CN105110321A - Preparation method for nano-pores on surface of graphene by metal phthalocyanine and its alloy precursor - Google Patents
Preparation method for nano-pores on surface of graphene by metal phthalocyanine and its alloy precursor Download PDFInfo
- Publication number
- CN105110321A CN105110321A CN201510453544.8A CN201510453544A CN105110321A CN 105110321 A CN105110321 A CN 105110321A CN 201510453544 A CN201510453544 A CN 201510453544A CN 105110321 A CN105110321 A CN 105110321A
- Authority
- CN
- China
- Prior art keywords
- metal phthalocyanine
- nanoporous
- alloy
- metal
- graphene
- 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.)
- Pending
Links
Landscapes
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method for nano-pores on surface of graphene by metal phthalocyanine and its alloy precursor. The apertures of the nano-pores on graphene are 30 to 50 nanometers. The preparation method includes preparing a 0.04 to 5 mg/ml oxidized graphene dispersion liquid by chemical oxidation ultrasonic dispersion method; mixing uniformly with a 0.1 to 5 mg/ml metal phthalocyanine or its alloy precursor dispersion liquid; vacuum filtrating by a polycarbonate porous membrane and drying to remove the solvent; heating the getting black powder to 400 to 1000 DEG C in inert atmosphere with the heating rate of 1 to 10 DEG C/min; maintaining the temperature for 1 to 10 hours at the temperature segment to get the nano-pores. The preparation method for nano-pores on surface of graphene by metal phthalocyanine and its alloy precursor has the characteristics of simple preparation method, short preparation period, cheap equipment, and can be prepared in large scale. The prepared graphene with nano-pores can be used in the fields of DNA sequencing, gas separating and purifying, ion channel and so on.
Description
Technical field
The invention belongs to graphene film parting material and technical field of modification thereof, particularly relate to a kind of metal phthalocyanine and alloy presoma prepares the method for nanoporous at graphenic surface.
Background technology
Graphene is a kind of Two-dimensional Carbon material, and its thickness only has a carbon atom size, is the thinnest planar materials found in the world up to now.It has excellent physics and chemistry character.Nanoporous Graphene, as the term suggests the material being exactly graphenic surface also exists the hole of Nano grade.Research shows, on Graphene, the existence of nanoporous can improve perviousness and the selective penetrated property of Graphene greatly.This character of nanoporous Graphene makes it have potential application in a lot of field.As: gas delivery and purification, water demineralizing process, ionic channel and DNA sequencing etc.The preparation method of nanoporous Graphene has Physical and chemical method.Physical mainly by high energy particle as: helium particle, electron beam and laser etc. carry out bombardment to Graphene and obtain nanoporous.Chemical method has and obtains nanoporous Graphene by the aryl coupling reaction of two-dimentional polyphenylene at Ag surface deposition, also has the carbothermic reduction reaction utilizing Graphene and metal oxide or polyoxometallate, obtains nanoporous Graphene after cleanup acid treatment.But Physical is restricted because using expensive electronics; Chemical method, and can not scale operation and being restricted because preparation method is complicated or preparation cycle is long.Given this, be necessary that providing a kind of prepares nanoporous Graphene or the novel method for Graphene perforate.
Summary of the invention
For the above-mentioned problems in the prior art, the object of the present invention is to provide a kind of simple to operate, a kind of metal phthalocyanine that facility investment is little and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it has the advantages that equipment is cheap, preparation method is simple, preparation cycle is short and can prepare on a large scale, and its application prospect is good.
Described a kind of metal phthalocyanine and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that comprising the steps:
1) graphene oxide ultrasonic disperse is obtained graphene oxide dispersion in solvent, for subsequent use;
2) metal phthalocyanine ultrasonic disperse is obtained metal phthalocyanine dispersion liquid or preparing metal phthalocyanine alloy presoma dispersion liquid in solvent, for subsequent use;
3) dropwise add metal phthalocyanine dispersion liquid or metal phthalocyanine alloy presoma dispersion liquid in the graphene oxide dispersion obtained toward step 1), magnetic agitation 1-12h is to mixing simultaneously, obtains suspension;
4) suspension of step 3) gained is passed through polycarbonate porous-film vacuum filtration, then vacuum-drying 3-8h obtains dry black powder at 60-100 DEG C;
5) black powder that step 4) obtains is put in quartz boat, then quartz boat is placed in the silica tube in tube furnace, closed quartz tube;
6) in the silica tube of step 5), logical protection gas carries out air tight test, and the gas flow of protection gas is 20-200ml/min, and resistance to air loss well continues logical protection gas 10-30min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 1-10 DEG C/min, reaction tubes is warming up to 400-1000 DEG C, and at this temperature section constant temperature 1-10h, Temperature fall afterwards; after temperature is down to room temperature; close protection gas, gained black powder is nanoporous Graphene, and described nanoporous Graphene aperture is 3-50 nanometer.
