KR101796301B1 - Water adsorbent, method of preparing the same and method of adsorbing using the same - Google Patents
Water adsorbent, method of preparing the same and method of adsorbing using the same Download PDFInfo
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Abstract
The present invention relates to a moisture adsorbent, a method for producing the same, and a moisture adsorption method using the same. According to the present invention, a moisture adsorbent can be produced using a metal-organic structure having a high specific surface area, and a moisture adsorbent using such a porous material exhibits an excellent moisture adsorption capacity.
Description
The present invention relates to a moisture adsorbent, a method for producing the same, and a moisture adsorption method using the moisture adsorbent.
Metal Organic Framework (MOF) is a hollow, three-dimensional porous crystal material that is formed by self-assembly of metal ions and organic ligands. It has excellent gas adsorption characteristics based on high surface area It is known.
However, solvents such as dimethylformamide (DMF), which are bonded to metal ions in the pores, can not be completely removed by conventional methods such as a heat treatment method, and they are limited in increasing the surface area and gas adsorption capacity come.
In particular, in order to exhibit a high adsorption capacity for carbon dioxide and carbon monoxide at room temperature, the solvent bound to the metal must be completely removed.
It is expected that the crystallinity and the surface area can be remarkably improved by completely removing the solvent bound to the metal of the MOF, and it is expected that the use of the solvent as an adsorbent for other substances as well as gas is expected. It is necessary to continue to develop technology for
In order to solve the problems of the existing technology, it has been attempted to increase the water adsorption capacity by preparing a moisture adsorbent using a metal-organic skeleton which exhibits crystallinity and moisture adsorption characteristics.
According to a representative aspect of the present invention, there is provided a moisture adsorbent comprising a metal-organic skeleton of the following general formula (1) or (5).
[Chemical Formula 1]
[M 2 (DOBDC)]
[Chemical Formula 5]
[Ti 8 O 8 (OH) 4 (ABDC) 6 ]
In Formula 1, M is at least one divalent metal, DOBDC is 2,5-dioxido-1,4-benzenedicarboxylate having a negative tetravalent,
The metal-organic skeleton of the above formula (1) has (i) 1 H-NMR analysis that no peak of the substance of the following formula (2)
(ii) As a result of the FT-IR analysis, no amide peak was observed,
(iii) As a result of TGA analysis, when the temperature was raised from 200 ° C to 450 ° C, the weight change was less than 3%
(iv) the total pore volume is 0.70 to 1.00 cm < 3 > / g,
(v) BET surface area of from 1,500 to 2,000 m 2 / g,
(2)
R 1 -CO-NR 2 R 3
In
In the formula (5), ABDC is a 2-amino-1,4-benzenedicarboxylate having a negative divalent group,
The metal-organic skeleton of formula (5)
(i) the total pore volume is from 0.10 to 4.00 cc / g,
(ii) BET surface area of 1,000 to 2,000 m 2 / g.
According to various embodiments of the present invention, a highly crystalline metal-organic structure in which an organic solvent containing a hydroxyl group (-OH) is bonded to a metal ion in the pores is synthesized and bonded to the metal ion All of the organic solvents can be removed.
Further, by applying the metal-organic structure to a moisture adsorbent, a high moisture adsorption capacity can be obtained.
1 is a single crystal X-ray diffraction structure of a metal-organic skeleton synthesized using ethylene glycol having a hydrophilic OH functional group. It shows a structure in which ethylene glycol is bonded to a metal marked green.
FIG. 2 is a schematic diagram of a crystal structure in which six ethylene glycol OH groups in a [M 2 (DOBDC) (EG) 2 ] (M = Mg, Co, Ni) form a hexagonal structure through hydrogen bonding.
FIG. 3 shows a structure in which six ethylene glycol OH groups in the [M 2 (DOBDC) (EG) 2 ] (M = Mg, Co, Ni) form hexagonal pores through hydrogen bonding.
4 is powder X-ray diffraction data of a metal-organic skeleton synthesized using ethylene glycol having a hydrophilic OH functional group.
5 is a thermogravimetric analysis (TGA) data of [Mg 2 (DOBDC)].
6 is a thermogravimetric analysis of [Co 2 (DOBDC)] ( TGA) is the data.
7 is a thermogravimetric analysis (TGA) data of [Ni 2 (DOBDC)].
8 is a single crystal X-ray diffraction structure of a metal-organic skeleton synthesized by exchanging ethylene-glycol bonded to a metal with methanol. It shows a structure in which methanol is bonded to a metal represented by a green color.
9 is a thermogravimetric analysis (TGA) data of [Mg 2 (DOBDC) (MeOH) 2 ].
10 is 1 H-NMR data of [Mg 2 (DOBDC)].
11 is an FT-IR spectrum of [[Mg 2 (DOBDC)].
12 is a thermogravimetric analysis (TGA) data of [Mg 2 (DOBDC)].
Figure 13 is the nitrogen adsorption isotherm of [Mg 2 (DOBDC)] at 77 K after pretreatment.
14 is powder X-ray diffraction data of [Ti 8 O 8 (OH) 4 (ABDC) 6 ].
15 is a 77 K nitrogen adsorption isotherm of [Ti 8 O 8 (OH) 4 (ABDC) 6 ].
16 is a single crystal X-ray diffraction structure of [Mg 2 (DOBDC) (DMF) 2 ] synthesized according to the literature.
