CN104788309A - Metal organic framework, preparation method and use thereof, and carbon dioxide conversion method - Google Patents
Metal organic framework, preparation method and use thereof, and carbon dioxide conversion method Download PDFInfo
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- CN104788309A CN104788309A CN201410025467.1A CN201410025467A CN104788309A CN 104788309 A CN104788309 A CN 104788309A CN 201410025467 A CN201410025467 A CN 201410025467A CN 104788309 A CN104788309 A CN 104788309A
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Abstract
The invention discloses a metal organic framework preparation method. The method is characterized in that a metal source contacts with a polydentate organic ligand and a structure directing agent under conditions capable of forming a crystalline porous network structure; the structure directing agent is a derivative obtained through substituting at least one coordination function group in the polydentate organic ligand by a competitive function group; and the metal coordination ability of the competitive function group is weaker than the metal coordination ability of the coordination function group. The invention also provides a metal organic framework prepared through the method. The invention also provides a use of the metal organic framework in catalysis of carbon dioxide cycloaddition. The metal organic framework prepared by adopting the above technical scheme has an excellent catalysis performance.
Description
Technical field
The present invention relates to applied chemistry field, particularly, relate to a kind of prepare metallic organic framework method, metallic organic framework, the purposes of this metallic organic framework and the method for a chemical recycling of carbon dioxide that the method prepares.
Background technology
Metallic organic framework (Metal-organic frameworks, MOFs) is a crystalloid porous material, and it is formed by coordination by metal cluster or metal ion and organo linking group, has the pore passage structure of repetition.Metallic organic framework has several functions, and such as, except gas absorption and storage attribute, metallic organic framework usually can as effective catalyzer.
But the catalytic performance of current metallic organic framework still has much room for improvement.
Summary of the invention
The object of this invention is to provide a kind of method preparing metallic organic framework, the method can make the metallic organic framework prepared have higher catalytic performance.
To achieve these goals, the invention provides a kind of method preparing metallic organic framework, the method comprises: source metal contacted under the condition that can form lenticular porous network structure with structure directing agent with multiple tooth organic ligand; Described source metal forms the metal in described metallic organic framework; Described multiple tooth organic ligand forms the organo linking group in described metallic organic framework; Described structure directing agent is that in described multiple tooth organic ligand, at least one co-ordinating functionality is competed the derivative of functional group's replacement gained; The metal-complexing ability of described competition functional group is weaker than the metal-complexing ability of described co-ordinating functionality.
Preferably, the co-ordinating functionality in described multiple tooth organic ligand is-CO
2h, the competition functional group in described structure directing agent is-NH
2or-NO
2; Metal ion in described source metal is Zn
2+.
Preferably, described multiple tooth organic ligand is trimesic acid, and described structure directing agent is 5-amino isophthalic acid and/or 5-nitroisophthalic acid; Described source metal is zinc nitrate.
Preferably, the described multiple tooth organic ligand relative to 1 mole, the consumption of described source metal is 0.1-10 mole.
Preferably, the condition that can form lenticular porous network structure comprises: contact is carried out in a solvent, and described solvent is the mixed solution of dimethyl formamide and methyl alcohol, the multiple tooth organic ligand relative to 1 mole, and the consumption of solvent is 0.01-20L; The temperature of contact is 10-200 DEG C; The time of contact is 0.1-36h.
Preferably, contact and carry out under CETRIMIDE POWDER and polyvinylpyrrolidone exist, multiple tooth organic ligand relative to 1 mole, the consumption of CETRIMIDE POWDER is 0.005-0.5 mole, and the consumption of polyvinylpyrrolidone is 0.005-0.5 mole.
Preferably, described multiple tooth organic ligand is trimesic acid, and described source metal is Zn (NO
3)
26H
2o; Described structure directing agent is 5-amino isophthalic acid.
Preferably, described multiple tooth organic ligand is trimesic acid, and described source metal is Zn (NO
3)
26H
2o; Described structure directing agent is 5-nitroisophthalic acid.