Described a kind of metal phthalocyanine and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that the concentration of graphene oxide dispersion is 0.04-5mg/ml.
Described a kind of metal phthalocyanine and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that the concentration of metal phthalocyanine dispersion liquid and metal phthalocyanine alloy presoma dispersion liquid is respectively 0.1-5mg/ml, are preferably 0.2-4mg/ml.
Described a kind of metal phthalocyanine and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that step 1) and step 2) described in solvent comprise organic solvent and inorganic solvent, be preferably dehydrated alcohol, DMF, methyl alcohol, deionized water, tetrahydrofuran (THF), N-Methyl pyrrolidone and ethylene glycol.
Described a kind of metal phthalocyanine and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that step 2) in metal phthalocyanine alloy comprise binary alloy, ternary alloy and multicomponent alloy.
Described a kind of metal phthalocyanine and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that described metal phthalocyanine is phthalocyanine platinum or palladium phthalocyanine.
Described a kind of metal phthalocyanine and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that the volume ratio of graphene oxide dispersion and metal phthalocyanine dispersion liquid or metal phthalocyanine alloy presoma dispersion liquid in step 3) is 1:1.
Described a kind of metal phthalocyanine and alloy presoma thereof prepare the method for nanoporous at graphenic surface, and it is characterized in that step 6) leads to the gas flow protecting gas when protection gas carries out air tight test is 20-200ml/min.
Described a kind of metal phthalocyanine and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that alloy presoma comprises any alloy presoma obtaining alloy through roasting except metal phthalocyanine external enwergy and metal phthalocyanine and comprises metal nitrate, metal chloride, metal sulfate, metal acetate salt or transition metal phthalocyanine.Metal nitrate comprises iron nitrate, nickelous nitrate; Metal chloride comprises cobalt chloride, iron(ic) chloride; Metal sulfate comprises ferric sulfate, zinc sulfate; Metal phthalocyanine comprises CuPc, FePC; Metal acetate salt comprise manganese acetate, acetic acid every.
Described a kind of metal phthalocyanine and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that protecting described in step 6) gas to be any one in nitrogen, argon gas, helium or hydrogen.
Metal phthalocyanine of the present invention and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is simple to operate, the feature that facility investment is little, preparation method is simple, preparation cycle is short and can prepare on a large scale, and the nanoporous Graphene obtained can apply to DNA sequencing, the fields such as gas delivery purification, water treatment and ionic channel.
Accompanying drawing explanation
Fig. 1 is the surperficial SEM photo of grapheme nano-pore prepared by embodiment 1;
Fig. 2 is the surperficial TEM photo of grapheme nano-pore prepared by embodiment 6;
Fig. 3 is the TEM photo of graphenic surface nanoporous prepared by embodiment 11.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail; Should be appreciated that preferred embodiment only in order to the present invention is described, instead of in order to limit the scope of the invention.
Embodiment 1
1) graphene oxide ultrasonic disperse is obtained in deionized water the graphene oxide dispersion of 0.04mg/ml, for subsequent use;
2) phthalocyanine platinum ultrasonic disperse is obtained in deionized water the phthalocyanine platinum dispersion liquid of 0.1mg/ml;
3) in graphene oxide dispersion described in step 1), isopyknic step 2 is dropwise added) the phthalocyanine platinum dispersion liquid of gained, magnetic agitation 1h is to mixing to obtain suspension simultaneously;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 60 DEG C of vacuum-drying 3h obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in the silica tube of tube furnace, closed quartz tube;
6) before experiment starts, logical nitrogen carries out air tight test, and nitrogen flow is 20ml/min, and resistance to air loss well continues logical nitrogen 10min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 2 DEG C/min, reaction tubes is warming up to 900 DEG C, and at this temperature section constant temperature 1h, Temperature fall afterwards;
8), after temperature is down to room temperature, close nitrogen, gained black powder is nanoporous Graphene;
9) adopt scanning electron microscope to characterize, acquired results as shown in Figure 1.As seen from the figure, the aperture of this nanoporous Graphene is 10-30nm.
