CN101734653B - Method for preparing graphite oxide-based aperture adjustable nano porous material - Google Patents
Method for preparing graphite oxide-based aperture adjustable nano porous material Download PDFInfo
- Publication number
- CN101734653B CN101734653B CN2008102260243A CN200810226024A CN101734653B CN 101734653 B CN101734653 B CN 101734653B CN 2008102260243 A CN2008102260243 A CN 2008102260243A CN 200810226024 A CN200810226024 A CN 200810226024A CN 101734653 B CN101734653 B CN 101734653B
- Authority
- CN
- China
- Prior art keywords
- graphite oxide
- flake graphite
- oxide compound
- molecule
- suspension
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing a graphite oxide-based aperture adjustable nano porous material, which comprises the following steps: performing thermo-chemical intercalation treatment by using natural crystalline flake graphite as a raw material, using concentrated sulfuric acid and sodium nitrate as intercalation agents and using potassium permanganate as an oxidant; then, freeze-drying deionized aqueous solution of flake graphite oxide to obtain powdery flake graphite oxide, or performing solvent exchange on deionized aqueous solution of flake graphite oxide to obtain organic solvent suspension of the flake graphite oxide by using a polar organic solvent; and modifying the powdery flake graphite oxide or the organic solvent suspension of the flake graphite oxide to obtain the flake graphite oxide-based aperture adjustable nano porous material by adopting one of a direct modifying method and a super-molecular construction method. The nano porous material prepared by the method has stable porous structure through connecting construction of a covalent bond or a metal coordinate bond, the used modifying molecule has wide range, and the size of the aperture of the nano porous material can be adjusted in a larger range.
Description
Technical field
The invention belongs to the preparation method of graphite oxide nano-porous materials in the technical field of nano material, be specifically related to a kind of preparation method based on the adjustable nano-porous materials in the aperture of graphite oxide.
Background technology
The porous graphite material is a kind of main product form of graphite in application.The preparation method of porous graphite mainly is through thermochemical method or electrochemical method at present; Natural flaky graphite starting material are carried out intercalation processing; Under hot environment, carry out expanded then and obtain to have the porous graphite material of high porosity, then the large-area preparation porous graphite of the method product through roller-compaction again.All there is application a lot of aspects of porous graphite product, comprise as sorbing material cleaning oil pollution material, shielding material, sealing material; Can also be used as catalyzer, fixation support and solid electrolyte etc.
But the void ratio of the porous graphite that the method that adopts existing high temperature puffing prepares is thicker, generally all more than micron order.Excessive hole has seriously retrained each item performance of porous graphite, comprises adsorptive power, heat transfer exchange capability of heat and sound insulation capabilities etc.Therefore, the porous graphite material that utilizes various physics and method chemistry to obtain to have the nano level hole seems and means a great.Preparation nano level graphite porous material not only can improve each item performance of graphite porous material; Can also produce some effect and performances based on the novelty of nanoscale, this has important effect for the range of application of expanding the graphite porous material and its potential application of exploitation.
Summary of the invention
The objective of the invention is to propose a kind of method of constructing graphite porous material with nano level hole; The pore size of the graphite porous material of this method preparation is all at nanoscale; Its pore structure is to construct formation through the connection of covalent linkage or metal-complexing key; Therefore pore structure is more stable relatively, and the scope of available decorating molecule is wide, can in a big way, regulate the pore size of material.
Technical scheme of the present invention is following:
Preparing method based on the adjustable nano-porous materials in the aperture of graphite oxide provided by the invention, its concrete steps are following:
(1) preparation of flake graphite oxide compound
With natural flake graphite as starting material; With the vitriol oil and SODIUMNITRATE as intercalator; As oxygenant it is carried out thermochemical intercalation processing with potassium permanganate: natural flake graphite and SODIUMNITRATE are joined in the vitriol oil; The mixture that obtains cools off with ice-water bath, and under the ice-water bath cooling, adds potassium permanganate; The weight ratio of said each component of mixture is a natural flake graphite: SODIUMNITRATE: the vitriol oil: potassium permanganate=1:0.5-1:45-80:3-5; Said thermochemical intercalation processing condition is 20-40 ℃ of TR internal reaction 120 hours;
Reaction finishes the water-bath of recession deicing, adds the hydrogen peroxide solution of 3wt%, and the Manganse Dioxide that generates in remaining potassium permanganate and the reaction is transformed into manganous sulfate, obtains jonquilleous suspension-s; The 3wt% hydrogen peroxide solution that is added and the weight ratio of above-mentioned potassium permanganate are 1:1.5;
Afterwards with not having sulfate ion in deionized water repetitive scrubbing to the suspension-s; Again suspension-s is carried out spinning with 3000-8000rpm, the upper solution that obtains is the flake graphite oxide compound deionized water solution that is scattered in the deionized water;
Then the flake graphite oxide compound deionized water solution that obtains is obtained Powdered flake graphite oxide compound through lyophilize, perhaps resulting flake graphite oxide compound deionized water solution is carried out solvent exchange and obtain flake graphite oxide compound organic solvent suspension with the polar organic solvent;
