CN105152167A - Large-scale synthesis method of two-dimensional graphene-like carbon material by using sodium citrate - Google Patents
Large-scale synthesis method of two-dimensional graphene-like carbon material by using sodium citrate Download PDFInfo
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Abstract
The invention relates to a large-scale synthesis method of a two-dimensional graphene-like carbon material by using sodium citrate, which comprises the following step: in an oxygen-free environment, by using sodium citrate as a carbon source, respectively synthesizing an amorphous carbon material, a nitrogen-doped amorphous carbon material, a graphene-like carbon material and a nitrogen-doped graphene-like carbon material by regulating the mass ratio of the sodium citrate, graphitization catalyst and nitrogen dopant. The high-quality graphene-like carbon material is obtained at lower temperature under atmospheric pressure, thereby solving the technical problem of mass controllable production of the graphene-like-structure carbon material to some extent, and having wide application prospects.
Description
Technical field
The present invention relates to the synthesis technical field of two-dimentional class Graphene Carbon Materials, be specifically related to a kind of method utilizing Trisodium Citrate mass-producing to synthesize two-dimentional amorphous Carbon Materials, N doping amorphous Carbon Materials, class Graphene Carbon Materials, N doping class Graphene Carbon Materials.
Background technology
Graphene is thickness is an atomic shell, has the novel material of two dimensional crystal structure.In Graphene, connect with s key between carbon atom, combination is sp
2hydridization, these s keys impart the high physical strength of Graphene and good chemical stability.In addition each carbon atom p electronics of having a non-Cheng Jian, can moving freely in crystal, makes Graphene have excellent conductivity.Graphene and class Graphene are owing to having good electronic conduction performance and large specific surface area, and having a wide range of applications in fields such as electrical condenser, energy storage, sensor, catalysis, is a kind of type material with great potential.Current Graphene is raw material mainly with graphite greatly, by method preparations such as micromechanics stripping method, SiC thermal decomposition epitaxy growth method, chemical Vapor deposition process, chemistry redox methods.These methods preparing Graphene have the shortcoming that productive rate is low, cost is high, toxicity is large usually, cannot meet large-scale industrial demand, constrain its application in every field to a certain extent.
Patent CN102951631B discloses a kind of preparation method of Graphene.The method that the method adopts chemical reduction to combine with microwave reduction prepares Graphene, first the alkyl derivative of lithium and tungsten hexachloride are added in organic solvent and react, again the organic solution of graphene oxide is joined in above-mentioned mixing solutions and carry out reduction reaction, obtain Graphene crude product, Graphene crude product is obtained Graphene through microwave treatment.This inventive method shortcoming is that the organic solvent toxicity that experimentation is used is comparatively large, and the Graphene defect obtained is many, and conduction, heat conductivility are relatively poor.
Patent CN102976315A discloses a kind of method that microwave-assisted reduction of sodium citrate prepares Graphene.The method utilizes microwave treatment, and take Trisodium Citrate as reductive agent reduction-oxidation preparing graphite alkene, its usage ratio is graphite oxide 0.05 ~ 0.3g, Trisodium Citrate 1 ~ 30g.But this patent of invention is just reductive agent with Trisodium Citrate, and its essence still utilizes the method for reduction-oxidation graphite to prepare Graphene, and its operating process is complicated, cost is high, is difficult to realize large-scale production.
Trisodium Citrate is Citrate trianion important at present, has safety non-toxic, good biological degradability, lower-price characteristic.The present invention take Trisodium Citrate as amorphous Carbon Materials, N doping amorphous Carbon Materials, class Graphene Carbon Materials, the N doping class Graphene Carbon Materials that the synthesis of charcoal source has two-dirnentional structure; Its product has good chemical property, and with low cost, environmental protection, can scale operation, the aspects such as electrical condenser, solar cell and energy storage can be widely used in.
