CN105692573A - Preparation method of nano-structure carbon nitride - Google Patents
Preparation method of nano-structure carbon nitride Download PDFInfo
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Abstract
The invention relates to a preparation method of nano-structure carbon nitride. The method comprises the following steps: (1) grinding dicyanodiamine, screening, putting in a heater, introducing nitrogen, heating to 400-700 DEG C, keeping the temperature for 1-2 hours, and carrying out furnace cooling to room temperature, thereby obtaining a light yellow solid g-C3N4; (2) grinding the g-C3N4 obtained in the step (1), screening, adding into a potassium hydroxide or sodium hydroxide water or alcohol solution, carrying out heating and condensation under reflux, stirring, cooling to room temperature, carrying out ultrasonic treatment on the sample for 10-60 minutes, filtering to obtain a filtrate and a filter residue, and dialyzing the filtrate to obtain a nano-structure carbon nitride water solution; and (3) carrying out freeze-drying on the nano-structure carbon nitride water solution to constant weight, thereby obtaining the nano-structure carbon nitride. The nano-structure carbon nitride prepared by the method has the advantages of various shapes, favorable peeling degree, high specific area (up to 320 m<2>g<-1>), high water solubility and high stability. The method is simple, and has the advantages of mild reaction conditions, short production cycle and low cost.
Description
Technical field
The present invention relates to the preparation method that a kind of nanostructured nitrogenizes carbon。
Background technology
Nano material is a study hotspot in recent years, some special effectses that it has, such as skin effect, small-size effect, quantum size effect, macro quanta tunnel effect etc., make nano material in mechanical property, magnetic performance, thermal property, optical property, electric property and chemistry and catalytic performance etc., have the unrivaled characteristic of other material。
Carbonitride is elementary composition by carbon and two kinds of nitrogen, element rich reserves, wide material sources, simple synthetic method, good economy performance and being easily obtained。Graphite phase carbon nitride (g-C3N4) belonging to narrow gap semiconductor, its band gap width is about 2.7eV, nontoxic, without metal；Meanwhile, g-C3N4Visible ray has certain absorption, and the corrosion of antiacid, alkali, light, good stability, structure and performance are prone to regulation and control, have good photocatalysis performance；G-C3N4Also in other multiple fields, there is huge application potential, thus, one of its focus becoming photocatalysis field, modern material and chemical research。
The preparation method that carbonitride is conventional mainly has hot high pressure solution, vapour deposition process, ion implantation, hydro-thermal or solvent-thermal process method and electrochemical deposition method etc.。In recent years, a kind of method directly heating the organic matter precursors such as condensation polymerization cyanamide, cyanamid dimerization and tripolycyanamide, become the preparation g-C that the comparison of application is many3N4The method of crystal。But, block materials specific surface area prepared by these methods is often below 10m2/ g, practical ranges is limited。For this, generally consideration introduces the adjustable pore structure in aperture in body phase carbon nitride, or changes nanometer particle size and the pattern of carbonitride and increase its specific surface area by means preparation layer or the monolayer less peeled off, to strengthen its application in every field。
In recent years, existing many work is devoted to prepare the g-C of bigger serface3N4。Such as, SiO is utilized2As hard template, the g-C of loose structure can be synthesized3N4, its surface area is up to 505m2g-1, but porous g-C3N4After synthesis, it is necessary to remove hard template, generally require HF or NH using severe toxicity4HF2, to the injury of human body relatively big (Preparationandcharacterizationofwell-orderedhexagonalmes oporouscarbonnitride, AdvMater, 2005,17:1648)。Except loose structure, it is also with space confinement method, synthesis is smashed method, hot stripping method, solvent stripping method etc. and prepared the carbonitride quantum dot of a series of different-shape, nano wire, nanotube, nano belt, nanometer rods, nano-particle, nanosphere, nano-cluster etc.。