CN109876776A - Indium base MOF micro-nano powder and its room temperature preparation method and application - Google Patents
Indium base MOF micro-nano powder and its room temperature preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of metal-organic framework materials, in particular to a kind of indium base MOF micro-nano powder and its preparation method and application, the indium base MOF micro-nano powder passes through using indium nitrate and carboxylic acid as reaction raw materials, water or salt or water and salt are added in the reaction raw materials, especially preferential reaction at room temperature is prepared at 15-45 DEG C.The mild technology of preparing of room temperature of indium base MOF micro-nano powder of the invention operates simplification, abundant classics MOF type, develops its application field and realize that industrial applications are of great significance.
Description
Technical field
The present invention relates to a kind of metal organic framework (MOF) materials, and in particular to one kind passes through the pervasive simple and easy method of room temperature
The indium base MOF material being prepared.
Background technique
Metal organic framework (MOF) material, because pore size Modulatory character, functional duct cause extensively due to the advantages that
Concern.Though MOF is many kinds of, at present micro-nano powder material (such as ZIF, MIL series) quilt of only a small number of classics MOF
It limits its application and develops this is because majority MOF exists usually in the form of bulk crystals applied to photocatalysis field.According to
The preparation of report majority MOF mostly uses hydro-thermal method or solvent-thermal method, and which has limited its development and industrial applications.
Summary of the invention
Technical problem solved by the invention is that the existing method for preparing indium base MOF is mostly hydro-thermal method, solvent-thermal method
With high temperature bath method, present invention aims at regulation experiment parameters, develop the pervasive preparation of room temperature of indium base MOF micro-nano powder
Technology reduces energy consumption.The present invention simplifies the preparation method of indium Base Metal organic backbone (MOF) material, reduces the system of indium base MOF
Energy consumption during standby researches and develops the room temperature preparation that the pervasive preparation method of one kind realizes a variety of indium base MOF micro-nano powders.Tool
For body, in order to solve the above technical problems, The present invention provides following technical solutions:
A kind of indium base MOF micro-nano powder, by using indium nitrate and carboxylic acid as reaction raw materials, in the reaction raw materials
Water or salt or water and salt is added, (preferably room temperature) reaction is prepared at 15-45 DEG C.
For indium base MOF micro-nano powder of the present invention, wherein preferably, the carboxylic acid is selected from polybasic carboxylic acid, institute
Stating polybasic carboxylic acid is preferably one or more of dicarboxylic acids, tricarboxylic acid, quaternary carboxylic acid；It is further preferably described more
First carboxylic acid is selected from terephthalic acid (TPA), 2- amino phthalic acid, 2- nitroterephthalic, 2,5- dihydric para-phthalic acid, 1,
4- naphthalenedicarboxylic acid, 1,1 '-cyclobutane dicarboxylic acids, 1,4- cyclohexane dicarboxylic acid, 1,2,3,4,5,6- hexamethylene hexacarboxylic acid, 4,4 '-
Oxydibenzoic acid, 2,5- thiophene dicarboxylic acid, fumaric acid, 1,2,3,4- butane tetracarboxylic acid, trimesic acid, 1,1 '-ferrocene
Any one of dicarboxylic acids or two kinds or more, the still more preferably described polybasic carboxylic acid be selected from fumaric acid, Isosorbide-5-Nitrae-naphthalenedicarboxylic acid,
Trimesic acid, 2,5- thiophene dicarboxylic acid, 4,4 '-phenylate dioctyl phthalate, 1,1 '-cyclobutane diacid, 1,6- cyclohexane diacid, 1,
2,3,4,5,6- hexamethylene hexacarboxylic acids, 1,2,3,4- butane tetracarboxylic acid, 1,1 '-ferrocene dicarboxylic acid；The salt is selected from formic acid
One of sodium, sodium acetate, sodium propionate or sodium fluoride or two kinds or more, are preferably selected from sodium formate, sodium propionate or sodium fluoride
One or two or more kinds；Further preferably it is selected from sodium fluoride.
For indium base MOF micro-nano powder of the present invention, wherein preferably, being additionally added in the reaction raw materials
Solvent is reacted；Preferably, the organic solvent is selected from alcohols solvent or amide solvent；Further preferably selected from methanol,
Ethyl alcohol, propyl alcohol, butanol, N, one or more of N- dimethylformamide acetamide, n,N-Dimethylformamide, further preferably
For N,N-dimethylformamide.
For indium base MOF micro-nano powder of the present invention, wherein preferably, by the inclusion of the method for following step
It obtains: indium nitrate plus water being formed into indium nitrate aqueous solution, which are added to the organic solvent solution of carboxylic acid
In, it is prepared at 15-30 DEG C.
For indium base MOF micro-nano powder of the present invention, wherein preferably, the organic solvent solution of the carboxylic acid
Middle addition has salt.