Present invention also offers the metallic organic framework that method as above prepares.
Present invention also offers the metallic organic framework that a kind of particularly preferred embodiment in method as above obtains; This metallic organic framework is as Zn
22(BTC)
12(H
2o)
22(16.23) DMF (13.02) DMAC (26.63) H
2shown in O, the spacer of this metallic organic framework is P3m, and unit cell parameters is
α=β=γ=90 °.
Present invention also offers the metallic organic framework that a kind of particularly preferred embodiment in method as above obtains; This metallic organic framework is as Zn
22(BTC)
12(H
2o)
14(NO
3 -)
8(8.02) DMF (23.16) DMAC (4.74) H
2shown in O, the spacer of this metallic organic framework is P3m, and unit cell parameters is
α=β=γ=90 °.
Present invention also offers the purposes of metallic organic framework as above in the cycloaddition of catalysis carbonic acid gas.
Present invention also offers a kind of method of chemical recycling of carbon dioxide, the method comprises: contacted under cycloaddition condition with epoxide with catalyzer by the gas containing carbonic acid gas; Described catalyzer is metallic organic framework as above.
By technique scheme, the present invention can make the metallic organic framework prepared have more excellent catalytic performance.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the adsorptive capacity variation diagram of the metallic organic framework absorbing ring Ethylene Oxide that embodiment 1 obtains.
Fig. 2 is the adsorptive capacity variation diagram of the metallic organic framework absorbing ring Ethylene Oxide that embodiment 2 obtains.
Fig. 3 is the adsorptive capacity variation diagram of the metallic organic framework absorbing ring Ethylene Oxide that comparative example 1 obtains.
Fig. 4 is the structural representation of the metallic organic framework that embodiment 1 obtains.
Fig. 5 is the crystallogram of the metallic organic framework that embodiment 1 obtains.
Fig. 6 is the structural representation of the metallic organic framework that embodiment 2 obtains.
Fig. 7 is the crystallogram of the metallic organic framework that embodiment 2 obtains.
Fig. 8 is the structural representation of the metallic organic framework that comparative example 1 obtains.
Fig. 9 is the crystallogram of the metallic organic framework that comparative example 1 obtains.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
In the present invention, when not doing contrary explanation, the liquid of use or the volumetric quantities of gas are all 20 DEG C, the numerical value of 1 standard atmosphere pressure.
The invention provides a kind of method preparing metallic organic framework, the method comprises: source metal contacted under the condition that can form lenticular porous network structure with structure directing agent with multiple tooth organic ligand; Described source metal forms the metal in described metallic organic framework; Described multiple tooth organic ligand forms the organo linking group in described metallic organic framework; Described structure directing agent is that in described multiple tooth organic ligand, at least one co-ordinating functionality is competed the derivative of functional group's replacement gained; The metal-complexing ability of described competition functional group is weaker than the metal-complexing ability of described co-ordinating functionality.
Wherein, described source metal can be metal-salt and/or metal oxide.Wherein multiple tooth organic ligand refers to the organic ligand containing plural co-ordinating functionality in molecular structure.
Wherein, the described multiple tooth organic ligand relative to 1 mole, the consumption of described structure directing agent can be 0.005-3 mole, is preferably 0.05-1 mole, is more preferably 0.1-0.5 mole.
Wherein, the co-ordinating functionality in described multiple tooth organic ligand can form the functional group of coordinate bond with metal ion for various, includes but not limited to-CO
2h ,-CS
2h ,-NO
2,-SO
3h ,-PO
4h
2,-SH,
-AsO
3h ,-AsO
4h ,-CH (RSH)
2,-C (RSH)
3,-CH (RNH
2)
2,-C (RNH
2)
3,-CH (ROH)
2,-C (ROH)
3,-CH (RCN)
2,-C (RCN)
3,-CH (NH
2)
2,-C (NH
2)
3,-CH (CN)
2with-C (CN)
3in at least one, wherein, the R in co-ordinating functionality is independently of one another for comprising the alkyl of 1 to 5 phenyl ring.
