CN105713208A - CuZn bi-metal organic framework material and preparing method thereof - Google Patents
CuZn bi-metal organic framework material and preparing method thereof Download PDFInfo
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Abstract
The invention discloses a CuZn bi-metal organic framework material and a preparing method thereof.The metal organic framework material ZIF-8 containing metal Zn and soluble copper salt are dissolved in a mixed solvent containing H2O, ethyl alcohol and N,N-dimethylformamide, and then 1,3,5-benzene tricarboxylic acid is added for hydrothermal crystallization, separation, washing and drying, so that the CuZn bi-metal organic framework material is obtained.Different from traditional bi-metal MOF preparing methods, the preparing method has the advantages that preparing time is short, replacement rate is high, and the crystal structure of the product varies.
Description
Technical field
The present invention relates to hybrid inorganic-organic materials technical field, be specifically related to a kind of CuZn bimetallic organic framework material and
Its preparation method.
Background technology
Metal-organic framework materials (Metal Organic Frameworks, MOFs) is to utilize between metal ion and organic ligand
Complexing, is self-assembly of the orderly crystalline material with high specific surface area, porosity and adjusting porous structure.Dan Jin
Belong to MOF preparation method the most ripe, can combine with flexible metal-ligand, pore structure and crystal structure.But
Bimetallic MOF preparation method is the most immature, currently mainly has following several preparation method:
1. nucleocapsid structure bimetallic MOF: the MOF-A containing metal A is placed in containing metal precursor B and organic ligand
Solution, stirring at normal temperature or hydrothermal condition prepare MOF-A@MOF-B. feature and be: two kinds of MOF preparation conditions are similar,
MOF-A still stable existence in the synthetic environment of MOF-B.Thus form well-bedded nucleocapsid structure MOF-A
The ZIF-8@ZIF-67 etc. of@MOF-B. such as Jing Tang.(Jing Tang,Yusuke Yamauchi,J.Am.Chem.Soc.
2015,137,1572-1580)
2. one-step method Hydrothermal Synthesis bimetallic MOF: the organic ligand that metal A, precursor B are all suitable for two kinds of metals is put
In suitable solvent, it is similar to monometallic MOF preparation method that hydro-thermal reaction prepares MOF-A/B. the method, and manufacturing cycle is relatively
Short.But Julia Torres research shows: the method is only applicable to metal A, B and is present in same transition metal system, minority
In the case of be applicable to different transition metal system.CoMn, ZnMn, MnNi bimetallic MOF that the most prepared by success are 3d
Transition metal (d district First Transition series elements).Different transition metal systems are only applicable to 3d-4f (lanthanide series metal) at present. (Julia
Torres,Journal of Molecular Structure,2011,1004,215-221.)
3. ion exchange (Postsynthetic Exchange, PSE) after synthesis: conjunction will be placed in containing the MOF-A of metal A
Suitable solvent, is subsequently added metal precursor B or the MOF-B containing metal B, realizes under stirring at normal temperature or hydrothermal condition
Metal B, for the exchange of metal in MOF-A, prepares MOF-A/B.Compare with method 1, the method no longer very critical
In same transition metal subregion, even without being transition metal.Only need that metal A, B's and MOF-A in reaction system is organic
Part can form the MOF of same topological structure, and product MOF-A/B keeps the crystalline substance of the front monometallic MOF of exchange
Body structure.Such as, UiO-66 (Zr) is soaked in TiCl by Min Kim4(THF)2Solution, obtains UiO-66 (Zr/Ti)；Will tool
MIL-53 (Al)-Br and MIL-53 (the Fe)-Br hydrothermal exchange having part of the same race and topological structure obtains 39% productivity
MIL-53 (Al/Fe)-Br. the method shortcoming: preparation time is longer, and examples detailed above is 5 days；Replacement rate is on the low side (less than 20%)；
Require that the monometallic MOF that metal A, B relate to has part of the same race, topological structure and skeleton stability.(Min Kim,John
F.Cahill and Seth M.Cohen,J.Am.Chem.Soc.2012,134,18082-18088).
