CN106674290A - Preparation method of monodispersed cobalt and nickel composite MOF-74 - Google Patents
Preparation method of monodispersed cobalt and nickel composite MOF-74 Download PDFInfo
- Publication number
- CN106674290A CN106674290A CN201611021525.9A CN201611021525A CN106674290A CN 106674290 A CN106674290 A CN 106674290A CN 201611021525 A CN201611021525 A CN 201611021525A CN 106674290 A CN106674290 A CN 106674290A
- Authority
- CN
- China
- Prior art keywords
- mof
- water
- volume ratio
- preparation
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
Abstract
A preparation method of monodispersed cobalt and nickel composite MOF-74 relates to a preparation method of MOF. The invention aims to solve the problem that particles of MOF prepared by existing methods are not uniform such that MOF has poor stability when used for catalysis and gas separation. The method comprises the following steps: 1, preparing MOF-74Ni; 2, carrying out aftertreatment on MOF-74Ni; 3, preparing cobalt and nickel composite MOF and obtaining monodispersed cobalt and nickel composite MOF-74. The prepared monodispersed MOF has controllable dimension and the dimension distribution is narrow. Thus, it is convenient to prepare a sample with special purpose. The dimension of the prepared monodispersed MOF is 0.5-20 microns. The method is suitable for preparation of monodispersed cobalt and nickel composite MOF-74.
Description
Technical field
The present invention relates to a kind of preparation method of MOF.
Background technology
In recent years, it is a kind of that metal-organic framework crystal material is formed by self assembling process by organic ligand and metal ion
Material (MOF) causes the very big attention of catalysis scholar.Its part be mainly based on carboxylic organic anion, or with contain
Azacyclo- organic neutral ligands are used in conjunction with；Metal is mainly with transition metal (such as Zn, Cu, Co) and lanthanide element etc.
Based on.The seminar such as external Yaghi, Ferey, Kitagawa, Kim and Chen little Ming, Cheng Peng, Qiu Shilun, Zhao Dong of the country
Unit etc. has made intensive studies to the synthesis of MOF, sign, application.With traditional solid catalytic material (such as oxide, molecular sieve
With carbon etc.) compare, MOF has following outstanding feature：(1) with high-specific surface area (such as the Langmuir ratios of MOF-177
Surface area can reach 4500m2g- 1)；(2) by modulation metal ion and Organic substance part, can flexibly and easily regulate and control it and knit
Structure property (such as the expansion or compression in aperture) and surface functional group, make it to reactant with homogeneous controllable aperture size and
Product has " shape selective catalysis " characteristic as molecular sieve；(3) it is a kind of porous crystalline material, with very high voidage, completely
Being exposed to the metal ion in surface/duct can provide 100% availability, and this creates bar for Immobilized homogenous catalyst
Part.
Although MOF as above plurality of advantages, however it is necessary that design synthesis organic ligand, here it is the application of MOF is restricted.
Therefore scientists are proposed using constitutionally stable MOF as platform, explore simple, pervasive new method, by by function energy
Material (small molecule, drug molecule, nanoparticle etc.) and MOF carry out effectively coating and combining, and controllable standby functionalization MOF is entered
One step expands MOF application spaces.Although the method can effectively expand the application space of MOF, due to existing synthesis condition system
It is uneven for the particle for going out MOF, necessarily cause its performance inhomogeneities, affect its service efficiency.
The content of the invention
The invention aims to solve existing method prepare MOF particle it is uneven, and the MOF for causing catalysis and
The problem of the stability difference in gas separation, and a kind of preparation method of the compound MOF-74 of single dispersing cobalt nickel is provided.
