.4g 1- phenyl-cyclohexane-carboxylic acids, other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage
Material E.
Embodiment 6
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.8.97g phenylacetic acids are changed to
12.54g 1- phenyl cyclopentane-carboxylic acids, other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage
Material F.
Embodiment 7
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.Extremely by phenylacetic acid Mass lost
5.43g, other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage material G.
Embodiment 8
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.Extremely by DMF Mass losts
25.55g, other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage material H.
Embodiment 9
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.It is ultrasonically treated temperature liter for the first time
For height to 80 DEG C, other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage material I.
Embodiment 10
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.Sonication treatment time prolongs for the first time
For length to 50min, other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage material J.
Embodiment 11
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.By 2,2'- union IIs thiophene -5,
5'- oxalic acid additions are reduced to 0.030g, and other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer
Hydrogen storage material K.
Embodiment 12
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.Continue to be ultrasonically treated temperature liter
Up to 50 DEG C, other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage material L.
Embodiment 13
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.Continue sonication treatment time contracting
It is short to 5min, other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage material M.
Embodiment 14
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.Solution is transferred to 1mL high boron
In silicone tube reactor, 80 DEG C are warming up to, other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage
Material N.
Embodiment 15
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.Solution is transferred to 1mL high
In borosilicate pipe reactor, 120 DEG C of synthesis 50h are warming up to, other reaction conditions and material composition are constant, obtain copper-based porous coordination
Polymer hydrogen storage material O.
Embodiment 16
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.It waits for that product is cooled to room temperature, takes out
Filter, is only rinsed with DMF, and other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage material P.
Embodiment 17
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.Wait for that product is cooled to room temperature,
It filters, according to the sequential irrigation of first dichloromethane DMF again, other reaction conditions and material composition are constant, obtain copper-based porous match
Position polymer hydrogen storage material Q.
Embodiment 18
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.Anaerobic dynamic vacuum is dried
Vacuum degree be increased to 800Pa, other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage material
R。
Embodiment 19
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.Anaerobic dynamic vacuum is dried
Temperature be increased to 50 DEG C, other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage material S.
Embodiment 20
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.Anaerobic dynamic vacuum is dried
Time foreshorten to 10h, other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage material T.
Comparative example 1
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.Anaerobic dynamic vacuum is dried
Conventional vacuum drying is replaced with, other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage material
U。
Comparative example 2
In embodiment 1,2,2'- union II thiophene -5,5'- oxalic acid is prepared according to same method.In ultrasonication, always
It is 50 DEG C to keep treatment temperature, and other reaction conditions and material composition are constant, obtain copper-based Porous coordination polymer hydrogen storage material
V。
Comparative example 3
With embodiment 1, difference is that organic ligand uses the terephthalic acid (TPA) of identical molal quantity, other anti-for preparation process and condition
It answers condition and material to form constant, obtains copper-based Porous coordination polymer hydrogen storage material W.
Comparative example 4
According to Nadeen Al-Janabi etc.（Chemical Engineering Journal, 281(2015)669-677）It retouches
The method stated weighs 2mmol trimesic acids, is dissolved in 24mL ethanol waters, is added 3.62mmol's after stirring 10min
Gerhardite continues to stir 10min, blue solution is placed in the stainless steel cauldron of 50mL tetrafluoro liners, at 100 DEG C
Crystallization synthesis.After the completion of synthesis, product is down to room temperature, is rinsed to the processing of solution suction filtration, and using 60mL ethanol waters
Obtained blue colored crystal is put into vacuum drying chamber, dries 16h at 120 DEG C, obtain the porous coordination of HKUST-1 types by crystallized product
Polymer material X.
Comparative example 5
According to the method that CN104138746A is described, 2.416g copper acetates and 1.620g trimesic acids are weighed, is placed in 80mL's
In stainless steel jar mill, the stainless steel ball-milling pearl of four φ 10mm is added, is put into QM-3C vibration at high speed ball mills, then will
The rotating speed of ball mill is set as 1100rpm（44.73Hz）, ball milling 30min obtains blue solid powder；Blue solid powder is used
Ethanol water washs 3 times, impregnates in ethanol three times, 6min is centrifuged under 5000rpm rotating speeds, by lower layer's product 150
It is dried in vacuo 6h at DEG C, obtains bluish violet powder Y.