Such as, Yang et al. utilizes tripolycyanamide for presoma, nano strip product (the Synthesisandcharacterizationofnitrogen-richcarbonnitride nanobeltsbypyrolysisofmelamine of fiber morphology is obtained respectively at 700 DEG C, 1000 DEG C two-step pretreatment, ApplPhysA, 2011,105:161), its specific surface area is 60m2g-1, but in this growth preparation method, it is necessary to long period pyroreaction, and the nanostructured of high growth temperature is difficult to carry out secondary groups dress again, it is difficult to construct the nanostructured of higher level；Li et al. is using anodised aluminium as template, nitrile amine for presoma, the azotized carbon nano rod (Condensedgraphiticcarbonnitridenanorodsbynanoconfinement: promotionofcrystallinityonphotocatalyticconversion with high-crystallinity and photocatalysis performance is prepared by confinement thermal polycondensation, ChemMater, 2011,23:4344), but its specific surface area only has 25m2g-1, and removes difficulty as hard template silicon oxide in the method；Former rich et al. with sodium chloride be template, tripolycyanamide is for the water miscible azotized carbon nano band of precursor power, and is obtained the carbonitride (CN104108688B/Water-solubleribbon-likegraphiticcarbonnitr ide (g-C of different-shape by the self assembly effect of difference alcohol3N4): greensynthesis, seLf-assemblyanduniqueopticalproperties), sample specific surface area prepared by the method reaches 120m2g-1。But participate in reaction, Na owing to adding more sodium chloride when the method operates+Ionic radius less, be reacted into carbonitride intramolecule, it is difficult to remove, cause this azotized carbon nano band to lose original optical property。
Due to g-C3N4There is the layer structure of class Graphene, so can by g-C3N4Make the nano flake even structure of monolayer。At present, g-C3N4The stripping of stratified material mainly has three kinds of methods, namely aoxidizes stripping, solvent stripping and intercalation and peels off, but, there is also many problems, for instance ultrasonic stripping need to be peeled off for a long time, and productivity is low；Oxidation stripping needs high pressure or supercritical, and hardly results in the g-C that can increase the good water solubility with remaining reaction thing contact area when application3N4。Therefore, how cheaply, quickly, green, produce the g-C of good water solubility in bulk3N4Also it is a hot needed to be studied。
Summary of the invention
The technical problem to be solved is, overcomes the drawbacks described above that prior art exists, it is provided that a kind of method is simple, with short production cycle, with low cost, and gained nanostructured nitrogenizes carbon ratio surface area nanostructured big, good water solubility and nitrogenizes the preparation method of carbon。
The technical solution adopted for the present invention to solve the technical problems is as follows: the preparation method that a kind of nanostructured nitrogenizes carbon, comprises the following steps:
(1) dicyanodiamine is ground, porcelain boat is put into after crossing 400～600 orders (preferably 450～550 order) sieve, it is placed in heater, pass into nitrogen (passing into nitrogen rate preferably 2～6mL/min), then with 1～30 DEG C/min(preferably 5～20 DEG C/min, more preferably 8～15 DEG C/min) ramp to 400～700 DEG C (preferably 500～600 DEG C), and be incubated 1～2h, cool to room temperature with the furnace, obtain faint yellow solid g-C3N4；
(2) by step (1) gained faint yellow solid g-C3N4It is ground, cross 400～600 mesh sieves, then the concentration being added into potassium hydroxide or sodium hydroxide be 0.1～12.0mol/L(preferably 0.2～6.0mol/L) aqueous solution or alcoholic solution in, heating-condensing reflux, and stir 0.5～72.0h(preferably 4～48h, it is preferred that 12～40h), it is cooled to room temperature, then by sample ultrasonic, filter, obtain filtrate and filtering residue, filtrate of dialysing, obtain nanostructured and nitrogenize carbon aqueous solution；
(3) step (2) gained nanostructured is nitrogenized carbon aqueous solution lyophilization to constant weight, obtain nanostructured and nitrogenize carbon。
In above-mentioned steps (1), described dicyanodiamine heating gained faint yellow solid g-C3N4Can pass through to grind so that it is 450～550 mesh sieves can be crossed, obtain the more uniform carbonitride of particle diameter。