Wherein, metal-complexing ability refers to the bond energy of the coordinate bond formed between co-ordinating functionality and metal, and common coordinate bond bond energy has record in textbook and reference book, such as document (Luo Qinhui, coordination chemistry, Science Press, 2012), such as, for Zn
2+, the sequence of metal-complexing ability power is
>-SH>-CO
2h>
>-NH
2>-SO
3h> halide-ions >-NO
2.
Wherein, preferably, the co-ordinating functionality in described multiple tooth organic ligand is-CO
2h, the competition functional group in described structure directing agent is-NH
2or-NO
2;
Or the co-ordinating functionality in described multiple tooth organic ligand is-PO
4h
2,-SH,
or
competition functional group in described structure directing agent is
or-SO
3h.
Wherein, the metal ion in described source metal can be Mg
2+, Ca
2+, Sr
2+, Ba
2+, Sc
3+, Y
3+, Ti
4+, Zr
4+, Hf
4+, V
4+, V
3+, V
2+, Nb
3+, Ta
3+, Cr
3+, Mo
3+, W
3+, Mn
3+, Mn
2+, Re
3+, Re
2+, Fe
3+, Fe
2+, Ru
3+, Ru
2+, Os
3+, Os
2+, Co
3+, Co
2+, Rh
2+, Rh
+, Ir
2+, Ir
+, Ni
2+, Ni
+, Pd
2+, Pd
+, Pt
2+, Pt
+, Cu
2+, Cu
+, Ag
+, Au
+, Zn
2+, Cd
2+, Hg
2+, Al
3+, Ga
3+, In
3+, Tl
3+, Si
4+, Si
2+, Ge
4+, Ge
2+, Sn
4+, Sn
2+, Pb
4+, Pb
2+, As
5+, As
3+, As
+, Sb
5+, Sb
3+, Sb
+, Bi
5+, Bi
3+and Bi
+in at least one.
Wherein, particularly preferably, the co-ordinating functionality in described multiple tooth organic ligand is-CO
2h, the competition functional group in described structure directing agent is-NH
2or-NO
2; Metal ion in described source metal is Zn
2+.
Wherein, particularly preferably, described multiple tooth organic ligand is trimesic acid, and described structure directing agent is 5-amino isophthalic acid and/or 5-nitroisophthalic acid; Described source metal is zinc nitrate.
Wherein, the described multiple tooth organic ligand relative to 1 mole, the consumption of described source metal can be 0.1-10 mole, is preferably 0.2-5 mole, is more preferably 0.4-3 mole.
Wherein, the condition that can form lenticular porous network structure can for forming the condition of the routine of metallic organic framework, such as stir, dry, calcine, the condition such as ball milling, hydro-thermal, preferred use solvent thermal condition, the condition that can form lenticular porous network structure comprises: contact is carried out in a solvent, and described solvent is the mixed solution of dimethyl formamide and methyl alcohol, the multiple tooth organic ligand relative to 1 mole, the consumption of solvent is 0.01-20L, is more preferably 0.05-3L; The temperature of contact is 10-200 DEG C; The time of contact is 0.1-36h, is more preferably 1-12h.In described solvent, relative to the dimethyl formamide of 1 mole, the consumption of methyl alcohol can be 0.03-3 mole, is preferably 0.1-2 mole.
Wherein, preferably, contact and carry out under CETRIMIDE POWDER and polyvinylpyrrolidone exist, multiple tooth organic ligand relative to 1 mole, the consumption of CETRIMIDE POWDER is 0.005-0.5 mole, be preferably 0.02-0.2 mole, the consumption of polyvinylpyrrolidone is 0.005-0.5 mole, is preferably as 0.02-0.2 mole.Wherein, the weight-average molecular weight of polyvinylpyrrolidone can be 10000-100000, is preferably 20000-40000.