Summary of the invention
The object of the invention is to provide a kind of method utilizing Trisodium Citrate mass-producing to synthesize two-dimentional class Graphene Carbon Materials.The method take Trisodium Citrate as amorphous Carbon Materials, the N doping amorphous Carbon Materials of charcoal source mass-producing synthesis two dimension.In order to improve conduction, the heat conductivility of Carbon Materials further, in said system, add graphitization catalyst, and then obtain high-quality class Graphene Carbon Materials, the N doping class Graphene Carbon Materials with two-dirnentional structure.The method low production cost, operating procedure are simple, are a kind of environmental protections, fast effectively, can synthesize the method for the amorphous Carbon Materials of two dimension, N doping amorphous Carbon Materials, class Graphene Carbon Materials, N doping class Graphene Carbon Materials on a large scale.
Technical solution problem of the present invention, adopts following technical scheme:
Utilizing Trisodium Citrate mass-producing to synthesize the method for two-dimentional class Graphene Carbon Materials, is carry out as follows:
Taking Trisodium Citrate, graphitization catalyst and nitrogen dopant by proportioning is raw material, and mixing is also fully ground;
Raw material after grinding is carried out carbonizing (namely carrying out high-temperature calcination at inert gas atmosphere) under oxygen-free environment;
After product will be calcined through overpickling, washing, oven dry, namely obtain two-dimentional class Graphene Carbon Materials;
By changing the mass ratio of Trisodium Citrate, graphitization catalyst and nitrogen dopant, change the type of products therefrom two dimension class Graphene Carbon Materials, obtain having the amorphous Carbon Materials of two-dirnentional structure, N doping amorphous Carbon Materials, class Graphene Carbon Materials or N doping class Graphene Carbon Materials.
In above-mentioned steps, the mass ratio of Trisodium Citrate, graphitization catalyst, nitrogen dopant is 1 ~ 10:0 ~ 10:0 ~ 20.
Described graphitization catalyst is at least one in metal simple-substance, metal oxide, metal chloride, metal nitrate, metal acetate, metal carbonate, metal oxalate and metal citrate.
Described metal simple-substance is nickel, cobalt or iron; Described metal oxide is nickel oxide, cobalt oxide or ferric oxide; Described metal chloride is nickelous chloride, cobalt chloride or iron(ic) chloride; Described metal nitrate is nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or iron nitrate; Described metal acetate is nickelous acetate, cobaltous acetate or ironic acetate; Described metal carbonate is nickelous carbonate, cobaltous carbonate or iron carbonate; Described metal oxalate is nickelous oxalate, cobalt oxalate or ironic oxalate; Described metal citrate is citric acid nickel, citric acid cobalt or ironic citrate.
Described nitrogen dopant is at least one in trimeric cyanamide, ammonium chloride, imidazoles, hydrazo-benzene, pyridine, Dopamine HCL, quadrol, amino acid, thiophene, phthalocyanine, vulkacit H, urea, polypyridine, polypyrrole, phenanthroline and methylamine.
The temperature of described high-temperature calcination is 600 ~ 1000 DEG C, the time is 1 ~ 10h, temperature rise rate is 4 ~ 30 DEG C of min
– 1.
Compared with prior art, beneficial effect of the present invention is embodied in:
1, the charcoal source that the present invention is used is Trisodium Citrate, and its cheap, safety non-toxic, can realize green production.
2, the two-dimentional class Graphene Carbon Materials of the present invention's synthesis has good conduction and heat conductivility, can be widely used in super capacitor, energy storage, sensor aspect.
3, reaction time of the present invention is short, and easy handling is less demanding to reaction conditions, and the large-scale industrial that can realize two-dimentional class Graphene Carbon Materials is produced.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that the present invention synthesizes two-dimentional class Graphene Carbon Materials;
Fig. 2 is the scanning electron microscope (SEM) photograph of the amorphous Carbon Materials obtained in embodiment 1;
Fig. 3 is the X-ray diffractogram of the amorphous Carbon Materials obtained in embodiment 1;
Fig. 4 is the charge and discharge electrograph carrying out charge-discharge test under different current density of the amorphous Carbon Materials obtained in embodiment 1.
Fig. 5 is the scanning electron microscope (SEM) photograph of the N doping amorphous Carbon Materials obtained in embodiment 2;
Fig. 6 is the X-ray diffractogram of the class Graphene Carbon Materials obtained in embodiment 9;
Fig. 7 is the X-ray diffractogram of the class Graphene Carbon Materials obtained in embodiment 10;
Fig. 8 is the X-ray diffractogram of the class Graphene Carbon Materials obtained in embodiment 11.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the synthetic method of two-dimentional class Graphene Carbon Materials of the present invention is described further.