A kind of preparation method of the compound MOF-74 of single dispersing cobalt nickel, completes according to the following steps：
First, MOF-74Ni is prepared：
2,5-Dihydroxyterephthalic acid and six water nickel nitrates are dissolved in solvent I, 2,5- dihydroxy is obtained to benzene two
The mixed solution of formic acid and six water nickel nitrates；Add in the mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates
Acetic acid and mass fraction are 1%~30% aqueous povidone solution, obtain reactant liquor；It is in temperature by reactant liquor
12h~72h is reacted at 100 DEG C~180 DEG C, MOF-74Ni is obtained；
2,5- dihydric para-phthalic acids described in step one and 2,5- dihydroxy in the mixed solution of six water nickel nitrates
The concentration of p-phthalic acid is 5mmol/L~30mmol/L；
2,5- dihydric para-phthalic acids described in step one and six water nickel nitrates in the mixed solution of six water nickel nitrates
Concentration be 15mmol/L~90mmol/L；
The mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates described in step one and the volume of acetic acid
Than for 100:(1~5)；
The mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates described in step one is with mass fraction
The volume ratio of 1%~30% aqueous povidone solution is 100:(1~50)；
2nd, the post processing of MOF-74Ni：
The MOF-74Ni that step one is obtained is centrifuged in the case where rotating speed is 3500rpm/min~10000rpm/min, removes
Clear liquid, obtains yellow solid powder；With solvent II as abluent, first by yellow solid powder carry out ultrasonic cleaning 5min~
40min, then with solvent II as abluent, centrifuge washing 3 times~5 times, then temperature be dried at 75 DEG C~150 DEG C 12h~
72h, the MOF-74Ni after being processed；
3rd, the compound MOF of cobalt nickel is prepared：
MOF-74Ni and cobalt nitrate hexahydrate after the process obtained in step 2 is dissolved in solvent III, then is in temperature
2h~40h is reacted respectively under the conditions of 75 DEG C~150 DEG C, obtains the compound MOF-74 of single dispersing cobalt nickel；
The MOF-74Ni after process described in step 3 is 1 with the mass ratio of cobalt nitrate hexahydrate:(1~9)；
The quality of the MOF-74Ni after process described in step 3 is 1g with the volume ratio of solvent III:(10mL~
200mL)。
Beneficial effects of the present invention：
First, technical process of the invention is safe and simple, and without the need for expensive device, and operating process is simple；
2nd, general reaction atom utilization of the present invention is high, and environmental pollution is little；
3rd, the size of single dispersing MOF prepared by the present invention is controllable, and size dispersion is extremely narrow, is easy to prepare with specific use
Sample；
4th, the size of single dispersing MOF prepared by the present invention is 0.5 μm~20 μm；
5th, single dispersing MOF prepared by the present invention overcomes the uneven of catalytic reaction that MOF particle inequalities cause and asks
Topic.
The present invention MOF-74 compound suitable for preparing single dispersing cobalt nickel.
Description of the drawings
Fig. 1 is the SEM figures of the MOF-74Ni after the process that the step 2 of embodiment one is obtained；
Fig. 2 is the SEM figures of the MOF-74Ni after the process that the step 2 of embodiment two is obtained；
Fig. 3 is the SEM figures of the MOF-74Ni after the process that the step 2 of embodiment three is obtained；
The SEM figures of the MOF-74 that Fig. 4 is combined for the single dispersing cobalt nickel that example IV is obtained；
Fig. 5 is the SEM figures of the MOF-74 that the single dispersing cobalt nickel that embodiment five is obtained is combined.
Specific embodiment
Specific embodiment one：Present embodiment is a kind of preparation method of the compound MOF-74 of single dispersing cobalt nickel, be by
What following steps were completed：
First, MOF-74Ni is prepared：
2,5-Dihydroxyterephthalic acid and six water nickel nitrates are dissolved in solvent I, 2,5- dihydroxy is obtained to benzene two
The mixed solution of formic acid and six water nickel nitrates；Add in the mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates
Acetic acid and mass fraction are 1%~30% aqueous povidone solution, obtain reactant liquor；It is in temperature by reactant liquor
12h~72h is reacted at 100 DEG C~180 DEG C, MOF-74Ni is obtained；
2,5- dihydric para-phthalic acids described in step one and 2,5- dihydroxy in the mixed solution of six water nickel nitrates
The concentration of p-phthalic acid is 5mmol/L~30mmol/L；
2,5- dihydric para-phthalic acids described in step one and six water nickel nitrates in the mixed solution of six water nickel nitrates
Concentration be 15mmol/L~90mmol/L；
The mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates described in step one and the volume of acetic acid
Than for 100:(1~5)；
The mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates described in step one is with mass fraction
The volume ratio of 1%~30% aqueous povidone solution is 100:(1~50)；
2nd, the post processing of MOF-74Ni：
The MOF-74Ni that step one is obtained is centrifuged in the case where rotating speed is 3500rpm/min~10000rpm/min, removes
Clear liquid, obtains yellow solid powder；With solvent II as abluent, first by yellow solid powder carry out ultrasonic cleaning 5min~
40min, then with solvent II as abluent, centrifuge washing 3 times~5 times, then temperature be dried at 75 DEG C~150 DEG C 12h~
72h, the MOF-74Ni after being processed；
3rd, the compound MOF of cobalt nickel is prepared：
MOF-74Ni and cobalt nitrate hexahydrate after the process obtained in step 2 is dissolved in solvent III, then is in temperature
2h~40h is reacted respectively under the conditions of 75 DEG C~150 DEG C, obtains the compound MOF-74 of single dispersing cobalt nickel；
The MOF-74Ni after process described in step 3 is 1 with the mass ratio of cobalt nitrate hexahydrate:(1~9)；
The quality of the MOF-74Ni after process described in step 3 is 1g with the volume ratio of solvent III:(10mL~
200mL)。
The beneficial effect of present embodiment：
First, the technical process of present embodiment is safe and simple, and without the need for expensive device, and operating process is simple；
2nd, present embodiment general reaction atom utilization is high, and environmental pollution is little；
3rd, the size of single dispersing MOF prepared by present embodiment is controllable, and size dispersion is extremely narrow, is easy to prepare with special
The sample of purposes；
4th, the size of single dispersing MOF prepared by present embodiment is 0.5 μm~20 μm；
5th, single dispersing MOF prepared by present embodiment overcomes the uneven of the catalytic reaction that MOF particle inequalities cause
Problem.