Wherein, preferably, described multiple tooth organic ligand is trimesic acid, and described source metal is Zn (NO
3)
26H
2o; Described structure directing agent is 5-amino isophthalic acid.
Wherein, preferably, described multiple tooth organic ligand is trimesic acid, and described source metal is Zn (NO
3)
26H
2o; Described structure directing agent is 5-nitroisophthalic acid.
Present invention also offers the metallic organic framework that method as above prepares.
Present invention also offers the metallic organic framework that a kind of particularly preferred embodiment in method as above obtains; This metallic organic framework is as Zn
22(BTC)
12(H
2o)
22(16.23) DMF (13.02) DMAC (26.63) H
2shown in O, the spacer of this metallic organic framework is P3m, and unit cell parameters is
α=β=γ=90 °.It is trimesic acid that this particularly preferred embodiment comprises described multiple tooth organic ligand, and described source metal is Zn (NO
3)
26H
2o; Described structure directing agent is 5-amino isophthalic acid; Contact and carry out under CETRIMIDE POWDER and polyvinylpyrrolidone exist, the multiple tooth organic ligand relative to 1 mole, the consumption of CETRIMIDE POWDER is 0.02-0.2 mole, and the consumption of polyvinylpyrrolidone is 0.02-0.2 mole; Contact is carried out in a solvent, and described solvent is the mixed solution of dimethyl formamide and methyl alcohol, the multiple tooth organic ligand relative to 1 mole, and the consumption of solvent is 0.05-3L; The temperature of contact is 10-200 DEG C; The time 1-12h of contact.
Present invention also offers the metallic organic framework that a kind of particularly preferred embodiment in method as above obtains; This metallic organic framework is as Zn
22(BTC)
12(H
2o)
14(NO
3 -)
8(8.02) DMF (23.16) DMAC (4.74) H
2shown in O, the spacer of this metallic organic framework is P3m, and unit cell parameters is
α=β=γ=90 °.It is trimesic acid that this particularly preferred embodiment comprises described multiple tooth organic ligand, and described source metal is Zn (NO
3)
26H
2o; Described structure directing agent is 5-nitroisophthalic acid; Contact and carry out under CETRIMIDE POWDER and polyvinylpyrrolidone exist, the multiple tooth organic ligand relative to 1 mole, the consumption of CETRIMIDE POWDER is 0.02-0.2 mole, and the consumption of polyvinylpyrrolidone is 0.02-0.2 mole; Contact is carried out in a solvent, and described solvent is the mixed solution of dimethyl formamide and methyl alcohol, the multiple tooth organic ligand relative to 1 mole, and the consumption of solvent is 0.05-3L; The temperature of contact is 10-200 DEG C; The time 1-12h of contact.
Present invention also offers the purposes of metallic organic framework as above in the cycloaddition of catalysis carbonic acid gas.
Present invention also offers a kind of method of chemical recycling of carbon dioxide, the method comprises: contacted under cycloaddition condition with epoxide with catalyzer by the gas containing carbonic acid gas; Described catalyzer is metallic organic framework as above.
Wherein, described cycloaddition condition can be conventional cycloaddition condition, and such as, temperature can be 80-260 DEG C, and the time can be 5-500 minute, and pressure can be 0.1-5MPa.Described epoxide can be at least one in oxyethane, propylene oxide and butylene oxide ring.
Further describe the present invention by the following examples.
Embodiment 1
By source metal (Zn (NO
3)
2.6H
2o) with multiple tooth organic ligand (trimesic acid) and structure directing agent (5-amino isophthalic acid) and CETRIMIDE POWDER, polyvinylpyrrolidone (weight-average molecular weight is 30000) and solvent evenly, obtain raw material liq.Wherein, the multiple tooth organic ligand relative to 1 mole, the consumption of structure directing agent is 0.21 mole, the consumption of source metal is 1.5 moles, the consumption of CETRIMIDE POWDER is 0.05 mole, and the consumption of polyvinylpyrrolidone is 0.05 mole, and the consumption of solvent is 0.35L; Solvent is the mixed solution of dimethyl formamide and methyl alcohol, and relative to the dimethyl formamide of 1 mole, the consumption of methyl alcohol is 0.2 mole.