The present invention also provides the preparation methods of indium base MOF micro-nano powder above-mentioned, which is characterized in that the preparation method
Including following preparation steps:
1) it configures carboxylic acid solution: carboxylic acid is dissolved in organic solvent (preferably n,N-Dimethylformamide), it is anti-to form carboxylic acid
Answer solution；
2) nitric acid solution of indium is configured；
3) the nitric acid solution of indium that step 2) obtains is incorporated in the carboxylic acid solution that step 1) obtains, 15-45 DEG C, preferably
After 15-30 DEG C DEG C is reacted, separation is dried to obtain indium base MOF micro Nano material；
Wherein, salt is added in step 1) and forms carboxylic acid reaction solution；And/or water is added in step 2), form nitric acid
Indium aqueous solution.
For preparation method of the present invention, wherein preferably, organic solvent being added in step 1) and salt forms carboxylic
Sour reaction solution, and water is added in step 2) and forms indium nitrate aqueous solution.
For preparation method of the present invention, wherein preferably, addition organic solvent is not added salt and is formed in step 1)
Carboxylic acid reaction solution, and water is added in step 2) and forms indium nitrate aqueous solution.
For preparation method of the present invention, wherein preferably, organic solvent being added in step 1) and salt is added to form carboxylic
Sour reaction solution, and organic solvent is added in step 2) and forms nitric acid solution of indium.
For preparation method of the present invention, wherein preferably, in step 1), when forming carboxylic acid solution, carboxylic acid with
Mmol meter, for salt in terms of mg, the mass ratio of carboxylic acid and salt is 2:45-100, preferably 2:45-60；
When step 2) forms nitric acid solution of indium, indium nitrate is counted according to mmol, and water is counted according to mL, and the two ratio is 2:5-2:
10；Alternatively, indium nitrate is counted according to mmol, organic solvent is counted according to mL, and the two ratio is 2:5-2:10.
For preparation method of the present invention, wherein preferably, in step 1), when forming carboxylic acid solution, carboxylic acid according to
Mmol meter, organic solvent are counted according to mL, and the usage ratio of carboxylic acid and organic solvent is 2:20-2:30, preferably 2:25-2:30.
For preparation method of the present invention, wherein preferably, the indium base MOF material be MIL-68 (In) or
Person's amino MIL-68 (In).
The present invention also provides the indium base MOF micro-nano powders that aforementioned any preparation method obtains.
The present invention also provides application of the indium base MOF micro-nano powder above-mentioned in adsorbent or photocatalytic product.
The present invention is mostly hydro-thermal method, solvent-thermal method and high temperature bath method, hair for the existing method for preparing indium base MOF
The temperature of indium base MOF micro-nano powder has been opened up down to the mild technology of preparing of room temperature, operation has not only been enormously simplified, also makes
The MOF material particle size of preparation becomes smaller, and improves specific surface area, so as to improve adsorptivity, this to abundant classics MOF type,
Develop its application field and realizes that industrial applications are of great significance.Therefore one kind is provided by means of the present invention in room
The lower preparation of temperature has the pervasive technology of preparing of the indium base MOF micro-nano powder of specific morphology, with easy to operate, low energy consumption, nothing
Need special reaction device.
Detailed description of the invention
Fig. 1 is the XRD figure of the MIL-68 micro-nano powder prepared under 1,3,4,5.6,7 different condition of embodiment；
NH prepared by Fig. 2 embodiment 8,9 and 102The XRD diagram of-MIL-68 micro-nano powder；
Fig. 3 a is the XRD diagram of indium base MOF micro-nano powder and respective ligand prepared by embodiment 11；
Fig. 3 b is the XRD diagram of indium base MOF micro-nano powder and respective ligand prepared by embodiment 12；
Fig. 3 c is the XRD diagram of indium base MOF micro-nano powder and respective ligand prepared by embodiment 13；
Fig. 3 d is the XRD diagram of indium base MOF micro-nano powder and respective ligand prepared by embodiment 14；
Fig. 3 e is the XRD diagram of indium base MOF micro-nano powder and respective ligand prepared by embodiment 15；
Fig. 3 f is the XRD diagram of indium base MOF micro-nano powder and respective ligand prepared by embodiment 16；