The present embodiment MOF-74 compound suitable for preparing single dispersing cobalt nickel.
Specific embodiment two：Present embodiment is with the difference of specific embodiment one：Solvent I described in step one
For the one kind in acetone, tetrahydrofuran, methanol, DMAC N,N' dimethyl acetamide, dehydrated alcohol and water or wherein several mixed liquors.
Other steps are identical with specific embodiment one.
Specific embodiment three：Present embodiment is with the difference of specific embodiment one or one of two：Institute in step one
The solvent I stated is acetone, DMAC N,N' dimethyl acetamide and dehydrated alcohol with 1:1:Mixed liquor, water, the N of 1 volume ratio mixing, N-
Dimethyl acetylamide and dehydrated alcohol are with 1:2:The mixed liquor or tetrahydrofuran, DMAC N,N' dimethyl acetamide of 1 volume ratio mixing
With dehydrated alcohol with 1:2:The mixed liquor of 1 volume ratio mixing.Other steps are identical with specific embodiment one or two.
Specific embodiment four：One of present embodiment and specific embodiment one to three difference is：Institute in step 2
The one kind or wherein several mixing of the solvent II stated for ethanol, acetone and water.Other steps and specific embodiment one to three
It is identical.
Specific embodiment five：One of present embodiment and specific embodiment one to four difference is：Institute in step 2
The solvent II stated is acetone, DMAC N,N' dimethyl acetamide and dehydrated alcohol with 1:1:Mixed liquor, water, the N of 1 volume ratio mixing,
N- dimethyl acetylamide and dehydrated alcohol are with 1:2:The mixed liquor or tetrahydrofuran, N of 1 volume ratio mixing, N- dimethylacetamides
Amine and dehydrated alcohol are with 1:2:The mixed liquor of 1 volume ratio mixing.Other steps are identical with specific embodiment one to four.
Specific embodiment six：One of present embodiment and specific embodiment one to five difference is：Institute in step 3
The solvent III stated is the one kind or wherein several in acetone, tetrahydrofuran, methanol, DMAC N,N' dimethyl acetamide, dehydrated alcohol and water
The mixed liquor planted.Other steps are identical with specific embodiment one to five.
Specific embodiment seven：One of present embodiment and specific embodiment one to six difference is：Institute in step 3
The solvent III stated is tetrahydrofuran, DMAC N,N' dimethyl acetamide, dehydrated alcohol and water with 1:2:The mixing of 1 volume ratio mixing
Liquid, DMAC N,N' dimethyl acetamide, dehydrated alcohol and water are with 2:1:The mixed liquor or N, N- dimethylacetamide of 1 volume ratio mixing
Amine, dehydrated alcohol and water are with 1:1:The mixed liquor of 1 volume ratio mixing.Other steps are identical with specific embodiment one to six.
Specific embodiment eight：One of present embodiment and specific embodiment one to seven difference is：Will in step one
Reactant liquor reacts 36h~48h in the case where temperature is for 100 DEG C~105 DEG C, obtains MOF-74Ni.Other steps and specific embodiment
One to seven is identical.
Specific embodiment nine：One of present embodiment and specific embodiment one to eight difference is：Will in step one
Reactant liquor reacts 36h~72h in the case where temperature is for 135 DEG C~180 DEG C, obtains MOF-74Ni.Other steps and specific embodiment
One to eight is identical.