In this embodiment; solvent dehydrated alcohol, N; other organic solvents such as dinethylformamide, methyl alcohol tetrahydrofuran (THF), N-Methyl pyrrolidone and ethylene glycol or inorganic solvent replace deionized water; metal phthalocyanine palladium phthalocyanine or its alloy presoma replace phthalocyanine platinum; protect any one replacement nitrogen in gas argon gas, helium or hydrogen described in step 6), all can obtain same technique effect.
Embodiment 2
1) graphene oxide ultrasonic disperse is obtained in dehydrated alcohol the graphene oxide dispersion of 1mg/ml, for subsequent use;
2) phthalocyanine platinum ultrasonic disperse is obtained in dehydrated alcohol the phthalocyanine platinum dispersion liquid of 0.5mg/ml;
3) in graphene oxide dispersion described in step 1), dropwise add isopyknic step 2) phthalocyanine platinum dispersion liquid, simultaneously magnetic agitation 4hr is to mixing;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 70 DEG C of vacuum-drying 5h obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in the silica tube of tube furnace, closed quartz tube;
6) before experiment starts, logical nitrogen carries out air tight test, and nitrogen flow is 40ml/min, and resistance to air loss well continues logical nitrogen 20min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 4 DEG C/min, reaction tubes is warming up to 800 DEG C, and at this temperature section constant temperature 3h, Temperature fall afterwards;
8), after temperature is down to room temperature, close nitrogen, gained black powder is nanoporous Graphene, and described nanoporous Graphene aperture is 3-10 nanometer.
Embodiment 3
1) graphene oxide ultrasonic disperse is obtained in deionized water the graphene oxide dispersion of 2mg/ml, for subsequent use;
2) phthalocyanine platinum ultrasonic disperse is obtained in deionized water the phthalocyanine platinum dispersion liquid of 1mg/ml;
3) in graphene oxide dispersion described in step 1), dropwise add the phthalocyanine platinum dispersion liquid of isopyknic step 1), magnetic agitation 8h is to mixing simultaneously;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 60 DEG C of vacuum-drying 5h obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in the silica tube of tube furnace, closed quartz tube;
6) before experiment starts, logical argon gas carries out air tight test, and argon flow amount is 60ml/min, and resistance to air loss well continues logical argon gas 30min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 8 DEG C/min, reaction tubes is warming up to 600 DEG C, and at this temperature section constant temperature 6h, Temperature fall afterwards;
8), after temperature is down to room temperature, close argon gas, gained black powder is nanoporous Graphene, and described nanoporous Graphene aperture is 3-10 nanometer.
Embodiment 4
1) graphene oxide ultrasonic disperse is obtained in deionized water the graphene oxide dispersion of 5mg/ml, for subsequent use;
2) phthalocyanine platinum ultrasonic disperse is obtained in deionized water the phthalocyanine platinum dispersion liquid of 5mg/ml;
3) in graphene oxide dispersion described in step 1), dropwise add isopyknic step 2) phthalocyanine platinum dispersion liquid, simultaneously magnetic agitation 12hr is to mixing;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 80 DEG C of vacuum-drying 8h obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in the silica tube of tube furnace, closed quartz tube;
6) before experiment starts, logical nitrogen carries out air tight test, and nitrogen flow is 100ml/min, and resistance to air loss well continues logical nitrogen 30min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 2 DEG C/min, reaction tubes is warming up to 700 DEG C, and at this temperature section constant temperature 10h, Temperature fall afterwards;
8), after temperature is down to room temperature, close nitrogen, gained black powder is nanoporous Graphene, and described nanoporous Graphene aperture is 10-50 nanometer.
Embodiment 5
1) graphene oxide ultrasonic disperse is obtained in dehydrated alcohol the graphene oxide dispersion of 5mg/ml, for subsequent use;
2) phthalocyanine platinum and Cobalt Phthalocyanine ultrasonic disperse are obtained the phthalocyanine platinum of 5mg/ml and the binary alloy presoma dispersion liquid of Cobalt Phthalocyanine in dehydrated alcohol;
3) in graphene oxide dispersion described in step 1), dropwise add isopyknic step 2) phthalocyanine platinum and Cobalt Phthalocyanine dispersion liquid, simultaneously magnetic agitation 12h is to mixing;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 80 DEG C of vacuum-drying 8hr obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in the silica tube of tube furnace, closed quartz tube;
6) before experiment starts, logical nitrogen carries out air tight test, and nitrogen flow is 50ml/min, and resistance to air loss well continues logical nitrogen 30min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 2 DEG C/min, reaction tubes is warming up to 900 DEG C, and at this temperature section constant temperature 10h, Temperature fall afterwards;
8), after temperature is down to room temperature, close nitrogen, gained black powder is nanoporous Graphene, and described nanoporous Graphene aperture is 20-50 nanometer.