Summary of the invention
It is an object of the invention to overcome the defect of prior art, it is provided that a kind of CuZn bimetallic organic framework material and preparation thereof
Method, is dissolved in the metal-organic framework materials ZIF-8 containing metal Zn with soluble copper salt and includes H2O, ethanol and N, N-
In the mixed solvent of dimethylformamide, adding 1,3,5-benzenetricarboxylic acids carry out hydrothermal crystallizing, separate, wash and be dried, i.e.
Obtain described CuZn bimetallic organic framework material.It is short that described preparation method has preparation time, and replacement rate is high, and product occurs
The features such as changes in crystal structure, are different from conventional dual-metal MOF preparation method.
The present invention is achieved by the following technical solutions:
First aspect present invention provides the preparation method of a kind of CuZn bimetallic organic framework material, by the metal containing metal Zn
Organic framework material ZIF-8 and soluble copper salt are dissolved in and include H2In the mixed solvent of O, ethanol and DMF,
Adding 1,3,5-benzenetricarboxylic acids carry out hydrothermal crystallizing, separate, wash and be dried, i.e. obtain the described organic bone of CuZn bimetallic
Frame material.
In the process, ZIF-8 progressively hydrolyzes generation Zn2+, free state 2-methylimidazole and ZIF-8 fragment, due to Cu2+、
Zn2+All can be with 1,3,5-benzenetricarboxylic acids form the MOFs material of HKUST-1 structure, therefore Cu2+Exist with 1,3,5-benzenetricarboxylic acid
Can be by Zn in self assembling process2+Include formation CuZn bimetallic MOFs, the i.e. organic bone of CuZn bimetallic in MOFs skeleton in
Frame material.
Preferably, H in described mixed solvent2The volume ratio of O, ethanol and N,N-dimethylformamide be 1:0.5～2:0.2～
3, such as H2O, the volume ratio of ethanol are 1:0.5～1 or 1:1～2；H2O, the volume ratio of N,N-dimethylformamide are 1:
0.2～1,1:1～2 or 1:2～3.
Preferably, described hydrothermal crystallizing is carried out in being furnished with teflon-lined stainless steel cauldron.
Preferably, sucking filtration it is separated into described in.
Preferably, described soluble copper salt is Cu (NO3)2·3H2O or Cu (CH3COO)2·H2O。
Preferably, soluble copper salt in terms of Cu, ZIF-8: soluble copper salt: 1,3,5-benzenetricarboxylic acid: H2The mol ratio of O is
1:0.2～3:0.336～1.12:228～1368, such as ZIF-8: the mol ratio of soluble copper salt be 1:0.2～0.25,1:0.25～0.33,
1:0.33～0.5,1:0.5～1,1:1～2 or 1:2～3；The mol ratio of ZIF-8:1,3,5-benzenetricarboxylic acid be 1:0.336～0.35,
1:0.35～0.37,1:0.37～0.42,1:0.42～0.56,1:0.56～0.84 or 1:0.84～1.12；ZIF-8:H2O's
Mol ratio is 1:228～456,1:456～684,1:684～912,1:912～1140 or 1:1140～1368.
Preferably, the temperature of hydrothermal crystallizing is 70～150 DEG C, as 70～85 DEG C, 85～90 DEG C, 90～100 DEG C, 100～110 DEG C,
110～120 DEG C, 120～130 DEG C, 130～140 DEG C or 140～150 DEG C, the time is 12～48h, as 12～20h, 20～24h,
24～28h, 28～32h, 32～36h, 36～40h, 40～44h or 44～48h.
Preferably, baking temperature is 90～120 DEG C, as 90～95 DEG C, 95～100 DEG C, 100～105 DEG C, 105～110 DEG C,
110～115 DEG C or 115～120 DEG C, drying time is 12～48h, as 12～16h, 16～24h, 24～28h, 28～32h, 32～36h,
36～44h or 44～48h.