Specific embodiment ten：One of present embodiment and specific embodiment one to nine difference is：In step one to
Acetic acid and mass fraction is added to be 20%~25% in the mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates
Aqueous povidone solution, obtains reactant liquor.Other steps are identical with specific embodiment one to nine.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：A kind of method for preparing MOF-74Ni, is specifically realized by the following steps：
First, 2,5-Dihydroxyterephthalic acid and six water nickel nitrates are dissolved in solvent I, obtain 2,5- dihydroxy to benzene
The mixed solution of dioctyl phthalate and six water nickel nitrates；By the mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates in temperature
Spend to react 36h at 120 DEG C, obtain MOF-74Ni；
2,5- dihydric para-phthalic acids described in step one and 2,5- dihydroxy in the mixed solution of six water nickel nitrates
The concentration of p-phthalic acid is 15mmol/L；
2,5- dihydric para-phthalic acids described in step one and six water nickel nitrates in the mixed solution of six water nickel nitrates
Concentration be 35mmol/L；
Solvent I described in step one is N,N-dimethylacetamide, and dehydrated alcohol and water are with 1:1:1 volume ratio mixing
Mixed liquor；
2nd, post processing：
The MOF-74Ni that step one is obtained is centrifuged in the case where rotating speed is 6500rpm/min, removes supernatant, obtains yellow and consolidates
Body powder；With solvent II as abluent, first yellow solid powder is carried out into ultrasonic cleaning 10min, then with solvent II as abluent,
Centrifuge washing 5 times, then 12h is dried in the case where temperature is for 100 DEG C, the MOF-74Ni after being processed；
Solvent II described in step 2 is water, DMAC N,N' dimethyl acetamide and dehydrated alcohol with 1:2:1 volume ratio is mixed
The mixed liquor or tetrahydrofuran of conjunction.
Fig. 1 is the SEM figures of the MOF-74Ni after the process that the step 2 of embodiment one is obtained；From fig. 1, it can be seen that the step of embodiment one
The spherical nanoparticle that MOF-74Ni after rapid two process for obtaining is made up of multiple little nanocrystals, his divides
Cloth is wider；This is that nucleation site is excessive because MOF resynthesis processes are crossed, the nucleus aggregation for causing, and formed it is uneven
MOF particles, it is unfavorable to the uniformity of performance.
Embodiment two：A kind of method for preparing single dispersing MOF-74Ni, is specifically realized by the following steps：
First, 2,5-Dihydroxyterephthalic acid and six water nickel nitrates are dissolved in solvent I, obtain 2,5- dihydroxy to benzene
The mixed solution of dioctyl phthalate and six water nickel nitrates；Add in the mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates
Enter the aqueous povidone solution that mass fraction is 30%, obtain reactant liquor；Reactant liquor is reacted in the case where temperature is for 135 DEG C
36h, obtains MOF-74Ni；
2,5- dihydric para-phthalic acids described in step one and 2,5- dihydroxy in the mixed solution of six water nickel nitrates
The concentration of p-phthalic acid is 15mmol/L；
2,5- dihydric para-phthalic acids described in step one and six water nickel nitrates in the mixed solution of six water nickel nitrates
Concentration be 35mmol/L；
The mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates described in step one is with mass fraction
The volume ratio of 30% aqueous povidone solution is 100:25；
2nd, post processing：
The MOF-74Ni that step one is obtained is centrifuged in the case where rotating speed is 6500rpm/min, removes supernatant, obtains yellow and consolidates
Body powder；With solvent II as abluent, first yellow solid powder is carried out into ultrasonic cleaning 10min, then with solvent II as abluent,
Centrifuge washing 5 times, then 12h is dried in the case where temperature is for 100 DEG C, the MOF-74Ni after being processed；
Solvent II described in step 2 is water, DMAC N,N' dimethyl acetamide and dehydrated alcohol with 1:2:1 volume ratio is mixed
The mixed liquor or tetrahydrofuran of conjunction.
Fig. 2 is the SEM figures of the MOF-74Ni after the process that the step 2 of embodiment two is obtained；As can be seen from Figure 2, the step of embodiment two
MOF-74Ni after rapid two process for obtaining is spindle-type α-Fe2O3, and his particle size is 3.8 μm, is evenly distributed, and calculates and obtains
Single dispersing index is 4.3%, illustrates that the MOF-74Ni after the process that the step 2 of embodiment two is obtained has fabulous point dispersibility.
The addition of PVP can suppress MOF nucleation, because MOF is along original nucleus growth, therefore can obtain fusiform single dispersing
MOF particles.