Embodiment 6
1) graphene oxide ultrasonic disperse is obtained in deionized water the graphene oxide dispersion of 2mg/ml, for subsequent use;
2) phthalocyanine platinum and iron nitrate ultrasonic disperse are obtained in deionized water the dispersion liquid of 1mg/ml;
3) in graphene oxide dispersion described in step 1), isopyknic step 2 is dropwise added) phthalocyanine platinum and iron nitrate dispersion liquid, magnetic agitation 8h is to mixing simultaneously;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 70 DEG C of vacuum-drying 6hr obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in tube furnace, closed quartz tube;
6) before experiment starts, logical nitrogen carries out air tight test, and nitrogen flow is 60ml/min, and resistance to air loss well continues logical nitrogen 30min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 4 DEG C/min, reaction tubes is warming up to 800 DEG C, and at this temperature section constant temperature 8h.Temperature fall afterwards;
8), after temperature is down to room temperature, close nitrogen, gained black powder is nanoporous Graphene.
9) adopt scanning electron microscope to characterize, as shown in Figure 2, as seen from the figure, the aperture of this nanoporous Graphene is 8-20nm to acquired results.
Embodiment 7
1) graphene oxide ultrasonic disperse is obtained in deionized water the graphene oxide dispersion of 2mg/ml, for subsequent use;
2) phthalocyanine platinum and zinc sulfate ultrasonic disperse are obtained in deionized water the dispersion liquid of 1mg/ml;
3) in graphene oxide dispersion described in step 1), isopyknic step 2 is dropwise added) phthalocyanine platinum and zinc sulfate dispersion liquid, magnetic agitation 8h is to mixing simultaneously;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 70 DEG C of vacuum-drying 6hr obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in tube furnace, closed quartz tube;
6) before experiment starts, logical nitrogen carries out air tight test, and nitrogen flow is 60ml/min, and resistance to air loss well continues logical nitrogen 30min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 4 DEG C/min, reaction tubes is warming up to 800 DEG C, and at this temperature section constant temperature 8h.Temperature fall afterwards;
8), after temperature is down to room temperature, close nitrogen, gained black powder is nanoporous Graphene, and described nanoporous Graphene aperture is 8-20 nanometer.
Embodiment 8
1) graphene oxide ultrasonic disperse is obtained in deionized water the graphene oxide dispersion of 2mg/ml, for subsequent use;
2) phthalocyanine platinum and cobalt chloride ultrasonic disperse are obtained in deionized water the dispersion liquid of 1mg/ml;
3) in graphene oxide dispersion described in step 1), isopyknic step 2 is dropwise added) phthalocyanine platinum and cobalt chloride dispersion liquid, magnetic agitation 8h is to mixing simultaneously;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 70 DEG C of vacuum-drying 6hr obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in tube furnace, closed quartz tube;
6) before experiment starts, logical nitrogen carries out air tight test, and nitrogen flow is 60ml/min, and resistance to air loss well continues logical nitrogen 30min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 4 DEG C/min, reaction tubes is warming up to 800 DEG C, and at this temperature section constant temperature 8h.Temperature fall afterwards;
8), after temperature is down to room temperature, close nitrogen, gained black powder is nanoporous Graphene, and described nanoporous Graphene aperture is 8-20 nanometer.
Embodiment 9
1) graphene oxide ultrasonic disperse is obtained in deionized water the graphene oxide dispersion of 2mg/ml, for subsequent use;
2) phthalocyanine platinum and manganese acetate ultrasonic disperse are obtained in deionized water the dispersion liquid of 1mg/ml;
3) in graphene oxide dispersion described in step 1), isopyknic step 2 is dropwise added) phthalocyanine platinum and manganese acetate dispersion liquid, magnetic agitation 8h is to mixing simultaneously;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 70 DEG C of vacuum-drying 6hr obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in tube furnace, closed quartz tube;
6) before experiment starts, logical nitrogen carries out air tight test, and nitrogen flow is 60ml/min, and resistance to air loss well continues logical nitrogen 30min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 4 DEG C/min, reaction tubes is warming up to 800 DEG C, and at this temperature section constant temperature 8h.Temperature fall afterwards;
8), after temperature is down to room temperature, close nitrogen, gained black powder is nanoporous Graphene, and described nanoporous Graphene aperture is 8-20 nanometer.