Preferably, the described metal-organic framework materials ZIF-8 containing metal Zn uses following preparation method to prepare:
1) by Zn (NO3)2·6H2O is soluble in water obtains the first solution；
2) 2-methylimidazole is dissolved in ammonium hydroxide obtains the second solution；
3) the second solution is added in the first solution, form suspension；
4) whipping step 3) the middle suspension formed is to being fully crystallized, centrifugal, washs and is dried, and i.e. obtains described containing metal
The metal-organic framework materials ZIF-8 of Zn.
It is furthermore preferred that NH in ammonium hydroxide3Mass concentration be 28-30%.
It is furthermore preferred that any one also included in following characteristics or multinomial:
1) step 4) in, whipping temp is 25 DEG C, mixing time 10min；
2) step 4) in, centrifugal condition: centrifugal rotational speed is 5000rpm, centrifugation time is 5min；
3) step 4) in, drying condition: baking temperature is 60 DEG C, drying time is 12h.
The above-mentioned metal-organic framework materials ZIF-8 (C containing metal Zn8H10N4Zn) can be by preparation known in the field
Method prepares, and prepares (Ming He, Jianfeng Yao, Microporous and Meso-for example with following preparation method
Porous Materials, 184 (2014) 55-60):
1) by Zn (NO3)2·6H2O is soluble in water obtains the first solution；
2) 2-methylimidazole is dissolved in ammonium hydroxide obtains the second solution；
3) the second solution is added in the first solution, form suspension；
4) whipping step 3) the middle suspension formed is to being fully crystallized, centrifugal, washs and is dried, and i.e. obtains described containing metal
The metal-organic framework materials ZIF-8 of Zn.
Preferably, including any one in following characteristics or multinomial:
1) step 4) in, whipping temp is 25 DEG C, mixing time 10min；
2) step 4) in, centrifugal condition: centrifugal rotational speed is 5000rpm, centrifugation time is 5min；
3) step 4) in, drying condition: baking temperature is 60 DEG C, drying time is 12h.
Second aspect present invention provides a kind of CuZn bimetallic organic framework material, uses the preparation method described in any of the above-described item
Prepare.
The preparation method of the CuZn bimetallic organic framework material of the present invention, is placed in Cu-HKUST-1 using ZIF-8 as Zn source
Metal precursor Cu (NO3)2With organic ligand 1, in the solvent environment of 3,5-benzenetricarboxylic acids, hydrothermal condition prepares bimetallic
MOF.It is with tradition " ion exchange after synthesis " difference: 1) Cu (NO3)2With organic ligand 1,3,5-benzenetricarboxylic acid simultaneously
Participate in ZIF-8 ion exchange process；2) ion exchange process not only replaces ZIF-8 metal component, changes organic ligand simultaneously
Component and crystal structure.Test result indicate that: reach identical replacement rate (part by weight: Cu/ (Cu+Zn) ≈ 60%), the party
Method needed 20h, hence it is evident that less than 3 days of traditional method.After displacement, in bimetallic MOF, Cu/ (Cu+Zn) proportion can be
Regulate in the range of 20%～80%.During traditional method 20h Cu replacement rate less than 5%. (Xiaokai Song, CrystEngComm,
2012,14,5753-5756).CuZn bimetallic organic framework material not nucleocapsid structure prepared by the method, does not the most inherit
The crystal structure of ZIF and HKUST series MOF, is different from ZIF-8 and Cu-HKUST-1 crystal structure product, XRD
Prove new crystal structure.It is short that the preparation method of described CuZn bimetallic organic framework material has preparation time, replacement rate
Height, the feature such as product generation changes in crystal structure, it is different from conventional dual-metal MOF preparation method.
Accompanying drawing explanation
The XRD spectra of the monometallic MOF related in Fig. 1 embodiment 1 sample S-1 and preparation process.
The SEM photograph (low power) of Fig. 2 embodiment 1 sample S-1.
The SEM photograph (high power) of Fig. 3 embodiment 1 sample S-1.
The SEM photograph of Fig. 4 embodiment 4 sample S-4.
The SEM photograph of Fig. 5 embodiment 5 sample S-5.