Fig. 3 g is the XRD diagram of indium base MOF micro-nano powder and respective ligand prepared by embodiment 17；
Fig. 3 h is the XRD diagram of indium base MOF micro-nano powder and respective ligand prepared by embodiment 18；
Fig. 3 i is the XRD diagram of indium base MOF micro-nano powder and respective ligand prepared by embodiment 19；
Fig. 3 j is the XRD diagram of indium base MOF micro-nano powder and respective ligand prepared by embodiment 20；
Fig. 3 k is the XRD diagram of indium base MOF micro-nano powder and respective ligand prepared by embodiment 21；
Fig. 3 l is the XRD diagram of indium base MOF micro-nano powder and respective ligand prepared by embodiment 22；
Fig. 4 a is that the electromicroscopic photograph SEM of MIL-68 (In) micro Nano material of embodiment 1 (5ml water) preparation schemes (times magnification
Number is 10k)；
Fig. 4 b is the electromicroscopic photograph SEM figure (amplification of MIL-68 (In) micro Nano material of embodiment 2 (10ml water) preparation
Multiple is 10k)；
Fig. 5 a is rodlike MIL-68 (In) micro-nano material of embodiment 4 (25 DEG C are reacted 24 hours, 50mg NaAc) preparation
The electromicroscopic photograph SEM of material schemes (amplification factor 10k)；
Fig. 5 b is rodlike MIL-68 (In) micro-nano material of embodiment 4A (90 DEG C are reacted 2 hours, 50mg NaAc) preparation
The electromicroscopic photograph SEM of material schemes (amplification factor 10k)；
Fig. 6 a is the Electronic Speculum of rodlike MIL-68 (In) micro Nano material of embodiment 6 (50mg NaF) preparation
Photo SEM schemes (amplification factor 5k)；
Fig. 6 b is the Electronic Speculum of rodlike MIL-68 (In) micro Nano material of embodiment 6A (100mg NaF) preparation
Photo SEM schemes (amplification factor 5k)；
Fig. 7 a is that (amplification factor is for the electromicroscopic photograph SEM figure of rodlike MIL-68 micro Nano material prepared by embodiment 7
10k)；
Fig. 7 b is rodlike NH prepared by embodiment 102The electromicroscopic photograph SEM figure of-MIL-68 micro Nano material (is put
Big multiple is 10k)；
Fig. 8 a is that the indium base MOF micro-nano powder SEM of embodiment 11 (2- nitroterephthalic) preparation schemes (times magnification
Number is 10k)；
Fig. 8 b is that the indium base MOF micro-nano powder SEM figure of embodiment 12 (2,5- dihydric para-phthalic acid) preparation (is put
Big multiple is 10k)；
Fig. 8 c is that (amplification factor is for the indium base MOF micro-nano powder SEM figure of embodiment 13 (1,4- naphthalenedicarboxylic acid) preparation
10k)；
Fig. 8 d is the indium base MOF micro-nano powder SEM figure of embodiment 14 (1,2,3,4,5,6- hexamethylene hexacarboxylic acid) preparation
(amplification factor 10k)；
Fig. 8 e is that the indium base MOF micro-nano powder SEM of embodiment 15 (1,4- cyclohexane dicarboxylic acid) preparation schemes (times magnification
Number is 30k)；
Fig. 8 f is that the indium base MOF micro-nano powder SEM of embodiment 16 (1,1 '-cyclobutane dicarboxylic acid) preparation schemes (times magnification
Number is 10k)；
Fig. 8 g is that the indium base MOF micro-nano powder SEM of embodiment 17 (4,4 '-oxydibenzoic acid) preparation schemes (times magnification
Number is 10k)；
Fig. 8 h is that the indium base MOF micro-nano powder SEM of embodiment 18 (2,5- thiophene dicarboxylic acid) preparation schemes (amplification factor
For 10k)；
Fig. 8 i is the indium base MOF micro-nano powder SEM figure (amplification of embodiment 19 (1,2,3,4- butane tetracarboxylic acid) preparation
Multiple is 50k)；
Fig. 8 j is the SEM figure (amplification of the indium base MOF micro-nano powder of embodiment 20 (1,1 '-ferrocenedicarboxylic acid) preparation
Multiple is 20k)；
Fig. 8 k is that the indium base MOF micro-nano powder SEM of embodiment 21 (fumaric acid) preparation schemes (amplification factor 5k)；
Fig. 8 l is that (amplification factor is for the indium base MOF micro-nano powder SEM figure of embodiment 22 (trimesic acid) preparation
10k)。
Specific embodiment
A kind of MOF of the MIL-68 (In) as classics, micro-nano powder is usually with n,N-Dimethylformamide (DMF)
For reaction dissolvent, could be obtained under 90 DEG C of hot conditions.The existing method for preparing indium base MOF is mostly hydro-thermal method, solvent
Thermal method and high temperature bath method, therefore, the mild technology of preparing for developing indium base MOF micro-nano powder are a problem to be solved, this
To simplified operation, abundant classics MOF type, develops its application field and realize that industrial applications are of great significance.