Embodiment three：A kind of method for preparing single dispersing MOF-74Ni, is specifically realized by the following steps：
First, 2,5-Dihydroxyterephthalic acid and six water nickel nitrates are dissolved in solvent I, obtain 2,5- dihydroxy to benzene
The mixed solution of dioctyl phthalate and six water nickel nitrates；Add in the mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates
Enter acetic acid and aqueous povidone solution that mass fraction is 30%, obtain reactant liquor, add 0.5m acetic acid solutions；Will
Reactant liquor reacts 36h in the case where temperature is for 135 DEG C, obtains MOF-74Ni；
2,5- dihydric para-phthalic acids described in step one and 2,5- dihydroxy in the mixed solution of six water nickel nitrates
The concentration of p-phthalic acid is 15mmol/L；
2,5- dihydric para-phthalic acids described in step one and six water nickel nitrates in the mixed solution of six water nickel nitrates
Concentration be 35mmol/L；
The mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates described in step one and the volume of acetic acid
Than for 100:2.5；
The mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates described in step one is with mass fraction
The volume ratio of 30% aqueous povidone solution is 100:25；
2nd, post processing：
The MOF-74Ni that step one is obtained is centrifuged in the case where rotating speed is 6500rpm/min, removes supernatant, obtains yellow and consolidates
Body powder；With solvent II as abluent, first yellow solid powder is carried out into ultrasonic cleaning 10min, then with solvent II as abluent,
Centrifuge washing 5 times, then 12h is dried in the case where temperature is for 100 DEG C, the MOF-74Ni after being processed；
Solvent II described in step 2 is water, DMAC N,N' dimethyl acetamide and dehydrated alcohol with 1:2:1 volume ratio is mixed
The mixed liquor of conjunction；
Fig. 3 is the SEM figures of the MOF-74Ni after the process that the step 2 of embodiment three is obtained；As can be seen from Figure 3, acetic acid is MOF-
The crystal face regulator of 74Ni, by the addition of acetic acid the growth curve of MOF can be adjusted, and here acetic acid suppresses MOF-74Ni 100 brilliant
The growth in face, therefore obtain the particle of the MOF for being nano strip.
Example IV：A kind of preparation method of the compound MOF-74 of single dispersing cobalt nickel, is specifically realized by the following steps：
MOF-74Ni the and 4.5g cobalt nitrate hexahydrates prepared in 2.0g embodiments two are dissolved in the solvent III of 100mL,
Again 15h is reacted respectively under conditions of temperature is for 110 DEG C, obtain the compound MOF-74 of single dispersing cobalt nickel；
Described solvent III is DMAC N,N' dimethyl acetamide, dehydrated alcohol and water with 1:1:The mixing of 1 volume ratio mixing
Liquid.
The SEM figures of the MOF-74 that Fig. 4 is combined for the single dispersing cobalt nickel that example IV is obtained；As can be seen from Figure 4, example IV is obtained
The MOF-74 that the single dispersing cobalt nickel for arriving is combined, maintains the original structure of MOF, pattern and the figure of the structure during exchange
2 pattern is similar.
Embodiment five：A kind of preparation method of the compound MOF-74 of single dispersing cobalt nickel, is specifically realized by the following steps：
MOF-74Ni the and 4.5g cobalt nitrate hexahydrates prepared in 2.0g embodiments two are dissolved in into the N of 100mL, N- dimethyl
In acetamide, then 15h is reacted respectively under conditions of temperature is for 110 DEG C, obtain the compound MOF-74 of single dispersing cobalt nickel.
Fig. 5 is the SEM figures of the MOF-74 that the single dispersing cobalt nickel that embodiment five is obtained is combined；As can be seen from Figure 5, embodiment five is obtained
The MOF-74 that the single dispersing cobalt nickel for arriving is combined, maintains the original structure of MOF, pattern and the figure of the structure during exchange
3 pattern is similar.
Knowable to Fig. 1~Fig. 5, PVP can reduce MOF nucleation, and acetic acid is the growth of crystal face regulator energy effective control MOF
Curve, thus using PVP and acetic acid content adjust MOF particles pattern and size, while also can obtain monodispersed
MOF nanoparticles.