The invention provides a kind of environmental protection, cheap, reaction time is short, easy handling, synthetic method to the lower two-dimentional class Graphene Carbon Materials of reaction conditions requirement.The technical process of the synthetic method of this two-dimentional class Graphene Carbon Materials as shown in Figure 1, specifically comprises the steps:
S1: taking the Trisodium Citrate of certain mass ratio, graphitization catalyst and nitrogen dopant is raw material, mixing is also fully ground;
S2: the raw material after grinding is carbonized under oxygen-free environment, obtains two-dimentional class Graphene Carbon Materials crude product;
S3: by crude product purified for described two-dimentional class Graphene Carbon Materials, obtains the class Graphene Carbon Materials sample of two dimension;
S4: dry sample, obtains two-dimentional class Graphene Carbon Materials.
By changing the mass ratio of Trisodium Citrate, graphitization catalyst and nitrogen dopant, amorphous Carbon Materials, N doping amorphous Carbon Materials, class Graphene Carbon Materials, the N doping class Graphene Carbon Materials of two dimension can be obtained respectively.
Particularly, in above-mentioned steps S1, the mass ratio of Trisodium Citrate, graphitization catalyst, nitrogen dopant is 1 ~ 10:0 ~ 10:0 ~ 20.
Described graphitization catalyst is metal simple-substance (nickel, cobalt, iron), metal oxide (nickel oxide, cobalt oxide, ferric oxide), metal chloride (nickelous chloride, cobalt chloride, iron(ic) chloride), metal nitrate (nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, iron nitrate), metal acetate (nickelous acetate, cobaltous acetate, ironic acetate), metal carbonate (nickelous carbonate, cobaltous carbonate, iron carbonate), metal oxalate (nickelous oxalate, cobalt oxalate, ironic oxalate) and metal citrate (citric acid nickel, citric acid cobalt, ironic citrate) at least one.
Described nitrogen dopant is at least one in trimeric cyanamide, ammonium chloride, imidazoles, hydrazo-benzene, pyridine, Dopamine HCL, quadrol, amino acid, thiophene, phthalocyanine, vulkacit H, urea, polypyridine, polypyrrole, phenanthroline and methylamine.
In above-mentioned steps S2, the method of described charing is: transfer in the porcelain boat of horizontal pipe furnace by the mixture after grinding, under oxygen-free environment, horizontal pipe furnace is heated to temperature of reaction with certain temperature rise rate, take out after charing for some time, obtain the class Graphene Carbon Materials crude product of two dimension.
The present embodiment adopts the method passing into rare gas element to manufacture oxygen-free environment, and the time that passes into of rare gas element is preferably 30min.The temperature rise rate of described horizontal pipe furnace is preferably 4 ~ 30 DEG C of min
– 1, described temperature of reaction is preferably 600 ~ 1000 DEG C.The time that described porcelain boat keeps in described inert gas is advisable with 1 ~ 10h.The described rare gas element be filled with is the rare gas element known by the art, such as argon gas, nitrogen etc.Because nitrogen cost is low, easily obtain, therefore, preferred nitrogen.In other embodiments, vacuum can also be adopted to realize oxygen-free environment.
In above-mentioned steps S3, described in purifying, the method for two-dimentional class Graphene Carbon Materials crude product comprises: described two-dimentional class Graphene Carbon Materials crude product is put into acid solution and floods, removing impurity and graphitization catalyst; Suction filtration, obtains described two-dimentional class Graphene Carbon Materials sample.Particularly, during suction filtration, use two-dimentional class Graphene Carbon Materials sample described in deionized water rinsing, until described two-dimentional class Graphene Carbon Materials sample is in neutral.
In above-mentioned steps S4, described two-dimentional class Graphene Carbon Materials sample can be placed in vacuum drying oven dry, drying temperature the best is 110 DEG C, and time of drying is preferably 12h.
Now for the synthetic method of concrete two-dimentional class Graphene Carbon Materials, the present invention is further illustrated.
Embodiment 1
S1: take 1.0g Trisodium Citrate, fully grind.