Embodiment 10
1) graphene oxide ultrasonic disperse is obtained in deionized water the graphene oxide dispersion of 0.04mg/ml, for subsequent use;
2) palladium phthalocyanine ultrasonic disperse is obtained in deionized water the palladium phthalocyanine dispersion liquid of 0.2mg/ml;
3) in graphene oxide dispersion described in step 1), isopyknic step 2 is dropwise added) palladium phthalocyanine dispersion liquid, magnetic agitation 2hr is to mixing simultaneously;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 60 DEG C of vacuum-drying 3hr obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in tube furnace, closed quartz tube;
6) before experiment starts, logical nitrogen carries out air tight test, and nitrogen flow is 20ml/min, and resistance to air loss well continues logical nitrogen 20min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 1 DEG C/min, reaction tubes is warming up to 600 DEG C, and at this temperature section constant temperature 4h, Temperature fall afterwards;
8), after temperature is down to room temperature, close nitrogen, gained black powder is nanoporous Graphene, and described nanoporous Graphene aperture is 5-10 nanometer.
Embodiment 11
1) graphene oxide ultrasonic disperse is obtained in DMF the graphene oxide dispersion of 2mg/ml, for subsequent use;
2) palladium phthalocyanine and iron nitrate ultrasonic disperse are obtained in DMF the dispersion liquid of 1mg/ml;
3) in graphene oxide dispersion described in step 1), isopyknic step 2 is dropwise added) dispersion liquid, magnetic agitation 3hr is to mixing simultaneously;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 60 DEG C of vacuum-drying 8hr obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in tube furnace, closed quartz tube;
6) before experiment starts, logical nitrogen carries out air tight test, and nitrogen flow is 100ml/min, and resistance to air loss well continues logical nitrogen 30min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 3 DEG C/min, reaction tubes is warming up to 700 DEG C, and at this temperature section constant temperature 8h.Temperature fall afterwards;
8), after temperature is down to room temperature, close nitrogen, gained black powder is nanoporous Graphene.
9) adopt scanning electron microscope to characterize, as shown in Figure 3, as seen from the figure, the aperture of this nanoporous Graphene is 5-30nm to acquired results.
Embodiment 12
1) graphene oxide ultrasonic disperse is obtained in deionized water the graphene oxide dispersion of 5mg/ml, for subsequent use;
2) palladium phthalocyanine and cupric chloride ultrasonic disperse are obtained in deionized water the palladium phthalocyanine dispersion liquid of 4mg/ml;
3) in graphene oxide dispersion described in step 1), isopyknic step 2 is dropwise added) palladium phthalocyanine and cupric chloride dispersion liquid, magnetic agitation 10hr is to mixing simultaneously;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 70 DEG C of vacuum-drying 5hr obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in tube furnace, closed quartz tube;
6) before experiment starts, logical argon gas carries out air tight test, and argon flow amount is 70ml/min, and resistance to air loss well continues logical argon gas 20min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 7 DEG C/min, reaction tubes is warming up to 1000 DEG C, and at this temperature section constant temperature 6h, Temperature fall afterwards;
8), after temperature is down to room temperature, close argon gas, gained black powder is nanoporous Graphene, and described nanoporous Graphene aperture is 10-35 nanometer.
Embodiment 13
1) graphene oxide ultrasonic disperse is obtained in deionized water the graphene oxide dispersion of 5mg/ml, for subsequent use;
2) palladium phthalocyanine and ferric sulfate ultrasonic disperse are obtained in deionized water the dispersion liquid of 4mg/ml;
3) in graphene oxide dispersion described in step 1), isopyknic step 2 is dropwise added) palladium phthalocyanine and ferric sulfate dispersion liquid, magnetic agitation 10hr is to mixing simultaneously;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 70 DEG C of vacuum-drying 5hr obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in tube furnace, closed quartz tube;
6) before experiment starts, logical argon gas carries out air tight test, and argon flow amount is 70ml/min, and resistance to air loss well continues logical argon gas 20min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 7 DEG C/min, reaction tubes is warming up to 1000 DEG C, and at this temperature section constant temperature 6h, Temperature fall afterwards;
8), after temperature is down to room temperature, close argon gas, gained black powder is nanoporous Graphene, and described nanoporous Graphene aperture is 10-35 nanometer.