Detailed description of the invention
Below by way of specific instantiation, technical scheme is described.Should be understood that one or more sides that the present invention mentions
Method step do not repel there is also before and after described combination step additive method step or between these steps specifically mentioned also
May be inserted into additive method step；Should also be understood that these embodiments are merely to illustrate the present invention rather than limit the model of the present invention
Enclose.And, except as otherwise noted, the numbering of various method steps is only the convenient tool differentiating various method steps, rather than for limit
The ordering of various method steps or the restriction enforceable scope of the present invention, being altered or modified of its relativeness, becoming without essence
In the case of more technology contents, when being also considered as the enforceable category of the present invention.
The technology of the present invention details is by the detailed description in addition of following embodiment.It should be noted that lifted embodiment, its effect is only
It is to further illustrate the technical characteristic of the present invention rather than limit the present invention.
[embodiment 1]
2.97g zinc nitrate hexahydrate is dissolved in 15mL deionized water formation solution A respectively, and 1.64g methylimidazole is dissolved in
18.8g ammonia (NH3Mass concentration be 28%) formed solution B, solution B is added dropwise in solution A, in mixed solution
Zn:Hmim:NH3:H2O molar ratio 1:2:32:157.Stir centrifugation gained solid after 10min under room temperature condition, use
Deionized water wash, to supernatant pH ≈ 7, is then centrifuged for separating obtained solid at 60 DEG C, is dried to obtain containing metal after being dried 12h
The metal-organic framework materials ZIF-8 of Zn.Weigh ZIF-8 with the 0.532g Gerhardite prepared by 0.5g to be dissolved in by going
Ionized water (H2O): ethanol: the mixed solution (45mL) of N, N-dimethyl formyl (DMF)=1:1:1 (volume ratio),
Stirring to after forming uniform suspension, add 0.256g 1,3,5-benzenetricarboxylic acid, solution is transferred to be furnished with poly-by stirring 15min
In the 100mL stainless steel cauldron of tetrafluoroethene liner, in 85 DEG C of condition hydro-thermal reactions 20h, sucking filtration also uses deionized water
Washing, 90 DEG C of dry 12h obtain solid sample S-1, preparation time and replacement rate and are shown in Table 1.
[embodiment 2]
2.97g zinc nitrate hexahydrate is dissolved in 15mL deionized water formation solution A respectively, and 1.64g methylimidazole is dissolved in
18.8g ammonia (NH3Mass concentration be 28%) formed solution B, solution B is added dropwise in solution A, in mixed solution
Zn:Hmim:NH3:H2O molar ratio 1:2:32:157.Stir centrifugation gained solid after 10min under room temperature condition, use
Deionized water wash, to supernatant pH ≈ 7, is then centrifuged for separating obtained solid at 60 DEG C, is dried to obtain containing metal after being dried 12h
The metal-organic framework materials ZIF-8 of Zn.Weigh ZIF-8 with the 1.596g Gerhardite prepared by 0.5g to be dissolved in by going
Ionized water (H2O): ethanol: the mixed solution (51mL) of N, N-dimethyl formyl (DMF)=1:0.5:0.2 (volume ratio),
Stirring to after forming uniform suspension, add 0.512g 1,3,5-benzenetricarboxylic acid, solution is transferred to be furnished with poly-by stirring 15min
In the 100mL stainless steel cauldron of tetrafluoroethene liner, in 70 DEG C of condition hydro-thermal reactions 12h, sucking filtration also uses deionized water
Washing, 110 DEG C of dry 16h obtain solid sample S-2, preparation time and replacement rate and are shown in Table 1.