Further, in step (2), step (1) the gained g-C of described addition3N4With the mass volume ratio of the aqueous solution of potassium hydroxide or alcoholic solution it is: 100mg:10～30mL。
Further, in step (2), the temperature of described heating-condensing backflow is 20～150 DEG C。The purpose of condensing reflux be make solvent cool back in condensing tube in reaction bulb non-volatile walk, use different temperature and mixing time will obtain the product of different productivity and different size size。
Further, step (2) filters the nylon leaching film using porosity to be 0.45 μm, obtains filtrate and filtering residue by buchner funnel decompression sucking filtration。
Further, in step (2), described dialysis refers to that with molecular weight be the bag filter of 500～3000, and dialysis 1～4d is to neutral。That carry out dialysing in order that the potassium hydroxide that removes in backflow and alcohol, make solution to neutral and alcohol is replaced as water。Dialysis is to put in the middle of the deionized water of mobile phase by bag filter, principle according to gradient elution or infiltration, high solubility is walked toward low solubility, and solvent or ion exchange occur, water penetration outside dialysis band enters in dialysis band, and the dialysis from the inside of the potassium hydroxide of the inside and alcohol is out pulled away。Use the time that the dialysis sample of alcohol reaction needs longer, so that alcohol dialysis is clean。
Further, add water 20 ~ 50mL by step (2) gained filtering residue, condition be under 180w power ultrasonic 10 ~ 60min so as to disperse。After ultrasonic disperse, being the bag filter of 500～3000 with molecular weight, dialysis 1～4d is to neutral, then freezing is done to constant weight。The sample being obtained by reacting dissolution degree in alcohol is limited, can react completely in water, but can continue well dispersion in highly polar water, so needing to add water ultrasonic disperse so that reaction yield obtains optimization。
Further, the condition of the response sample ultrasonic disperse under step (2) described cooling, it is preferred to ultrasonic 30min under 180w power, makes reaction sample peel off fully and obtains the comparatively uniform product of size。
Further, in step (3), described cryodesiccated temperature is-40～-10 DEG C, and drying time is 10～72h to product constant weight。
In step (2), the alkylol that the alcohol optimization experiment room in described alcoholic solution is conventional, can be one or more in methanol, ethanol, propanol, n-butyl alcohol, isopropanol, ethylene glycol or glycerol。
Described in the inventive method, room temperature refers to indoor environment temperature, it is preferable that 18 DEG C-25 DEG C, more preferably 20 DEG C。
Compared with prior art, the having the beneficial effect that of the inventive method:
(1) according to the inventive method, by adjusting response parameter, the nanostructured of gained carbonitride has nano flake, nanometer rods, nanosphere etc. respectively, can be seen that from AFM and TEM, g-C3N4Peeling off very well, specific surface area may be up to 320m2g-1；Water solublity is very good, can reach 5g/L；The aqueous solution of the nanostructured of carbonitride can not produce precipitation, good stability after standing 30 days；
(2) by the present invention in that with different alkylols and water as solvent, obtain different-shape and the different water solublity carbonitride of each pattern ratio, the different higher structures obtained add its surface area so that it can be fully contacted with remaining reaction thing so that it is have and be more widely applied。
(3) the raw materials used wide material sources of the inventive method, simple to operate, and reaction condition is gentle, with short production cycle, with low cost, it is possible to remove alkali or the alcohol of introducing easily。
The present invention is the preparation of carbonitride and application provides a kind of new approaches, has broad application prospects and important realistic meaning at environmental protection, the energy, national defence and chemical field。
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1 gained g-C3N4The scanning electron microscope (SEM) photograph of-water-1；
Fig. 2 is the embodiment of the present invention 1 gained g-C3N4The transmission electron microscope picture of-water-1；
Fig. 3 is the embodiment of the present invention 1 gained g-C3N4The atomic force microscope figure of-water-1；