(2) modification of flake graphite oxide compound is constructed
Adopt in following two kinds of modifying method any respectively Powdered flake graphite oxide compound or flake graphite oxide compound organic solvent suspension that step (1) obtains to be modified; The mixture that obtains is removed unreacted decorating molecule with solvent wash again, constructs and obtain based on the adjustable nano-porous materials in the aperture of flake graphite oxide compound:
(a) directly modify method: with Powdered flake graphite oxide compound ultra-sonic dispersion in the exsiccant polar organic solvent; In nitrogen protection and 25 ℃ of-150 ℃ of range of reaction temperature, flake graphite oxide compound is wherein modified with having the rigidity organic molecule of 2 active functional groups or nanoparticle that finishing has 2 to 10 active functional groups; The mixture that obtains is removed unreacted decorating molecule with solvent wash again, construct and obtain based on the adjustable nano-porous materials in the aperture of flake graphite oxide compound; Or
Directly said flake graphite oxide compound organic solvent suspension is modified flake graphite oxide compound wherein with having the rigidity organic molecule of 2 active functional groups or nanoparticle that finishing has 2 to 10 active functional groups under the temperature of reaction of nitrogen protection and 25 ℃-150 ℃; The mixture that obtains is removed unreacted decorating molecule with solvent wash again, construct and obtain based on the adjustable nano-porous materials in the aperture of flake graphite oxide compound;
(b) supramolecule method for constructing: be connected with the Powdered flake graphite oxide compound of coordination assembling function molecular modification with coordination assembling function of active functional group or the flake graphite oxide compound in the flake graphite oxide compound organic solvent suspension with an end earlier; And then introduce the rigidity organic molecule that transition metal ion and two ends all are connected with the different lengths of coordination assembling function molecule, utilize coordination assembling function molecule and the coordination between the transition metal ion at coordination assembling function molecule and rigidity organic molecule two ends to assemble to construct and obtain based on the adjustable nano-porous materials in the aperture of flake graphite oxide compound.
The used rigidity organic molecule that has 2 active functional groups of said direct modification method is the planar rigidity organic molecule that has 2 active functional groups; Described active functional group is isocyano or amino group; Described planar rigidity organic molecule is a condensed-nuclei aromatics series molecule;
It is the three-dimensional arrangement heteropolyacid serial nano particle, the three-dimensional arrangement heteropolyacid serial nano particle that has 2 to 6 amino groups that have 2 to 6 isocyanos that described finishing has the nanoparticle of 2 to 10 active functional groups, have the three-dimensional arrangement soccerballene nanoparticle of 6 to 10 isocyanos or have the three-dimensional arrangement silsesquioxane nano particle of 8 amino.
Coordination assembling function molecule described in the said supramolecule method for constructing is the terpyridyl molecule that an end is connected with isocyano; Described rigidity organic molecule is the stiff molecule that two ends all have the different lengths of terpyridyl molecule.
The pore size of the graphite porous material of method preparation of the present invention is all at nanoscale; Its pore structure is to construct formation through the connection of covalent linkage or metal-complexing key; Therefore pore structure is more stable relatively; And the scope of available decorating molecule is wide, can in a big way, regulate the pore size of material.
Description of drawings
Fig. 1 is the infrared figure of embodiment 2 flake graphite oxide compound after lyophilize.
The infrared comparison diagram of the graphite porous material that Fig. 2 obtains for flake graphite oxide compound and the embodiment 6 of embodiment 2 after lyophilize.
Embodiment
Embodiment 1
Getting the 2.0g fineness is that 325 purpose flaky graphite starting material and 1.0g SODIUMNITRATE are added in the 90g vitriol oil, the mixture that obtains is placed in the container of 500mL and with ice-water bath to cool off.
When keeping violent stirring, 6.0g potassium permanganate is added in the suspension-s; The speed that control is reinforced makes the temperature of suspension-s be no more than 20 ℃ (in 1 hour, adding); After adding potassium permanganate, ice-water bath is withdrawn, at this moment the temperature of suspension-s is 35 ± 5 ℃, keeps 120 hours, obtains the mixture of brown; After reaction finishes, get in the mixture that the 100mL deionized water slowly adds brown, cause violent bubbling, and temperature rises to 98 ℃ rapidly, with 98 ℃ of brown suspension-s maintenances of dilute 1 hour; Then with warm water with the suspension-s redilution to about 1L, with the hydrogen peroxide solution of the 3wt% of 4g remaining potassium permanganate and Manganse Dioxide are transformed into manganous sulfate and obtain jonquilleous suspension-s; Constantly with the existence that does not have sulfate ion in deionized water centrifuge washing about 15 times to the suspension-s, then suspension-s is used the 3000rpm spinning afterwards, its upper solution is the flake graphite oxide compound deionized water solution that is scattered in the deionized water; Resulting in deionized water better dispersive flake graphite oxide compound deionized water solution can obtain Powdered flake graphite oxide compound to its lyophilize through cryodesiccated method, preserve subsequent use; Also can use exsiccant N; N '-N (DMF) organic solvent carries out solvent exchange to flake graphite oxide compound deionized water solution and is dispersed in exsiccant N preferably; Flake graphite oxide compound N among the N '-N (DMF), N '-N organic solution suspension-s.
