CN101041429B - Method for producing carbon nano-ball by using polyacrylonitile as precursor - Google Patents
Method for producing carbon nano-ball by using polyacrylonitile as precursor Download PDFInfo
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- CN101041429B CN101041429B CN2007100381056A CN200710038105A CN101041429B CN 101041429 B CN101041429 B CN 101041429B CN 2007100381056 A CN2007100381056 A CN 2007100381056A CN 200710038105 A CN200710038105 A CN 200710038105A CN 101041429 B CN101041429 B CN 101041429B
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Abstract
The invention discloses a preparing method of carbon nanometer ball with polyacryl-nitrile as pioneer body, which comprises the following steps: polymerizing emulsion to get polyacryl-nitrile latex nanometer ball; using inorganic salt to cover the surface of polyacryl-nitrile latex nanometer ball; calcining with high temperature; making polyacryl-nitrile latex nanometer ball carbonize; removing covered lay of inorganic salt. The carbon nanometer ball grain diameter is adjustable with 20-250 nm grain diameters on average.
Description
Technical field
The invention belongs to the carbon nanomaterial technical field, be specifically related to a kind of method of producing Nano carbon balls, more particularly, the present invention relates to a kind of is presoma with inorganic salt coating letex polymerization gained polyacrylonitrile latex particle, by the method for high temperature pyrolysis production nano-sized carbon bead.
Background technology
Carbon nanotube and soccerballene synthetic caused the very big concern of people to carbon nanomaterial.Because its particular structure, machinery and electrochemical characteristic, carbon nanomaterial in many aspects as: lithium ion battery electrode material, gas storage medium (the particularly storage of fuel cell hydrogen), support of the catalyst, sorbent material and microelectronic device etc., all have visible and potential using value, therefore be subjected to paying close attention to widely and studying.Existing preparation carbon nanomaterial mainly contains two kinds of approach: a kind of is organism presoma (mainly being polymkeric substance) high temperature pyrolysis under inert atmosphere; Another kind is the physical/chemical vapour deposition.Preceding a kind of technology is suitable for a large amount of synthetic, and shortcoming is the carbon nano-structured control that is not easy, and the latter can accurately control carbon nano-structured, but cost is higher comparatively speaking, output is limited, and the equipment complexity.The main method of existing preparation Nano carbon balls is to be presoma pyrolytic decomposition gained under inert atmosphere with the polymer nanocomposite ball.
Polyacrylonitrile has higher carbonization productive rate, is used to business-like carbon fiber production, and is synthesized high-sequential graphite nano plate and other carbon nanomaterials by successful being used for.Owing to contain nitrogenous functional group, the prepared activated carbon fiber of polyacrylonitrile is the outstanding catalyzer of dehydrochlorination and oxysulfide.Therefore, polyacrylonitrile is that the Nano carbon balls of presoma is because its nanostructure and nitrogen-containing group have the potential using value.But because polyacrylonitrile contains undersaturated-CN group, in the process of carbonization crosslinked gathering and the fusion that causes the polyacrylonitrile nano ball can take place.For avoiding the crosslinked of polyacrylonitrile nano ball in the carbonization process, people are with the nanoparticle of vinyl cyanide and another kind of small molecule monomer copolymerization product nucleus shell structure (polyacrylonitrile is nuclear), under inert atmosphere high temperature, the carbonization of polyacrylonitrile nuclear generates Nano carbon balls (referring to Chuanbing Tang et al. thereby shell vapors away, Angwe.Chem.Int.Edi., 2004,43,2783-2787).This technical process is complicated, the difficult control of the copolymer nano ball preparation of nucleocapsid structure.
Summary of the invention
The purpose of this invention is to provide a kind of is the method that presoma is produced Nano carbon balls with the polyacrylonitrile, and this method can effectively be avoided the hot crosslinked problem of polyacrylonitrile nano ball, and relatively is easy to control the microballoon size.
The present inventor has carried out series of studies to Nano carbon balls preparation, finds to coat one deck inorganic salt can prevent to calcine the time in the polyacrylonitrile-crosslinked reunion that causes Nano carbon balls of CN at letex polymerization gained polyacrylonitrile nano particle surface.The present invention just is being based on this discovery and is being accomplished.
The method of production Nano carbon balls provided by the invention, concrete steps are as follows:
(1) letex polymerization: monomer vinyl cyanide, emulsifying agent, initiator are dissolved in the distilled water, stir logical nitrogen down, be warming up to 60～80 ℃ after air eliminates, reaction 2～15h, get white emulsion, lyophilize obtains white powder, and promptly particle diameter is the polyacrylonitrile latex nanometer ball of 35～270nm.
(2) coating of inorganic salt: get step (1) gained white polypropylene nitrile powder, immerse in the inorganic salt A solution, leave standstill 5～30min behind the ultra-sonic dispersion, centrifugal, get throw out; Throw out is distributed in the inorganic salt B solution, replacement(metathesis)reaction can take place in described inorganic salt A and inorganic salt B, generation is coated on the inorganic salt on polyacrylonitrile nano ball surface, leave standstill centrifugation behind 30～80min, get throw out, use distilled water wash, oven dry, polyacrylonitrile nano ball surface has coated one deck and by inorganic salt A and inorganic salt B the throw out (inorganic salt) that replacement(metathesis)reaction generates has taken place.