Test case 1
Measure the adsorption conditions of the hydrogen adsorption amount of the copper-based Porous coordination polymer hydrogen storage materials of embodiment 1-20 and comparative example 1-5
Respectively 1bar, 77K and 1bar, 233K, test result are shown in Table 1.Hydrogen adsorption uses Micromeritics HPVA-100 types
Adsorption instrument before sample test, first vacuumizes 12h, evacuated pressure is less than 10 μm of Hg, then in program on adsorption instrument under 473K
Under processing module of boosting guidance, specified pressure is reached, and obtain corrresponding quality gas-storing capacity.The BET specific surface area of all samples and
Pore volume test is carried out using U.S.'s Micromeritics ASAP2020 type physical adsorption appearances, is first taken out sample at 473K true
It is empty（About 2.0Pa）Deaerate 12h, then measures N at 77K2Adsorption and desorption isotherms obtain concrete outcome.
By table 1 as it can be seen that using 2,2'- union II thiophene -5,5'- oxalic acid is as organic ligand, according to preparation side of the invention
Copper-based Porous coordination polymer hydrogen storage material made from method has higher BET specific surface area and pore volume, and it is in low pressure
（1bar）With close to room temperature（233K）Under the conditions of obtain higher quality hydrogen storage content, 1 sample of embodiment reaches 2.17wt%, this is
What previous copper-based Porous coordination polymer hydrogen storage material did not reach.Mainly due to introducing S hetero atoms in ligand structure, have
Conducive to enhancing porous coordination polymer material surface polarity and electronegativity, material is improved for the small H of dipole moment active force2Suction
Attached effect.
The effect that 1 embodiment of table and comparative example prepare product compares
Test case 2
Measure adsorption effects of the copper-based Porous coordination polymer hydrogen storage material A to gas with various of embodiment 1, adsorption conditions difference
For 1bar, 77K and 1bar, 233K, test result is shown in Table 2.Gas absorption amount is inhaled using Micromeritics HPVA-100 types
Attached instrument before sample test, first vacuumizes 12h, evacuated pressure is less than 10 μm of Hg, then in program liter on adsorption instrument under 473K
It presses under processing module guidance, reaches specified pressure, and obtain corresponding quality gas-storing capacity（wt%）.
The quality gas-storing capacity effect that 2 embodiment 1 of table prepares product compares
As seen from the data in Table 2, the copper-based Porous coordination polymer hydrogen storage material that prepared by the present invention has higher quality hydrogen storage content,
And under same adsorption conditions, the material is for CH4Adsorption effect it is general, and for ethylene, CO2, acetylene gas absorption
Amount is not but high, at 233K and 1bar, CO2Adsorbance be only 0.36wt%.Mainly due to 2,2'- union IIs thiophene -5,
The nonlinear organization of 5'- oxalic acid ligands causes Porous coordination polymer that warp architecture by a small margin is presented, and similar copper-based porous
Coordination polymer compares, and effective aperture moderately narrows, and is conducive to H2Absorption, and it is unfavorable for the larger gas molecule of molecular diameter
Caused by absorbing into.
Test case 1
Embodiment 1, embodiment 2, comparative example 4 and 5 porous coordination polymer material of comparative example are measured for hydrogen adsorption enthalpy curve
It by Materials Studio molecular simulation software for calculation, is calculated according to dual station point Lang Gemiaoer models, selects hydrogen point
Records of values when son zero covers, it is as shown in Figure 3 to obtain curve.In conjunction with Fig. 3 as can be seen that according to Materials Studio molecules
The calculated hydrogen adsorption enthalpy curve of analogue further illustrates the present invention the sample of preparation during hydrogen storage, tool
There is higher isosteric heat of adsorption, is conducive to the small H of dipole moment active force2、CH4The suction-operated of gas molecule.Using anaerobic dynamic
Vacuum drying treatment technology effectively avoids in usual drying processes because readily oxidizable substance is rotten in skeleton component caused by oxygen-containing
And crystalline form is exceeded, the problems such as influencing product quality stability.
Claims (17)
1. a kind of copper-based Porous coordination polymer hydrogen storage material, it is characterised in that：Its molecular formula is Cu3C32H17O16S6, molecular weight
For 1041g/mol, crystal morphology is light blue octahedron, and crystal structure belongs to cubic system, space group Pn-3, cell parameter
A=24.225, b=24.225, c=24.225, α=90 °, β=90 °, γ=90 °；In this Porous coordination polymer, six
A copper atom and 8 μ on 2,2'- union II thiophene -5,5'- oxalic acid ligands3- O and 12 2,2'- union II thiophene -5,5'-
12 carboxyls on oxalic acid ligand are connected, and constitute 12 connection secondary building unit [Cu of six cores6O4(OH)4], this
A secondary building unit connects two level by 2,2'- union II thiophene -5,5'- oxalic acid ligands with the 12 of adjacent 12 six cores again
Structural unit is connected, and constitutes the copper-based Porous coordination polymer of a three dimensional skeletal structure.