Getting the 2.0g fineness is that 325 purpose flaky graphite starting material and 1.5g SODIUMNITRATE are added in the 124g vitriol oil, mixture is placed in the container of 500mL and with ice-water bath to cool off;
When keeping violent stirring, 9.0g potassium permanganate is added in the suspension-s; The speed that control is reinforced makes the temperature of suspension-s be no more than 20 ℃ (in 1 hour, adding); After adding potassium permanganate, ice-water bath is withdrawn, at this moment the temperature of suspension-s is 35 ± 5 ℃, keeps 120 hours, obtains the mixture of brown; After reaction finishes, get in the mixture that the 120mL deionized water slowly adds brown, cause violent bubbling, and temperature rises to 98 ℃ rapidly, with 98 ℃ of brown suspension-s maintenances of dilute 1 hour; Then with warm water with the suspension-s redilution to about 1L, with the 3wt% hydrogen peroxide solution of 6g remaining potassium permanganate and Manganse Dioxide are transformed into manganous sulfate and obtain jonquilleous suspension-s; Constantly with the existence that does not have sulfate ion in deionized water centrifuge washing about 15 times to the suspension-s, then suspension-s is used the 5000rpm spinning afterwards, its upper solution is the flake graphite oxide compound deionized water solution in being scattered in deionized water; Resulting in deionized water better dispersive flake graphite oxide compound deionized water solution can obtain Powdered flake graphite oxide compound to its lyophilize through cryodesiccated method, preserve subsequent use; Perhaps the method with solvent exchange is dispersed in exsiccant N preferably with it, among the N '-N (DMF), obtains flake graphite oxide compound N, N '-N organic solution suspension-s.The infared spectrum of the Powdered flake graphite oxide compound that accompanying drawing 1 obtains for lyophilize, wherein 1736cm
-1, 1409cm
-1, 1226cm
-1, 1056cm
-1The absorption peak at place shows the active function groups that contains carboxyl and hydroxyl on the resulting flake graphite oxide compound.
Embodiment 3
Getting the 2.0g fineness is that 325 purpose flaky graphite starting material and 2.0g SODIUMNITRATE are added in the 160g vitriol oil, mixture is placed in the container of 500mL and with ice-water bath to cool off;
When keeping violent stirring, 10.0g potassium permanganate is added in the suspension-s; The speed that control is reinforced makes the temperature of suspension-s be no more than 20 ℃ (in 1 hour, adding).After adding potassium permanganate, ice-water bath is withdrawn, at this moment the temperature of suspension-s is 35 ± 5 ℃, keeps 120 hours, obtains the mixture of brown; After reaction finishes, get in the mixture that the 200mL deionized water slowly adds brown, cause violent bubbling, and temperature rises to 98 ℃ rapidly, with 98 ℃ of brown suspension-s maintenances of dilute 1 hour; Then, with warm water with the suspension-s redilution to about 1.5L, with the 3wt% hydrogen peroxide solution of 6.8g remaining potassium permanganate and Manganse Dioxide are transformed into manganous sulfate and obtain jonquilleous suspension-s; Constantly with the existence that does not have sulfate ion in deionized water centrifuge washing about 15 times to the suspension-s, then suspension-s is used the 8000rpm spinning afterwards, its upper solution is the flake graphite oxide compound deionized water solution in being scattered in deionized water; Resulting in deionized water better dispersive flake graphite oxide compound deionized water solution can carry out lyophilize to it through cryodesiccated method and obtain Powdered flake graphite oxide compound, preserve subsequent use; Perhaps the method with solvent exchange is dispersed in exsiccant N preferably with it; Among the N '-N (DMF); Be dispersed in exsiccant N preferably, the flake graphite oxide compound N among the N '-N (DMF), N '-N organic solution suspension-s.
Get among the embodiment 2 (can certainly get implement 1 or implement 3) Powdered flake graphite oxide compound 0.1g through lyophilize in a reaction vessel; Add the DMF that the 10mL drying treatment is crossed, ultra-sonic dispersion is more than 30 minutes and with the logical nitrogen protection of reaction vessel; Adopt direct modification method it to be modified promptly then: with 1 with the condensed-nuclei aromatics molecule that has two isocyanos; 4-two isocyanic acid benzene 0.16g are dissolved in 3mL and in the DMF of drying treatment, under nitrogen protection, join in the DMF solution of flake graphite oxide compound, and reaction mixture stirred 7 days down at 25 ℃;
After reaction finishes; Obtain black solid with adding 50mL methylene dichloride stirring after-filtration in the reaction mixture; It is unreacted 1 to remove fully repeatedly to wash black solid with methylene dichloride, and 4-two isocyanic acid benzene obtain the adjustable nano-porous materials in the aperture based on graphite oxide of black.