Under raw material liq can being formed the condition of lenticular porous network structure, by the temperature of raw material liq in 180 minutes by 30 DEG C all be increased to 80 DEG C, and at 80 DEG C, maintain 1440 minutes, then in 180 minutes, be cooled to 30 DEG C, obtain the liquid containing crystal.Metallic organic framework should be containing the crystal in the liquid of crystal.
The above-mentioned crystal of centrifugation, and clean above-mentioned crystal with dimethyl formamide, chloroform and methenyl bromide successively, obtain the metallic organic framework of purifying.With source metal (Zn (NO
3)
2.6H
2o) gauge is calculated, and the productive rate of the metallic organic framework of purifying is 48 % by mole.Carry out Infrared spectroscopy to this metallic organic framework, result is: ν (cm
-1): 2928 (m), 1634 (s), 1578 (s), 1503 (s), 1447 (m), 1372 (s), 1259 (s), 1193 (s), 1099 (s), 1015 (m), 940 (m), 780 (s), 716 (s) cm
-1.As shown in Figure 4, crystallogram as shown in Figure 5 for the structural representation of this metallic organic framework.
Embodiment 2
By source metal (Zn (NO
3)
2.6H
2o) with multiple tooth organic ligand (trimesic acid) and structure directing agent (5-nitroisophthalic acid) and CETRIMIDE POWDER, polyvinylpyrrolidone (weight-average molecular weight is 30000) and solvent evenly, obtain raw material liq.Wherein, the multiple tooth organic ligand relative to 1 mole, the consumption of structure directing agent is 0.4 mole, the consumption of source metal is 2.1 moles, the consumption of CETRIMIDE POWDER is 0.01 mole, and the consumption of polyvinylpyrrolidone is 0.01 mole, and the consumption of solvent is 0.35L; Solvent is the mixed solution of dimethyl formamide and methyl alcohol, and relative to the dimethyl formamide of 1 mole, the consumption of methyl alcohol is 0.05 mole.
Under raw material liq can being formed the condition of lenticular porous network structure, by the temperature of raw material liq in 180 minutes by 30 DEG C all be increased to 80 DEG C, and at 80 DEG C, maintain 1440 minutes, then in 180 minutes, be cooled to 30 DEG C, obtain the liquid containing crystal.Metallic organic framework should be containing the crystal in the liquid of crystal.
The above-mentioned crystal of centrifugation, and clean above-mentioned crystal with dimethyl formamide, chloroform and methenyl bromide successively, obtain the metallic organic framework of purifying.With source metal (Zn (NO
3)
2.6H
2o) gauge is calculated, and the productive rate of the metallic organic framework of purifying is 25 % by mole.Carry out Infrared spectroscopy to this metallic organic framework, result is: ν (cm
-1): 2937 (m), 1625 (s), 1578 (s), 1501 (s), 1435 (m), 1382 (s), 1257 (s), 1191 (s), 1102 (s), 1021 (m), 764 (s), 719 (s) cm
-1.As shown in Figure 6, crystallogram as shown in Figure 7 for the structural representation of this metallic organic framework.
Comparative example 1
By source metal (Zn (NO
3)
2.6H
2o) with multiple tooth organic ligand (trimesic acid) and CETRIMIDE POWDER, polyvinylpyrrolidone (weight-average molecular weight is 30000) and solvent evenly, obtain raw material liq.Wherein, the multiple tooth organic ligand relative to 1 mole, the consumption of structure directing agent is 0 mole, the consumption of source metal is 1.2 moles, the consumption of CETRIMIDE POWDER is 0.1 mole, and the consumption of polyvinylpyrrolidone is 0.1 mole, and the consumption of solvent is 0.35L; Solvent is the mixed solution of dimethyl formamide and methyl alcohol, and relative to the dimethyl formamide of 1 mole, the consumption of methyl alcohol is 0.1 mole.