2. hydrogen storage material according to claim 1, it is characterised in that：In this Porous coordination polymer, exist simultaneously
Two kinds of basket structures, one is the tetrahedron cage that four adjacent secondary building units surround, another kind is six adjacent two levels
The octahedra cage that structural unit surrounds.
3. hydrogen storage material according to claim 2, it is characterised in that：The port size of octahedra cage and tetrahedron cage is distinguished
It is 1.06nm and 0.59nm.
4. the preparation method of copper-based Porous coordination polymer hydrogen storage material described in claim 1, it is characterised in that：Using solvent heat
Synthetic method：（1）Weigh a certain amount of nitric hydrate mantoquita, phenyl carboxylic acid and N, N'- dimethylformamide（DMF）, ultrasound at
Manage certain time；（2）A certain amount of 2,2'- union IIs thiophene -5,5'- oxalic acid is added into reactant again, continues supersound process one
It fixes time；（3）Solution is shifted in supreme borosilicate tube reactor, heating treatment certain time；（4）After cooling product through filtering,
After organic solvent rinses, copper-based Porous coordination polymer hydrogen storage material is dried to obtain through anaerobic dynamic vacuum.
5. according to the method described in claim 4, it is characterized in that：Step（1）The 2,2'- union IIs thiophene -5,5'- oxalic acid
It is made by 2,2'- union II -5,5'-3- methylthiophene carboxylation reactions.
6. according to the method described in claim 5, it is characterized in that：The 2,2'- union IIs thiophene -5,5'- oxalic acid is using such as
Lower method：By 6~10mmol 2,2'- union II -5,5'-3- methylthiophenes and 80~120mL anhydrous tetrahydro furans in nitrogen protection
Lower uniformly mixing, is added concentration 1~2mol/L, 30~60mL of n-BuLi at 150~200K, waits for that temperature of reaction system increases
Continue to be cooled to 200K after to 273K；1~5g dry ice is added into reaction system, persistently stirs 10~15h, adds concentration 1
60~90mL of hydrochloric acid of~1.5mol/L, 3~6h of acidification reaction filter reaction product, washing, 70-90 DEG C of vacuum drying 8
~12h obtains required organic ligand.
7. according to the method described in claim 4, it is characterized in that：Step（1）The nitric hydrate mantoquita, phenyl carboxylic acid and N,
N'- dimethylformamides（DMF）Molar ratio be 1：（40~80）：（350~900）, preferably 1：（60~75）：（500~
700）.
8. the method according to claim 4 or 7, it is characterised in that：Step（1）The nitric hydrate mantoquita is selected from three water nitre
One or more of sour copper, Copper nitrate hexahydrate and nine water copper nitrates etc., preferably nitrate trihydrate copper.
9. the method according to claim 4 or 7, it is characterised in that：Step（1）The phenyl carboxylic acid is selected from benzoic acid, benzene
One or more of acetic acid, 1- phenyl-cyclohexane-carboxylic acids and 1- phenyl cyclopentane-carboxylic acids etc., preferably phenylacetic acid.
10. according to the method described in claim 4, it is characterized in that：Step（1）The supersound process temperature is 25 DEG C~80
DEG C, sonication treatment time is 5min~50min.
11. the method according to claim 4 or 6, it is characterised in that：Step（2）The organic ligand 2,2'- union II thiophenes
Pheno -5,5'- oxalic acid and the molar ratio of nitric hydrate mantoquita are（0.1~1）：1.
12. according to the method described in claim 4, it is characterized in that：Step（2）Continue to be ultrasonically treated temperature to be 15 DEG C~50
DEG C, sonication treatment time is 5min~50min.
13. according to the method described in claim 4, it is characterized in that：Step（3）After shifting supreme borosilicate tube reactor, reaction
Temperature is 75 DEG C~150 DEG C, and the reaction time is 40h~150h.
14. according to the method described in claim 4, it is characterized in that：Step（4）The organic solvent is selected from methanol, ethyl alcohol, chlorine
One or more of imitative, dichloromethane, DMF and deionized water etc..
15. according to the method described in claim 4, it is characterized in that：Step（4）The anaerobic dynamic vacuum drying control equipment
Vacuum degree is in 450Pa~850Pa, 10 DEG C~50 DEG C of drying temperature, drying time 10h~60h.
16. the application of copper-based Porous coordination polymer hydrogen storage material described in claim 1, it is characterised in that：For absorbing and storing
H2、CH4Etc. the small micro-molecular gas of dipole moments active force.
17. application according to claim 16, it is characterised in that：Adsorption conditions are adsorptive pressure 1bar~5bar, absorption
Temperature is 200K~233K.
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