CN103007889B - Preparation method of metal-organic frame material La-BDC adsorbing CO2 and modified product of metal-organic frame material La-BDC - Google Patents
Preparation method of metal-organic frame material La-BDC adsorbing CO2 and modified product of metal-organic frame material La-BDC Download PDFInfo
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Abstract
The invention discloses a preparation of a metal-organic frame material La-BDC adsorbing CO2, which comprises the following steps of: dissolving La(NO3)3 in de-ionized water, to obtain a solution A; dissolving 1,4-phthalic acid in an inorganic base solution, to obtain a solution B; at room temperature, mixing the solution A with the solution B to obtain a first mixing solution, and crystallizing the first mixing solution at 150-180 DEG C for 18-30hours to obtain a first solid product; washing the first solid product by de-ionized water until the first solid product is neutral; heating the washed neutral first solid product in a muffle to 180-200 DEG C at a speed of 5-10 DEG C/min; and keeping for 4-6hours to obtain the metal-organic frame material La-BDC. The metal-organic frame material La-BDC adsorbing CO2, and has a great absorption capacity on CO2 at comparatively low temperature and in a low-pressure environment; and the desorption temperature is comparatively low.
Description
[technical field]
The present invention relates to CO
2sorbing material, be specifically related to one can be in lower temperature and environment under low pressure efficient adsorption CO
2metal-organic framework materials La-BDC and the preparation method of modifier.
[background technology]
Carbon dioxide (CO
2) be topmost greenhouse gases in the world at present, the most cheap in Ye Shi C1 family, rich in natural resources, and CO simultaneously
2application is extensive, for example CO
2as extinguishing chemical; CO
2as extractant, food, beverage, oil plant, spices, medicine etc. are processed to extraction; CO
2as food preservative, can effectively prevent the growth of bacterium in food, mould, avoid food spoilage, and can be fresh-keeping and maintain the original local flavor of food and nutritional labeling; CO
2as the raw material of the chemical products such as methanol, methane, methyl ether, Merlon; CO
2as oil field injectant, effectively the displacement of reservoir oil improves tar productivity; CO
2for the protection of arc welding, avoid oxidation on metal surface, improve speed of welding etc. simultaneously.Therefore, CO
2separation and collection has become various countries' focus, and develops efficient CO
2sorbing material is its key point.
The industrial liquefied ammonia that mainly utilizes is to CO at present
2absorb, but the method has to produce in absorption process and in the accessory substances such as carbaminate,, regenerative process serious to equipment corrosion, needs to consume a large amount of steam and cause the shortcomings such as the wasting of resources.For existing CO
2the deficiency of capture technique, designs and develops and has the CO that adsorption capacity is large, adsorption-desorption temperature is low and energy consumption is little
2sorbing material is that industry is explored.
Metal-organic framework (Metal-organic framework, be abbreviated as MOFs) material is the functional material of the novel porous inorganic-organic hybridization of a class, this type of material has large, the regular internal arrangement of specific area, the special features such as mending structure of opening up, also CO absorption 2 effectively of common metal-organic frame (MOFs) material, but they are normally made up of the material from crude oil, and conventionally containing toxic heavy metal.
In metal-organic framework (MOFs) material building-up process, the solvent using and deprotonation reagent can carry out coordination with exposed metal position on metallic element sometimes, thereby obtain metal-organic framework (MOFs) material of different structure.The design of metal current-organic frame (MOFs) material mainly concentrates on and changes organic ligand to synthesize dissimilar metal-organic framework (MOFs) material, and ligand structure is increasingly sophisticated.And the preparation of La-BDC metalloid-organic framework materials mainly makes by changing the factors such as metal salt solution, organic ligand, solvent, deprotonation reagent.As to utilize two (4-pyridine radicals) ethane (BPE) of 1,2-be deprotonation reagent, by the La (NO of amount of calculation
3)
36H
2o, M-phthalic acid, BPE and deionized water are mixed, and at 180 DEG C, crystallization 2 days, makes yellow crystals [La
4(BDC)
6(H
2o)
5] (H
2o).
But, at present La-BDC class framework material is main mainly with single crystal cultivation, is applied to gas absorption segregator very little, and the respective material that is applied to this field is deprotonation reagent mainly with organic matter, as DMF, pyridine, bipyridyl etc., these organic matters are obvious to harm.In addition, prepared metal-organic framework materials adsorbance is less, can not reach the object of gas being carried out to efficient adsorption.Therefore, simplicity of design easily row and the large La-BDC metalloid-organic framework materials of adsorbance be a major challenge.
[summary of the invention]
The object of this invention is to provide one and there is efficient CO
2the metal-organic framework materials La-BDC of absorption property and the preparation method of modifier thereof.
For achieving the above object, the invention provides a kind of CO absorption
2the preparation method of metal-organic framework materials La-BDC, comprise the steps:
By La (NO
3)
3be dissolved in deionized water, form solution A;
Isosorbide-5-Nitrae-phthalic acid is dissolved in to inorganic alkali solution, forms solution B;
At room temperature, this solution A is mixed with this solution B, obtain the first mixed solution, at 150 DEG C-180 DEG C, make this first mixed solution crystallization 18 hours-30 hours, obtain the first solid product, by extremely neutral this first solid product washing, this washing to the first neutral solid product is warming up to 180 DEG C-200 DEG C with the speed of 5 DEG C of-10 DEG C/min by deionized water in Muffle furnace, keep 4 hours-6 hours, obtain metal-organic framework materials La-BDC.
In above-mentioned preparation method, this inorganic alkali solution is NaOH solution, KOH solution, Na
2cO
3solution or K
2cO
3solution.
In above-mentioned preparation method, this washing to the first neutral solid product is warming up to 190 DEG C with the speed of 5 DEG C/min in Muffle furnace, keeps 5 hours, obtain metal-organic framework materials La-BDC.