17 is 1 H-NMR data of [Mg 2 (DOBDC) (DMF) 2 ] before pretreatment.
18 is 1 H-NMR data of [Mg 2 (DOBDC) (DMF) 2 ] after the pretreatment.
19 is an FT-IR spectrum of [Mg 2 (DOBDC) (DMF) 2 ] before and after the pretreatment.
FIG. 20 is a thermogravimetric analysis (TGA) data of [Mg 2 (DOBDC) (DMF) 2 ] after the pretreatment.
21 is the nitrogen adsorption isotherm of [Mg 2 (DOBDC) (DMF) 2 ] at 77 K after pretreatment.
22 is the moisture adsorption isotherm of [Mg 2 (DOBDC) (EG) 2 ] at 308.15 K;
23 is the moisture adsorption isotherm of [[Mg 2 (DOBDC)] (M = Mg, Co, Ni) at 308.15K.
24 is the moisture adsorption isotherm of [Ti 8 O 8 (OH) 4 (ABDC) 6 ] at 308.15 K;
Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.
One aspect of the present invention relates to a moisture adsorbent comprising a metal-organic skeleton of the following general formula (1) or (5).
[Chemical Formula 1]
[M 2 (DOBDC)]
[Chemical Formula 5]
[Ti 8 O 8 (OH) 4 (ABDC) 6 ]
In
In particular, the metal-organic skeleton of the above formula (1) has (i) no peak of a substance of the following formula (2) is observed as a result of 1 H-NMR analysis, (ii) an amide peak is not observed as a result of FT- (iv) a total pore volume of 0.70 to 1.00 cm < 3 > / g, (v) a BET surface area of 1,500 to 2,000 m 2 / g.
In the present invention, examples of the divalent metal include, but are not limited to, Mg 2+ , Ni 2+ , Co 2+ , Zn 2+ , Fe 2+ , Cu 2+ , Mn 2+ and the like. In the present invention, preferred examples of the bivalent metal include Mg 2+ , Ni 2+ , Co 2+ , Zn 2+ , Fe 2+ , Cu 2+ and Mn 2+ , It may be advantageous in terms of excellent crystallinity as compared with the case of a bivalent metal which is not.
(2)
R 1 -CO-NR 2 R 3
In
The compound of formula (2) serves as a solvent in the metal-organic skeleton of the present invention. Examples of the solvent of formula (2) include dimethylformamide, diethylformamide, dimethylacetamide (DMA) But is not limited thereto.
According to the conventional method, the metal-organic skeleton of formula (1) can be prepared only by using an excessive amount of the solvent of formula (2). The solvent of formula (2) And the dimethylformamide bonded to the metal in green in the structure shown in Fig. 21 corresponds to the ligand compound of the formula (2).
Specific amounts of the solvent and the like of formula (2) will be described in detail in the production process part according to various embodiments of the present invention.
Since the carbonyl group of the solvent of
On the other hand, the water sorbent containing the metal-organic skeleton according to the present invention is produced by using an excess amount of an organic solvent containing a hydroxyl group such as ethylene glycol (EG) Is easily combined with the organic solvent. Thus, the porous material according to the present invention can be obtained according to the present invention, in which the solvent is not bonded to the metal-organic structure.
As a result, the amide peak is not observed by the FT-IR analysis as described above. As a result of the TGA analysis, when the temperature is raised from 200 ° C. to 450 ° C., the heat resistance is so high that the weight change is less than 3%.
In addition, it exhibits a total pore volume of 0.70 to 1.00 cm 3 / g of high porosity and a very high surface area of BET surface area of 1,500 to 2,000 m 2 / g. In particular, the amount of carbon dioxide adsorbed at 30 wt% (6.79 mmol / g) at room temperature and 0.1 atm, 42 wt% (9.50 mmol / g) at 1 atm and 86 wt% (19.5 mmol / g) The amount of carbon dioxide adsorbed by the organic skeleton is remarkably improved, which is one of the various meanings of the present invention.
According to another embodiment, there is provided a moisture adsorbent comprising a metal-organic skeleton, wherein the metal-organic skeleton is any one selected from the following formulas (1a) to (1e).
[Formula 1a]
[M 1 n1 (DOBDC)]
In Formula (1a), n1 is 2, and M 1 is a divalent metal.
[Chemical Formula 1b]
[M 1 n 1 M 2 n 2 (DOBDC)]
In Formula 1b, n1 and n2 are real numbers of 0 or more satisfying n1 + n2 = 2; M 1 and M 2 are different from each other and each independently a divalent metal.
[Chemical Formula 1c]
[M 1 M 2 n1 n2 n3 M 3 (DOBDC)]
In the formula 1c, n1, n2 and n3 are real numbers of 0 or more satisfying n1 + n2 + n3 = 2; M 1 , M 2 and M 3 are different from each other and each independently a divalent metal.
≪ RTI ID = 0.0 &
[N1 M 1 M 2 M 3 n2 n3 n4 M 4 (DOBDC)]
In the above formula (1d), n1, n2, n3 and n4 are real numbers of 0 or more satisfying n1 + n2 + n3 + n4 = 2; M 1 , M 2 , M 3 and M 4 are different from each other and each independently a divalent metal.
[Formula 1e]
[M 1 M 2 n1 n2 n3 M 3 M 4 M 5 n4 n5 (DOBDC)]
In Formula 1e, n1, n2, n3, n4 and n5 are real numbers of 0 or more satisfying n1 + n2 + n3 + n4 + n5 = 2; M 1 , M 2 , M 3 , M 4 and M 5 are different from each other and each independently a divalent metal.