Under raw material liq can being formed the condition of lenticular porous network structure, by the temperature of raw material liq in 180 minutes by 30 DEG C all be increased to 80 DEG C, and at 80 DEG C, maintain 1440 minutes, then in 180 minutes, be cooled to 30 DEG C, obtain the liquid containing crystal.Metallic organic framework should be containing the crystal in the liquid of crystal.
The above-mentioned crystal of centrifugation, and clean above-mentioned crystal with dimethyl formamide, chloroform and methenyl bromide successively, obtain the metallic organic framework of purifying.With source metal (Zn (NO
3)
2.6H
2o) gauge is calculated, and the productive rate of the metallic organic framework of purifying is 31 % by mole.As shown in Figure 8, crystallogram as shown in Figure 9 for the structural representation of this metallic organic framework.
Testing example 1
Carry out ultimate analysis and X ray diffractive crystal Epidemiological Analysis respectively to the metallic organic framework that embodiment 1,2 and comparative example 1 obtain, result as shown in Table 1 and Table 2.
Table 1
| Metallic organic framework | Molecular formula |
| Embodiment 1 | Zn 22(BTC) 12(H 2O) 22·(16.23)DMF·(13.02)DMAC·(26.63)H 2O |
| Embodiment 2 | Zn 22(BTC) 12(H 2O) 14(NO 3 -) 8·(8.02)DMF·(23.16)DMAC·(4.74)H 2O |
| Comparative example 1 | C 36H 48N 6O 17Zn 4 |
Table 2
Testing example 2
The catalyst performance of metallic organic framework that obtains of testing example 1,2 and comparative example 1 by the following method:
In the stainless steel cauldron of the band magnetic stirring apparatus of 50mL, do not add solvent and promotor, add the metallic organic framework of 3.76 μm of ol and the propylene oxide of 20mmol, at the temperature of 160 DEG C, pass into the CO that pressure is 3MPa
2, maintain 30 minutes, carry out qualitative and quantitative analysis by GC-MS to the material in reactor, result is as shown in table 3.Wherein, utilize stratographic analysis target product and amount thereof, output refers to the transformation efficiency of propylene oxide.TON represents the upper substrate (CO of every mol catalyst (metallic organic framework) units activity center (Zn)
2) turn over number (mole).
Table 3
| Metallic organic framework | Output (% by mole) | TON |
| Comparative example 1 | 84.7 | 174.9 |
| Embodiment 1 | 89.4 | 216.2 |
| Embodiment 2 | 95.2 | 230.2 |
Testing example 3
The ability of the metallic organic framework absorbing ring Ethylene Oxide that testing example 1,2 and comparative example 1 obtain, result as Figure 1-3.Wherein, under 298K, the maximum absorption of metallic organic framework to propylene oxide that embodiment 1,2 and comparative example 1 obtain is respectively 0.72%, 0.64% and 0.44%.
Visible according to the data of table 2, adding by structure directing agent, method of the present invention can change the crystal characteristic of metallic organic framework significantly; Visible by the data of table 3, the metallic organic framework that method of the present invention prepares has better catalytic performance; Visible by the data of testing example 3, the metallic organic framework that method of the present invention prepares can absorbing ring Ethylene Oxide more.
Below the preferred embodiment of the present invention is described in detail by reference to the accompanying drawings; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. prepare a method for metallic organic framework, it is characterized in that: the method comprises:
Source metal is contacted with structure directing agent with multiple tooth organic ligand under the condition that can form lenticular porous network structure;
Described source metal forms the metal in described metallic organic framework;
Described multiple tooth organic ligand forms the organo linking group in described metallic organic framework;
Described structure directing agent is that in described multiple tooth organic ligand, at least one co-ordinating functionality is competed the derivative of functional group's replacement gained;
The metal-complexing ability of described competition functional group is weaker than the metal-complexing ability of described co-ordinating functionality.