[embodiment 3]
2.97g zinc nitrate hexahydrate is dissolved in 15mL deionized water formation solution A respectively, and 1.64g methylimidazole is dissolved in
18.8g ammonia (NH3Mass concentration be 28%) formed solution B, solution B is added dropwise in solution A, in mixed solution
Zn:Hmim:NH3:H2O molar ratio 1:2:32:157.Stir centrifugation gained solid after 10min under room temperature condition, use
Deionized water wash, to supernatant pH ≈ 7, is then centrifuged for separating obtained solid at 60 DEG C, is dried to obtain containing metal after being dried 12h
The metal-organic framework materials ZIF-8 of Zn.Weigh ZIF-8 with the 1.064g Gerhardite prepared by 0.5g to be dissolved in by going
Ionized water (H2O): ethanol: the mixed solution (87.5mL) of N, N-dimethyl formyl (DMF)=1:0.5:2 (volume ratio),
Stirring to after forming uniform suspension, add 0.384g 1,3,5-benzenetricarboxylic acid, solution is transferred to be furnished with poly-by stirring 15min
In the 100mL stainless steel cauldron of tetrafluoroethene liner, in 90 DEG C of condition hydro-thermal reactions 36h, sucking filtration also uses deionized water
Washing, 90 DEG C of dry 24h obtain solid sample S-3, preparation time and replacement rate and are shown in Table 1.
[embodiment 4]
2.97g zinc nitrate hexahydrate is dissolved in 15mL deionized water formation solution A respectively, and 1.64g methylimidazole is dissolved in
18.8g ammonia (NH3Mass concentration be 28%) formed solution B, solution B is added dropwise in solution A, in mixed solution
Zn:Hmim:NH3:H2O molar ratio 1:2:32:157.Stir centrifugation gained solid after 10min under room temperature condition, use
Deionized water wash, to supernatant pH ≈ 7, is then centrifuged for separating obtained solid at 60 DEG C, is dried to obtain containing metal after being dried 12h
The metal-organic framework materials ZIF-8 of Zn.Weigh ZIF-8 with the 0.266g Gerhardite prepared by 0.5g to be dissolved in by going
Ionized water (H2O): ethanol: the mixed solution (45mL) of N, N-dimethyl formyl (DMF)=1:0.5:3 (volume ratio),
Stirring to after forming uniform suspension, add 0.194g 1,3,5-benzenetricarboxylic acid, solution is transferred to be furnished with poly-by stirring 15min
In the 100mL stainless steel cauldron of tetrafluoroethene liner, in 100 DEG C of condition hydro-thermal reactions 24h, sucking filtration also uses deionization
Water washs, and 120 DEG C of dry 32h obtain solid sample S-4, preparation time and replacement rate and are shown in Table 1.
[embodiment 5]
2.97g zinc nitrate hexahydrate is dissolved in 15mL deionized water formation solution A respectively, and 1.64g methylimidazole is dissolved in
18.8g ammonia (NH3Mass concentration be 28%) formed solution B, solution B is added dropwise in solution A, in mixed solution
Zn:Hmim:NH3:H2O molar ratio 1:2:32:157.Centrifugation gained solid after 10min is stirred, bravely under room temperature condition
Deionized water wash, to supernatant pH ≈ 7, is then centrifuged for separating obtained solid at 60 DEG C, is dried to obtain containing metal after being dried 12h
The metal-organic framework materials ZIF-8 of Zn.Weigh ZIF-8 with the 0.178g Gerhardite prepared by 0.5g to be dissolved in by going
Ionized water (H2O): ethanol: the mixed solution (64mL) of N, N-dimethyl formyl (DMF)=1:2:0.2 (volume ratio),
Stirring to after forming uniform suspension, add 0.171g 1,3,5-benzenetricarboxylic acid, solution is transferred to be furnished with poly-by stirring 15min
In the 100mL stainless steel cauldron of tetrafluoroethene liner, in 110 DEG C of condition hydro-thermal reactions 32h, sucking filtration also uses deionized water
Washing, 115 DEG C of dry 28h obtain solid sample S-5, preparation time and replacement rate and are shown in Table 1.