S2: transfer in the porcelain boat of horizontal pipe furnace by the Trisodium Citrate after grinding, passes into rare gas element 30min and makes in horizontal pipe furnace to be oxygen-free environment, then continue under an inert atmosphere with 4 DEG C of min
– 1temperature rise rate be heated to 600 DEG C, take out after constant temperature 1h in inert gas, obtain two-dimentional amorphous Carbon Materials crude product;
S3: gained two dimension amorphous Carbon Materials crude product is put into acid and floods, removing impurity.Suction filtration subsequently, and with deionized water rinsing to neutral.
S4: be placed on by sample in vacuum drying oven and be heated to 110 DEG C and keep 12h, obtains two-dimentional amorphous Carbon Materials.
Fig. 2 is the scanning electron microscope (SEM) photograph of the present embodiment gained sample, and as can be seen from the figure this sample presents typical two-dimensional sheet structure, and its thickness is about 10 ~ 20nm.
Fig. 3 is the X-ray diffractogram of the present embodiment gained sample, and as can be seen from the figure (002) and (10) diffraction peak of this sample is more wide in range and intensity is lower, shows that this sample is amorphous Carbon Materials.
Fig. 4 is that the amorphous Carbon Materials obtained in embodiment 1 carries out the charge and discharge electrograph of charge-discharge test (current density that in figure, each curve is corresponding in turn to from left to right is 5Ag under different current density
-1, 4Ag
-1, 3Ag
-1, 2Ag
-1, 1Ag
-1), as can be seen from the figure gained amorphous Carbon Materials has longer discharge time, shows that this sample has good chemical property.
Embodiment 2
S1: take 1.0g Trisodium Citrate, 1.0g trimeric cyanamide, mixing is also fully ground.
S2: transfer in the porcelain boat of horizontal pipe furnace by the mixture after grinding, passes into rare gas element 30min and makes in horizontal pipe furnace to be oxygen-free environment, then continue under an inert atmosphere with 4 DEG C of min
– 1temperature rise rate be heated to 1000 DEG C, take out after then keeping 4h in inert gas, obtain two-dimentional amorphous N doping Carbon Materials crude product.
S3: gained two dimension amorphous N doping Carbon Materials crude product is put into acid and floods, removing impurity.Suction filtration subsequently, and with deionized water rinsing to neutral.
S4: be placed on by sample in vacuum drying oven and be heated to 110 DEG C and keep 12h, namely obtains two-dimentional amorphous N doping Carbon Materials.
Fig. 5 is the scanning electron microscope (SEM) photograph of the present embodiment gained sample, and as can be seen from the figure this sample presents two-dimensional sheet structure, and its thickness is about 10 ~ 20nm.
Embodiment 3
S1: take 1.0g Trisodium Citrate, 1.0g nickel, mixing is also fully ground.
S2: transfer in the porcelain boat of horizontal pipe furnace by the mixture after grinding, passes into rare gas element 30min and makes in horizontal pipe furnace to be oxygen-free environment, then continue under an inert atmosphere with 4 DEG C of min
– 1temperature rise rate be heated to 800 DEG C, take out after then keeping 2h in inert gas, obtain two-dimentional class Graphene Carbon Materials crude product.
S3: gained two dimension class Graphene Carbon Materials crude product is put into acid and floods, removing impurity and graphitization catalyst.Suction filtration subsequently, and with deionized water rinsing to neutral.
S4: be placed on by sample in vacuum drying oven and be heated to 110 DEG C and keep 12h, namely obtains two-dimentional class Graphene Carbon Materials.
Embodiment 4
S1: take 1.0g Trisodium Citrate, 1.0g ferric oxide, mixing is also fully ground.
S2: transfer in the porcelain boat of horizontal pipe furnace by the mixture after grinding, passes into rare gas element 30min and makes in horizontal pipe furnace to be oxygen-free environment, then continue under an inert atmosphere with 4 DEG C of min
– 1temperature rise rate be heated to 800 DEG C, then keep 2h to take out in inert gas, obtain two-dimentional class Graphene Carbon Materials crude product.
S3: gained two dimension class Graphene Carbon Materials crude product is put into acid and floods, removing impurity and graphitization catalyst.Suction filtration subsequently, and with deionized water rinsing to neutral.