Another aspect of the present invention relates to a water adsorbent comprising a metal-organic skeleton having the following general formula (3).
(3)
[M 2 (DOBDC) (S OH ) 2 ]
In
Examples of the organic solvent containing a hydroxyl group in the present invention include ethylene glycol (EG), methanol (MeOH), ethanol (EtOH), glycerol (Gly), isopropyl alcohol (IPA), 1-propanol, propylene glycol But are not limited thereto.
In particular, the solvent containing the hydroxyl group preferably has at least one hydroxyl group, and one of them may be bonded to a metal and may be exchanged with another solvent such as ethanol or methanol through a post-treatment method.
More preferably, the solvent containing the hydroxy group may contain two or more hydroxy groups. One of the hydroxyl groups is bonded to the metal while the other hydroxy group is pushed out toward the pore to form a hydrophilic surface. Thus, the exchange with another solvent such as ethanol or methanol is further facilitated This can be achieved with a high conversion rate.
According to another embodiment, there is provided a moisture adsorbent comprising a metal-organic skeleton, wherein the metal-organic skeleton is any one selected from the following formulas (3a) to (3e).
[Chemical Formula 3]
[M 1 n1 (DOBDC) (S OH ) 2 ]
In the above formula (3a), n1 is 2 and M 1 is a divalent metal.
(3b)
[M 1 n 1 M 2 n 2 (DOBDC) (S OH ) 2 ]
In the formula (3b), n1 and n2 are real numbers of 0 or more satisfying n1 + n2 = 2; M 1 and M 2 are different from each other and each independently a divalent metal.
[Chemical Formula 3c]
[M 1 M 2 n1 n2 n3 M 3 (DOBDC) (S OH) 2]
In the formula (3c), n1, n2 and n3 are real numbers of 0 or more satisfying n1 + n2 + n3 = 2; M 1 , M 2 and M 3 are different from each other and each independently a divalent metal.
(3d)
[N1 M 1 M 2 M 3 n2 n3 n4 M 4 (DOBDC) (S OH) 2]
In Formula (3), n1, n2, n3 and n4 are real numbers of 0 or more satisfying n1 + n2 + n3 + n4 = 2; M 1 , M 2 , M 3 and M 4 are different from each other and each independently a divalent metal.
[Formula 3e]
[M 1 M 2 n1 n2 n3 M 3 M 4 M 5 n4 n5 (DOBDC) (S OH) 2]
In Formula 3e, n1, n2, n3, n4 and n5 are real numbers of 0 or more satisfying n1 + n2 + n3 + n4 + n5 = 2; M 1 , M 2 , M 3 , M 4 and M 5 are different from each other and each independently a divalent metal.
Another aspect of the invention relates to a process for preparing a water sorbent comprising a metal-organic skeleton of formula (4a), comprising the steps of:
(A) (i) M 1 A 1 y 1 .x 1 H 2 O, M 2 A 2 y 2 .x 2 H 2 O, M 3 A 3 y 3 .x 3 H 2 O, M 4 A 4 y 4 .x 4 H 2 O, M 5 A 5 y5 · x 5 H 2 O at least one selected from a metal precursor; (ii) 2,5-dihydroxy-1,4-benzenedicarboxylic acid or derivatives thereof; (iii) S 1 OH ; (iv) an amine-based first additive; (v) preparing a solution containing at least one second additive selected from diethylformamide, dimethylacetamide, benzylamine, diisopropylformamide, and dimethylformamide to conduct a reaction to obtain a metal-organic Obtaining a moisture adsorbent comprising a skeleton:
[Chemical Formula 4a]
[M 1 M 2 n1 n2 n3 M 3 M 4 M 5 n4 n5 (DOBDC) (S 1 OH) 2]
In Formula 4a, n1, n2, n3, n4 and n5 are real numbers of 0 or more satisfying n1 + n2 + n3 + n4 + n5 = 2; M 1 , M 2 , M 3 , M 4 and M 5 are different from each other and each independently a divalent metal;
Wherein A 1 , A 2 , A 3 , A 4 and A 5 are the same or different and are each independently a monovalent anion selected from NO 3 - , Cl - , ClO 4 - , OH - and CH 3 CO 2 - Or a bivalent anion selected from ClO 4 2- , SO 4 2- , CO 3 2- ;
X 1 , x 2 , x 3 , x 4 , and x 5 are the same or different from each other, and each independently is an integer of 1 to 50;
When A 1 is a monovalent anion or a divalent anion,
The derivative of 2,5-dihydroxy-1,4-benzenedicarboxylic acid is at least one selected from dehydrogen ions or salts of 2,5-dihydroxy-1,4-benzenedicarboxylic acid ;
Wherein S 1 OH is an organic solvent comprising a hydroxy group and is used in an amount of 50 to 95% by volume based on the total volume of the solution;
The second additive is used in an amount of 5 to 50% based on the total volume of the solution, and in a range of 1% to 100% of the volume of the S 1 OH .
Wherein (i) the S 1 OH is used in an amount of 50 to 95 vol% based on the total volume of the solution, (ii) the second additive is used in an amount of 5 to 50% based on the total volume of the solution, , (iii) within 1% to 100% of the S 1 OH volume.