For achieving the above object, the invention provides a kind of CO absorption
2the preparation method of the material modified La of metal-organic framework (Li)-BDC, comprise the steps:
By the CO absorption of above-mentioned preparation
2metal-organic framework materials La-BDC be at room temperature dissolved in deionized water, then add the LiNO of reacting dose
3the aqueous solution, obtain the second mixed solution, at 150 DEG C-180 DEG C, make this second mixed solution crystallization 10 hours-15 hours, naturally cooling, obtain the second solid product, by extremely neutral this second solid product washing, this washing to the second neutral solid product is warming up to 180 DEG C-200 DEG C with the speed of 5 DEG C of-10 DEG C/min by deionized water in Muffle furnace, keep 4 hours-6 hours, obtain the material modified La of metal-organic framework (Li)-BDC.
In above-mentioned preparation method, the LiNO of this reacting dose
3the LiNO of the reacting dose in the aqueous solution
3quality account for La-BDC and LiNO
35%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of gross mass.
For achieving the above object, the invention provides a kind of CO absorption
2the preparation method of the material modified La of metal-organic framework (Li)-BDC, comprise the steps:
By La (NO
3)
3be dissolved in deionized water, form solution A;
Isosorbide-5-Nitrae-phthalic acid is dissolved in to inorganic alkali solution, forms solution B;
At room temperature, this solution A is mixed with this solution B, obtain the first mixed solution;
Make the LiNO of reacting dose
3the aqueous solution mixes with this first mixed solution, obtain the 3rd mixed solution, at 150 DEG C-180 DEG C, make the 3rd mixed solution crystallization 18 hours-30 hours, obtain the 3rd solid product, by deionized water by the 3rd solid product washing to neutral, this washing to the 3rd neutral solid product is warming up to 180 DEG C-200 DEG C with the speed of 5 DEG C of-10 DEG C/min in Muffle furnace, keeps 4 hours-6 hours, obtain the material modified La of metal-organic framework (Li)-BDC.
In above-mentioned preparation method, this inorganic alkali solution is NaOH solution, KOH solution, Na
2cO
3solution or K
2cO
3solution.
In above-mentioned preparation method, this washing to the 3rd neutral solid product is warming up to 190 DEG C with the speed of 5 DEG C/min in Muffle furnace, keeps 5 hours, obtain the material modified La of metal-organic framework (Li)-BDC.
According to experimental result, metal-organic framework materials provided by the present invention, in lower temperature and environment under low pressure, has CO
2the features such as adsorption capacity is large, adsorption-desorption temperature is lower, the method has solved common CO
2low pressure adsorbance is little, the more high deficiency of desorption temperature, has good prospects for commercial application.
[Brief Description Of Drawings]
Figure 1 shows that the CO of the embodiment of the present invention 1
2-TPD curve map.
[detailed description of the invention]
Below in conjunction with embodiments of the invention and comparative example, the invention will be further described.The CO that the following embodiment of the present invention uses
2the AutoChem chemical adsorption instrument AutoChem II 2920 that adsorbance determining instrument adopts Micromeritics Instrument Corp. U.S.A to produce.
the preparation of metal-organic framework materials La-BDC:
Preparation example 1
A. by 3.409g La (NO
3)
2be dissolved in 30ml deionized water, after stirring and dissolving, form solution A;
B. 0.28g NaOH is dissolved in 50ml deionized water, after stirring and dissolving, adds wherein amount of calculation Isosorbide-5-Nitrae-phthalic acid (H
2bDC),, after vigorous stirring is dissolved, form solution B;
C. at room temperature, A solution is dropwise added in B solution, stirs, A solution is evenly mixed with B solution, obtain the mixed solution of A solution and B solution;
D. at 160 DEG C, the mixed solution crystallization 24h of A solution and B solution, obtains solid product;
E. the solid matter with deionized water of gained in d step is washed until the pH of washings approaches 7, then will in Muffle furnace, be warming up to 180 DEG C with 5 DEG C/min heating rate with the solid product after deionized water washing, keep 6 hours, obtain metal-organic framework materials La-BDC.
Preparation example 2
A. by 3.409g La (NO
3)
2be dissolved in 30ml deionized water, after stirring and dissolving, form solution A;
B. 0.392g KOH is dissolved in 50ml deionized water, after stirring and dissolving, adds wherein amount of calculation Isosorbide-5-Nitrae-phthalic acid (H
2bDC),, after vigorous stirring is dissolved, form solution B;
C. at room temperature, A solution is dropwise added in B solution, stirs, A solution is evenly mixed with B solution, obtain the mixed solution of A solution and B solution;
D. at 170 DEG C, the mixed solution crystallization 24h of A solution and B solution, obtains solid product;
E. the solid matter with deionized water of gained in d step is washed until the pH of washings approaches 7, then will in Muffle furnace, be warming up to 190 DEG C with 5 DEG C/min heating rate with the solid product after deionized water washing, keep 5 hours, obtain metal-organic framework materials La-BDC.
Preparation example 3
A. by 3.409g La (NO
3)
2be dissolved in 30ml deionized water, after stirring and dissolving, form solution A;
B. by 0.371g Na
2cO
3be dissolved in 50ml deionized water, after stirring and dissolving, add wherein amount of calculation Isosorbide-5-Nitrae-phthalic acid (H
2bDC),, after vigorous stirring is dissolved, form solution B;
C. at room temperature, A solution is dropwise added in B solution, stirs, A solution is evenly mixed with B solution, obtain the mixed solution of A solution and B solution;
D. at 180 DEG C, the mixed solution crystallization 18h of A solution and B solution, obtains solid product;
E. the solid matter with deionized water of gained in d step is washed until the pH of washings approaches 7, then the solid product with after deionized water washing is warming up to 190 DEG C with 5 DEG C/min heating rate in Muffle furnace and keeps 5 hours, obtain metal-organic framework materials La-BDC.