The inventors discovered that in the reaction system of MIL-68 (In) micro-nano powder, in carboxylic acid solution especially carboxylic acid
The organic solvent solutions such as DMF in indium nitrate organic solvent solution or aqueous solution is added its reaction temperature can be reduced to room
Uniform club shaped structure is presented in temperature, obtained micro-nano powder.In addition, inventor's discovery is in MIL-68 (In) micro-nano powder
Reaction system in, the salt such as sodium formate, sodium acetate, sodium propionate and sodium fluoride are added in carboxylic acid organic solvent solution can also will
Its reaction temperature is reduced to room temperature.Amination MIL-68 (NH can also successfully be prepared at room temperature in this way2-MIL-
68).Then, this method is applied in the room temperature preparation of other indium base MOF micro-nano powders by we, finds 2- nitro pair
Phthalic acid, 2,5- dihydric para-phthalic acid, 1,4- naphthalenedicarboxylic acid, 1,2,3,4,5,6- hexamethylene hexacarboxylic acid, 1,4- ring
Hexane dicarboxylic acid, 1,1 '-cyclobutane dicarboxylic acids, 4,4 '-oxydibenzoic acids, 2,5- thiophene dicarboxylic acid, 1,2,3,4- butane four
Carboxylic acid, 1,1 '-ferrocenedicarboxylic acids, fumaric acid, trimesic acid these organic ligands can form regular appearance and with indium
Even MOF micro-nano powder, especially, fumaric acid, Isosorbide-5-Nitrae-naphthalenedicarboxylic acid, trimesic acid, 2,5- thiophene dicarboxylic acid, 4,4 '-
Phenylate dioctyl phthalate, 1,1 '-cyclobutane diacid, 1,6- cyclohexane diacid, 1,2,3,4,5,6- hexamethylene hexacarboxylic acid, 1,2,3,4-
Butane tetracarboxylic acid, 1,1 '-ferrocene dicarboxylic acid these organic ligands can prepare indium base MOF micro-nano powder with indium room temperature.
Specifically, 2 schemes for preparing indium base MOF material of the prior art most similar with the present invention are as follows:
1. preparing indium base MOF under high-temperature and high-pressure conditions using hydro-thermal method or solvent-thermal method；
2. preparing indium base MOF micro-nano powder under the conditions of high temperature (90 DEG C) using immersion method.
For the present inventor after sharp study, designing for the first time and have developed one kind can be at 15-45 DEG C preferably 20-25 DEG C
Room temperature or room temperature under prepare the pervasive schemes of a variety of indium base MOF micro-nano powders, key means are:
(1) using indium nitrate and terephthalic acid (TPA) as reactant, DMF is primary solvent, by individually adding water for example with nitre
Sour indium aqueous solution form addition, the mode individually added salt while adding salt and the addition of indium nitrate aqueous solution form can be in rooms
The rodlike MIL-68 micro-nano powder that partial size becomes smaller, specific surface area increases, adsorptivity greatly improves is prepared under temperature；
(2) using indium nitrate and 2- amino terephthalic acid (TPA) as reactant, DMF is primary solvent, by individually adding nitric acid
Indium aqueous solution, the mode individually added salt, add salt and indium nitrate aqueous solution simultaneously can prepare that partial size is small, ratio at room temperature
The rodlike NH that surface area is big, adsorptivity is excellent2- MIL-68 micro-nano powder；(3) using DMF as primary solvent, by adding water
It may make fumaric acid, 1,4- naphthalenedicarboxylic acid, trimesic acid, 2,5- thiophene dicarboxylic acid, 4,4 '-phenylate diformazans with the mode of salt
Acid, 1,1 '-cyclobutane diacid, 1,6- cyclohexane diacid, 1,2,3,4,5,6- hexamethylene hexacarboxylic acid, 1,2,3,4- butane tetracarboxylic
Acid, this 10 kinds of organic ligands of 1,1 '-ferrocene dicarboxylic acid can react with indium nitrate at room temperature and obtain that partial size is small, compares table
Area is big, the indium base MOF micro-nano powder excellent with specific morphology adsorptivity.
The room temperature universal method for preparing indium base MOF micro-nano powder of the invention is illustrated below by embodiment.
Wherein, SEM instrument used when the SEM photograph of indium base MOF micro-nano powder is measured used in embodiment 1-22
Type number are as follows: SU8020 field emission scanning electron microscope.
Measure instrument model used in indium base MOF micro-nano powder XRD: the great member DX-2700B type X-ray powder in Dandong spreads out
Instrument is penetrated, test condition is as follows: Cu target, sweep spacing: 0.02o, scanning range: 5-50 degree.