Get among the embodiment 2 (can certainly get implement 1 or implement 3) Powdered flake graphite oxide compound 0.1g through lyophilize in a reaction vessel; Add the DMF that the 10mL drying treatment is crossed, ultra-sonic dispersion is more than 30 minutes and with the logical nitrogen protection of reaction vessel.Adopt direct modification method it to be modified promptly then: with 1 with the condensed-nuclei aromatics molecule that has two isocyanos; 4-two isocyanic acid benzene 0.16g are dissolved in 3mL and in the DMF of drying treatment, under nitrogen protection, join in the DMF solution of flake graphite oxide compound, and reaction mixture is in nitrogen protection and be heated to 60 ℃ of reactions 48 hours;
After reaction finishes; Obtain big blocky black solid with adding 50mL methylene dichloride stirring after-filtration in the reaction mixture; Repeatedly wash black solid to remove unreacted 1 fully with methylene dichloride; 4-two isocyanic acid benzene obtain the adjustable nano-porous materials in the aperture based on graphite oxide of black.
Get among the embodiment 2 (can certainly get implement 1 or implement 3) Powdered flake graphite oxide compound 0.1g through lyophilize in a reaction vessel; Add the DMF that the 10mL drying treatment is crossed, ultra-sonic dispersion is more than 30 minutes and with the logical nitrogen protection of reaction vessel; Adopt direct modification method it to be modified promptly then: with 3 with the condensed-nuclei aromatics molecule that has two isocyanos; 3 '-dimethyl--4; 4 '-two isocyanic acid biphenyl 0.41g are dissolved in 3mL and in the DMF of drying treatment, under nitrogen protection, join in the DMF solution of flake graphite oxide compound, and reaction mixture is in nitrogen protection and be heated to 100 ℃ of reactions 48 hours.
After reaction finishes; Obtain big blocky black solid with adding 50mL methylene dichloride stirring after-filtration in the reaction mixture; Repeatedly wash black solid to remove unreacted 3 fully with methylene dichloride; 3 '-dimethyl--4,4 '-two isocyanic acid biphenyl obtain based on the adjustable nano-porous materials in the aperture of graphite oxide.Accompanying drawing 2 is the infrared comparison diagram of the Powdered flake graphite oxide compound that obtains among the graphite porous material that obtains and the embodiment 2, wherein 1702cm
-1, 1641cm
-1, 1531cm
-1The absorption peak at place shows that the graphite porous material that obtains constructs and form for connecting the flake graphite oxide compound of going up decorating molecule.
Embodiment 7
Get among the embodiment 2 (implement 1 or implement 3) and well be dispersed in the flake graphite oxide compound N among the DMF with solvent exchange process; N '-N organic solution suspension-s 10mL; Wherein contain flake graphite oxide compound 50mg approximately, be stored in the reaction vessel under the nitrogen atmosphere; Adopt direct modification method it to be modified promptly then: with 3 with the condensed-nuclei aromatics molecule that has two isocyanos; 3 '-dimethyl--4; 4 '-two isocyanic acid biphenyl 0.26g are dissolved in 3mL and in the DMF of drying treatment, under nitrogen protection, join in the DMF solution of flake graphite oxide compound, and reaction mixture is in nitrogen protection and be heated to 100 ℃ of reactions 48 hours;
After reaction finishes; Stir the big blocks of solid that after-filtration obtains black with adding the 25mL methylene dichloride in the reaction mixture; Repeatedly wash black solid to remove unreacted 3 fully with methylene dichloride; 3 '-dimethyl--4,4 '-two isocyanic acid biphenyl obtain based on the adjustable nano-porous materials in the aperture of graphite oxide.
Embodiment 8
Get among the embodiment 2 (can certainly get implement 1 or implement 3) Powdered flake graphite oxide compound 0.1g through lyophilize in a reaction vessel; Add the DMF that the 10mL drying treatment is crossed, ultra-sonic dispersion is more than 30 minutes and with the logical nitrogen protection of reaction vessel; Adopt direct modification method it to be modified promptly then: with 1 with the condensed-nuclei aromatics molecule that has two amino groups; 4-diaminobenzene 70.2mg is dissolved in 1mL and in the DMF of drying treatment, under nitrogen protection, joins in the DMF solution of flake graphite oxide compound, and under nitrogen protection, in reaction system, adds the pyridine that the 0.6mL drying treatment is crossed.Then reaction mixture is heated to 150 ℃ under nitrogen protection, in reaction system, adds the 50.4mg triphenylphosphine again.Reaction mixture was nitrogen protection and 150 ℃ reaction 15 hours.
After reaction finishes; Obtain pulverous black solid with adding 50mL methylene dichloride stirring after-filtration in the reaction mixture; Repeatedly wash black solid to remove unreacted 1 fully with methylene dichloride; The 4-diaminobenzene, pyridine and triphenylphosphine obtain the adjustable nano-porous materials in the aperture based on graphite oxide of black.