It was confirmed that the desired effect of the present invention can not be achieved when the above range of the amount of S 1 OH and the amount of the second additive deviates. In other words, (i) the 1 H- (Ii) the amide peak was not observed as a result of FT-IR analysis; (iii) the weight change was less than 3% when the temperature was raised from 200 ° C to 450 ° C as a result of TGA analysis; (iv) and 0.70 to 1.00 cm 3 / g, (v ) BET surface area of 1,500 to 2,000 m 2 / g of the metal of the general formula (1) - was confirmed that it is not possible to obtain an organic skeleton body, it is in this respect to keep the range very important.
In the present invention, the first amine-based additive may be an amine-based organic base selected from aromatic amines, cyclic amines, alicyclic amines, and aliphatic linear amines. Examples of the aromatic amine include p-phenylenediamine, m-phenylenediamine, aniline, 3,5-diaminobenzoic acid, melamine, and the like. Examples of the cyclic amines include cyclohexylamine, cyclopentylamine, Norbornene amine, adamantane amine, and the like. Examples of the cyclic amines may include pyridine, piperidine and azole-based compounds. Examples of the thiol-based compounds may include pyrrole, imidazole, pyrazole, triazole and the like. The aliphatic linear amine may be C 1 -C 7 may be the amine group with from one to five amine bonded to an aliphatic hydrocarbon.
Particularly, the first additive is preferably selected from among melamine, aniline and methylamine as a substance which converts DOBDC to an organic base and converts it to DOBDC 4- . In particular, when melamine is used, It is advantageous in that a product having a higher surface area can be obtained, unlike the case of using another substance listed as a candidate substance.
The amine-based first additive is used in an amount of 1 to 50 wt% based on the weight of the metal precursor and 5 to 200 wt% based on the weight of the 2,5-dihydroxy-1,4-benzenedicarboxylic acid or its derivative If the lower limit is less than the upper limit, the yield of the metal-organic skeleton is rapidly decreased. If the upper limit is exceeded, the metal-organic skeleton may not be formed to bind with the metal.
The 2,5-dihydroxy-1,4-benzenedicarboxylic acid or its derivative is preferably used in an amount of 10 to 200% by weight based on the weight of the metal precursor.
In addition, the second additive acts as a solvent for dissolving DOBDC, and in particular, when diethylformamide is used, a product having a high yield can be obtained unlike the case of using other materials listed as the second additive candidate substance .
In particular, in the use of dimethylformamide in a second additive listed in the present invention, used as a value outside the range of 5 to 50% based on the total volume of the solution, or 1% to 100% of the S 1 OH by volume If it is used out of the range, the metal-organic skeleton is trapped in the ligand form of the formula (2), and the gas adsorption performance can be remarkably lowered, which is not preferable.
Another aspect of the invention relates to a process for preparing a water sorbent comprising a metal-organic skeleton of formula (4b), comprising the steps of:
(A) (i) M 1 A 1 y 1 .x 1 H 2 O, M 2 A 2 y 2 .x 2 H 2 O, M 3 A 3 y 3 .x 3 H 2 O, M 4 A 4 y 4 .x 4 H 2 O, M 5 A 5 y5 · x 5 H 2 O at least one selected from a metal precursor; (ii) 2,5-dihydroxy-1,4-benzenedicarboxylic acid or derivatives thereof; (iii) S 1 OH (iv) amine-based first additive; (v) preparing a solution containing at least one second additive selected from diethylformamide, dimethylacetamide, benzylamine, diisopropylformamide, and dimethylformamide to conduct a reaction to obtain a metal-organic Obtaining a skeleton;
[Chemical Formula 4a]
[M 1 M 2 n1 n2 n3 M 3 M 4 M 5 n4 n5 (DOBDC) (S 1 OH) 2]
(B) contacting the metal-organic skeleton of formula (4a) with S 2 OH to obtain a moisture sorbent comprising a metal-organic skeleton of formula (4b);
(4b)
[M 1 M 2 n1 n2 n3 M 3 M 4 M 5 n4 n5 (DOBDC) (S 2 OH) 2]
In Formula 4a and Formula 4b, n1, n2, n3, n4 and n5 are real numbers of 0 or more satisfying n1 + n2 + n3 + n4 + n5 = 2; M 1 , M 2 , M 3 , M 4 and M 5 are different from each other and each independently a divalent metal;
Wherein A 1 , A 2 , A 3 , A 4 and A 5 are the same or different and are each independently a monovalent anion selected from NO 3 - , Cl - , ClO 4 - , OH - and CH 3 CO 2 - Or a bivalent anion selected from ClO 4 2- , SO 4 2- , CO 3 2- ;
X 1 , x 2 , x 3 , x 4 , and x 5 are the same or different from each other, and each independently is an integer of 1 to 50;
When A 1 is a monovalent anion or a divalent anion,
The derivative of 2,5-dihydroxy-1,4-benzenedicarboxylic acid is at least one selected from dehydrogen ions and salts of 2,5-dihydroxy-1,4-benzenedicarboxylic acid ;
Wherein S 1 OH is a first organic solvent comprising a hydroxyl group; Wherein S 2 OH is a second organic solvent containing a hydroxyl group, S 2 OH is lower in boiling point than S 1 OH ;
The S 1 OH is used in an amount of 50 to 95% by volume based on the total volume of the solution;
The second additive is used in an amount of 5 to 50% based on the total volume of the solution, and in a range of 1% to 100% of the volume of the S 1 OH .