Fig. 4 is the embodiment of the present invention 1 gained g-C3N4The Tyndall effect figure of-water-1；
Fig. 5 is embodiment of the present invention 1-5 gained g-C3N4The pictorial diagram of the different time of-water；
Fig. 6 is the embodiment of the present invention 9 gained g-C3N4The scanning electron microscope (SEM) photograph of-methanol-1；
Fig. 7 is the embodiment of the present invention 10 gained g-C3N4The scanning electron microscope (SEM) photograph of-ethanol-1；
Fig. 8 is the embodiment of the present invention 10 gained g-C3N4The transmission electron microscope picture of-ethanol-1。
Fig. 9 is the embodiment of the present invention 12 gained g-C3N4The scanning electron microscope (SEM) photograph of-isopropanol-1。
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail。
The chemical reagent that the embodiment of the present invention uses, if no special instructions, obtains each through routine business approach。Room temperature described in each embodiment refers to 20 DEG C。
Embodiment 1
(1) dicyanodiamine is ground, put into porcelain boat after crossing 500 mesh sieves, be placed in tube furnace, pass into nitrogen with the flow velocity of 5mL/min, then with the ramp of 10 DEG C/min to 550 DEG C, and be incubated 2h, cool to room temperature, faint yellow solid g-C with the furnace3N4；
(2) by step (1) gained faint yellow solid g-C3N4It is ground, crosses 500 mesh sieves, then take the 100mg g-C sieved3N4Join in the aqueous solution of 20mL concentration of potassium hydroxide 3mol/L, 80 DEG C of heating-condensing backflows, and stir 24h, it is cooled to room temperature, then by sample ultrasonic 30min, then is the bag filter of 1500 by filtrate molecular weight, dialysis 3d, to neutral, obtains 20mL azotized carbon nano thin slice aqueous solution；
(3) by step (2) gained azotized carbon nano band aqueous solution at-25 DEG C, lyophilization 72h, to constant weight, obtains azotized carbon nano thin slice, is labeled as g-C3N4-water-1。
The present embodiment gained azotized carbon nano thin slice g-C3N4The specific surface area of-water-1 is 320m2g-1, productivity reaches 100wt%；Its surface sweeping Electronic Speculum (SEM), transmission electron microscope (TEM), atomic force microscope (AFM) is respectively as shown in Figure 1, 2, 3。As seen from Figure 1, the nanometer sheet obtained is high-visible, and the nanometer sheet obtained after lyophilization can pass through himself hydrogen bond energy with independently filling formation fold " cloud ear "。
By Fig. 2 and Fig. 3 it can be seen that g-C3N4After potassium hydroxide aqueous solution reacts 24h, obtaining the nanometer sheet of single or few layer thickness, its width is about 0.2～1.8 μm；It is 0.34nm that its thickness is about 0.52～0.9nm(theoretical value), this receives due to hydroxyl intercalation and oxygen-containing functional group and causes on azotized carbon nano thin slice。
Fig. 4 is g-C3N4-Water-1 aqueous solution Tyndall effect figure after standing month, it can be seen that g-C3N4-water-1 aqueous solution is extremely stable, it does not have produce precipitation。This is owing to the intercalation of hydroxyl makes to form strong hydrogen bond action between the functional group obtaining on Melon energy and hydrone, so the dispersion liquid of stable clarification can be formed, provides a kind of new thinking for its application。
Embodiment 2
The present embodiment differs only in embodiment 1:
In step (2), the time of return stirring is 18h；Final products therefrom is azotized carbon nano thin slice, is labeled as g-C3N4-water-2。Remaining with embodiment 1。
After testing, the present embodiment gained azotized carbon nano sheet specific surface area is 280m2g-1, productivity also reaches 100wt%。Obtaining the nanometer sheet of few layer thickness, the nanometer sheet width obtained is about 0.8～3.3 μm, and lamella is many greatly compared with what embodiment 1 obtained, causes that obtaining solution does not have embodiment 1 to clarify。G-C3N4-water-2 aqueous solution produces minimal amount of precipitation after standing one month bottom bottle, stability is not so good as g-C3N4-Water-1。
Embodiment 3
The present embodiment differs only in embodiment 1:
In step (2), the time of return stirring is 12h, is labeled as g-C3N4-water-3。Remaining with embodiment 1。After testing, the present embodiment gained azotized carbon nano sheet specific surface area is 235m2g-1, the nanometer sheet width obtained is about 1.2～3.6 μm, and productivity is 75wt%。The aqueous solution that the present embodiment obtains is light oyster white, produces a small amount of precipitation after standing one week bottom bottle。