Embodiment 14
1) graphene oxide ultrasonic disperse is obtained in deionized water the graphene oxide dispersion of 5mg/ml, for subsequent use;
2) palladium phthalocyanine and cadmium acetate ultrasonic disperse are obtained in deionized water the dispersion liquid of 4mg/ml;
3) in graphene oxide dispersion described in step 1), isopyknic step 2 is dropwise added) palladium phthalocyanine and cadmium acetate dispersion liquid, magnetic agitation 10hr is to mixing simultaneously;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 70 DEG C of vacuum-drying 5hr obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in tube furnace, closed quartz tube;
6) before experiment starts, logical argon gas carries out air tight test, and argon flow amount is 70ml/min, and resistance to air loss well continues logical argon gas 20min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 7 DEG C/min, reaction tubes is warming up to 1000 DEG C, and at this temperature section constant temperature 6h, Temperature fall afterwards;
8), after temperature is down to room temperature, close argon gas, gained black powder is nanoporous Graphene, and described nanoporous Graphene aperture is 10-35 nanometer.
Example 15,
1) graphene oxide ultrasonic disperse is obtained in dehydrated alcohol the graphene oxide dispersion of 5mg/ml, for subsequent use;
2) palladium phthalocyanine, CuPc and Nickel Phthalocyanine ultrasonic disperse are obtained in dehydrated alcohol the dispersion liquid of 3mg/ml;
3) in graphene oxide dispersion described in step 1), isopyknic step 2 is dropwise added) dispersion liquid of palladium phthalocyanine, CuPc and Nickel Phthalocyanine, magnetic agitation 5hr is to mixing simultaneously;
4) step 3) gained suspension is passed through polycarbonate porous-film vacuum filtration, 70 DEG C of vacuum-drying 5h obtain dry black powder afterwards;
5) described black powder is put in quartz boat, then quartz boat is placed in tube furnace, closed quartz tube;
6) before experiment starts, logical nitrogen carries out air tight test, and nitrogen flow is 40ml/min, and resistance to air loss well continues logical nitrogen 30min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 5 DEG C/min, reaction tubes is warming up to 900 DEG C, and at this temperature section constant temperature 4h.Temperature fall afterwards;
8), after temperature is down to room temperature, close nitrogen, gained black powder is nanoporous Graphene, and described nanoporous Graphene aperture is 20-40 nanometer.
Claims (10)
1. metal phthalocyanine and alloy presoma thereof prepare a method for nanoporous at graphenic surface, it is characterized in that comprising the steps:
1) graphene oxide ultrasonic disperse is obtained graphene oxide dispersion in solvent, for subsequent use;
2) metal phthalocyanine ultrasonic disperse is obtained metal phthalocyanine dispersion liquid or preparing metal phthalocyanine alloy presoma dispersion liquid in solvent, for subsequent use;
3) dropwise add metal phthalocyanine dispersion liquid or metal phthalocyanine alloy presoma dispersion liquid in the graphene oxide dispersion obtained toward step 1), magnetic agitation 1-12h is to mixing simultaneously, obtains suspension;
4) suspension of step 3) gained is passed through polycarbonate porous-film vacuum filtration, then vacuum-drying 3-8h obtains dry black powder at 60-100 DEG C;
5) black powder that step 4) obtains is put in quartz boat, then quartz boat is placed in the silica tube in tube furnace, closed quartz tube;
6) in the silica tube of step 5), logical protection gas carries out air tight test, and the gas flow of protection gas is 20-200ml/min, and resistance to air loss well continues logical protection gas 10-30min afterwards, discharges the air of reaction tubes inside;
7) with the temperature rise rate of 1-10 DEG C/min, reaction tubes is warming up to 400-1000 DEG C, and at this temperature section constant temperature 1-10h, Temperature fall afterwards; after temperature is down to room temperature; close protection gas, gained black powder is nanoporous Graphene, and described nanoporous Graphene aperture is 3-50 nanometer.
2. a kind of metal phthalocyanine according to claim 1 and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that the concentration of graphene oxide dispersion is 0.04-5mg/ml.
3. a kind of metal phthalocyanine according to claim 1 and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that the concentration of metal phthalocyanine dispersion liquid and metal phthalocyanine alloy presoma dispersion liquid is respectively 0.1-5mg/ml, be preferably 0.2-4mg/ml.