Preparation example 4
A. by 3.409g La (NO
3)
2be dissolved in 30ml deionized water, after stirring and dissolving, form solution A;
B. by 0.483g K
2cO
3be dissolved in 50ml deionized water, after stirring and dissolving, add wherein amount of calculation Isosorbide-5-Nitrae-phthalic acid (H
2bDC),, after vigorous stirring is dissolved, form solution B;
C. at room temperature, A solution is dropwise added in B solution, stirs, A solution is evenly mixed with B solution, obtain the mixed solution of A solution and B solution;
D. at 150 DEG C, the mixed solution crystallization 30h of A solution and B solution, obtains solid product;
E. the solid matter with deionized water of gained in d step is washed until the pH of washings approaches 7, then will in Muffle furnace, be warming up to 200 DEG C with 5 DEG C/min heating rate with the solid product after deionized water washing, keep 4 hours, obtain metal-organic framework materials La-BDC.
the preparation of the material modified La of metal-organic framework (Li)-BDC:
Preparation example 5
A. at room temperature, pass through metal-organic framework materials La-BDC prepared by preparation example 1 and be added in 30ml deionized water appropriate, fully stir, form the aqueous solution of La-BDC, repeat aforesaid operations, the aqueous solution of 10 parts of La-BDC of preparation, in addition, by the LiNO of 10 parts of different amounts of calculation
3be dissolved in respectively after 10 parts of 30ml deionized waters, obtain the LiNO of 10 parts of different amounts of calculation
3the aqueous solution, by the LiNO of 1 part of amount of calculation
3the aqueous solution add in the aqueous solution of a La-BDC, stir 3h, make LiNO
3the aqueous solution evenly mix with the aqueous solution of La-BDC, repeat aforesaid operations, obtain 10 parts of LiNO
3the aqueous solution and the mixed solution of the aqueous solution of La-BDC, wherein, LiNO
3quality account for respectively La-BDC and LiNO
35%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of gross mass;
B. at 160 DEG C, make 10 parts of LiNO
3the aqueous solution and the mixed solution crystallization 10h respectively of the aqueous solution of La-BDC, obtain 10 parts of solid products;
C. by 10 parts of solid products of gained in b step respectively with deionized water washing until the pH of washings to neutrality, by respectively with 10 parts of solid products after deionized water washing respectively at being warming up to 190 DEG C with 5 DEG C/min heating rate in Muffle furnace, keep 5 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 6
A. at room temperature, pass through metal-organic framework materials La-BDC prepared by preparation example 1 and be added in 30ml deionized water appropriate, fully stir, form the aqueous solution of La-BDC, repeat aforesaid operations, the aqueous solution of 10 parts of La-BDC of preparation, in addition, by the LiNO of 10 parts of different amounts of calculation
3be dissolved in respectively after 10 parts of 30ml deionized waters, obtain the LiNO of 10 parts of different amounts of calculation
3the aqueous solution, by the LiNO of 1 part of amount of calculation
3the aqueous solution add in the aqueous solution of a La-BDC, stir 3h, make LiNO
3the aqueous solution evenly mix with the aqueous solution of La-BDC, repeat aforesaid operations, obtain 10 parts of LiNO
3the aqueous solution and the mixed solution of the aqueous solution of La-BDC, wherein, LiNO
3quality account for respectively La-BDC and LiNO
35%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of gross mass;
B. at 160 DEG C, make 10 parts of LiNO
3the aqueous solution and the mixed solution crystallization 12h respectively of the aqueous solution of La-BDC, obtain 10 parts of solid products;
C. by 10 parts of solid products of gained in b step respectively with deionized water washing until the pH of washings to neutrality, by respectively with 10 parts of solid products after deionized water washing respectively at being warming up to 190 DEG C with 5 DEG C/min heating rate in Muffle furnace, keep 5 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 7
A. at room temperature, pass through metal-organic framework materials La-BDC prepared by preparation example 1 and be added in 30ml deionized water appropriate, fully stir, form the aqueous solution of La-BDC, repeat aforesaid operations, the aqueous solution of 10 parts of La-BDC of preparation, in addition, by the LiNO of 10 parts of different amounts of calculation
3be dissolved in respectively after 10 parts of 30ml deionized waters, obtain the LiNO of 10 parts of different amounts of calculation
3the aqueous solution, by the LiNO of 1 part of amount of calculation
3the aqueous solution add in the aqueous solution of a La-BDC, stir 3h, make LiNO
3the aqueous solution evenly mix with the aqueous solution of La-BDC, repeat aforesaid operations, obtain 10 parts of LiNO
3the aqueous solution and the mixed solution of the aqueous solution of La-BDC, wherein, LiNO
3quality account for respectively La-BDC and LiNO
35%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of gross mass;
B. at 160 DEG C, make 10 parts of LiNO
3the aqueous solution and the mixed solution crystallization 15h respectively of the aqueous solution of La-BDC, obtain 10 parts of solid products;
C. by 10 parts of solid products of gained in b step respectively with deionized water washing until the pH of washings to neutrality, by respectively with 10 parts of solid products after deionized water washing respectively at being warming up to 190 DEG C with 5 DEG C/min heating rate in Muffle furnace, keep 5 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 8
A. at room temperature, pass through metal-organic framework materials La-BDC prepared by preparation example 2 and be added in 30ml deionized water appropriate, fully stir, form the aqueous solution of La-BDC, repeat aforesaid operations, the aqueous solution of 10 parts of La-BDC of preparation, in addition, by the LiNO of 10 parts of different amounts of calculation
3be dissolved in respectively after 10 parts of 30ml deionized waters, obtain the LiNO of 10 parts of different amounts of calculation
3the aqueous solution, by the LiNO of 1 part of amount of calculation
3the aqueous solution add in the aqueous solution of a La-BDC, stir 3h, make LiNO
3the aqueous solution evenly mix with the aqueous solution of La-BDC, repeat aforesaid operations, obtain 10 parts of LiNO
3the aqueous solution and the mixed solution of the aqueous solution of La-BDC, wherein, LiNO
3quality account for respectively La-BDC and LiNO
35%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of gross mass;
B. at 170 DEG C, make 10 parts of LiNO
3the aqueous solution and the mixed solution crystallization 10h respectively of the aqueous solution of La-BDC, obtain 10 parts of solid products;