Embodiment 4
The present embodiment differs only in embodiment 1:
In step (2), the time of return stirring is 8h, is labeled as g-C3N4-water-4。Remaining with embodiment 1。After testing, the present embodiment gained azotized carbon nano sheet specific surface area is 160m2g-1, the nanometer sheet width obtained is about 1.3～4 μm, and productivity is 58wt%。The aqueous solution that the present embodiment obtains is milky, produces precipitation after standing one week bottom bottle。
Embodiment 5
The present embodiment differs only in embodiment 1:
In step (2), the time of return stirring is 4h, is labeled as g-C3N4-water-5。Remaining with embodiment 1。After testing, the present embodiment gained azotized carbon nano sheet specific surface area is 98m2g-1, the nanometer sheet width obtained is about 1.5～4.5 μm, and productivity is 46wt%。The aqueous solution that the present embodiment obtains is milky turbidity liquid, produces more precipitation after standing one week bottom bottle。
Embodiment 6
The present embodiment differs only in embodiment 1:
In step (2), it is heated to reflux 20 DEG C of condensation temperature, is labeled as g-C3N4-water-6。Remaining with embodiment 1。After testing, the present embodiment gained azotized carbon nano sheet specific surface area is 63m2g-1, the nanometer sheet width obtained is about 1.5～4.6 μm, and productivity is 36wt%。The aqueous solution that the present embodiment obtains is milky turbidity liquid, produces more precipitation after standing one week bottom bottle。
Embodiment 7
The present embodiment differs only in embodiment 1:
In step (2), what add reaction is the aqueous solution of concentration of potassium hydroxide 0.2mol/L, is labeled as g-C3N4-water-7。Remaining with embodiment 1。After testing, the present embodiment gained azotized carbon nano sheet specific surface area is 38m2g-1, the nanometer sheet width obtained is about 0.5～2.2 μm, and productivity is 94.2wt%。The aqueous solution that the present embodiment obtains is, after standing January, produces minimal amount of precipitation bottom bottle。
Embodiment 8
The present embodiment differs only in embodiment 1:
In step (2), add the sodium hydroxide of concentration 3mol/L in reaction solution, be labeled as g-C3N4-water-8。Remaining with embodiment 1。After testing, the present embodiment gained azotized carbon nano sheet specific surface area is 52m2g-1, the nanometer sheet width obtained is about 0.5～1.8 μm, and productivity is 100wt%。The aqueous solution that the present embodiment obtains is stable clarification ground dispersion liquid, does not produce precipitation after standing January。
Resolve: g-C3N4With the reaction principle figure of alkali as shown in Figure 1；Ultimate principle is: OH under heated reflux condition-Insert g-C3N4Layer structure and attack g-C3N4The hydrogen bond N of its interlayer...C-NH-C key in H-N and layer, the hydrogen bond between linear polymer chain is by new hydrogen bond-O-H...N and H-O-...H-N key replaces, and causes the melon chain (g-C of polymerization3N4) it is stripped the formation melon chain that comes；Additionally, CN polymeric chain is at heating and OH-Under the effect of intercalation, the C-NH-C key between two 3-s-triazine rings, by carrying out local cracking further, obtains various sizes of azotized carbon nano sheet。As it is shown in figure 5, prolongation over time, reaction is more and more abundant, and reaching 24h is that reaction can reach 100wt%；Wherein sample starts gelation at about 2h, increases the response time, and degree of gelation is more big, to finally obtaining a stable clarification ground dispersion liquid。After dialysis, due to the effect of hydrogen bond, sample stability in water is all fine。
Additionally, along with the increase of alkali-soluble degree, response speed is also increasingly faster, but if the solubility of alkali is excessively big, will make the little molecule of melon chain formation, and destroy its original character；In addition, it is contemplated that Na+G-C can be made3N4" poisoning ", destroys its original optical property, and reaction efficiency is good not as potassium hydroxide, and all the other examples of this patent are all with potassium hydroxide for reaction base。The rising of temperature is also beneficial to the carrying out of reaction, but considers that the boiling point of solvent and high temperature are probably the little molecule of melon chain formation, should not use too high temperature。