Claims (10)
1. the preparation method of the compound MOF-74 of a kind of single dispersing cobalt nickel, it is characterised in that the method is specifically complete according to the following steps
Into：
First, MOF-74Ni is prepared：
2,5-Dihydroxyterephthalic acid and six water nickel nitrates are dissolved in solvent I, 2,5-Dihydroxyterephthalic acid is obtained
With the mixed solution of six water nickel nitrates；Acetic acid is added in the mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates
Aqueous povidone solution with mass fraction is 1%~30%, obtains reactant liquor；By reactant liquor temperature be 100 DEG C
12h~72h is reacted at~180 DEG C, MOF-74Ni is obtained；
2,5- dihydric para-phthalic acids described in step one and in the mixed solution of six water nickel nitrates 2,5- dihydroxy to benzene
The concentration of dioctyl phthalate is 5mmol/L~30mmol/L；
2,5- dihydric para-phthalic acids described in step one and in the mixed solution of six water nickel nitrates six water nickel nitrates it is dense
Spend for 15mmol/L~90mmol/L；
The mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates described in step one is with the volume ratio of acetic acid
100:(1~5)；
The mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates described in step one and mass fraction be 1%~
The volume ratio of 30% aqueous povidone solution is 100:(1~50)；
2nd, the post processing of MOF-74Ni：
The MOF-74Ni that step one is obtained is centrifuged in the case where rotating speed is 3500rpm/min~10000rpm/min, removes supernatant,
Obtain yellow solid powder；With solvent II as abluent, first yellow solid powder is carried out into ultrasonic cleaning 5min~40min, then
With solvent II as abluent, centrifuge washing 3 times~5 times, then 12h~72h is dried in the case where temperature is for 75 DEG C~150 DEG C, obtain everywhere
MOF-74Ni after reason；
3rd, the compound MOF of cobalt nickel is prepared：
MOF-74Ni and cobalt nitrate hexahydrate after the process obtained in step 2 is dissolved in solvent III, then is 75 DEG C in temperature
React 2h~40h under the conditions of~150 DEG C respectively, obtain the compound MOF-74 of single dispersing cobalt nickel；
The MOF-74Ni after process described in step 3 is 1 with the mass ratio of cobalt nitrate hexahydrate:(1~9)；
The quality of the MOF-74Ni after process described in step 3 is 1g with the volume ratio of solvent III:(10mL~200mL).
2. a kind of preparation method of the compound MOF-74 of single dispersing cobalt nickel according to claim 1, it is characterised in that step
Solvent I described in one be acetone, tetrahydrofuran, methanol, DMAC N,N' dimethyl acetamide, dehydrated alcohol and water in one kind or its
In several mixed liquor.
3. a kind of preparation method of the compound MOF-74 of single dispersing cobalt nickel according to claim 1 and 2, it is characterised in that step
Solvent I described in rapid one is acetone, DMAC N,N' dimethyl acetamide and dehydrated alcohol with 1:1:The mixing of 1 volume ratio mixing
Liquid, water, DMAC N,N' dimethyl acetamide and dehydrated alcohol are with 1:2:The mixed liquor or tetrahydrofuran, N of 1 volume ratio mixing, N- bis-
Methylacetamide and dehydrated alcohol are with 1:2:The mixed liquor of 1 volume ratio mixing.
4. a kind of preparation method of the compound MOF-74 of single dispersing cobalt nickel according to claim 1, it is characterised in that step
The one kind or wherein several mixing of solvent II described in two for ethanol, acetone and water.
5. a kind of preparation method of the compound MOF-74 of single dispersing cobalt nickel according to claim 1 or 4, it is characterised in that step
Solvent II described in rapid two is acetone, DMAC N,N' dimethyl acetamide and dehydrated alcohol with 1:1:The mixing of 1 volume ratio mixing
Liquid, water, DMAC N,N' dimethyl acetamide and dehydrated alcohol are with 1:2:The mixed liquor or tetrahydrofuran, N of 1 volume ratio mixing, N- bis-
Methylacetamide and dehydrated alcohol are with 1:2:The mixed liquor of 1 volume ratio mixing.
6. a kind of preparation method of the compound MOF-74 of single dispersing cobalt nickel according to claim 1, it is characterised in that step
Solvent III described in three be acetone, tetrahydrofuran, methanol, DMAC N,N' dimethyl acetamide, dehydrated alcohol and water in one kind or
Wherein several mixed liquors.
7. a kind of preparation method of the compound MOF-74 of single dispersing cobalt nickel according to claim 5, it is characterised in that step
Solvent III described in three is tetrahydrofuran, DMAC N,N' dimethyl acetamide, dehydrated alcohol and water with 1:2:1 volume ratio mixing
Mixed liquor, DMAC N,N' dimethyl acetamide, dehydrated alcohol and water are with 2:1:The mixed liquor or N, N- dimethyl second of 1 volume ratio mixing
Amide, dehydrated alcohol and water are with 1:1:The mixed liquor of 1 volume ratio mixing.