[embodiment 6]
2.97g zinc nitrate hexahydrate is dissolved in 15mL deionized water formation solution A respectively, and 1.64g methylimidazole is dissolved in
18.8g ammonia (NH3Mass concentration be 28%) formed solution B, solution B is added dropwise in solution A, in mixed solution
Zn:Hmim:NH3:H2O molar ratio 1:2:32:157.Centrifugation gained solid after 10min is stirred, bravely under room temperature condition
Deionized water wash, to supernatant pH ≈ 7, is then centrifuged for separating obtained solid at 60 DEG C, is dried to obtain containing metal after being dried 12h
The metal-organic framework materials ZIF-8 of Zn.Weigh ZIF-8 with the 0.133g Gerhardite prepared by 0.5g to be dissolved in by going
Ionized water (H2O): ethanol: the mixed solution (20mL) of N, N-dimethyl formyl (DMF)=1:2:1 (volume ratio),
Stirring to after forming uniform suspension, add 0.16g 1,3,5-benzenetricarboxylic acid, solution is transferred to be furnished with poly-by stirring 15min
In the 100mL stainless steel cauldron of tetrafluoroethene liner, in 120 DEG C of condition hydro-thermal reactions 40h, sucking filtration also uses deionization
Water washs, and 95 DEG C of dry 44h obtain solid sample S-6, preparation time and replacement rate and are shown in Table 1.
[embodiment 7]
2.97g zinc nitrate hexahydrate is dissolved in 15mL deionized water formation solution A respectively, and 1.64g methylimidazole is dissolved in
18.8g ammonia (NH3Mass concentration be 28%) formed solution B, solution B is added dropwise in solution A, in mixed solution
Zn:Hmim:NH3:H2O molar ratio 1:2:32:157.Centrifugation gained solid after 10min is stirred, bravely under room temperature condition
Deionized water wash, to supernatant pH ≈ 7, is then centrifuged for separating obtained solid at 60 DEG C, is dried to obtain containing metal after being dried 12h
The metal-organic framework materials ZIF-8 of Zn.Weigh ZIF-8 with the 0.107g Gerhardite prepared by 0.5g to be dissolved in by going
Ionized water (H2O): ethanol: the mixed solution (60mL) of N, N-dimethyl formyl (DMF)=1:2:3 (volume ratio),
Stirring to after forming uniform suspension, add 0.155g 1,3,5-benzenetricarboxylic acid, solution is transferred to be furnished with poly-by stirring 15min
In the 100mL stainless steel cauldron of tetrafluoroethene liner, in 130 DEG C of condition hydro-thermal reactions 44h, sucking filtration also uses deionization
Water washs, and 105 DEG C of dry 48h obtain solid sample S-7, preparation time and replacement rate and are shown in Table 1.
[embodiment 8]
2.97g zinc nitrate hexahydrate is dissolved in 15mL deionized water formation solution A respectively, and 1.64g methylimidazole is dissolved in
18.8g ammonia (NH3Mass concentration be 28%) formed solution B, solution B is added dropwise in solution A, in mixed solution
Zn:Hmim:NH3:H2O molar ratio 1:2:32:157.Centrifugation gained solid after 10min is stirred, bravely under room temperature condition
Deionized water wash, to supernatant pH ≈ 7, is then centrifuged for separating obtained solid at 60 DEG C, is dried to obtain containing metal after being dried 12h
The metal-organic framework materials ZIF-8 of Zn.Weigh ZIF-8 with the 0.532g Gerhardite prepared by 0.5g to be dissolved in by going
Ionized water (H2O): ethanol: the mixed solution (48mL) of N, N-dimethyl formyl (DMF)=1:2:0.2 (volume ratio),
Stirring to after forming uniform suspension, add 0.256g 1,3,5-benzenetricarboxylic acid, solution is transferred to be furnished with poly-by stirring 15min
In the 100mL stainless steel cauldron of tetrafluoroethene liner, in 140 DEG C of condition hydro-thermal reactions 28h, sucking filtration also uses deionization
Water washs, and 100 DEG C of dry 36h obtain solid sample S-8, preparation time and replacement rate and are shown in Table 1.