4. a kind of metal phthalocyanine according to claim 1 and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that step 1) and step 2) described in solvent comprise organic solvent and inorganic solvent, be preferably dehydrated alcohol, DMF, methyl alcohol, deionized water, tetrahydrofuran (THF), N-Methyl pyrrolidone and ethylene glycol.
5. a kind of metal phthalocyanine according to claim 1 and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that step 2) in metal phthalocyanine alloy comprise binary alloy, ternary alloy and multicomponent alloy.
6. a kind of metal phthalocyanine according to claim 1 and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that described metal phthalocyanine is phthalocyanine platinum or palladium phthalocyanine.
7. a kind of metal phthalocyanine according to claim 1 and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that the volume ratio of graphene oxide dispersion and metal phthalocyanine dispersion liquid or metal phthalocyanine alloy presoma dispersion liquid in step 3) is 1:1.
8. a kind of metal phthalocyanine according to claim 1 and alloy presoma thereof prepare the method for nanoporous at graphenic surface, and it is characterized in that step 6) leads to the gas flow protecting gas when protection gas carries out air tight test is 20-200ml/min.
9. a kind of metal phthalocyanine according to claim 1 and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that alloy presoma comprises any alloy presoma obtaining alloy through roasting except metal phthalocyanine external enwergy and metal phthalocyanine and comprises metal nitrate, metal chloride, metal sulfate, metal acetate salt or transition metal phthalocyanine, metal nitrate comprises iron nitrate, nickelous nitrate; Metal chloride comprises cobalt chloride, iron(ic) chloride; Metal sulfate comprises ferric sulfate, zinc sulfate; Metal phthalocyanine comprises CuPc, FePC; Metal acetate salt comprise manganese acetate, acetic acid every.
10. a kind of metal phthalocyanine according to claim 1 and alloy presoma thereof prepare the method for nanoporous at graphenic surface, it is characterized in that protecting described in step 6) gas to be any one in nitrogen, argon gas, helium or hydrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510453544.8A CN105110321A (en) | 2015-07-29 | 2015-07-29 | Preparation method for nano-pores on surface of graphene by metal phthalocyanine and its alloy precursor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510453544.8A CN105110321A (en) | 2015-07-29 | 2015-07-29 | Preparation method for nano-pores on surface of graphene by metal phthalocyanine and its alloy precursor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105110321A true CN105110321A (en) | 2015-12-02 |
Family
ID=54658494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510453544.8A Pending CN105110321A (en) | 2015-07-29 | 2015-07-29 | Preparation method for nano-pores on surface of graphene by metal phthalocyanine and its alloy precursor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105110321A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967176A (en) * | 2016-05-17 | 2016-09-28 | 四川环碳科技有限公司 | Preparation method of cellular three-dimensional graphene |
| CN108355651A (en) * | 2018-02-08 | 2018-08-03 | 电子科技大学 | A kind of ruthenium nano metal elctro-catalyst and preparation method |
| CN110554546A (en) * | 2019-09-26 | 2019-12-10 | 中国科学院长春光学精密机械与物理研究所 | Graphene phthalocyanine composite material and preparation method thereof |
| CN111013623A (en) * | 2019-12-13 | 2020-04-17 | 西北大学 | Nitrogen-doped graphene catalyst and preparation method thereof |
| CN111589465A (en) * | 2020-06-03 | 2020-08-28 | 浙江理工大学 | Preparation method and application of high-dispersity three-dimensional porous carbon-based metal catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103407991A (en) * | 2013-07-10 | 2013-11-27 | 西北工业大学 | Preparation method of nickel/nickel oxide-decorated nitrogen-doped graphene material |
| CN103990484A (en) * | 2014-05-26 | 2014-08-20 | 西北工业大学 | Preparation method of nitrogen doped and graphene loaded Cu-Cu2O nanocomposites |
| CN104319395A (en) * | 2014-10-22 | 2015-01-28 | 上海大学 | Method for preparing three-dimensional nitrogen-doped graphene/CoOx composite material |
-
2015
- 2015-07-29 CN CN201510453544.8A patent/CN105110321A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103407991A (en) * | 2013-07-10 | 2013-11-27 | 西北工业大学 | Preparation method of nickel/nickel oxide-decorated nitrogen-doped graphene material |
| CN103990484A (en) * | 2014-05-26 | 2014-08-20 | 西北工业大学 | Preparation method of nitrogen doped and graphene loaded Cu-Cu2O nanocomposites |