[embodiment 9-12 is the reaction embodiment in alcoholic solution]。
Embodiment 9
The present embodiment and embodiment 1 are distinctive in that: in step (2), take the 100mg g-C sieved3N4Join in the methanol solution of 20mL concentration of potassium hydroxide 3mol/L, 80 DEG C of heating-condensing backflows, and stir 24h, it is cooled to room temperature, then by sample ultrasonic 30min, the nylon leaching film then using porosity to be 0.45 μm, obtain filtrate and filtering residue by buchner funnel decompression sucking filtration；Being the bag filter of 1500 by filtrate molecular weight again, dialysis 4d, to neutral, obtains azotized carbon nano thin slice and nanometer rods aqueous solution；It is labeled as g-C3N4-methanol-1, its SEM schemes as shown in Figure 6。
After testing, the present embodiment filtrate gained azotized carbon nano sheet and nanometer rods specific surface area are 208m2g-1, the nanometer sheet obtaining single or few layer thickness is peeled off in reaction, and the nanometer sheet width obtained is about 1.2～2.5 μm；The width of nanometer rods is 50nm～200nm, and height is 300nm～650nm；The productivity of filtrate is 32wt%。
The filtering residue obtained in the present embodiment step (2) adds water 50mL, condition be under 180w power ultrasonic 10 ~ 60min so as to disperse。Obtain azotized carbon nano block dispersion soln, be labeled as g-C3N4-Methanol-2, its specific surface area is 42m2g-1。The azotized carbon nano block relatively g-C obtained3N4Crystallinity is better, and layer structure is due to OH-Insertion action be also partially stripped so that it is the dispersibility in water is better。
Embodiment 10
The present embodiment and embodiment 9 are distinctive in that: in step (2), use the alcoholic solution of 20mL concentration of potassium hydroxide 3mol/L, remaining same embodiment 9；Filtrate is labeled as g-C3N4-ethanol-1, filtering residue is labeled as g-C3N4-ethanol-2。G-C3N4Its SEM and TEM of-ethanol-1 is respectively as shown in FIG. 7 and 8。After testing, the present embodiment filtrate gained azotized carbon nano sheet and nanosphere specific surface area are 272m2g-1, the nanometer sheet obtaining single or few layer thickness is peeled off in reaction, and the nanometer sheet width obtained is about 1.5～3.0 μm；The diameter of nanosphere is 150nm-500nm, and the productivity of filtrate is 58wt%。The filtering residue g-C obtained3N4-ethanol-2, its surface area is 65m2g-1。
Embodiment 11
The present embodiment and embodiment 9 are distinctive in that: in step (2), use the propanol solution of 20mL concentration of potassium hydroxide 3mol/L, remaining same embodiment 9；Filtrate is labeled as g-C3N4-propanol-1, filtering residue is labeled as g-C3N4-propanol-2。After testing, the present embodiment filtrate gained azotized carbon nano sheet and nanosphere specific surface area are 254m2g-1, the nanometer sheet obtaining single or few layer thickness is peeled off in reaction, and the nanometer sheet width obtained is about 1.8～3.4 μm；The diameter of nanosphere is 135nm-425nm, and the productivity of filtrate is 46wt%。The filtering residue g-C obtained3N4-propanol-2, its surface area is 46m2g-1。
Embodiment 12
The present embodiment and embodiment 9 are distinctive in that: in step (2), use the aqueous isopropanol of 20mL concentration of potassium hydroxide 3mol/L, remaining same embodiment 9；Filtrate is labeled as g-C3N4-isopropanol-1, filtering residue is labeled as g-C3N4-isopropanol-2。G-C3N4The SEM of-isopropanol-1 is as shown in Figure 9。After testing, the present embodiment filtrate gained azotized carbon nano sheet and nanosphere specific surface area are 298m2g-1, the nanometer sheet width obtained is about 1.3～3.2 μm；The diameter of nanosphere is 105nm～365nm, and the productivity of filtrate is 32wt%。The filtering residue g-C obtained3N4-isopropanol-2, its surface area is 79m2g-1。