2. method according to claim 1, is characterized in that: the described multiple tooth organic ligand relative to 1 mole, and the consumption of described structure directing agent is 0.005-3 mole.
3. method according to claim 1 and 2, is characterized in that: the co-ordinating functionality in described multiple tooth organic ligand is-CO
2h ,-CS
2h ,-NO
2,-SO
3h ,-PO
4h
2,-SH,
-AsO
3h ,-AsO
4h ,-CH (RSH)
2,-C (RSH)
3,-CH (RNH
2)
2,-C (RNH
2)
3,-CH (ROH)
2,-C (ROH)
3,-CH (RCN)
2,-C (RCN)
3,-CH (NH
2)
2,-C (NH
2)
3,-CH (CN)
2with-C (CN)
3in at least one, wherein, the R in co-ordinating functionality is independently of one another for comprising the alkyl of 1 to 5 phenyl ring.
4. method according to claim 1 and 2, is characterized in that: the co-ordinating functionality in described multiple tooth organic ligand is-CO
2h, the competition functional group in described structure directing agent is-NH
2or-NO
2;
Or the co-ordinating functionality in described multiple tooth organic ligand is-PO
4h
2,-SH,
or
competition functional group in described structure directing agent is
or-SO
3h.
5. the method according to claim 1,2 or 4, is characterized in that: the metal ion in described source metal is Mg
2+, Ca
2+, Sr
2+, Ba
2+, Sc
3+, Y
3+, Ti
4+, Zr
4+, Hf
4+, V
4+, V
3+, V
2+, Nb
3+, Ta
3+, Cr
3+, Mo
3+, W
3+, Mn
3+, Mn
2+, Re
3+, Re
2+, Fe
3+, Fe
2+, Ru
3+, Ru
2+, Os
3+, Os
2+, Co
3+, Co
2+, Rh
2+, Rh
+, Ir
2+, Ir
+, Ni
2+, Ni
+, Pd
2+, Pd
+, Pt
2+, Pt
+, Cu
2+, Cu
+, Ag
+, Au
+, Zn
2+, Cd
2+, Hg
2+, Al
3+, Ga
3+, In
3+, Tl
3+, Si
4+, Si
2+, Ge
4+, Ge
2+, Sn
4+, Sn
2+, Pb
4+, Pb
2+, As
5+, As
3+, As
+, Sb
5+, Sb
3+, Sb
+, Bi
5+, Bi
3+and Bi
+in at least one.
6. the metallic organic framework that the method in claim 1-5 described in any one prepares.
7. a metallic organic framework, is characterized in that: this metallic organic framework is as Zn
22(BTC)
12(H
2o)
22(16.23) DMF (13.02) DMAC (26.63) H
2shown in O, the spacer of this metallic organic framework is P3m, and unit cell parameters is
α=β=γ=90 °.
8. a metallic organic framework, is characterized in that: this metallic organic framework is as Zn
22(BTC)
12(H
2o)
14(NO
3 -)
8(8.02) DMF (23.16) DMAC (4.74) H
2shown in O, the spacer of this metallic organic framework is P3m, and unit cell parameters is
α=β=γ=90 °.
9. the purposes of the metallic organic framework in claim 6-8 described in any one in the cycloaddition of catalysis carbonic acid gas.
10. a method for chemical recycling of carbon dioxide, the method comprises: contacted under cycloaddition condition with epoxide with catalyzer by the gas containing carbonic acid gas; It is characterized in that: described catalyzer is the metallic organic framework in claim 6-8 described in any one.