C. by 10 parts of solid products of gained in b step respectively with deionized water washing until the pH of washings to neutrality, by respectively with 10 parts of solid products after deionized water washing respectively at being warming up to 190 DEG C with 5 DEG C/min heating rate in Muffle furnace, keep 5 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 9
A. at room temperature, pass through metal-organic framework materials La-BDC prepared by preparation example 2 and be added in 30ml deionized water appropriate, fully stir, form the aqueous solution of La-BDC, repeat aforesaid operations, the aqueous solution of 10 parts of La-BDC of preparation, in addition, by the LiNO of 10 parts of different amounts of calculation
3be dissolved in respectively after 10 parts of 30ml deionized waters, obtain the LiNO of 10 parts of different amounts of calculation
3the aqueous solution, by the LiNO of 1 part of amount of calculation
3the aqueous solution add in the aqueous solution of a La-BDC, stir 3h, make LiNO
3the aqueous solution evenly mix with the aqueous solution of La-BDC, repeat aforesaid operations, obtain 10 parts of LiNO
3the aqueous solution and the mixed solution of the aqueous solution of La-BDC, wherein, LiNO
3quality account for respectively La-BDC and LiNO
35%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of gross mass;
B. at 170 DEG C, make 10 parts of LiNO
3the aqueous solution and the mixed solution crystallization 12h respectively of the aqueous solution of La-BDC, obtain 10 parts of solid products;
C. by 10 parts of solid products of gained in b step respectively with deionized water washing until the pH of washings to neutrality, by respectively with 10 parts of solid products after deionized water washing respectively at being warming up to 190 DEG C with 5 DEG C/min heating rate in Muffle furnace, keep 5 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 10
A. at room temperature, pass through metal-organic framework materials La-BDC prepared by preparation example 2 and be added in 30ml deionized water appropriate, fully stir, form the aqueous solution of La-BDC, repeat aforesaid operations, the aqueous solution of 10 parts of La-BDC of preparation, in addition, by the LiNO of 10 parts of different amounts of calculation
3be dissolved in respectively after 10 parts of 30mi deionized waters, obtain the LiNO of 10 parts of different amounts of calculation
3the aqueous solution, by the LiNO of 1 part of amount of calculation
3the aqueous solution add in the aqueous solution of a La-BDC, stir 3h, make LiNO
3the aqueous solution evenly mix with the aqueous solution of La-BDC, repeat aforesaid operations, obtain 10 parts of LiNO
3the aqueous solution and the mixed solution of the aqueous solution of La-BDC, wherein, LiNO
3quality account for respectively La-BDC and LiNO
35%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of gross mass;
B. at 170 DEG C, make 10 parts of LiNO
3the aqueous solution and the mixed solution crystallization 15h respectively of the aqueous solution of La-BDC, obtain 10 parts of solid products;
C. by 10 parts of solid products of gained in b step respectively with deionized water washing until the pH of washings to neutrality, by respectively with 10 parts of solid products after deionized water washing respectively at being warming up to 190 DEG C with 5 DEG C/min heating rate in Muffle furnace, keep 5 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 11
A. at room temperature, pass through metal-organic framework materials La-BDC prepared by preparation example 3 and be added in 30ml deionized water appropriate, fully stir, form the aqueous solution of La-BDC, repeat aforesaid operations, the aqueous solution of 10 parts of La-BDC of preparation, in addition, by the LiNO of 10 parts of different amounts of calculation
3be dissolved in respectively after 10 parts of 30mi deionized waters, obtain the LiNO of 10 parts of different amounts of calculation
3the aqueous solution, by the LiNO of 1 part of amount of calculation
3the aqueous solution add in the aqueous solution of a La-BDC, stir 3h, make LiNO
3the aqueous solution evenly mix with the aqueous solution of La-BDC, repeat aforesaid operations, obtain 10 parts of LiNO
3the aqueous solution and the mixed solution of the aqueous solution of La-BDC, wherein, LiNO
3quality account for respectively La-BDC and LiNO
35%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of gross mass;
B. at 180 DEG C, make 10 parts of LiNO
3the aqueous solution and the mixed solution crystallization 10h respectively of the aqueous solution of La-BDC, obtain 10 parts of solid products;
C. by 10 parts of solid products of gained in b step respectively with deionized water washing until the pH of washings to neutrality, by respectively with 10 parts of solid products after deionized water washing respectively at being warming up to 200 DEG C with 5 DEG C/min heating rate in Muffle furnace, keep 4 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 12
A. at room temperature, pass through metal-organic framework materials La-BDC prepared by preparation example 3 and be added in 30ml deionized water appropriate, fully stir, form the aqueous solution of La-BDC, repeat aforesaid operations, the aqueous solution of 10 parts of La-BDC of preparation, in addition, by the LiNO of 10 parts of different amounts of calculation
3be dissolved in respectively after 10 parts of 30ml deionized waters, obtain the LiNO of 10 parts of different amounts of calculation
3the aqueous solution, by the LiNO of 1 part of amount of calculation
3the aqueous solution add in the aqueous solution of a La-BDC, stir 3h, make LiNO
3the aqueous solution evenly mix with the aqueous solution of La-BDC, repeat aforesaid operations, obtain 10 parts of LiNO
3the aqueous solution and the mixed solution of the aqueous solution of La-BDC, wherein, LiNO
3quality account for respectively La-BDC and LiNO
35%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of gross mass;
B. at 180 DEG C, make 10 parts of LiNO
3the aqueous solution and the mixed solution crystallization 12h respectively of the aqueous solution of La-BDC, obtain 10 parts of solid products;
C. by 10 parts of solid products of gained in b step respectively with deionized water washing until the pH of washings to neutrality, by respectively with 10 parts of solid products after deionized water washing respectively at being warming up to 200 DEG C with 5 DEG C/min heating rate in Muffle furnace, keep 4 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 13
A. at room temperature, pass through metal-organic framework materials La-BDC prepared by preparation example 3 and be added in 30ml deionized water appropriate, fully stir, form the aqueous solution of La-BDC, repeat aforesaid operations, the aqueous solution of 10 parts of La-BDC of preparation, in addition, by the LiNO of 10 parts of different amounts of calculation