Examples of the organic solvent containing a hydroxyl group in the present invention include ethylene glycol (EG), methanol (MeOH), ethanol (EtOH), glycerol (Gly), isopropyl alcohol (IPA), 1-propanol, propylene glycol But are not limited thereto.
In particular, it is preferable to sequentially use the organic solvent containing a hydroxy group as a first organic solvent and a second organic solvent. That is, in the step of preparing the metal-organic skeleton, the first organic solvent having a high boiling point , And it is advantageous to prepare a moisture adsorbent comprising a metal-organic skeleton which does not contain a hydroxy group at last, thereby replacing the molecule with a second organic solvent having a low boiling point.
In the present invention, the first organic solvent containing a hydroxyl group includes a hydroxyl group-containing ligand having a relatively high boiling point, and preferred examples thereof include ethylene glycol, glycerol, propylene glycol, 1-propanol and the like, but are not limited thereto.
The second organic solvent containing a hydroxyl group is a solvent having a relatively low boiling point, and preferred examples thereof include, but are not limited to, methanol, ethanol, isopropyl alcohol, and the like.
In the formula (5), ABDC is a 2-amino-1,4-benzenedicarboxylate having a negative divalent group,
The metal-organic skeleton of formula (5)
(i) the total pore volume is from 0.10 to 4.00 cc / g,
(ii) BET surface area of 1,000 to 2,000 m 2 / g.
Another aspect of the invention relates to a process for preparing a water sorbent comprising a metal-organic skeleton of formula (Ie) comprising the steps of:
(A) (i) M 1 A 1 y 1 .x 1 H 2 O, M 2 A 2 y 2 .x 2 H 2 O, M 3 A 3 y 3 .x 3 H 2 O, M 4 A 4 y 4 .x 4 H 2 O, M 5 A 5 y5 · x 5 H 2 O at least one selected from a metal precursor; (ii) 2,5-dihydroxy-1,4-benzenedicarboxylic acid or derivatives thereof; (iii) S 1 OH (iv) amine-based first additive; (v) preparing a solution containing at least one second additive selected from diethylformamide, dimethylacetamide, benzylamine, diisopropylformamide, and dimethylformamide to conduct a reaction to obtain a metal-organic Obtaining a skeleton;
[Chemical Formula 4a]
[M 1 M 2 n1 n2 n3 M 3 M 4 M 5 n4 n5 (DOBDC) (S 1 OH) 2]
(B) contacting the metal-organic skeleton of formula (4a) with S 2 OH to obtain a metal-organic skeleton of formula (4b);
(4b)
[M 1 M 2 n1 n2 n3 M 3 M 4 M 5 n4 n5 (DOBDC) (S 2 OH) 2]
(C) drying the metal-organic skeleton of formula (4b) to obtain a moisture adsorbent comprising a metal-organic skeleton of formula (1e);
[Formula 1e]
[M 1 M 2 n1 n2 n3 M 3 M 4 M 5 n4 n5 (DOBDC)]
N1, n2, n3, n4 and n5 are real numbers of 0 or more satisfying n1 + n2 + n3 + n4 + n5 = 2 in the general formulas 4a, 4b and 1e; M 1 , M 2 , M 3 , M 4 and M 5 are different from each other and each independently a divalent metal;
Wherein A 1 , A 2 , A 3 , A 4 and A 5 are the same or different and are each independently a monovalent anion selected from NO 3 - , Cl - , ClO 4 - , OH - and CH 3 CO 2 - Or a bivalent anion selected from ClO 4 2- , SO 4 2- , CO 3 2- ;
X 1 , x 2 , x 3 , x 4 , and x 5 are the same or different from each other, and each independently is an integer of 1 to 50;
When A 1 is a monovalent anion or a divalent anion,
The derivative of 2,5-dihydroxy-1,4-benzenedicarboxylic acid is at least one selected from dehydrogen ions and salts of 2,5-dihydroxy-1,4-benzenedicarboxylic acid ;
Wherein S 1 OH is a first organic solvent comprising a hydroxyl group; Wherein S 2 OH is a second organic solvent containing a hydroxyl group, S 2 OH is lower in boiling point than S 1 OH ;
The S 1 OH is used in an amount of 50 to 95% by volume based on the total volume of the solution;
The second additive is used in an amount of 5 to 50% based on the total volume of the solution, and in a range of 1% to 100% of the volume of the S 1 OH .
Another aspect of the present invention relates to a water adsorption process comprising contacting metal-organic skeletons of formula (1) or (5) with water.
[Chemical Formula 1]
[M 2 (DOBDC)]
[Chemical Formula 5]
[Ti 8 O 8 (OH) 4 (ABDC) 6 ]
In
The metal-organic skeleton of the formula (1) can be obtained by (i) 1 H-NMR analysis,
(ii) As a result of the FT-IR analysis, no amide peak was observed,
(iii) As a result of TGA analysis, when the temperature was raised from 200 ° C to 450 ° C, the weight change was less than 3%
(iv) the total pore volume is 0.70 to 1.00 cm < 3 > / g,
(v) BET surface area of up to 1,500 to 2,000 m 2 / g.
(2)
R 1 -CO-NR 2 R 3
In
In the formula (5), ABDC is a 2-amino-1,4-benzenedicarboxylate having a negative divalent group,
The metal-organic skeleton of formula (5)
(i) the total pore volume is from 0.10 to 4.00 cc / g,
(ii) BET surface area of 1,000 to 2,000 m 2 / g.