Embodiment 9
Get among the embodiment 2 (can certainly get enforcement 1 or implement 3) and well be dispersed in the flake graphite oxide compound N among the DMF with solvent exchange process; N '-N organic solution suspension-s 10mL; Wherein contain flake graphite oxide compound 50mg approximately, be stored in the reaction vessel under the nitrogen atmosphere; Adopt direct modification method it to be modified promptly then: with 4 with the condensed-nuclei aromatics molecule that has two amino groups; 4 '-benzidine 60.9mg is dissolved in 1mL and in the DMF of drying treatment, under nitrogen protection, joins in the DMF solution of flake graphite oxide compound, and under nitrogen protection, in reaction system, adds the pyridine that the 0.6mL drying treatment is crossed.Then reaction mixture is heated to 150 ℃ under nitrogen protection, in reaction system, adds the 25.6mg triphenylphosphine again.Reaction mixture was nitrogen protection and 150 ℃ reaction 36 hours.
After reaction finishes; Obtain pulverous black solid with adding 50mL methylene dichloride stirring after-filtration in the reaction mixture; Repeatedly wash black solid to remove unreacted 4 fully with methylene dichloride; 4 '-benzidine and triphenylphosphine obtain the adjustable nano-porous materials in the aperture based on graphite oxide of black.
Get among the embodiment 2 (implement 1 or implement 3) and well be dispersed in the flake graphite oxide compound N among the DMF with solvent exchange process; N '-N organic solution suspension-s 2mL; Wherein contain flake graphite oxide compound 10mg approximately, be stored in the reaction vessel under the nitrogen atmosphere; Adopt direct modification method it to be modified promptly then: the surface is had two K to six isocyanic acid propyl group with the heteropolyacid nanoparticle that the surface has two to six isocyanos
12.5Na
1.5[NaP
5W
30O
110] heteropolyacid nanoparticle (or KNaPW
30The heteropolyacid nanoparticle) 1.63g is dissolved in 8mL and in the DMF of drying treatment, under nitrogen protection, joins in the DMF solution of flake graphite oxide compound, and reaction mixture is in nitrogen protection and be heated to 100 ℃ of reactions 56 hours;
After reaction finishes; Stir the pulverulent solids that after-filtration obtains black with adding the 25mL methylene dichloride in the reaction mixture;, obtain to remove unreacted heteropolyacid nanoparticle fully with many washings of DMF black solid based on the adjustable nano-porous materials in the aperture of graphite oxide.
Get among the embodiment 2 (implement 1 or implement 3) and well be dispersed in the flake graphite oxide compound N among the DMF with solvent exchange process; N '-N organic solution suspension-s 2mL; Wherein contain flake graphite oxide compound 10mg approximately, be stored in the reaction vessel under the nitrogen atmosphere; Adopt direct modification method it to be modified promptly then: the surface is had two K to six aminopropyls with the heteropolyacid nanoparticle that the surface has two to six amino groups
12.5Na
1.5[NaP
5W
30O
110] heteropolyacid nanoparticle (or KNaPW
30The heteropolyacid nanoparticle) 1.62g is dissolved in 8mL and in the DMF of drying treatment, under nitrogen protection, joins in the DMF solution of flake graphite oxide compound, and under nitrogen protection, in reaction system, adds the pyridine that the 0.5mL drying treatment is crossed.Then reaction mixture is heated to 150 ℃ under nitrogen protection, in reaction system, adds the 20.3mg triphenylphosphine again.Reaction mixture was nitrogen protection and 150 ℃ reaction 48 hours;
After reaction finishes; Stir the pulverulent solids that after-filtration obtains black with adding the 25mL methylene dichloride in the reaction mixture, obtain based on the adjustable nano-porous materials in the aperture of graphite oxide to remove unreacted heteropolyacid nanoparticle and triphenylphosphine fully with many washings of DMF black solid.
Get among the embodiment 2 (implement 1 or implement 3) and well be dispersed in the flake graphite oxide compound N among the DMF with solvent exchange process; N '-N organic solution suspension-s 2mL; Wherein contain flake graphite oxide compound 10mg approximately, be stored in the reaction vessel under the nitrogen atmosphere; Adopt direct modification method with the soccerballene nanoparticle that the surface has six to ten isocyanos it to be modified promptly then: the surface is had six to ten the soccerballene nanoparticle 0.40g to the isocyanic acid phenyl be dissolved in 5mL and in the DMSO 99.8MIN. of drying treatment, under nitrogen protection, join in the DMF solution of flake graphite oxide compound, reaction mixture is in nitrogen protection and be heated to 100 ℃ of reactions 56 hours;
After reaction finishes; Stir the pulverulent solids that after-filtration obtains black with adding the 25mL methylene dichloride in the reaction mixture; Repeatedly wash black solid to remove unreacted soccerballene nanoparticle fully with DMSO 99.8MIN., obtain based on the adjustable nano-porous materials in the aperture of graphite oxide.