3be dissolved in respectively after 10 parts of 30ml deionized waters, obtain the LiNO of 10 parts of different amounts of calculation
3the aqueous solution, by the LiNO of 1 part of amount of calculation
3the aqueous solution add in the aqueous solution of a La-BDC, stir 3h, make LiNO
3the aqueous solution evenly mix with the aqueous solution of La-BDC, repeat aforesaid operations, obtain 10 parts of LiNO
3the aqueous solution and the mixed solution of the aqueous solution of La-BDC, wherein, LiNO
3quality account for respectively La-BDC and LiNO
35%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of gross mass;
B. at 180 DEG C, make 10 parts of LiNO
3the aqueous solution and the mixed solution crystallization 15h respectively of the aqueous solution of La-BDC, obtain 10 parts of solid products;
C. by 10 parts of solid products of gained in b step respectively with deionized water washing until the pH of washings to neutrality, by respectively with 10 parts of solid products after deionized water washing respectively at being warming up to 200 DEG C with 5 DEG C/min heating rate in Muffle furnace, keep 4 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 14
A. at room temperature, pass through metal-organic framework materials La-BDC prepared by preparation example 4 and be added in 30ml deionized water appropriate, fully stir, form the aqueous solution of La-BDC, repeat aforesaid operations, the aqueous solution of 10 parts of La-BDC of preparation, in addition, by the LiNO of 10 parts of different amounts of calculation
3be dissolved in respectively after 10 parts of 30ml deionized waters, obtain the LiNO of 10 parts of different amounts of calculation
3the aqueous solution, by the LiNO of 1 part of amount of calculation
3the aqueous solution add in the aqueous solution of a La-BDC, stir 3h, make LiNO
3the aqueous solution evenly mix with the aqueous solution of La-BDC, repeat aforesaid operations, obtain 10 parts of LiNO
3the aqueous solution and the mixed solution of the aqueous solution of La-BDC, wherein, LiNO
3quality account for respectively La-BDC and LiNO
35%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of gross mass;
B. at 150 DEG C, make 10 parts of LiNO
3the aqueous solution and the mixed solution crystallization 10h respectively of the aqueous solution of La-BDC, obtain 10 parts of solid products;
C. by 10 parts of solid products of gained in b step respectively with deionized water washing until the pH of washings to neutrality, by respectively with 10 parts of solid products after deionized water washing respectively at being warming up to 180 DEG C with 8 DEG C/min heating rate in Muffle furnace, keep 6 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 15
A. at room temperature, pass through metal-organic framework materials La-BDC prepared by preparation example 4 and be added in 30ml deionized water appropriate, fully stir, form the aqueous solution of La-BDC, repeat aforesaid operations, the aqueous solution of 10 parts of La-BDC of preparation, in addition, by the LiNO of 10 parts of different amounts of calculation
3be dissolved in respectively after 10 parts of 30ml deionized waters, obtain the LiNO of 10 parts of different amounts of calculation
3the aqueous solution, by the LiNO of 1 part of amount of calculation
3the aqueous solution add in the aqueous solution of a La-BDC, stir 3h, make LiNO
3the aqueous solution evenly mix with the aqueous solution of La-BDC, repeat aforesaid operations, obtain 10 parts of LiNO
3the aqueous solution and the mixed solution of the aqueous solution of La-BDC, wherein, LiNO
3quality account for respectively La-BDC and LiNO
35%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of gross mass;
B. at 150 DEG C, make 10 parts of LiNO
3the aqueous solution and the mixed solution crystallization 12h respectively of the aqueous solution of La-BDC, obtain 10 parts of solid products;
C. by 10 parts of solid products of gained in b step respectively with deionized water washing until the pH of washings to neutrality, by respectively with 10 parts of solid products after deionized water washing respectively at being warming up to 180 DEG C with 5 DEG C/min heating rate in Muffle furnace, keep 6 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 16
A. at room temperature, pass through metal-organic framework materials La-BDC prepared by preparation example 4 and be added in 30ml deionized water appropriate, fully stir, form the aqueous solution of La-BDC, repeat aforesaid operations, the aqueous solution of 10 parts of La-BDC of preparation, in addition, by the LiNO of 10 parts of different amounts of calculation
3be dissolved in respectively after 10 parts of 30ml deionized waters, obtain the LiNO of 10 parts of different amounts of calculation
3the aqueous solution, by the LiNO of 1 part of amount of calculation
3the aqueous solution add in the aqueous solution of a La-BDC, stir 3h, make LiNO
3the aqueous solution evenly mix with the aqueous solution of La-BDC, repeat aforesaid operations, obtain 10 parts of LiNO
3the aqueous solution and the mixed solution of the aqueous solution of La-BDC, wherein, LiNO
3quality account for respectively La-BDC and LiNO
35%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of gross mass;
B. at 150 DEG C, make 10 parts of LiNO
3the aqueous solution and the mixed solution crystallization 15h respectively of the aqueous solution of La-BDC, obtain 10 parts of solid products;
C. by 10 parts of solid products of gained in b step respectively with deionized water washing until the pH of washings to neutrality, by respectively with 10 parts of solid products after deionized water washing respectively at being warming up to 180 DEG C with 10 DEG C/min heating rate in Muffle furnace, keep 6 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 17
A. by 3.409g La (NO
3)
2be dissolved in 30ml deionized water, after stirring and dissolving, form solution A, repeat aforesaid operations, prepare 10 parts of solution A;
B. 0.28g NaOH is dissolved in 50ml deionized water, after stirring and dissolving, adds wherein amount of calculation Isosorbide-5-Nitrae-phthalic acid (H
2bDC), after vigorous stirring is dissolved, form solution B, repeat aforesaid operations, prepare 10 parts of solution B;
C. at room temperature, a solution A is dropwise added in a solution B, stir, solution A is evenly mixed with solution B, obtain the mixed solution of solution A and solution B, repeat aforesaid operations, prepare the mixed solution of 10 parts of solution A and solution B;
D. with preparation example 5 prepare LiNO
3the operation of the aqueous solution identical, the LiNO of preparation and 10 parts of different amounts of calculation prepared in preparation example 5
3the LiNO of the identical 10 parts of different amounts of calculation of the aqueous solution