Embodiment
Embodiment 1:
(1) configuration of solution A: 2mmol terephthalic acid (TPA) is dissolved in 25mL n,N-Dimethylformamide (DMF), is stirred
10min is mixed, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, obtain rodlike MIL-68 (In) micro Nano material, (amplification of electromicroscopic photograph as shown in fig. 4 a of the electromicroscopic photograph of the material
Multiple is 10k), XRD diagram is as shown in Figure 1.In Fig. 1, standard MIL-68 refers to the XRD structure of known standard items MIL-68,
As seen from Figure 1, the indium base at the XRD diffractive features peak with standard items has successfully been prepared in the embodiment of the present invention
MIL-68。
Embodiment 2:
(1) configuration of solution A: 2mmol terephthalic acid (TPA) is dissolved in 20mL n,N-Dimethylformamide (DMF), is stirred
10min is mixed, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 10mL water and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, obtain rodlike MIL-68 (In) micro Nano material, the electromicroscopic photograph (amplification of electromicroscopic photograph as shown in Figure 4 b of the material
Multiple is 10k).
It can be seen from Fig. 4 b and Fig. 4 a in the method for the invention, the water of addition is more, and material morphology is more uneven.
When inventor shows to prepare indium nitrate aqueous solution after studying repeatedly, the water of addition cannot be too many, can make too much
The material morphology that must be prepared is undesirable, and especially the water needed for 2mmol indium nitrate is no more than 10mL, when being more than,
Pattern defect is more than ideal value, is deteriorated.
Embodiment 3:
(1) configuration of solution A: 2mmol terephthalic acid (TPA) is dissolved in 25mL n,N-Dimethylformamide (DMF), is stirred
10min is mixed, 50mg sodium formate is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mLDMF and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, rodlike MIL-68 (In) micro Nano material is obtained, XRD diagram is as shown in Fig. 1.In Fig. 1, standard MIL-68 refers to known
Standard items MIL-68 XRD structure, it can be seen from Fig. 1 the embodiment of the present invention be successfully prepared have standard items
XRD diffractive features peak indium base MIL-68.
Embodiment 4:
(1) configuration of solution A: 2mmol terephthalic acid (TPA) is dissolved in 25mL n,N-Dimethylformamide (DMF), is stirred
10min is mixed, 50mg sodium acetate is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL DMF and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, obtain rodlike MIL-68 (In) micro Nano material, the electromicroscopic photograph of the micro Nano material (electromicroscopic photograph as shown in Figure 5 a
Amplification factor 10k), XRD diagram is as shown in Figure 1.In Fig. 1, standard MIL-68 refers to the XRD knot of known standard items MIL-68
The indium base at the XRD diffractive features peak with standard items has successfully been prepared in structure, as seen from Figure 1, the embodiment of the present invention
MIL-68。
Embodiment 4A:
(1) configuration of solution A: 2mmol terephthalic acid (TPA) is dissolved in 25mL n,N-Dimethylformamide (DMF), is stirred
10min is mixed, 50mg sodium acetate is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL DMF and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react 2h at 90 DEG C of temperature, be centrifuged, ethanol washing 2 times,
It is dry, rodlike MIL-68 (In) micro Nano material is obtained, the electromicroscopic photograph of the micro Nano material as shown in Figure 5 b (put by electromicroscopic photograph
Big multiple is 10k).
After Fig. 5 a and Fig. 5 b are compared, it can be seen that can be prepared at room temperature by means of the present invention
Partial size is obviously smaller than micro Nano material prepared by 90 DEG C of reactions, and particle size is at least the micro-nano materials of 90 DEG C of reaction preparations
The half of material；Wherein, micro Nano material granularity described in Fig. 5 a is 250nm*1500nm；Micro Nano material grain described in Fig. 5 b
Degree is 500nm*3000nm.
Embodiment 5:
(1) configuration of solution A: 2mmol terephthalic acid (TPA) is dissolved in 25mL n,N-Dimethylformamide (DMF), is stirred
10min is mixed, 50mg sodium propionate is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL DMF and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, rodlike MIL-68 (In) micro Nano material is obtained, XRD diagram is as shown in Fig. 1.In Fig. 1, standard MIL-68 refers to known
Standard items MIL-68 XRD structure, it can be seen from Fig. 1 the embodiment of the present invention be successfully prepared have standard items
XRD diffractive features peak indium base MIL-68.
Embodiment 6:
(1) configuration of solution A: 2mmol terephthalic acid (TPA) is dissolved in 25mL n,N-Dimethylformamide (DMF), is stirred
10min is mixed, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mLDMF and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, obtain rodlike MIL-68 (In) micro Nano material, (electromicroscopic photograph amplification factor is electromicroscopic photograph as shown in figure Fig. 6 a
5k), XRD diagram is as shown in Figure 1.
Embodiment 6A:
(1) configuration of solution A: 2mmol terephthalic acid (TPA) is dissolved in 25mL n,N-Dimethylformamide (DMF), is stirred
10min is mixed, 100mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mLDMF and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, obtain rodlike MIL-68 (In) micro Nano material, (electromicroscopic photograph amplification factor is electromicroscopic photograph as shown in figure Fig. 6 b
5k)。
The additive amount of NaF has substantially no effect on prepared MIL-68 (In) micro-nano material it can be seen from Fig. 6 a and Fig. 6 b
The pattern of material.