S4: be placed on by sample in vacuum drying oven and be heated to 110 DEG C and keep 12h, namely obtains two-dimentional class Graphene Carbon Materials.
Embodiment 5
S1: take 1.0g Trisodium Citrate, 5.0g cobalt chloride, mixing is also fully ground.
S2: transfer in the porcelain boat of horizontal pipe furnace by the mixture after grinding, passes into rare gas element 30min and makes in horizontal pipe furnace to be oxygen-free environment, then continue under an inert atmosphere with 4 DEG C of min
– 1temperature rise rate be heated to 800 DEG C, then keep 2h to take out in inert gas, obtain two-dimentional class Graphene Carbon Materials crude product.
S3: gained two dimension class Graphene Carbon Materials crude product is put into acid and floods, removing impurity and graphitization catalyst.Suction filtration subsequently, and with deionized water rinsing to neutral.
S4: be placed on by sample in vacuum drying oven and be heated to 110 DEG C and keep 12h, namely obtains two-dimentional class Graphene Carbon Materials.
Embodiment 6
S1: take 1.0g Trisodium Citrate, 5.0g ironic acetate, mixing is also fully ground.
S2: transfer in the porcelain boat of horizontal pipe furnace by the mixture after grinding, passes into rare gas element 30min and makes in horizontal pipe furnace to be oxygen-free environment, then continue under an inert atmosphere with 5 DEG C of min
– 1temperature rise rate be heated to 800 DEG C, then keep 2h to take out in inert gas, obtain two-dimentional class Graphene Carbon Materials crude product.
S3: gained two dimension class Graphene Carbon Materials crude product is put into acid and floods, removing impurity and graphitization catalyst.Suction filtration subsequently, and with deionized water rinsing to neutral.
S4: be placed on by sample in vacuum drying oven and be heated to 110 DEG C and keep 12h, namely obtains two-dimentional class Graphene Carbon Materials.
Embodiment 7
S1: take 1.0g Trisodium Citrate, 10.0g nickelous oxalate, mixing is also fully ground.
S2: transfer in the porcelain boat of horizontal pipe furnace by the mixture after grinding, passes into rare gas element 30min and makes in horizontal pipe furnace to be oxygen-free environment, then continue under an inert atmosphere with 5 DEG C of min
– 1temperature rise rate be heated to 800 DEG C, then keep 2h to take out in inert gas, obtain two-dimentional class Graphene Carbon Materials crude product.
S3: gained two dimension class Graphene Carbon Materials crude product is put into acid and floods, removing impurity and graphitization catalyst.Suction filtration subsequently, and with deionized water rinsing to neutral.
S4: be placed on by sample in vacuum drying oven and be heated to 110 DEG C and keep 12h, namely obtains two-dimentional class Graphene Carbon Materials.
Embodiment 8
S1: take 1.0g Trisodium Citrate, 10.0g citric acid cobalt, mixing is also fully ground.
S2: transfer in the porcelain boat of horizontal pipe furnace by the mixture after grinding, passes into rare gas element 30min and makes in horizontal pipe furnace to be oxygen-free environment, then continue under an inert atmosphere with 5 DEG C of min
– 1temperature rise rate be heated to 900 DEG C, then keep 2h to take out in inert gas, obtain two-dimentional class Graphene Carbon Materials crude product.
S3: gained two dimension class Graphene Carbon Materials crude product is put into acid and floods, removing impurity and graphitization catalyst.Suction filtration subsequently, and with deionized water rinsing to neutral.
S4: be placed on by sample in vacuum drying oven and be heated to 110 DEG C and keep 12h, namely obtains two-dimentional class Graphene Carbon Materials.
Embodiment 9
S1: take 10.0g Trisodium Citrate, 1.0g nickelous nitrate, mixing is also fully ground.
S2: transfer in the porcelain boat of horizontal pipe furnace by the mixture after grinding, passes into rare gas element 30min and makes in horizontal pipe furnace to be oxygen-free environment, then continue under an inert atmosphere with 4 DEG C of min
– 1temperature rise rate be heated to 600 DEG C, then keep 2h to take out in inert gas, obtain two-dimentional class Graphene Carbon Materials crude product.
S3: gained two dimension class Graphene Carbon Materials crude product is put into acid and floods, removing impurity and graphitization catalyst.Suction filtration subsequently, and with deionized water rinsing to neutral.