Resolve: research shows,g-C 3 N 4 The nanostructured that can obtain pattern different under the effect of different alcohol from the reaction of alkali nitrogenizes carbon, and this is to cause owing to the sterically hindered and polarity of the alkylol of use is different and alcohol is different from the combined effect-ol solution ability of alkali。Along with the increase of alkylol carbon number, sterically hindered increasing, make the azotized carbon nano chip size that stripping obtains become big, cause the product specific surface area relatively water sample obtained to reduce；Owing to steric hindrance nanometer sheet starts from assembling, obtain methanol-nanometer rods；Ethanol, propanol, isopropanol-nanosphere, although isopropanol is equal with propanol carbon number, but its side chain makes its steric hindrance bigger, the quantity of nanosphere increases with steric hindrance and increases, the amount of nanometer sheet reduces therewith, it addition, the size of nanosphere reduces along with the increase of steric hindrance, these reasons make product specific surface area be gradually increased。Additionally, due to the alcoholysis of different alcohol and intercalation ability are different, ethanol the strongest, the product yield obtained is maximum。
Claims (10)
1. the preparation method that a nanostructured nitrogenizes carbon, it is characterised in that comprise the following steps:
(1) dicyanodiamine is ground, put into porcelain boat after crossing 400～600 mesh sieves, be placed in heater and pass into nitrogen, then with the ramp of 1～30 DEG C/min to 400～700 DEG C, and be incubated 1～4h, cool to room temperature with the furnace, obtain faint yellow solid g-C3N4；
(2) by step (1) gained faint yellow solid g-C3N4It is ground, cross 400～600 mesh sieves, it is added in the aqueous solution that concentration is 0.2～12.0mol/L or the alcoholic solution of potassium hydroxide or sodium hydroxide again, condensing reflux, and stir 0.5～72.0h, it is cooled to room temperature, then by sample ultrasonic, filtering, obtain filtrate and filtering residue, dialysis filtrate obtains nanostructured and nitrogenizes carbon aqueous solution；
(3) step (2) gained nanostructured is nitrogenized carbon aqueous solution lyophilization to constant weight, obtain nanostructured and nitrogenize carbon。
2. the preparation method that nanostructured nitrogenizes carbon according to claim 1, it is characterised in that: in step (2), step (1) the gained faint yellow solid g-C of described addition3N4With the mass volume ratio of the aqueous solution of potassium hydroxide or sodium hydroxide or alcoholic solution it is: 50～100mg:10～60mL。
3. the preparation method that nanostructured according to claim 1 or claim 2 nitrogenizes carbon, it is characterised in that: in step (2), the temperature of described heating-condensing backflow is 20～150 DEG C。
4. the preparation method nitrogenizing carbon according to the described nanostructured of one of claims 1 to 3, it is characterised in that: in step (2), described dialysis refers to that with molecular weight be the bag filter of 500～3000, and dialysis 1～4d is to neutral。
5. the preparation method nitrogenizing carbon according to the described nanostructured of one of Claims 1 to 4, it is characterised in that: step (2) filters the nylon leaching film using porosity to be 0.45 μm, obtains filtrate and filtering residue by buchner funnel decompression sucking filtration；Being added water by step (2) gained filtering residue after ultrasonic disperse, be the bag filter of 500～3000 with molecular weight, dialysis 1～4d is to neutral, then lyophilization is to constant weight。
6. the preparation method that nanostructured according to claims 1 to 5 nitrogenizes carbon, it is characterised in that: in step (2), the condition of described ultrasonic disperse is ultrasonic 10～60min under 180w power。
7. the preparation method nitrogenizing carbon according to the described nanostructured of one of claim 1～6, it is characterised in that: in step (3), described cryodesiccated temperature is-40～-10 DEG C, and the time is 10～72h。
8. the preparation method nitrogenizing carbon according to the described nanostructured of one of claim 1～7, it is characterised in that: in step (1), described in pass into the flow velocity of nitrogen be 1～10mL/min。
9. the preparation method nitrogenizing carbon according to the described nanostructured of one of claim 1～8, it is characterised in that: in step (1), with the ramp of 5～20 DEG C/min to 500～600 DEG C。
10. the preparation method nitrogenizing carbon according to the described nanostructured of one of claim 1～8, it is characterised in that: in claim 5, described filtering residue adds water 20～50mL, condition be under 180w power ultrasonic 10～60min so as to disperse。
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