3the aqueous solution, by 1 part of LiNO
3the aqueous solution add in the mixed solution of a solution A and solution B, stir 3h, make LiNO
3the aqueous solution evenly mix with the mixed solution of solution B with solution A, so operation, obtain 10 parts of LiNO
3the aqueous solution with the mixed solution of the mixed solution of solution A and solution B;
E. at 160 DEG C, make 10 parts of LiNO
3the aqueous solution with the mixed solution of the mixed solution of solution A and solution B crystallization 28h respectively, obtain 10 parts of solid products;
F. 10 parts of solid products of gained in e are washed until the pH of washings approaches 7 by deionized water respectively, to in Muffle furnace, be warming up to 190 DEG C with 5 DEG C/min heating rate respectively with 10 parts of solid products after deionized water washing respectively, keep 5 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 18
A. by 3.409g La (NO
3)
2be dissolved in 30ml deionized water, after stirring and dissolving, form solution A, repeat aforesaid operations, prepare 10 parts of solution A;
B. 0.392g KOH is dissolved in 50ml deionized water, after stirring and dissolving, adds wherein amount of calculation Isosorbide-5-Nitrae-phthalic acid (H
2bDC), after vigorous stirring is dissolved, form solution B, repeat aforesaid operations, prepare 10 parts of solution B;
C. at room temperature, a solution A is dropwise added in a solution B, stir, solution A is evenly mixed with solution B, obtain the mixed solution of solution A and solution B, repeat aforesaid operations, prepare the mixed solution of 10 parts of solution A and solution B;
In d and preparation example 8, prepare LiNO
3the operation of the aqueous solution identical, the LiNO of preparation and 10 parts of different amounts of calculation prepared in preparation example 8
3the LiNO of the identical 10 parts of different amounts of calculation of the aqueous solution
3the aqueous solution, by 1 part of LiNO
3the aqueous solution add in the mixed solution of a solution A and solution B, stir 3h, make LiNO
3the aqueous solution evenly mix with the mixed solution of solution B with solution A, so operation, obtain 10 parts of LiNO
3the aqueous solution with the mixed solution of the mixed solution of solution A and solution B;
E. at 150 DEG C, make 10 parts of LiNO
3the aqueous solution with the mixed solution of the mixed solution of solution A and solution B crystallization 30h respectively, obtain 10 parts of solid products;
F. 10 parts of solid products of gained in e are washed until the pH of washings approaches 7 by deionized water respectively, to in Muffle furnace, be warming up to 180 DEG C with 10 DEG C/min heating rate respectively with 10 parts of solid products after deionized water washing respectively, keep 6 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 19
A. by 3.409g La (NO
3)
2be dissolved in 30ml deionized water, after stirring and dissolving, form solution A, repeat aforesaid operations, prepare 10 parts of solution A;
B. by 0.371g Na
2cO
3be dissolved in 50ml deionized water, after stirring and dissolving, add wherein amount of calculation Isosorbide-5-Nitrae-phthalic acid (H
2bDC), after vigorous stirring is dissolved, form solution B, repeat aforesaid operations, prepare 10 parts of solution B;
C. at room temperature, a solution A is dropwise added in a solution B, stir, solution A is evenly mixed with solution B, obtain the mixed solution of solution A and solution B, repeat aforesaid operations, prepare the mixed solution of 10 parts of solution A and solution B;
In d and preparation example 11, prepare LiNO
3the operation of the aqueous solution identical, the LiNO of preparation and 10 parts of different amounts of calculation prepared in preparation example 11
3the LiNO of the identical 10 parts of different amounts of calculation of the aqueous solution
3the aqueous solution, by 1 part of LiNO
3the aqueous solution add in the mixed solution of a solution A and solution B, stir 3h, make LiNO
3the aqueous solution evenly mix with the mixed solution of solution B with solution A, so operation, obtain 10 parts of LiNO
3the aqueous solution with the mixed solution of the mixed solution of solution A and solution B;
E. at 170 DEG C, make 10 parts of LiNO
3the aqueous solution with the mixed solution of the mixed solution of solution A and solution B crystallization 30h respectively, obtain 10 parts of solid products;
F. 10 parts of solid products of gained in e are washed until the pH of washings approaches 7 by deionized water respectively, to in Muffle furnace, be warming up to 190 DEG C with 10 DEG C/min heating rate respectively with 10 parts of solid products after deionized water washing respectively, keep 5 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
Preparation example 20
A. by 3.409g La (NO
3)
2be dissolved in 30ml deionized water, after stirring and dissolving, form solution A, repeat aforesaid operations, prepare 10 parts of solution A;
B. by 0.483g K
2cO
3be dissolved in 50ml deionized water, after stirring and dissolving, add wherein amount of calculation Isosorbide-5-Nitrae-phthalic acid (H
2bDC), after vigorous stirring is dissolved, form solution B, repeat aforesaid operations, prepare 10 parts of solution B;
C. at room temperature, a solution A is dropwise added in a solution B, stir, solution A is evenly mixed with solution B, obtain the mixed solution of solution A and solution B, repeat aforesaid operations, prepare the mixed solution of 10 parts of solution A and solution B;
In d and preparation example 14, prepare LiNO
3the operation of the aqueous solution identical, the LiNO of preparation and 10 parts of different amounts of calculation prepared in preparation example 14
3the LiNO of the identical 10 parts of different amounts of calculation of the aqueous solution
3the aqueous solution, by 1 part of LiNO
3the aqueous solution add in the mixed solution of a solution A and solution B, stir 3h, make LiNO
3the aqueous solution evenly mix with the mixed solution of solution B with solution A, so operation, obtain 10 parts of LiNO
3the aqueous solution with the mixed solution of the mixed solution of solution A and solution B;
E. at 170 DEG C, make 10 parts of LiNO
3the aqueous solution with the mixed solution of the mixed solution of solution A and solution B crystallization 30h respectively, obtain 10 parts of solid products;
F. 10 parts of solid products of gained in e are washed until the pH of washings approaches 7 by deionized water respectively, to in Muffle furnace, be warming up to 200 DEG C with 10 DEG C/min heating rate respectively with 10 parts of solid products after deionized water washing respectively, keep 4 hours, obtain 10 parts of LiNO
3the material modified La of metal-organic framework (Li)-BDC that mass percent does not wait.