Embodiment 7:
(1) configuration of solution A: 2mmol terephthalic acid (TPA) is dissolved in 25mL n,N-Dimethylformamide (DMF), is stirred
10min is mixed, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, obtain rodlike MIL-68 (In) micro Nano material, (electromicroscopic photograph amplification factor is electromicroscopic photograph as shown in Figure 7a
10k), XRD diagram is as shown in Figure 1.In Fig. 1, standard MIL-68 refers to the XRD structure of known standard items MIL-68, by Fig. 1
As can be seen that the indium base MIL-68 at the XRD diffractive features peak with standard items has successfully been prepared in the embodiment of the present invention.
Embodiment 8:
(1) 2mmol 2- amino terephthalic acid (TPA) the configuration of solution A: is dissolved in 25mL N,N-dimethylformamide
(DMF) in, 10min is stirred, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, at 40 DEG C of temperature, is persistently stirred to react for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, obtain rodlike NH2- MIL-68 (In) micro Nano material；Its XRD diagram is as shown in Figure 2.In Fig. 2, standard MIL-68 refers to
The XRD structure of known standard items MIL-68, as seen from Figure 2, the embodiment of the present invention, which has successfully been prepared, has mark
The indium base MIL-68 at the XRD diffractive features peak of quasi- product.
Embodiment 9:
(1) 2mmol 2- amino terephthalic acid (TPA) the configuration of solution A: is dissolved in 25mL N,N-dimethylformamide
(DMF) in, 10min is stirred, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL DMF and forms uniform solution；
(3) solution B is poured into solution A, at 40 DEG C of temperature, is persistently stirred to react for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, obtain rodlike NH2- MIL-68 (In) micro Nano material；Its XRD diagram is as shown in Figure 2.In Fig. 2, standard MIL-68 refers to
The XRD structure of known standard items MIL-68, as seen from Figure 2, the embodiment of the present invention, which has successfully been prepared, has mark
The indium base MIL-68 at the XRD diffractive features peak of quasi- product.
Embodiment 10:
(1) 2mmol 2- amino terephthalic acid (TPA) the configuration of solution A: is dissolved in 25mL N,N-dimethylformamide
(DMF) in, 10min is stirred, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, at 40 DEG C of temperature, is persistently stirred to react for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, obtain rodlike NH2- MIL-68 (In) micro Nano material, electromicroscopic photograph SEM figure are as shown in Figure 7b；Its XRD diagram is as schemed
Shown in 2.In Fig. 2, standard MIL-68 refers to the XRD structure of known standard items MIL-68, as seen from Figure 2, of the invention
The indium base MIL-68 at the XRD diffractive features peak with standard items has successfully been prepared in embodiment.
Embodiment 11:
(1) 2mmol 2- nitroterephthalic the configuration of solution A: is dissolved in 25mL N,N-dimethylformamide
(DMF) in, 10min is stirred, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, indium base MOF micro-nano powder (being named as BUC-101) is obtained, electromicroscopic photograph is as shown in Figure 8 a；Its XRD diagram is as schemed
Shown in 3a.
Embodiment 12:
(1) 2mmol 2,5- dihydric para-phthalic acid the configuration of solution A: is dissolved in 25mL N, N- dimethylformamide
(DMF) in, 10min is stirred, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, indium base MOF micro-nano powder (being named as BUC-102) is obtained, electromicroscopic photograph is as shown in Figure 8 b；Its XRD diagram is as schemed
Shown in 3b.
Embodiment 13:
(1) configuration of solution A: 2mmol Isosorbide-5-Nitrae-naphthalenedicarboxylic acid is dissolved in 25mL n,N-Dimethylformamide (DMF),
10min is stirred, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, indium base MOF micro-nano powder (being named as BUC-103) is obtained, electromicroscopic photograph is as shown in Figure 8 c；Its XRD diagram is as schemed
Shown in 3c.
Embodiment 14:
(1) 2mmol 1,2,3,4,5,6- hexamethylene hexacarboxylic acid the configuration of solution A: is dissolved in 25mL N, N- dimethyl methyl
In amide (DMF), 10min is stirred, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, indium base MOF micro-nano powder (being named as BUC-104) is obtained, electromicroscopic photograph is as shown in figure 8d；Its XRD diagram is as schemed
Shown in 3d.
Embodiment 15:
(1) 2mmol 1,4- cyclohexane dicarboxylic acid the configuration of solution A: is dissolved in 25mL N,N-dimethylformamide
(DMF) in, 10min is stirred, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, indium base MOF micro-nano powder (being named as BUC-105) is obtained, electromicroscopic photograph is as figure 8 e shows；Its XRD diagram is as schemed
Shown in 3e.