[embodiment 9]
2.97g zinc nitrate hexahydrate is dissolved in 15mL deionized water formation solution A respectively, and 1.64g methylimidazole is dissolved in
18.8g ammonia (NH3Mass concentration be 28%) formed solution B, solution B is added dropwise in solution A, in mixed solution
Zn:Hmim:NH3:H2O molar ratio 1:2:32:157.Centrifugation gained solid after 10min is stirred, bravely under room temperature condition
Deionized water wash, to supernatant pH ≈ 7, is then centrifuged for separating obtained solid at 60 DEG C, is dried to obtain containing metal after being dried 12h
The metal-organic framework materials ZIF-8 of Zn.Weigh ZIF-8 with the 0.532g Gerhardite prepared by 0.5g to be dissolved in by going
Ionized water (H2O): ethanol: the mixed solution (90mL) of N, N-dimethyl formyl (DMF)=1:0.5:3 (volume ratio),
Stirring to after forming uniform suspension, add 0.256g 1,3,5-benzenetricarboxylic acid, solution is transferred to be furnished with poly-by stirring 15min
In the 100mL stainless steel cauldron of tetrafluoroethene liner, in 150 DEG C of condition hydro-thermal reactions 48h, sucking filtration also uses deionization
Water washs, and 90 DEG C of dry 24h obtain solid sample S-9, preparation time and replacement rate and are shown in Table 1.
Table 1 embodiment 1-9 prepares the Cu element substitution rate of CuZn bimetallic MOF
The above, only presently preferred embodiments of the present invention, not any formal and substantial to present invention restriction, should
When pointing out, for those skilled in the art, on the premise of without departing from the inventive method, also can make
Some improvement and supplement, these improve and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, make when available disclosed above technology contents a little more
The equivalent variations moved, modify and develop, is the Equivalent embodiments of the present invention；Meanwhile, all substantial technological according to the present invention
The change of any equivalent variations that above-described embodiment is made, modify and develop, all still fall within the model of technical scheme
In enclosing.
Claims (9)
1. the preparation method of a CuZn bimetallic organic framework material, it is characterised in that by the organic bone of metal containing metal Zn
Frame material ZIF-8 and soluble copper salt are dissolved in and include H2In the mixed solvent of O, ethanol and DMF, then add
Entering 1,3,5-benzenetricarboxylic acids carry out hydrothermal crystallizing, separate, wash and be dried, i.e. obtain described CuZn bimetallic organic backbone material
Material.
Preparation method the most according to claim 1, it is characterised in that H in described mixed solvent2O, ethanol and N, N-diformazan
The volume ratio of base Methanamide is 1:0.5～2:0.2～3.
Preparation method the most according to claim 1, it is characterised in that described hydrothermal crystallizing is being furnished with teflon-lined
Stainless steel cauldron is carried out.
Preparation method the most according to claim 1, it is characterised in that described in be separated into sucking filtration.
Preparation method the most according to claim 1, it is characterised in that described soluble copper salt is Cu (NO3)2·3H2O or
Cu(CH3COO)2·H2O。
Preparation method the most according to claim 1, it is characterised in that soluble copper salt in terms of Cu, ZIF-8: soluble copper
Salt: 1,3,5-benzenetricarboxylic acid: H2The mol ratio of O is 1:0.2～3:0.336～1.12:228～1368.
Preparation method the most according to claim 1, it is characterised in that the temperature of hydrothermal crystallizing is 70～150 DEG C, the time is
12～48h.
Preparation method the most according to claim 1, it is characterised in that baking temperature is 90～120 DEG C, drying time is
12～48h.
9. a CuZn bimetallic organic framework material, it is characterised in that use the preparation described in any one of claim 1 to 8
Method prepares.