the CO of metal-organic framework materials
2
-TPD measures
Embodiment 1
Get the appropriate metal-organic framework materials La-BDC prepared by preparation example 1 that passes through, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge metal-organic framework materials La-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50ml min
-1, keep 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously.The CO of gained La-BDC
2-TPD curve as shown in Figure 1.
Embodiment 2
Get the appropriate metal-organic framework materials La-BDC prepared by preparation example 2 that passes through, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge metal-organic framework materials La-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50ml min
-1, keep 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously.The CO of gained La-BDC
2shown in-TPD curve and Fig. 1, class of a curve seemingly.
Embodiment 3
Get the appropriate metal-organic framework materials La-BDC prepared by preparation example 3 that passes through, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge metal-organic framework materials La-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50ml min
-1, keep 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously.The CO of gained La-BDC
2shown in-TPD curve and Fig. 1, class of a curve seemingly.
Embodiment 4
Get the appropriate metal-organic framework materials La-BDC prepared by preparation example 4 that passes through, be placed in the U-shaped pipe of AutoChemII 2920, pass into high-purity Ar and purge metal-organic framework materials La-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50ml min
-1, keep 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously.The CO of gained La-BDC
2shown in-TPD curve and Fig. 1, class of a curve seemingly.
Embodiment 5
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 5 that passes through, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50ml min
-1, keep 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously.
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, and compared with metal-organic framework materials La-BDC adsorbance in preparation example 1, adsorbance obviously increases, between 3-5mmol g
-1between.
Embodiment 6
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 6 that passes through, be placed in the U-shaped pipe of AutoChemII 2920, pass into high-purity Ar and purge metal-the have material modified La of machine frame (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas,, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 120min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously.
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, and compared with metal-organic framework materials La-BDC adsorbance in preparation example 1, adsorbance obviously increases, between 3-5mmol g
-1between.
Embodiment 7
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 7 that passes through, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50ml min
-1, keep 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously.
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, and compared with metal-organic framework materials La-BDC adsorbance in preparation example 1, adsorbance obviously increases, between 3-5mmol g
-1between.
Embodiment 8
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 8 that passes through, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50ml min
-1, keep 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously.
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, and compared with metal-organic framework materials La-BDC adsorbance in preparation example 2, adsorbance obviously increases, between 3-5mmol g
-1between.
Embodiment 9
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 9 that passes through, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50ml min
-1, keep 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously.
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, and compared with metal-organic framework materials La-BDC adsorbance in preparation example 2, adsorbance obviously increases, between 3-5mmol g
-1between.
Embodiment 10
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 10 that passes through, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin-1, keeps 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously;
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, and compared with metal-organic framework materials La-BDC adsorbance in preparation example 2, adsorbance obviously increases, between 3-5mmol g
-1between.
Embodiment 11
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 11 that passes through, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin-1, keeps 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously;
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, and compared with metal-organic framework materials La-BDC adsorbance in preparation example 3, adsorbance obviously increases, between 3-5mmol g
-1between.
Embodiment 12
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 12 that passes through, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin-1, keeps 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously;
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, and compared with metal-organic framework materials La-BDC adsorbance in preparation example 3, adsorbance obviously increases, between 3-5mmol g
-1between.
Embodiment 13
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 13 that passes through, be placed in the U-shaped pipe of AutoChemII 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin-1, keeps 120min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously;
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, and compared with metal-organic framework materials La-BDC adsorbance in preparation example 3, adsorbance obviously increases, between 3-5mmol g
-1between.
Embodiment 14
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 14 that passes through, be placed in the U-shaped pipe of AutoChemII 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50ml min-1, keeps 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously;
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, and compared with metal-organic framework materials La-BDC adsorbance in preparation example 4, adsorbance obviously increases, between 3-5mmol g
-1between.
Embodiment 15
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 15 that passes through, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin-1, keeps 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously;
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, and compared with metal-organic framework materials La-BDC adsorbance in preparation example 4, adsorbance obviously increases, between 3-5mmol g
-1between.
Embodiment 16
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 16 that passes through, be placed in the U-shaped pipe of AutoChemII 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin-1, keeps 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously;
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, and compared with metal-organic framework materials La-BDC adsorbance in preparation example 4, adsorbance obviously increases, between 3-5mmol g
-1between.
Embodiment 17
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 9 that passes through, be placed in the U-shaped pipe of AutoChemII 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin-1, keeps 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously;
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, adsorbance can reach 3mmol g-1.
Embodiment 18
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 10 that passes through, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin-1, keeps 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously;
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, adsorbance can reach 3mmol g
-1.
Embodiment 19
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 11 that passes through, be placed in the U-shaped pipe of AutoChemII 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin-1, keeps 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously;
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, adsorbance can reach 3mmol g
-1.
Embodiment 20
Get respectively the appropriate material modified La of metal-organic framework (the Li)-BDC prepared by preparation example 12 that passes through, be placed in the U-shaped pipe of AutoChemII 2920, pass into high-purity Ar and purge the material modified La of metal-organic framework (Li)-BDC surface, be warming up to 190 DEG C simultaneously, keep, after 30min, being cooled to 40 DEG C;
Pass into 5% CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin-1, keeps 120min, 5% CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity He, be warming up to 190 DEG C simultaneously;
The CO of the material modified La of metal-organic framework (Li)-BDC
2desorption approximately 170 DEG C of temperature completely, adsorbance can reach 3mmol g
-1.