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| CN105601942A (en) * | 2016-01-22 | 2016-05-25 | 辽宁大学 | A metal-organic framework based on InIII and its preparation method and application |
| CN105732487A (en) * | 2016-01-28 | 2016-07-06 | 辽宁大学 | Pentanuclear-ytterbium-cluster-molecule-structure-unit-conitaning metal organic framework, and preparation method and application thereof |
| CN106784658A (en) * | 2016-12-01 | 2017-05-31 | 中南大学 | A kind of Morphological control method of lithium ion battery metal oxide/carbon negative pole material |
| CN107096569A (en) * | 2017-04-28 | 2017-08-29 | 新疆大学 | A kind of efficient catalytic carbon dioxide and the catalyst of epoxides cycloaddition reaction |
| CN107626308A (en) * | 2017-08-30 | 2018-01-26 | 江南大学 | One kind is used for CO2The hydrotalcite carried with doped Au catalyst and preparation method of cycloaddition reaction and bisphenol synthesis F |
| CN109824705A (en) * | 2019-02-28 | 2019-05-31 | 滨州学院 | A kind of preparation method of bis(N-(4-carboxy) phenyl) perylene imide zinc complex catalyst and use thereof |
| CN114206993A (en) * | 2019-08-15 | 2022-03-18 | 纽麦特科技公司 | Water-stabilized copper paddle wheel metal organic framework (MOF) compositions and methods of using the MOFs |
| CN114832863A (en) * | 2021-02-01 | 2022-08-02 | 中国科学技术大学 | Hierarchical porous metal organic framework material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105601942B (en) * | 2016-01-22 | 2019-03-15 | 辽宁大学 | A kind of metal organic framework based on InIII and its preparation method and application |
| CN105601942A (en) * | 2016-01-22 | 2016-05-25 | 辽宁大学 | A metal-organic framework based on InIII and its preparation method and application |
| CN105732487A (en) * | 2016-01-28 | 2016-07-06 | 辽宁大学 | Pentanuclear-ytterbium-cluster-molecule-structure-unit-conitaning metal organic framework, and preparation method and application thereof |
| CN105732487B (en) * | 2016-01-28 | 2018-04-17 | 辽宁大学 | A kind of metal organic frame containing five core ytterbium cluster molecule construction units and its preparation method and application |
| CN106784658A (en) * | 2016-12-01 | 2017-05-31 | 中南大学 | A kind of Morphological control method of lithium ion battery metal oxide/carbon negative pole material |
| CN106784658B (en) * | 2016-12-01 | 2020-04-10 | 中南大学 | Morphology regulation and control method of metal oxide/carbon negative electrode material for lithium ion battery |
| CN107096569A (en) * | 2017-04-28 | 2017-08-29 | 新疆大学 | A kind of efficient catalytic carbon dioxide and the catalyst of epoxides cycloaddition reaction |
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| CN107626308B (en) * | 2017-08-30 | 2020-08-04 | 江南大学 | For CO2Hydrotalcite loaded gold-doped catalyst for cycloaddition reaction and bisphenol F synthesis and preparation method thereof |
| CN109824705A (en) * | 2019-02-28 | 2019-05-31 | 滨州学院 | A kind of preparation method of bis(N-(4-carboxy) phenyl) perylene imide zinc complex catalyst and use thereof |
| CN109824705B (en) * | 2019-02-28 | 2021-02-09 | 滨州学院 | A kind of preparation method of bis(N-(4-carboxy) phenyl) perylene imide zinc complex catalyst and use thereof |
| CN114206993A (en) * | 2019-08-15 | 2022-03-18 | 纽麦特科技公司 | Water-stabilized copper paddle wheel metal organic framework (MOF) compositions and methods of using the MOFs |
| CN114206993B (en) * | 2019-08-15 | 2024-02-23 | 纽麦特科技公司 | Water stable copper paddle wheel Metal Organic Framework (MOF) compositions and methods of using the MOFs |
| CN114832863A (en) * | 2021-02-01 | 2022-08-02 | 中国科学技术大学 | Hierarchical porous metal organic framework material and preparation method and application thereof |
| CN114832863B (en) * | 2021-02-01 | 2023-08-29 | 中国科学技术大学 | Hierarchical pore metal organic framework material and preparation method and application thereof |
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