Embodiment 16:
(1) 2mmol 1,1 '-cyclobutane dicarboxylic acid the configuration of solution A: is dissolved in 25mL N,N-dimethylformamide
(DMF) in, 10min is stirred, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, indium base MOF micro-nano powder (being named as BUC-106) is obtained, electromicroscopic photograph is as illustrated in fig. 8f；Its XRD diagram is as schemed
Shown in 3f.
Embodiment 17:
(1) 2mmol 4,4 '-oxydibenzoic acid the configuration of solution A: is dissolved in 25mL N,N-dimethylformamide
(DMF) in, 10min is stirred, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, indium base MOF micro-nano powder (being named as BUC-107) is obtained, electromicroscopic photograph is as illustrated in fig.8g；Its XRD diagram is as schemed
Shown in 3g.
Embodiment 18:
(1) 2mmol 2,5- thiophene dicarboxylic acid the configuration of solution A: is dissolved in 25mL N,N-dimethylformamide (DMF)
In, 10min is stirred, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, indium base MOF micro-nano powder (being named as BUC-108) is obtained, electromicroscopic photograph is as shown in Fig. 8 h；Its XRD diagram is as schemed
Shown in 3h.
Embodiment 19:
(1) 2mmol 1,2,3,4- butane tetracarboxylic acid the configuration of solution A: is dissolved in 25mL N,N-dimethylformamide
(DMF) in, 10min is stirred, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, indium base MOF micro-nano powder (being named as BUC-109) is obtained, electromicroscopic photograph is as illustrated in fig. 8i；Its XRD diagram is as schemed
Shown in 3i.
Embodiment 20:
(1) 2mmol 1,1 '-ferrocenedicarboxylic acid the configuration of solution A: is dissolved in 25mL N,N-dimethylformamide
(DMF) in, 10min is stirred, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, indium base MOF micro-nano powder (being named as BUC-110) is obtained, electromicroscopic photograph is as shown in Fig. 8 j；Its XRD diagram is as schemed
Shown in 3j.
Embodiment 21:
(1) configuration of solution A: 2mmol fumaric acid is dissolved in 25mL n,N-Dimethylformamide (DMF), stirring
50mg sodium fluoride is added in 10min thereto, spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, is persistently stirred to react at 25 DEG C of temperature for 24 hours, centrifugation, ethanol washing 2
It is secondary, it is dry, indium base MOF micro-nano powder (being named as BUC-111) is obtained, electromicroscopic photograph is as shown in Fig. 8 k；Its XRD diagram is as schemed
Shown in 3k.
Embodiment 22:
(1) configuration of solution A: 2mmol trimesic acid is dissolved in 25mL n,N-Dimethylformamide (DMF), is stirred
10min is mixed, 50mg sodium fluoride is added thereto, it is spare；
(2) configuration of solution B: 2mmol indium nitrate is dissolved in 5mL water and forms uniform solution；
(3) solution B is poured into solution A, be persistently stirred to react at 25 DEG C of temperature (pair) 24 h, centrifugation, ethyl alcohol
Washing 2 times, it is dry, indium base MOF micro-nano powder (being named as BUC-112) is obtained, electromicroscopic photograph is as shown in Fig. 8 l；Its XRD diagram
As shown in Fig. 3 l.
Indium base MOF pattern in embodiment 11-22 is different, the difference of this pattern can be attributed to different carboxylic acids ligand with
The difference of the coordination mode of indium.
The XRD diffraction spectrogram of each acid used in embodiment 11-22 and made is respectively illustrated in Fig. 3 a- Fig. 3 l
The XRD diffraction spectrogram of standby indium base MOF micro-nano powder, it can be seen that each embodiment through the invention is successfully prepared into
Each indium base MOF micro-nano powder with typical XRD diffractive features peak is arrived.
Each SEM photograph of Fig. 8 a- Fig. 8 l shows indium base MOF micro-nano powder prepared in embodiment 11-22
SEM figure, prepared indium base MOF micro-nano powder is rodlike structure, can be used as absorption it can be seen from these figures
The excellent materials'use of property.
It can be seen that 8a, 8c, 8e, 8g, 8k is club shaped structure by Fig. 8 a- Fig. 8 l；8d, 8f, 8h, 8j, 8l are laminated structure；
8i is spherical particle shape；8b pattern is irregular.
Claims (14)
1. a kind of indium base MOF micro-nano powder, by being added in the reaction raw materials using indium nitrate and carboxylic acid as reaction raw materials
Water or salt or water and salt, react at 15-45 DEG C and are prepared.