Example
Hereinafter, the present invention will be described in more detail with reference to examples, but the scope and content of the present invention can not be construed to be limited or limited by the following examples and the like. In addition, it is apparent that, based on the teachings of the present invention including the following examples, those skilled in the art can easily carry out the present invention in which experimental results are not specifically shown.
Example 1: Mg 2 (DOBDC) (EG) 2 synthesis
116 mg of 2,5-dihydroxy-1,4-benzenedicarboxylic acid (2,5-DOBDC), 100 mg of melamine and 10 mL of ethylene glycol were added to 600 mg of Mg (NO 3 ) 2 .6H 2 O , And 2 mL of diethylformamide were used. The reaction temperature was 130 ° C and the reaction time was 24 hours. The single crystal X-ray structure for the prepared Mg 2 (DOBDC) (EG) 2 is shown in FIG. Single crystal structure parameters Trigonal, R -3, a = 25.951 (4) Å, b = 25.951 (4) Å, c = 13.632 (3), α = 90, β = 90, γ = 120, V = 7951 (2 ) Å 3, Z = 18, T = 100 (2) K, d calc = 1.635g / ㎤,
Example 2: Co 2 (DOBDC) (EG) 2 synthesis
166 mg of 2,5-dihydroxy-1,4-benzenedicarboxylic acid (2,5-DOBDC), 100 mg of melamine and 10 mL of ethylene glycol were added to 600 mg of Co (NO 3 ) 2揃 6H 2 O , And 2 mL of diethylformamide were used. The reaction temperature was 130 ° C and the reaction time was 24 hours. The single crystal x-ray structure for the prepared Co 2 (DOBDC) (EG) 2 is shown in FIG. Single crystal structure parameters Trigonal, R -3, a = 26.070 (4) Å, b = 26.070 (4) Å, c = 13.521 (3), α = 90, β = 90, γ = 120, V = 7958 (2 ) Å 3, Z = 18, T = 100 (2) K, d calc = 1.894g / ㎤,
Example 3: Ni 2 (DOBDC) (EG) 2 synthesis
116 mg of 2,5-dihydroxy-1,4-benzenedicarboxylic acid (2,5-DOBDC), 100 mg of melamine and 10 mL of ethylene glycol were added to 600 mg of Ni (NO 3 ) 2揃 6H 2 O , And 2 mL of diethylformamide were used. The reaction temperature was 130 ° C and the reaction time was 24 hours. The single crystal x-ray structure for the prepared Ni 2 (DOBDC) (EG) 2 is shown in FIG. Single crystal structure parameters Trigonal, R -3, a = 26.137 (4) Å, b = 26.137 (4) Å, c = 13.337 (3), α = 90, β = 90, γ = 120, V = 7890 (2 ) Å 3, Z = 18, T = 100 (2) K, d calc = 1.940g / ㎤,
Example 4: Preparation of M 2 (DOBDC) (MeOH) 2 Synthesis (M = Mg, Co, Ni)
1 to 3 g of Mg 2 (DOBDC) (EG) 2 , Co 2 (DOBDC) (EG) 2 and Ni 2 (DOBDC) (EG) 2 crystals prepared by the methods of Examples 1 to 3 were dissolved in 10 mL of methanol And the mixture was heated at a temperature of 50 to 200 DEG C to completely replace ethylene glycol with methanol. The single crystal X-ray crystal structure of Mg 2 (DOBDC) (MeOH) 2 , Co 2 (DOBDC) (MeOH) 2 and Ni 2 (DOBDC) (MeOH) 2 prepared in this manner is shown in FIG. The single crystal x-ray crystal structure parameters for Mg 2 (DOBDC) (EG) 2 are as follows. Trigonal, R -3, a = 26.023 (4) Å, b = 26.023 (4) Å, c = 13.305 (3), α = 90, β = 90, γ = 120, V = 7803 (2)
Example 5: Preparation of M 2 (DOBDC) Synthesis (M = Mg, Co, Ni)
Example 4 Mg 2 (DOBDC) prepared by the method of (MeOH) 2, Co 2 ( DOBDC) (MeOH) 2, Ni 2 (DOBDC) (MeOH) 2 for heating in vacuum at 250 ℃ for 1 day and in the interior After removing all the methanol and synthesizing [M 2 (DOBDC)] (M = Mg, Co, Ni), their structures were confirmed. 1 H-NMR for Mg 2 (DOBDC) is shown in FIG. The FT-IR for Mg 2 (DOBDC) is shown in FIG. Thermogravimetric analysis data (TGA) for Mg 2 (DOBDC) is shown in FIG. The nitrogen adsorption isotherm at 77 K for Mg 2 (DOBDC) is shown in FIG. The BET surface area is 1763 m 2 / g.
Considering the fact that no known BET surface area of more than 1,500 m 2 / g is reported for the same or similar substance, it can be considered to be a greatly improved effect, and it is advantageous to increase the amount of adsorption by further increasing the number of openings of the metal favoring moisture adsorption And can be said to be a material property capable of maintaining excellent adsorption characteristics even when the amount of the adsorbent is reduced.