Embodiment 13
Get among the embodiment 2 (implement 1 or implement 3) and well be dispersed in the flake graphite oxide compound N among the DMF with solvent exchange process; N '-N organic solution suspension-s 5mL; Wherein contain flake graphite oxide compound 25mg approximately, be stored in the reaction vessel under the nitrogen atmosphere; Adopt direct modification method it to be modified promptly then: silsesquioxane nano particle eight (4-aminophenyl) Si that the surface is had eight amino with the silsesquioxane nano particle that the surface has eight isocyanos
8O
12[or eight (3-aminopropyl) Si
8O
12] 0.28g is dissolved in 3mL and in the DMF of drying treatment, under nitrogen protection, joins in the DMF solution of flake graphite oxide compound, and under nitrogen protection, in reaction system, add the pyridine that the 1mL drying treatment is crossed.Then reaction mixture is heated to 150 ℃ under nitrogen protection, in reaction system, adds the 50.2mg triphenylphosphine again.Reaction mixture was nitrogen protection and 150 ℃ reaction 48 hours;
After reaction finishes; Stir the pulverulent solids that after-filtration obtains black with adding the 25mL methylene dichloride in the reaction mixture, obtain based on the adjustable nano-porous materials in the aperture of graphite oxide to remove unreacted silsesquioxane nano particle and triphenylphosphine fully with many washings of DMF black solid.
Embodiment 14
Get among the embodiment 2 (implement 1 or implement 3) and well be dispersed in the flake graphite oxide compound N among the DMF with solvent exchange process; N '-N organic solution suspension-s 10mL; Wherein contain flake graphite oxide compound 50mg approximately, be stored in the reaction vessel under the nitrogen atmosphere; Adopt the supramolecule method for constructing that it is modified promptly then: with 4 '-(4-isocyanic acid phenyl)-[2; 2 ': 6 '; 2 " ] terpyridyl 0.35g is dissolved among the dry DMF that crosses of 5mL and under nitrogen protection, joins in the DMF solution of flake graphite oxide compound, and reaction mixture is heated to 60 ℃ of reactions 48 hours; And then 0.25g four hydration Cobaltous diacetates (Presfersul or four hydration manganous chloride) are dissolved among the dry DMF that crosses of 2mL, join in the reaction system, continue reaction 4 hours; With 4,4 '-two (terpyridyl) biphenyl 0.31g is dissolved among the dry DMF that crosses of 4mL, under nitrogen protection, joins in the reaction system, temperature of reaction is increased to 100 ℃ continues reaction 36 hours.With 0.40g KPF
6Be dissolved among the dry DMF that crosses of 3mL, join in the reaction system, continue reaction 2 hours;
After reaction finishes; Reaction mixture is cooled to room temperature; Add the 50mL methylene dichloride and stir the pulverulent solids that after-filtration obtains black;, and then repeatedly wash black solid with secondary water and obtain based on the adjustable nano-porous materials in the aperture of graphite oxide removing unreacted raw material small molecules fully with DMF repeated ultrasonic washing black solid to remove various salts.
Embodiment 15
Get among the embodiment 2 (implement 1 or implement 3) and well be dispersed in the flake graphite oxide compound N among the DMF with solvent exchange process; N '-N organic solution suspension-s 5mL; Wherein contain flake graphite oxide compound 25mg approximately, be stored in the reaction vessel under the nitrogen atmosphere; Adopt the supramolecule method for constructing that it is modified promptly then: with 4 '-(4-isocyanic acid phenyl)-[2; 2 ': 6 '; 2 " ] terpyridyl 0.18g is dissolved among the dry DMF that crosses of 3mL and under nitrogen protection, joins in the DMF solution of flake graphite oxide compound, and reaction mixture is heated to 60 ℃ of reactions 48 hours; And then 0.13g four hydration Cobaltous diacetates (Presfersul or four hydration manganous chloride) are dissolved among the dry DMF that crosses of 2mL, join in the reaction system, continue reaction 4 hours; With 4,4 '-two (4-terpyridyl phenyl) biphenyl 0.20g is dissolved among the dry DMF that crosses of 5mL, under nitrogen protection, joins in the reaction system, temperature of reaction is increased to 100 ℃ continues reaction 36 hours.With 0.20g KPF
6Be dissolved among the dry DMF that crosses of 2mL, join in the reaction system, continue reaction 2 hours;
After reaction finishes; Reaction mixture is cooled to room temperature; Add the 25mL methylene dichloride and stir the pulverulent solids that after-filtration obtains black;, and then repeatedly wash black solid with secondary water and obtain based on the adjustable nano-porous materials in the aperture of graphite oxide removing unreacted raw material small molecules fully with DMF repeated ultrasonic washing black solid to remove various salts.