2. indium base MOF micro-nano powder according to claim 1, the carboxylic acid is polybasic carboxylic acid, and the polybasic carboxylic acid is excellent
It is selected as one or more of dicarboxylic acids, tricarboxylic acid, quaternary carboxylic acid；Further preferably it is selected from terephthalic acid (TPA), 2- aminobenzene
Dioctyl phthalate, 2- nitroterephthalic, 2,5- dihydric para-phthalic acid, 1,4- naphthalenedicarboxylic acid, 1,1 '-cyclobutane dicarboxylic acids,
1,4- cyclohexane dicarboxylic acid, 1,2,3,4,5,6- hexamethylene hexacarboxylic acid, 4,4 '-oxydibenzoic acids, 2,5- thiophene dicarboxylic acid, richness
Horse acid, 1,2,3,4- butane tetracarboxylic acid, trimesic acid, 1, any one of 1 '-ferrocenedicarboxylic acid or two kinds or more, into one
Step is preferably selected from fumaric acid, 1,4- naphthalenedicarboxylic acid, trimesic acid, 2,5- thiophene dicarboxylic acid, 4,4 '-phenylate dioctyl phthalate, 1,1 '-
Cyclobutane diacid, 1,6- cyclohexane diacid, 1,2,3,4,5,6- hexamethylene hexacarboxylic acids, 1,2,3,4- butane tetracarboxylic acid, 1,1 '-two
Luxuriant iron dioctyl phthalate；The salt is selected from one of sodium formate, sodium acetate, sodium propionate or sodium fluoride or two kinds or more, is preferably selected from
One of sodium formate, sodium propionate or sodium fluoride or two kinds or more；Further preferably it is selected from sodium fluoride.
3. indium base MOF micro-nano powder according to claim 1 or 2, wherein be additionally added in the reaction raw materials organic molten
Agent is reacted；Preferably, the organic solvent is selected from alcohols solvent or amide solvent；Further preferably selected from methanol, ethyl alcohol,
Propyl alcohol, butanol, N, one or more of N- dimethylformamide acetamide, n,N-Dimethylformamide, further preferably N, N-
Dimethylformamide.
4. indium base MOF micro-nano powder according to claim 1-3, obtains by the inclusion of the method for following step
It arrives: indium nitrate plus water being formed into indium nitrate aqueous solution, which are added in the organic solvent solution of dicarboxylic acids,
It is prepared at 15-30 DEG C.
5. indium base MOF micro-nano powder according to claim 4, wherein be added in the organic solvent solution of the carboxylic acid
There is salt.
6. the preparation method of the described in any item indium base MOF micro-nano powders of claim 1-3, which is characterized in that the preparation side
Method includes following preparation steps:
1) it configures carboxylic acid solution: carboxylic acid is dissolved in organic solvent (preferably n,N-Dimethylformamide), it is molten to form carboxylic acid reaction
Liquid；
2) nitric acid solution of indium is configured；
3) the nitric acid solution of indium that step 2) obtains is incorporated in the carboxylic acid solution that step 1) obtains, 15-45 DEG C, preferably 15-30
After DEG C being reacted, separation is dried to obtain indium base MOF micro Nano material；
Wherein, salt is added in step 1) and forms carboxylic acid reaction solution；And/or water is added in step 2), form indium nitrate water
Solution.
7. preparation method according to claim 6, wherein organic solvent is added in step 1) and salt forms carboxylic acid reaction
Solution, and water is added in step 2) and forms indium nitrate aqueous solution.
8. preparation method according to claim 6, wherein it is anti-that salt formation carboxylic acid is not added in addition organic solvent in step 1)
Solution is answered, and water is added in step 2) and forms indium nitrate aqueous solution.
9. preparation method according to claim 6, wherein organic solvent is added in step 1) and salt is added to form carboxylic acid reaction
Solution, and organic solvent is added in step 2) and forms nitric acid solution of indium.
10. according to the described in any item preparation methods of claim 6-9, wherein in step 1), when forming carboxylic acid solution, carboxylic acid with
Mmol meter, for salt in terms of mg, the ratio of carboxylic acid and salt is 2:45-100, preferably 2:45-60；
When step 2) forms nitric acid solution of indium, indium nitrate is counted according to mmol, and water is counted according to mL, and the two ratio is 2:5-2:10；Or
Person, indium nitrate are counted according to mmol, and organic solvent is counted according to mL, and the two ratio is 2:5-2:10.
11. according to the described in any item preparation methods of claim 4-8, wherein in step 1), when forming carboxylic acid solution, carboxylic acid
It is counted according to mmol, organic solvent is counted according to mL, and the usage ratio of carboxylic acid and organic solvent is 2:20-2:30, preferably 2:25-2:
30。
12. according to the described in any item preparation methods of claim 4-10, wherein the indium base MOF material is MIL-68
(In) or amino MIL-68 (In).
13. the indium base MOF micro-nano powder that any one of the claim 6-12 preparation method obtains.
14. indium base MOF micro-nano powder described in any one of claim 1-5 or claim 13 is produced in adsorbent or photocatalysis
Application in product.
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