Example 6: [Ti 8 O 8 (OH) 4 (ABDC) 6 ] synthesis
NH 2 -H 2 BDC (1.086 g, 6.0 mmol) is dissolved in anhydrous DMF (7 mL) and anhydrous methanol, and Ti (OBu) 4 (0.51 g, 1.5 mmol) is added. Orange colored precipitates and solutions are placed in a Teflon reactor and reacted at 150 ° C for 16 hours to obtain yellow crystalline particles. After centrifugation at 3200 rpm, obtain a precipitate that has settled down and wash it with DMF. Figure 14 shows powder X-ray diffraction data of the synthesized [Ti 8 O 8 (OH) 4 (ABDC) 6 ] metal-organic complex. Figure 15 shows the nitrogen adsorption isotherm at 77K. The BET surface area is 1432 m 2 / g.
Comparative Example 1: Mg 2 (DOBDC) (DMF) 2 synthesis
0.337 g of 2,5-dihydroxy-1,4-benzenedicarboxylic acid, 135 mL of DMF (dimethylformamide), 9.0 mL of ethanol, and 10 mL of H (dimethylformamide) were added to 1.40 g of Mg (NO 3 ) 2 .6H 2 O, 2 O 9.0 mL was used. The reaction temperature was 125 ° C and the reaction time was 48 hours.
The single crystal x-ray structure for Mg 2 (DOBDC) (DMF) 2 prepared according to the prior art is shown in FIG. Single crystal structure parameters Trigonal, R -3, a = 25.865 (4) Å, b = 25.865 (4) Å, c = 6.911 (3) Å, α = 90˚, β = 90˚, γ = 120˚, V = 4004 (1) Å 3, Z = 9, T = 100 (2) K, d calc = 1.474g / ㎤,
Comparative Example 2: Mg 2 (DOBDC) synthesis
In order to remove all of the solvent molecules inside the Mg 2 (DOBDC) (DMF) 2 pores prepared in Comparative Example 1, it was impregnated in methanol for 4 days and pretreated by vacuum heating at 250 ° C for 7 days. ≪ 1 > H-NMR is shown in Fig. FT-IR is shown in Fig. Thermogravimetric analysis data (TGA) is shown in Fig. The nitrogen adsorption isotherm at 77 K is shown in Fig. The BET surface area is 1495 m 2 / g.
The metal-organic skeleton of Comparative Example 1 prepared according to the existing literature (SR Caskey, AG Wong-Foy and AJ Matzger, J. Am. Chem. Soc. , 2008, 130 , 10870) And the metal-organic skeleton prepared in Examples 1 to 5 has an organic solvent having a hydrophilic OH functional group bonded to the metal. Examples 1 to 3 produced a M 2 (DOBDC) (EG) 2 (M = Mg, Co, Ni) of Example 4. Thus, M 2 (DOBDC) (MeOH) 2 in the synthesized according to and according to Example 5 When preprocessing, M 2 (DOBDC) can be produced. The metal-organic skeleton thus prepared exhibits higher specific surface area and moisture adsorption characteristics than the metal-organic skeleton prepared according to Comparative Example 2. [
Experimental Example 1: Measurement of moisture adsorption capacity
The moisture adsorption capacity measurement experiment for Mg 2 (DOBDC) (EG) 2 prepared in Example 1 was carried out.
22 shows the moisture adsorption isotherm of Mg 2 (DOBDC) (EG) 2 at 308.15 K, which shows that the adsorption amount of water of Mg 2 (DOBDC) (EG) 2 increases with increasing relative vapor pressure (P / P 0 ) .
Further, water absorption capacity measurement experiments were conducted on Mg 2 (DOBDC), Co 2 (DOBDC), and Ni 2 (DOBDC) prepared in Example 5.
FIG. 23 shows the moisture adsorption isotherm at 308.15 K. As the relative vapor pressure (P / P 0 ) increases, the amount of water adsorption of Mg 2 (DOBDC), Co 2 (DOBDC), and Ni 2 (DOBDC) Able to know.
24 shows the moisture adsorption isotherm at 308.15 K against [Ti 8 O 8 (OH) 4 (ABDC) 6 ]. When the relative vapor pressure (P / P 0 ) is 0.2, moisture adsorption hardly occurs. The amount of moisture adsorption is increased.
As described above, the moisture adsorbent according to the present invention can improve the moisture adsorption capacity by using the metal-organic skeleton having high crystallinity and high moisture adsorption capacity.
It will be apparent to those skilled in the art that the present invention is not limited to the embodiments described above and that various changes and modifications may be made without departing from the spirit and scope of the present invention as defined by the appended claims. As shown in FIG.
It will be understood by those skilled in the art that the present invention may be embodied in many other specific forms without departing from the spirit or scope of the invention as defined by the appended claims and their equivalents. .
Claims (4)
[Chemical Formula 1]
[M 2 (DOBDC)]
In Formula 1, M is at least one divalent metal, DOBDC is 2,5-dioxido-1,4-benzenedicarboxylate having a negative tetravalent,
The metal-organic skeleton can be obtained by (i) 1 H-NMR analysis, no peak of the material of the following formula (2) is observed, (ii) FT-
(Iv) the total pore volume is in the range of 0.70 to 1.00 cm < 3 > / g when the temperature of the metal-organic skeleton is increased from 200 DEG C to 450 DEG C as a result of TGA analysis;
Wherein the metal-organic skeleton is (v) a BET surface area of from 1,500 to 2,000 m 2 / g.
(2)
R 1 -CO-NR 2 R 3
In Formula 2, R 1 , R 2, and R 3 are the same or different from each other, and each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms.