8. a kind of preparation method of the compound MOF-74 of single dispersing cobalt nickel according to claim 1, it is characterised in that step
Reactant liquor is reacted into 36h~48h in the case where temperature is for 100 DEG C~105 DEG C in one, MOF-74Ni is obtained.
9. a kind of preparation method of the compound MOF-74 of single dispersing cobalt nickel according to claim 1, it is characterised in that step
Reactant liquor is reacted into 36h~72h in the case where temperature is for 135 DEG C~180 DEG C in one, MOF-74Ni is obtained.
10. a kind of preparation method of the compound MOF-74 of single dispersing cobalt nickel according to claim 1, it is characterised in that step
Add in the mixed solution of 2,5- dihydric para-phthalic acids and six water nickel nitrates in one acetic acid and mass fraction be 20%~
25% aqueous povidone solution, obtains reactant liquor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611021525.9A CN106674290B (en) | 2016-11-21 | 2016-11-21 | A kind of preparation method for the MOF-74 that monodisperse cobalt nickel is compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611021525.9A CN106674290B (en) | 2016-11-21 | 2016-11-21 | A kind of preparation method for the MOF-74 that monodisperse cobalt nickel is compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106674290A true CN106674290A (en) | 2017-05-17 |
| CN106674290B CN106674290B (en) | 2019-08-23 |
Family
ID=58867539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611021525.9A Active CN106674290B (en) | 2016-11-21 | 2016-11-21 | A kind of preparation method for the MOF-74 that monodisperse cobalt nickel is compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106674290B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107601580A (en) * | 2017-09-22 | 2018-01-19 | 合肥工业大学 | A kind of method for preparing nickel cobalt oxide as presoma by the use of metal organic framework and application thereof |
| CN109701657A (en) * | 2019-01-15 | 2019-05-03 | 大连理工大学 | A kind of synthetic method and its application of MOF-74-NiCo material |
| CN109821540A (en) * | 2019-03-05 | 2019-05-31 | 武汉理工大学 | MOF derived carbon carries the preparation method of non-noble metal alloys catalysts and catalysis produces hydrogen application |
| CN110496604A (en) * | 2019-07-18 | 2019-11-26 | 西安交通大学 | A kind of cobalt nickel bimetal organic frame carbon dioxide adsorbent and the preparation method and application thereof |
| CN113683784A (en) * | 2021-08-30 | 2021-11-23 | 西安理工大学 | Preparation method and application of carbon dioxide adsorbing material with metal organic framework |
| CN114497828A (en) * | 2021-12-24 | 2022-05-13 | 合肥国轩高科动力能源有限公司 | Fusiform Ag/Co3O4Composite material, preparation method thereof and application thereof in lithium air battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104324760A (en) * | 2014-10-09 | 2015-02-04 | 济南大学 | Preparation method and applications of functional coordination polymer |
| CN105037444A (en) * | 2015-06-19 | 2015-11-11 | 哈尔滨工业大学 | Synthetic method of metal organic frameworks Co-MOF-74 |
-
2016
- 2016-11-21 CN CN201611021525.9A patent/CN106674290B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104324760A (en) * | 2014-10-09 | 2015-02-04 | 济南大学 | Preparation method and applications of functional coordination polymer |
| CN105037444A (en) * | 2015-06-19 | 2015-11-11 | 哈尔滨工业大学 | Synthetic method of metal organic frameworks Co-MOF-74 |
Non-Patent Citations (1)
| Title |
|---|
| DENGRONG SUN ET AL.: "Mixed-Metal Strategy on Metal−Organic Frameworks (MOFs) for Functionalities Expansion: Co Substitution Induces Aerobic Oxidation of Cyclohexene over Inactive Ni-MOF-74", 《INORG. CHEM.》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107601580A (en) * | 2017-09-22 | 2018-01-19 | 合肥工业大学 | A kind of method for preparing nickel cobalt oxide as presoma by the use of metal organic framework and application thereof |
| CN109701657A (en) * | 2019-01-15 | 2019-05-03 | 大连理工大学 | A kind of synthetic method and its application of MOF-74-NiCo material |
| CN109701657B (en) * | 2019-01-15 | 2021-06-18 | 大连理工大学 | Synthesis method and application of MOF-74-NiCo material |
| CN109821540A (en) * | 2019-03-05 | 2019-05-31 | 武汉理工大学 | MOF derived carbon carries the preparation method of non-noble metal alloys catalysts and catalysis produces hydrogen application |
| CN110496604A (en) * | 2019-07-18 | 2019-11-26 | 西安交通大学 | A kind of cobalt nickel bimetal organic frame carbon dioxide adsorbent and the preparation method and application thereof |