Claims (3)
1. the preparation method based on the adjustable nano-porous materials in the aperture of graphite oxide is characterized in that, its concrete steps are following:
(1) preparation of flake graphite oxide compound
With natural flake graphite as starting material; With the vitriol oil and SODIUMNITRATE as intercalator; As oxygenant it is carried out thermochemical intercalation processing with potassium permanganate: natural flake graphite and SODIUMNITRATE are joined in the vitriol oil; The mixture that obtains cools off with ice-water bath, and under the ice-water bath cooling, adds potassium permanganate; The weight ratio of said each component of mixture is a natural flake graphite: SODIUMNITRATE: the vitriol oil: potassium permanganate=1: 0.5-1: 45-80: 3-5; Said thermochemical intercalation processing condition is 20-40 ℃ of TR internal reaction 120 hours;
Reaction finishes the water-bath of recession deicing, adds the hydrogen peroxide solution of 3wt%, and the Manganse Dioxide that generates in remaining potassium permanganate and the reaction is transformed into manganous sulfate, obtains jonquilleous suspension-s; The 3wt% hydrogen peroxide solution that is added and the weight ratio of above-mentioned potassium permanganate are 1: 1.5;
Afterwards with not having sulfate ion in deionized water repetitive scrubbing to the suspension-s; Again suspension-s is carried out spinning with 3000-8000rpm, the upper solution that obtains is the flake graphite oxide compound deionized water solution that is scattered in the deionized water;
Then the flake graphite oxide compound deionized water solution that obtains is obtained Powdered flake graphite oxide compound through lyophilize, perhaps resulting flake graphite oxide compound deionized water solution is carried out solvent exchange and obtain flake graphite oxide compound organic solvent suspension with the polar organic solvent;
(2) modification of flake graphite oxide compound is constructed
Adopt in following two kinds of modifying method any respectively Powdered flake graphite oxide compound or flake graphite oxide compound organic solvent suspension that step (1) obtains to be modified; The mixture that obtains is removed unreacted decorating molecule with solvent wash again, constructs and obtain based on the adjustable nano-porous materials in the aperture of flake graphite oxide compound:
(a) directly modify method: with Powdered flake graphite oxide compound ultra-sonic dispersion in the exsiccant polar organic solvent; In nitrogen protection and 25 ℃ of-150 ℃ of range of reaction temperature, flake graphite oxide compound is wherein modified with having the rigidity organic molecule of 2 active functional groups or nanoparticle that finishing has 2 to 10 active functional groups; The mixture that obtains is removed unreacted decorating molecule with solvent wash again, construct and obtain based on the adjustable nano-porous materials in the aperture of flake graphite oxide compound; Or
Directly said flake graphite oxide compound organic solvent suspension is modified flake graphite oxide compound wherein with having the rigidity organic molecule of 2 active functional groups or nanoparticle that finishing has 2 to 10 active functional groups under the temperature of reaction of nitrogen protection and 25 ℃-150 ℃; The mixture that obtains is removed unreacted decorating molecule with solvent wash again, construct and obtain based on the adjustable nano-porous materials in the aperture of flake graphite oxide compound;
(b) supramolecule method for constructing: be connected with the Powdered flake graphite oxide compound of coordination assembling function molecular modification with coordination assembling function of active functional group or the flake graphite oxide compound in the flake graphite oxide compound organic solvent suspension with an end earlier; And then introduce the rigidity organic molecule that transition metal ion and two ends all are connected with the different lengths of coordination assembling function molecule, utilize coordination assembling function molecule and the coordination between the transition metal ion at coordination assembling function molecule and rigidity organic molecule two ends to assemble to construct and obtain based on the adjustable nano-porous materials in the aperture of flake graphite oxide compound;
Said active functional group is isocyano or amino group, and said nanoparticle is three-dimensional arrangement heteropolyacid serial nano particle, three-dimensional arrangement soccerballene nanoparticle or three-dimensional arrangement silsesquioxane nano particle; Said coordination assembling function molecule is the terpyridyl molecule.
2. preparation method according to claim 1 is characterized in that, the used rigidity organic molecule that has 2 active functional groups of said direct modification method is the planar rigidity organic molecule that has 2 active functional groups; Described planar rigidity organic molecule is a condensed-nuclei aromatics series molecule;
It is the three-dimensional arrangement heteropolyacid serial nano particle, the three-dimensional arrangement heteropolyacid serial nano particle that has 2 to 6 amino groups that have 2 to 6 isocyanos that described finishing has the nanoparticle of 2 to 10 active functional groups, have the three-dimensional arrangement soccerballene nanoparticle of 6 to 10 isocyanos or have the three-dimensional arrangement silsesquioxane nano particle of 8 amino.