S4: be placed on by sample in vacuum drying oven and be heated to 110 DEG C and keep 12h, namely obtains two-dimentional class Graphene Carbon Materials.
Fig. 6 is the X-ray diffractogram of the present embodiment gained sample, as can be seen from the figure the intensity of this sample (002) diffraction peak is higher than the intensity of (002) diffraction peak in Fig. 4, show that the degree of graphitization of this sample is higher than the degree of graphitization of gained sample in embodiment 1, what describe graphitization catalyst adds the degree of crystallinity that effectively can improve Carbon Materials simultaneously, thus can realize the synthesis of two-dimentional class Graphene Carbon Materials.
Embodiment 10
S1: take 10.0g Trisodium Citrate, 5.0g nickelous nitrate, mixing is also fully ground.
S2: transfer in the porcelain boat of horizontal pipe furnace by the mixture after grinding, passes into rare gas element 30min and makes in horizontal pipe furnace to be oxygen-free environment, then continue under an inert atmosphere with 4 DEG C of min
– 1temperature rise rate be heated to 800 DEG C, then keep 2h to take out in inert gas, obtain two-dimentional class Graphene Carbon Materials crude product.
S3: gained two dimension class Graphene Carbon Materials crude product is put into acid and floods, removing impurity and graphitization catalyst.Suction filtration subsequently, and with deionized water rinsing to neutral.
S4: be placed on by sample in vacuum drying oven and be heated to 110 DEG C and keep 12h, namely obtains two-dimentional class Graphene Carbon Materials.
Fig. 7 is the X-ray diffractogram of the present embodiment gained sample, as can be seen from the figure (002) diffraction peak of this sample is higher than (002) diffraction peak intensity in Fig. 6, shows the degree of graphitization of the degree of graphitization of this sample higher than gained sample in embodiment 9.
Embodiment 11
S1: take 10.0g Trisodium Citrate, 10.0g nickelous nitrate, mixing is also fully ground.
S2: transfer in the porcelain boat of horizontal pipe furnace by the mixture after grinding, passes into rare gas element 30min and makes in horizontal pipe furnace to be oxygen-free environment, then continue under an inert atmosphere with 5 DEG C of min
– 1temperature rise rate be heated to 900 DEG C, then keep 5h to take out in inert gas, obtain two-dimentional class Graphene Carbon Materials crude product.
S3: gained two dimension class Graphene Carbon Materials crude product is put into acid and floods, removing impurity and graphitization catalyst.Suction filtration subsequently, and with deionized water rinsing to neutral.
S4: be placed on by sample in vacuum drying oven and be heated to 110 DEG C and keep 12h, namely obtains two-dimentional class Graphene Carbon Materials.
Fig. 8 is the X-ray diffractogram of the present embodiment gained sample, as can be seen from the figure (002) diffraction peak of this sample is higher than (002) diffraction peak intensity in Fig. 7, and the intensity of (10) diffraction peak also has and slightly improves, show the degree of graphitization of the degree of graphitization of this sample higher than gained sample in embodiment 10.Can be drawn by relatively above X-ray diffractogram, also increase gradually along with catalyst levels increases its degree of graphitization.
Embodiment 12
S1: take 10.0g Trisodium Citrate, 1.0g nickelous nitrate, 5.0g trimeric cyanamide, mixing is fully ground.
S2: transfer in the porcelain boat of horizontal pipe furnace by the mixture after grinding, passes into rare gas element 30min and makes in horizontal pipe furnace to be oxygen-free environment, then continue under an inert atmosphere with 4 DEG C of min
– 1temperature rise rate be heated to 800 DEG C, then keep 2h to take out in inert gas, obtain two-dimentional N doping class Graphene Carbon Materials crude product.
S3: gained two dimension N doping class Graphene Carbon Materials crude product is put into acid and floods, removing impurity and graphitization catalyst.Suction filtration subsequently, and with deionized water rinsing to neutral.
S4: be placed on by sample in vacuum drying oven and be heated to 110 DEG C and keep 12h, namely obtains two-dimentional N doping class Graphene Carbon Materials.