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| CN106311294A (en) * | 2016-07-26 | 2017-01-11 | 北京工业大学 | Method for preparing zinc phosphide/cobalt phosphide heterojunction photocatalyst based on MOFs template |
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| CN116063688A (en) * | 2021-11-01 | 2023-05-05 | 广东美的白色家电技术创新中心有限公司 | Flexible metal-organic framework material and preparation method thereof |
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| CN106311294A (en) * | 2016-07-26 | 2017-01-11 | 北京工业大学 | Method for preparing zinc phosphide/cobalt phosphide heterojunction photocatalyst based on MOFs template |
| CN106916315A (en) * | 2017-02-15 | 2017-07-04 | 南京医科大学 | Metal porous organic framework material, its preparation method and its application |
| CN107930586A (en) * | 2017-09-29 | 2018-04-20 | 天津大学 | A kind of method by copper incorporation zeolite imidazole salt frame synthesis Cu ZIF 67 |
| CN107930670B (en) * | 2017-11-30 | 2019-09-06 | 中国石油大学(北京) | A kind of heterogeneous catalysis material and its preparation method and application that self-cradling type is homogeneously changed |
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| CN108373538A (en) * | 2018-01-12 | 2018-08-07 | 华南理工大学 | Utilize the method for bimetal salt room temperature Fast back-projection algorithm multi-stage porous ZIF-90 materials |
| CN108676170A (en) * | 2018-04-19 | 2018-10-19 | 华南理工大学 | Utilize the method for bimetal salt room temperature Fast back-projection algorithm multi-stage porous ZIF-61 materials |
| CN109164076A (en) * | 2018-09-03 | 2019-01-08 | 中国药科大学 | Fluorescent nano probe, preparation method based on La-ZIF-8 and its application in bioluminescence sensing |
| CN110212194A (en) * | 2019-06-12 | 2019-09-06 | 合肥工业大学 | A kind of preparation method and applications of one-dimensional MOF@ZIF core-shell structure |
| CN110212194B (en) * | 2019-06-12 | 2021-01-08 | 合肥工业大学 | Preparation method and application of one-dimensional MOF @ ZIF core-shell structure |
| CN110330661A (en) * | 2019-06-28 | 2019-10-15 | 武汉工程大学 | The preparation method of gradient copper cobalt dual-metal organic framework materials |
| CN110283331A (en) * | 2019-07-03 | 2019-09-27 | 运城学院 | A kind of preparation method of copper zinc binary metal coordination polymer |
| CN110975912A (en) * | 2019-10-21 | 2020-04-10 | 长春理工大学 | Preparation and application of cobalt-nitrogen doped catalyst derived from bimetallic MOFs (metal-organic frameworks) |
| CN110975912B (en) * | 2019-10-21 | 2022-12-06 | 长春理工大学 | Preparation and application of cobalt-nitrogen doped catalyst derived from bimetallic MOFs (metal-organic frameworks) |
| CN110773197A (en) * | 2019-10-29 | 2020-02-11 | 李平 | Two-dimensional bimetallic sulfide nanosheet photocatalyst and preparation method thereof |
| CN113121834A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Composite metal organic framework material and preparation method thereof |
| CN113121834B (en) * | 2019-12-31 | 2022-07-12 | 中国石油化工股份有限公司 | Composite metal organic framework material and preparation method thereof |
| CN111454462A (en) * | 2020-04-23 | 2020-07-28 | 西安近代化学研究所 | Preparation method of Zn-Cu-ZIF bimetal organic framework compound |
| CN112744896A (en) * | 2020-12-15 | 2021-05-04 | 西南石油大学 | Photocatalytic oil-water separation material and preparation method thereof |
| CN112744896B (en) * | 2020-12-15 | 2021-12-28 | 西南石油大学 | Photocatalytic oil-water separation material and preparation method thereof |
| CN112979977A (en) * | 2021-02-04 | 2021-06-18 | 中国科学院山西煤炭化学研究所 | For CO2Trapped bimetallic MOFs material, preparation method and application |
| CN116063688A (en) * | 2021-11-01 | 2023-05-05 | 广东美的白色家电技术创新中心有限公司 | Flexible metal-organic framework material and preparation method thereof |
| CN117276652A (en) * | 2023-09-04 | 2023-12-22 | 广东聚圣科技有限公司 | Gel electrolyte and lithium battery |
| CN117276652B (en) * | 2023-09-04 | 2024-07-16 | 广东聚圣科技有限公司 | Gel electrolyte and lithium battery |
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