| CN104319395A (en) * | 2014-10-22 | 2015-01-28 | 上海大学 | Method for preparing three-dimensional nitrogen-doped graphene/CoOx composite material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967176A (en) * | 2016-05-17 | 2016-09-28 | 四川环碳科技有限公司 | Preparation method of cellular three-dimensional graphene |
| CN105967176B (en) * | 2016-05-17 | 2018-01-23 | 四川环碳科技有限公司 | A kind of preparation method of cellular three-dimensional grapheme |
| CN108355651A (en) * | 2018-02-08 | 2018-08-03 | 电子科技大学 | A kind of ruthenium nano metal elctro-catalyst and preparation method |
| CN108355651B (en) * | 2018-02-08 | 2021-02-05 | 电子科技大学 | Ruthenium nano metal electrocatalyst and preparation method thereof |
| CN110554546A (en) * | 2019-09-26 | 2019-12-10 | 中国科学院长春光学精密机械与物理研究所 | Graphene phthalocyanine composite material and preparation method thereof |
| CN111013623A (en) * | 2019-12-13 | 2020-04-17 | 西北大学 | Nitrogen-doped graphene catalyst and preparation method thereof |
| CN111589465A (en) * | 2020-06-03 | 2020-08-28 | 浙江理工大学 | Preparation method and application of high-dispersity three-dimensional porous carbon-based metal catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105110321A (en) | Preparation method for nano-pores on surface of graphene by metal phthalocyanine and its alloy precursor | |
| Niu et al. | A conveniently synthesized redox-active fluorescent covalent organic framework for selective detection and adsorption of uranium | |
| Li et al. | Stable sp2 carbon-conjugated covalent organic framework for detection and efficient adsorption of uranium from radioactive wastewater | |
| Wei et al. | Positively charged phosphonate-functionalized mesoporous silica for efficient uranium sorption from aqueous solution | |
| CN106492761A (en) | A kind of preparation method of magnetic hydrogel microsphere | |
| CN105251448B (en) | A kind of preparation method of magnetic graphene composite | |
| CN107029671B (en) | Modified Fe3O4Preparation method and application of @ MOF composite material | |
| CN107511132B (en) | Magnetic ferroferric oxide nano particle and plasma modification method and application thereof | |
| CN103007887B (en) | Carbon-nanotube-loaded multi-stage nanometer ferroferric oxide adsorbent and preparation method and application thereof | |
| CN103285817B (en) | Amino acid modified silicon-structure-containing ferriferrous oxide nanoparticle and its application in dye adsorption treatment | |
| Yang et al. | An effective lithium ion-imprinted membrane containing 12-crown ether-4 for selective recovery of lithium | |
| Ji et al. | Three-dimensional network graphene oxide/sodium alginate aerogel beads with slit-shaped structure: Synthesis, performance and selective adsorption mechanism for Cu (II) | |
| CN105692758A (en) | Poly-tannic acid coated Fe3O4 magnetic adsorbent for removing Hg2+ and Pb2+ | |
| CN111883869A (en) | Method for recycling lithium by using graphite cathode of waste power battery and preparing graphene by using lithium | |
| Liu et al. | Adsorption of thorium (IV) on magnetic multi-walled carbon nanotubes | |
| Liu et al. | Preparation of amidoxime polyacrylonitrile membrane with excellent mechanical strength for adsorption of uranium in simulated wastewater | |
| CN106268953A (en) | A kind of graphene oxide and bar-shaped composite porous and preparation method thereof containing cerium coordination polymer | |
| CN104826594A (en) | Preparation of high-reducibility magnetic graphene and application of magnetic graphene in adsorption of Cr(VI) | |
| Wang et al. | A smart potential-responsive ion exchange nanomaterial with superparamagnetism for cesium ion separation and recovery | |
| CN110385048A (en) | A kind of porous carbon nanosheet mixed substrate membrane containing nano-grade molecular sieve of two dimension and preparation method thereof | |
| CN101905331B (en) | Method for extracting nano-silver in aqueous phase by using ionic liquid | |
| Du et al. | Modulating the pore and electronic structure for targeted recovery of platinum: Accelerated kinetic and reinforced coordination | |
| CN105017482A (en) | Surface molecularly imprinted poly(ionic liquid) for detecting 4-nonyl phenol and its preparation method and use | |
| Wang et al. | A robust cationic covalent triazine framework-based nanotrap for fast and efficient recovery of gold from electronic waste | |
| CN104393259B (en) | Preparation method of porous carbon ball-supported MxOy nanoparticle composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20151202 |