[Formula 1a]
[M 1 n1 (DOBDC)]
In Formula (1a), n1 is 2 and M 1 is a divalent metal;
[Chemical Formula 1b]
[M 1 n 1 M 2 n 2 (DOBDC)]
In Formula 1b, n1 and n2 are real numbers of 0 or more satisfying n1 + n2 = 2; M 1 and M 2 are different from each other and each independently a divalent metal;
[Chemical Formula 1c]
[M 1 M 2 n1 n2 n3 M 3 (DOBDC)]
In the formula 1c, n1, n2 and n3 are real numbers of 0 or more satisfying n1 + n2 + n3 = 2; M 1 and M 2 and M 3 are different from each other and each independently a divalent metal;
≪ RTI ID = 0.0 &
[N1 M 1 M 2 M 3 n2 n3 n4 M 4 (DOBDC)]
In the above formula (1d), n1, n2, n3 and n4 are real numbers of 0 or more satisfying n1 + n2 + n3 + n4 = 2; M 1 , M 2 , M 3 and M 4 are different from each other and each independently a divalent metal;
[Formula 1e]
[M 1 M 2 n1 n2 n3 M 3 M 4 M 5 n4 n5 (DOBDC)]
In Formula 1e, n1, n2, n3, n4 and n5 are real numbers of 0 or more satisfying n1 + n2 + n3 + n4 + n5 = 2; M 1 , M 2 , M 3 , M 4 and M 5 are different from each other and each independently a divalent metal.
(A) (i) M 1 A 1 y 1 .x 1 H 2 O, M 2 A 2 y 2 .x 2 H 2 O, M 3 A 3 y 3 .x 3 H 2 O, M 4 A 4 y 4 .x 4 H 2 O, M 5 A 5 y5 · x 5 H 2 O at least one selected from a metal precursor; (ii) 2,5-dihydroxy-1,4-benzenedicarboxylic acid or derivatives thereof; (iii) S 1 OH ; (iv) an amine-based first additive; (v) preparing a solution containing at least one second additive selected from diethylformamide, dimethylacetamide, benzylamine, diisopropylformamide, and dimethylformamide to conduct a reaction to obtain a metal-organic Obtaining a skeleton;
[Chemical Formula 4a]
[M 1 M 2 n1 n2 n3 M 3 M 4 M 5 n4 n5 (DOBDC) (S 1 OH) 2]
(B) contacting the metal-organic skeleton of formula (4a) with S 2 OH to obtain a metal-organic skeleton of formula (4b);
(4b)
[M 1 M 2 n1 n2 n3 M 3 M 4 M 5 n4 n5 (DOBDC) (S 2 OH) 2]
(C) drying the metal-organic skeleton of formula (4b) to obtain a moisture adsorbent comprising a metal-organic skeleton of formula (1e);
[Formula 1e]
[M 1 M 2 n1 n2 n3 M 3 M 4 M 5 n4 n5 (DOBDC)]
N1, n2, n3, n4 and n5 are real numbers of 0 or more satisfying n1 + n2 + n3 + n4 + n5 = 2 in the general formulas 4a, 4b and 1e; M 1 , M 2 , M 3 , M 4 and M 5 are different from each other and each independently a divalent metal;
Wherein A 1 , A 2 , A 3 , A 4 and A 5 are the same or different and are each independently a monovalent anion selected from NO 3 - , Cl - , ClO 4 - , OH - and CH 3 CO 2 - Or a bivalent anion selected from ClO 4 2- , SO 4 2- , CO 3 2- ;
X 1 , x 2 , x 3 , x 4 , and x 5 are the same or different from each other, and each independently is an integer of 1 to 50;
When A 1 is a monovalent anion or a divalent anion, y 1 is 2 or 1, and when A 2 is a monovalent anion or a divalent anion, y 2 is 2 or 1, and A If 3 wherein the monovalent anion or a divalent anion is wherein y3 are each 2 or 1, and when the a 4 is the monovalent anion or a divalent anion has the y4 are each 2 or 1, wherein a 5 is Y5 is 2 or 1 when the monovalent anion is a divalent anion;
The derivative of 2,5-dihydroxy-1,4-benzenedicarboxylic acid is at least one selected from dehydrogen ions and salts of 2,5-dihydroxy-1,4-benzenedicarboxylic acid ;
Wherein S 1 OH is a first organic solvent comprising a hydroxyl group; Wherein S 2 OH is a second organic solvent containing a hydroxyl group, S 2 OH is lower in boiling point than S 1 OH ;
The S 1 OH is used in an amount of 50 to 95% by volume based on the total volume of the solution;
The second additive is used in an amount of 5 to 50% based on the total volume of the solution, and in a range of 1% to 100% of the volume of the S 1 OH .
[Chemical Formula 1]
[M 2 (DOBDC)]
In Formula 1, M is at least one divalent metal, DOBDC is 2,5-dioxido-1,4-benzenedicarboxylate having a negative tetravalent,
The metal-organic skeleton of the above formula (1) has (i) no peak of a substance of the following formula (2) is observed as a result of 1 H-NMR analysis, (ii) an amide peak is not observed as a result of FT-
(Iv) the total pore volume is in the range of 0.70 to 1.00 cm < 3 > / g when the temperature of the metal-organic skeleton is increased from 200 DEG C to 450 DEG C as a result of TGA analysis;
The metal-organic skeleton has (v) a BET surface area of up to 1,500 to 2,000 m 2 / g,
(2)
R 1 -CO-NR 2 R 3
In Formula 2, R 1 , R 2, and R 3 are the same or different from each other, and each independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms.
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