3. preparation method according to claim 1 is characterized in that, the coordination assembling function molecule described in the said supramolecule method for constructing is the terpyridyl molecule that an end is connected with isocyano; Described rigidity organic molecule is the stiff molecule that two ends all have the different lengths of terpyridyl molecule.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102260243A CN101734653B (en) | 2008-11-04 | 2008-11-04 | Method for preparing graphite oxide-based aperture adjustable nano porous material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102260243A CN101734653B (en) | 2008-11-04 | 2008-11-04 | Method for preparing graphite oxide-based aperture adjustable nano porous material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101734653A CN101734653A (en) | 2010-06-16 |
| CN101734653B true CN101734653B (en) | 2012-01-25 |
Family
ID=42458769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102260243A Expired - Fee Related CN101734653B (en) | 2008-11-04 | 2008-11-04 | Method for preparing graphite oxide-based aperture adjustable nano porous material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101734653B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199415B (en) * | 2010-12-27 | 2014-04-16 | 中国人民解放军空军油料研究所 | Preparation method of graphene oxide/nano-gold particulate composite material with mono-atomic thickness |
| CZ303513B6 (en) * | 2011-08-30 | 2012-10-31 | Vysoká Škola Bánská -Technická Univerzita Ostrava | Process for preparing fibrous and lamellar microstructures and nanostructures by controlled vacuum freeze-drying of nanoparticle liquid dispersion |
| CN103253653B (en) * | 2012-02-15 | 2016-01-27 | 国家纳米科学中心 | Graphene oxide membrane, graphene film and its preparation method and application |
| CN106587252B (en) * | 2016-12-29 | 2019-08-30 | 苏州科技大学 | Manganese oxide-application of the fullerene hybrid material near infrared light denitrogenation |
| CN107541177A (en) * | 2017-09-07 | 2018-01-05 | 深圳市康利邦科技有限公司 | The preparation method of silane work(graphene, antistatic silicone pressure sensitive adhesive and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1799651A (en) * | 2005-12-16 | 2006-07-12 | 南京师范大学 | Polymer/graphite oxide anticoagulant nano composite material and preparation method thereof |
| CN101186808A (en) * | 2007-12-14 | 2008-05-28 | 华南理工大学 | Method for preparing graphite series nano fluid |
-
2008
- 2008-11-04 CN CN2008102260243A patent/CN101734653B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1799651A (en) * | 2005-12-16 | 2006-07-12 | 南京师范大学 | Polymer/graphite oxide anticoagulant nano composite material and preparation method thereof |
| CN101186808A (en) * | 2007-12-14 | 2008-05-28 | 华南理工大学 | Method for preparing graphite series nano fluid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101734653A (en) | 2010-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101734653B (en) | Method for preparing graphite oxide-based aperture adjustable nano porous material | |
| CN103723716B (en) | Nitrogen-doped carbon cladding graphene oxide two-dimensional is composite porous and preparation method thereof | |
| CN109167066A (en) | A kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material | |
| CN103738945B (en) | A kind of method being connected the controlled three dimensional network Graphene of preparation by chemical bond | |
| CN107473261A (en) | A kind of preparation method of zinc oxide/redox graphene composite | |
| CN106521545B (en) | A kind of MoS2The preparation method of-CNT multi-level nano-structure water electrolysis hydrogen production materials | |
| CN105964193A (en) | Method for preparing graphene oxide-alumina composite aerogel | |
| CN106698430A (en) | Titanium carbide in-situ growth CNTs three-dimensional composite with polydopamine serving as transition layer and preparation method thereof | |
| CN102847533B (en) | Microwave method for synthesizing attapulgite and palladium nanocomposite catalyst | |
| CN106129377A (en) | The preparation method of a kind of sesquioxide/graphene composite material, lithium ion battery negative, lithium ion battery | |
| CN107154500B (en) | The synthetic method of mesoporous Nano carbon balls load manganous oxide material | |
| CN102398902A (en) | Method for preparing carbon nano material by using natural endellite as formwork | |
| CN107623137A (en) | A kind of preparation method of functional graphene oxide doping polybenzimidazole membrane | |
| CN108726515A (en) | Preparation method with three-dimensional structure redox graphene-ferrocene composite material | |
| CN106495175A (en) | A kind of preparation method of organic modification montmonrillonite | |
| CN104787751A (en) | Graphene powder and preparation method thereof | |
| CN106816603A (en) | A kind of three-dimensional grapheme aeroge carries sulphur composite and its preparation method and application | |
| CN108831757A (en) | A kind of preparation method of N and S codope graphene/carbon nano-tube aeroge | |
| Zare et al. | Magnetic chitosan supported covalent organic framework/copper nanocomposite as an efficient and recoverable catalyst for the unsymmetrical hantzsch reaction | |
| CN106099081A (en) | A kind of cobalt oxide/graphene nano composite material and preparation method thereof, lithium ion battery negative, lithium ion battery | |
| CN102199415B (en) | Preparation method of graphene oxide/nano-gold particulate composite material with mono-atomic thickness | |
| CN108298589A (en) | A kind of Preparation method and use of yolk type manganese dioxide microballoon | |
| CN106252080A (en) | A kind of carbon nanomaterial is prepared as the DSSC method to electrode | |
| CN107954417B (en) | A method of building graphene three-dimensional structure | |
| CN108455572A (en) | A kind of preparation method of graphene oxide and graphene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120125 Termination date: 20141104 |
|
| EXPY | Termination of patent right or utility model |