| CN110496604B (en) * | 2019-07-18 | 2020-10-27 | 西安交通大学 | Cobalt-nickel bimetallic organic framework carbon dioxide adsorption material and preparation method and application thereof |
| CN113683784A (en) * | 2021-08-30 | 2021-11-23 | 西安理工大学 | Preparation method and application of carbon dioxide adsorbing material with metal organic framework |
| CN114497828A (en) * | 2021-12-24 | 2022-05-13 | 合肥国轩高科动力能源有限公司 | Fusiform Ag/Co3O4Composite material, preparation method thereof and application thereof in lithium air battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106674290B (en) | 2019-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106674290A (en) | Preparation method of monodispersed cobalt and nickel composite MOF-74 | |
| CN103771544B (en) | Preparation method of hollow cobaltosic oxide microsphere | |
| CN103920462B (en) | There is the preparation method of the metal-organic framework nano-particle material of meso-hole structure | |
| CN112038648A (en) | Hollow-structure transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof | |
| CN107537571B (en) | Multi-walled carbon nanotube-based noble metal catalyst and preparation method thereof | |
| CN108465489B (en) | Fe3O4@ ZIF-8 core-shell composite material and preparation method and catalytic application thereof | |
| CN108906058B (en) | Non-noble metal catalyst and preparation method thereof | |
| CN111282405A (en) | Modified metal organic framework nanosheet and preparation method thereof | |
| Wang et al. | Au nanoparticle decorated N-containing polymer spheres: additive-free synthesis and remarkable catalytic behavior for reduction of 4-nitrophenol | |
| CN102993221A (en) | Method for preparing nano-zeolite metal-organic framework compounds by microreactor | |
| CN104324761A (en) | Preparation and applications of porous rare earth organic complex base catalyst | |
| CN106866741A (en) | A kind of method of solventless method Fast back-projection algorithm metal-organic framework materials MIL 100 (Cr) | |
| CN104671233A (en) | Preparation method of foam graphene | |
| Yang et al. | A cellulose monolith supported metal/organic framework as a hierarchical porous material for a flow reaction | |
| CN112705167A (en) | Preparation method of MOF (Metal organic framework) modified activated carbon brick and application of MOF modified activated carbon brick in large-air-volume air filtration | |
| CN112341630B (en) | Method for continuously preparing nano metal-organic framework material by using supergravity technology | |
| CN108706568A (en) | A kind of preparation method of N doping Porous hollow carbon Nano capsule material and the material of preparation | |
| CN110639474A (en) | Adsorbent for separating propylene and propane and preparation method thereof | |
| CN114260027B (en) | Method for preparing metal oxide@metal organic framework core-shell material | |
| CN106699550A (en) | Preparation method of nano Cu-CuBTC type metal organic framework material | |
| CN109293937A (en) | A method of tradition ZIF-90 material is prepared using bimetal salt room temperature | |
| CN110776645B (en) | Preparation method of ZIF series metal-organic framework with flower cluster-shaped hierarchical structure | |
| CN112341629B (en) | Method for preparing nano metal-organic framework material by using internal circulation rotating packed bed | |
| CN105413676A (en) | Method for preparing three-dimensional ordered macroporous V-Mg oxide materials and application thereof | |
| CN110152666B (en) | Porous carbon supported copper-based catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210115 Address after: Building 9, accelerator, 14955 Zhongyuan Avenue, Songbei District, Harbin City, Heilongjiang Province Patentee after: INDUSTRIAL TECHNOLOGY Research Institute OF HEILONGJIANG PROVINCE Address before: 150001 No. 92 West straight street, Nangang District, Heilongjiang, Harbin Patentee before: HARBIN INSTITUTE OF TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230223 Address after: 150027 Room 412, Unit 1, No. 14955, Zhongyuan Avenue, Building 9, Innovation and Entrepreneurship Plaza, Science and Technology Innovation City, Harbin Hi tech Industrial Development Zone, Heilongjiang Province Patentee after: Heilongjiang Industrial Technology Research Institute Asset Management Co.,Ltd. Address before: Building 9, accelerator, 14955 Zhongyuan Avenue, Songbei District, Harbin City, Heilongjiang Province Patentee before: INDUSTRIAL TECHNOLOGY Research Institute OF HEILONGJIANG PROVINCE |