Embodiment 13
S1: take 10.0g Trisodium Citrate, 1.0g ironic acetate, 10.0g ammonium chloride, mixing is also fully ground.
S2: transfer in the porcelain boat of horizontal pipe furnace by the mixture after grinding, passes into rare gas element 30min and makes in horizontal pipe furnace to be oxygen-free environment, then continue under an inert atmosphere with 4 DEG C of min
– 1temperature rise rate be heated to 900 DEG C, then keep 2h to take out in inert gas, obtain two-dimentional N doping class Graphene Carbon Materials crude product.
S3: gained two dimension N doping class Graphene Carbon Materials crude product is put into acid and floods, removing impurity and graphitization catalyst.Suction filtration subsequently, and with deionized water rinsing to neutral.
S4: be placed on by sample in vacuum drying oven and be heated to 110 DEG C and keep 12h, namely obtains two-dimentional N doping class Graphene Carbon Materials.
Embodiment 14
S1: take 10.0g Trisodium Citrate, 1.0g cobalt oxalate, 20.0g hydrazo-benzene, mixing is also fully ground.
S2: transfer in the porcelain boat of horizontal pipe furnace by the mixture after grinding, passes into rare gas element 30min and makes in horizontal pipe furnace to be oxygen-free environment, then continue under an inert atmosphere with 4 DEG C of min
– 1temperature rise rate be heated to 1000 DEG C, then keep 2h to take out in inert gas, obtain two-dimentional N doping class Graphene Carbon Materials crude product.
S3: gained two dimension N doping class Graphene Carbon Materials crude product is put into acid and floods, removing impurity and graphitization catalyst.Suction filtration subsequently, and with deionized water rinsing to neutral.
S4: be placed on by sample in vacuum drying oven and be heated to 110 DEG C and keep 12h, namely obtains two-dimentional N doping class Graphene Carbon Materials.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. utilize Trisodium Citrate mass-producing to synthesize a method for two-dimentional class Graphene Carbon Materials, it is characterized in that:
Taking Trisodium Citrate, graphitization catalyst and nitrogen dopant by proportioning is raw material, and mixing is also fully ground;
Raw material after grinding is carried out high-temperature calcination at inert gas atmosphere;
After product will be calcined through overpickling, washing, oven dry, namely obtain two-dimentional class Graphene Carbon Materials;
By changing the mass ratio of Trisodium Citrate, graphitization catalyst and nitrogen dopant, change the type of products therefrom two dimension class Graphene Carbon Materials, obtain having the amorphous Carbon Materials of two-dirnentional structure, N doping amorphous Carbon Materials, class Graphene Carbon Materials or N doping class Graphene Carbon Materials.
2. the method utilizing Trisodium Citrate mass-producing to synthesize two-dimentional class Graphene Carbon Materials according to claim 1, is characterized in that: the mass ratio of Trisodium Citrate, graphitization catalyst, nitrogen dopant is 1 ~ 10:0 ~ 10:0 ~ 20.
3. the method utilizing Trisodium Citrate mass-producing to synthesize two-dimentional class Graphene Carbon Materials according to claim 1 and 2, is characterized in that: described graphitization catalyst is at least one in metal simple-substance, metal oxide, metal chloride, metal nitrate, metal acetate, metal carbonate, metal oxalate and metal citrate.
4. the method utilizing Trisodium Citrate mass-producing to synthesize two-dimentional class Graphene Carbon Materials according to claim 3, is characterized in that: described metal simple-substance is nickel, cobalt or iron; Described metal oxide is nickel oxide, cobalt oxide or ferric oxide; Described metal chloride is nickelous chloride, cobalt chloride or iron(ic) chloride; Described metal nitrate is nickelous nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES or iron nitrate; Described metal acetate is nickelous acetate, cobaltous acetate or ironic acetate; Described metal carbonate is nickelous carbonate, cobaltous carbonate or iron carbonate; Described metal oxalate is nickelous oxalate, cobalt oxalate or ironic oxalate; Described metal citrate is citric acid nickel, citric acid cobalt or ironic citrate.