In order to further illustrate the superiority of metal-organic framework materials in the present invention, select following adsorbent as a comparison case.
Comparative example 1
40ml DMF (DMF) liquid is added in container and stirred after 60min, add respectively 1.664g Zn (NO
3)
26H
2o and 0.352g H
2bDC, seals this container.It is that 403K oil bath keeps being down to room temperature after 2h that this container is placed in to temperature, obtains colourless cubic crystal.Filter out this colourless cubic crystal, and clean this colourless cubic crystal to remove wherein unnecessary Zn (NO with DMF
3)
2.Gained crystal is immersed in 50ml chloroform, and the container that fills 50ml chloroform is placed in to temperature is that 343K baking oven keeps 3 days (regularly decant supplement in time chloroform).Finally, by gained sample colourless cubic crystal dried overnight in vacuum environment, baking temperature is 363K, obtains adsorbent MOF-5, for subsequent use.
Characterized and CO by this MOF-5 material
2adsorption experiment result learns, its BET specific area is 2517m
2g
-1; Temperature is 295.7K, CO
2when pressure is 1atm, adsorbance is 2.1mmol g
-1.
Comparative example 2
Respectively by the nitrate hydrate Er (NO of 0.353g lanthanide series metal
3)
35H
2o and 0.095g1,4-phenylenediacetic Acid (H
2pDA) be added in the polytetrafluoroethyllining lining containing 10ml deionized water and 1ml ethanol, at 170 DEG C, crystallization 3 days, is down to room temperature, obtain pink crystal, after being used deionized water, ethanol and acetone to clean, dry, obtain material Er2 (PDA) 3, for subsequent use.
By Er
2(PDA)
3cO
2adsorption isotherm is known, works as CO
2when pressure is 800Torr (about 1.05atm), CO
2adsorbance is less than 30mg g
-1, be less than 0.7mmol g
-1.
Claims (8)
1. a CO absorption
2the preparation method of metal-organic framework materials La-BDC, comprise the steps:
By La (NO
3)
3be dissolved in deionized water, form solution A;
Isosorbide-5-Nitrae-phthalic acid is dissolved in to inorganic alkali solution, forms solution B;
At room temperature, this solution A is mixed with this solution B, obtain the first mixed solution, at 150 DEG C-180 DEG C, make this first mixed solution crystallization 18 hours-30 hours, obtain the first solid product, by extremely neutral this first solid product washing, this washing to the first neutral solid product is warming up to 180 DEG C-200 DEG C with the speed of 5 DEG C of-10 DEG C/min by deionized water in Muffle furnace, keep 4 hours-6 hours, obtain metal-organic framework materials La-BDC.
2. CO absorption according to claim 1
2the preparation method of metal-organic framework materials La-BDC, it is characterized in that, this inorganic alkali solution is NaOH solution, KOH solution, Na
2cO
3solution or K
2cO
3solution.
3. CO absorption according to claim 1
2the preparation method of metal-organic framework materials La-BDC, it is characterized in that, this washing to the first neutral solid product is warming up to 190 DEG C with the speed of 5 DEG C/min in Muffle furnace, keep 5 hours, obtain metal-organic framework materials La-BDC.
4. a CO absorption
2the preparation method of the material modified La of metal-organic framework (Li)-BDC, comprise the steps:
By the CO absorption of claim 1,2 or 3 preparations
2metal-organic framework materials La-BDC be at room temperature dissolved in deionized water, then add the LiNO of reacting dose
3the aqueous solution, obtain the second mixed solution, at 150 DEG C-180 DEG C, make this second mixed solution crystallization 10 hours-15 hours, naturally cooling, obtain the second solid product, by extremely neutral this second solid product washing, this washing to the second neutral solid product is warming up to 180 DEG C-200 DEG C with the speed of 5 DEG C of-10 DEG C/min by deionized water in Muffle furnace, keep 4 hours-6 hours, obtain the material modified La of metal-organic framework (Li)-BDC.
5. CO absorption according to claim 4
2the preparation method of the material modified La of metal-organic framework (Li)-BDC, it is characterized in that the LiNO of this reacting dose
3the LiNO of the reacting dose in the aqueous solution
3quality account for La-BDC and LiNO
35%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of gross mass.
6. a CO absorption
2the preparation method of the material modified La of metal-organic framework (Li)-BDC, comprise the steps:
By La (NO
3)
3be dissolved in deionized water, form solution A;
Isosorbide-5-Nitrae-phthalic acid is dissolved in to inorganic alkali solution, forms solution B;
At room temperature, this solution A is mixed with this solution B, obtain the first mixed solution;
Make the LiNO of reacting dose
3the aqueous solution mixes with this first mixed solution, obtain the 3rd mixed solution, at 150 DEG C-180 DEG C, make the 3rd mixed solution crystallization 18 hours-30 hours, obtain the 3rd solid product, by deionized water by the 3rd solid product washing to neutral, this washing to the 3rd neutral solid product is warming up to 180 DEG C-200 DEG C with the speed of 5 DEG C of-10 DEG C/min in Muffle furnace, keeps 4 hours-6 hours, obtain the material modified La of metal-organic framework (Li)-BDC.
7. CO absorption according to claim 6
2the preparation method of the material modified La of metal-organic framework (Li)-BDC, it is characterized in that, this inorganic alkali solution is NaOH solution, KOH solution, Na
2cO
3solution or K
2cO
3solution.
8. CO absorption according to claim 6
2the preparation method of the material modified La of metal-organic framework (Li)-BDC, it is characterized in that, this washing to the 3rd neutral solid product is warming up to 190 DEG C with the speed of 5 DEG C/min in Muffle furnace, keep 5 hours, obtain the material modified La of metal-organic framework (Li)-BDC.
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