5. the method utilizing Trisodium Citrate mass-producing to synthesize two-dimentional class Graphene Carbon Materials according to claim 1 and 2, is characterized in that: described nitrogen dopant is at least one in trimeric cyanamide, ammonium chloride, imidazoles, hydrazo-benzene, pyridine, Dopamine HCL, quadrol, amino acid, thiophene, phthalocyanine, vulkacit H, urea, polypyridine, polypyrrole, phenanthroline and methylamine.
6. the method utilizing Trisodium Citrate mass-producing to synthesize two-dimentional class Graphene Carbon Materials according to claim 1 and 2, is characterized in that: the temperature of described high-temperature calcination is 600 ~ 1000 DEG C, the time is 1 ~ 10h, temperature rise rate is 4 ~ 30 DEG C of min
– 1.
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| CN106207239A (en) * | 2016-09-26 | 2016-12-07 | 南昌航空大学 | The synthetic method of a kind of N doping porous carbon and the application in terms of anode of microbial fuel cell thereof |
| CN107128902A (en) * | 2017-04-28 | 2017-09-05 | 多氟多化工股份有限公司 | A kind of network-like graphene nano material and its preparation method and application |
| CN108658060A (en) * | 2018-06-26 | 2018-10-16 | 北京理工大学 | A kind of preparation method of the graphene nanometer sheet of the adjustable single layer phosphorus doping of band gap |
| CN109081328A (en) * | 2018-09-08 | 2018-12-25 | 天津大学 | A method of preparing the three-dimensional porous carbon nanosheet ball of N doping |
| CN109755031A (en) * | 2019-02-21 | 2019-05-14 | 青岛科技大学 | A kind of NiO/NG/NF combination electrode material and preparation method thereof |
| CN110835104A (en) * | 2019-10-28 | 2020-02-25 | 深圳先进技术研究院 | Preparation method of nitrogen-doped carbon nanosheet, negative electrode active material and dual-ion battery |
| CN111842919A (en) * | 2020-07-31 | 2020-10-30 | 河北农业大学 | Preparation method of ultra-small nickel-iron nanocluster and ultra-small nickel-iron nanocluster |
| CN113003560A (en) * | 2021-03-30 | 2021-06-22 | 北京工业大学 | Method for hydro-thermal synthesis of 'sea urchin-like' nitrogen-doped hollow carbon microspheres by in-situ self-growth template |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106207239A (en) * | 2016-09-26 | 2016-12-07 | 南昌航空大学 | The synthetic method of a kind of N doping porous carbon and the application in terms of anode of microbial fuel cell thereof |
| CN107128902A (en) * | 2017-04-28 | 2017-09-05 | 多氟多化工股份有限公司 | A kind of network-like graphene nano material and its preparation method and application |
| CN107128902B (en) * | 2017-04-28 | 2019-03-15 | 多氟多化工股份有限公司 | A kind of network-like graphene nano material and its preparation method and application |
| CN108658060A (en) * | 2018-06-26 | 2018-10-16 | 北京理工大学 | A kind of preparation method of the graphene nanometer sheet of the adjustable single layer phosphorus doping of band gap |
| CN109081328A (en) * | 2018-09-08 | 2018-12-25 | 天津大学 | A method of preparing the three-dimensional porous carbon nanosheet ball of N doping |
| CN109755031A (en) * | 2019-02-21 | 2019-05-14 | 青岛科技大学 | A kind of NiO/NG/NF combination electrode material and preparation method thereof |
| CN109755031B (en) * | 2019-02-21 | 2020-04-03 | 青岛科技大学 | NiO/NG/NF composite electrode material and preparation method thereof |
| CN110835104A (en) * | 2019-10-28 | 2020-02-25 | 深圳先进技术研究院 | Preparation method of nitrogen-doped carbon nanosheet, negative electrode active material and dual-ion battery |
| CN111842919A (en) * | 2020-07-31 | 2020-10-30 | 河北农业大学 | Preparation method of ultra-small nickel-iron nanocluster and ultra-small nickel-iron nanocluster |
| CN113003560A (en) * | 2021-03-30 | 2021-06-22 | 北京工业大学 | Method for hydro-thermal synthesis of 'sea urchin-like' nitrogen-doped hollow carbon microspheres by in-situ self-growth template |
| CN113430537A (en) * | 2021-07-20 | 2021-09-24 | 兰州大学 | Preparation method of N-doped carbon-based material for oxygen evolution electrocatalyst |
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