(3) high-temperature calcination: the product grinding that step (2) is obtained is placed in the quartz boat, 200～300 ℃ of preoxidation in the air, time is 1～5h, after the logical rare gas element in cooling back is caught up with most air, is warming up to 400～1200 ℃ of calcining 1～24h and makes the carbonization of polyacrylonitrile nano ball.
(4) removal of inorganic salt: step (3) products therefrom is placed acid solution, leave standstill 1～36h to remove the inorganic salt coating layer, promptly get required Nano carbon balls, particle diameter is 20～250nm.
In Nano carbon balls production method of the present invention, step (1) relates to the letex polymerization of monomer vinyl cyanide, and this method can access the polyacrylonitrile latex nanometer ball of 35～270nm.Emulsifying agent can be sodium lauryl sulphate (SDS), sodium laurylsulfonate, sim alkylphenol Soxylat A 25-7 (OP in this step
10), polyoxyethylene nine ether (NP
9) wait tensio-active agent.Be absorption sedimentation coated phosphate in the performing step (3), the present invention has adopted and has made the electronegative ionic emulsifying agent of micella.Initiator can be Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate (AIBN) etc.The concentration of monomer, initiator, emulsifying agent in this step, all there are certain influence temperature of reaction and time to the particle diameter of reaction product, it is that 2～9% (w/v), initiator concentration are that 0.02～0.5% (w/v), emulsifier concentration are 0.2～0.5% (w/v) that the present invention controls monomer concentration, temperature of reaction is 60～80 ℃, reaction times 2～15h.
Step of the present invention (2) is at step (1) gained polyacrylonitrile nano ball surface coated inorganic salt.Because the product after coating is wanted high-temperature calcination, so the selection of inorganic salt will consider fusing point, and the present invention selects that solubleness such as titanium phosphate, lime carbonate, calcium phosphate, cupric phosphate are little, fusing point is high and easy removed inorganic salt.Polyacrylonitrile is immersed in the solvable inorganic salt A solution, and it is adsorbed on the nanometer ball surface to make inorganic salt, immerses and can generate in the solvable inorganic salt salt B solution of deposit C with the A reaction after centrifugal, get final product the polyacrylonitrile nano ball that coats of inorganic salt deposit C.In this step, inorganic salt A selects titanium sulfate (be dissolved in and make it keep stable in the sulphuric acid soln), calcium chloride or cupric chloride, and inorganic salt B then selects corresponding phosphoric acid salt or carbonate, and inorganic salt B concentration is 1-2M.Polyacrylonitrile institute in the aqueous solution is electrically charged should be electrically charged opposite with metal-salt or metal ion institute, to guarantee the adsorbed close of settled layer.Electrically charged identical as if institute, should carry out modification to polyacrylonitrile particles earlier.As select anion surfactant to make emulsifying agent, then polyacrylonitrile nano ball surface has negative electricity, it is immersed diallyl dimethyl ammoniumchloride (PDDA, Poly (diallyldimethylammonium chloride)) can make its surface have negative electricity in the solution, thereby absorption have the titanium sulfate of negative electricity.
In the step of the present invention (3), be heated to 200 ~ 300 ℃ in the air and make preoxidized polyacrylonitrile, this preoxidation process makes the catenate polyacrylonitrile become ring crosslinked so that the polyacrylonitrile nano ball stable, and improves the carbon productive rate.The preferred preoxidation temperature of the present invention is 230 ℃-250 ℃.It calcines carbonization process, preferably segmented temperature-programmed mode.Particularly, the speed with 4-6 ℃/min is warming up to 400-800 ℃ earlier, calcines 1-8 hour; Be warming up to 800-1200 ℃ with 4-6 ℃/min speed again, calcined 1-16 hour.
Step of the present invention (4) is to remove the inorganic salt mixt coating layer of step (3) gained.According to the difference of coating layer, can select different acid, example hydrochloric acid, nitric acid, dilute sulphuric acid, hydrofluoric acid or hydrofluoric acid and vitriolic mixing acid, soak time is 1min-48 hour, preferred 1-24 hour.
Among the present invention, the mean radius of polyacrylonitrile nano ball can be passed through to regulate adjustings such as monomer concentration, reaction times in step (1), so the mean radius of Nano carbon balls can be adjusted accordingly.
The inventive method is simple and convenient, and is workable, favorable reproducibility, products obtained therefrom steady quality.
Description of drawings
Fig. 1 is the transmission electron microscope photo of Comparative Examples gained decolorizing carbon of the present invention;
Fig. 2 is the X-ray diffraction spectrogram of the embodiment of the invention 2 gained Nano carbon balls;
Fig. 3 is the transmission electron microscope photo of the embodiment of the invention 2 gained Nano carbon balls.
Embodiment
To be described in more detail the present invention by embodiment below, but protection scope of the present invention is not limited to these embodiment.
Comparative Examples
Vinyl cyanide 6.2mL, Potassium Persulphate 0.1g, sodium lauryl sulphate 1g are dissolved in the 93.8mL water, stir down logical high purity nitrogen and after half an hour temperature is risen to 70 ℃, reaction 12h obtains white emulsion.Get white polypropylene nitrile powder after the lyophilize.The lyophilize products therefrom is put into quartz boat, 250 ℃ of calcining 2h in the air, the logical argon gas in cooling back is caught up with most air, and 450 ℃ of calcining 4h in argon gas atmosphere rise to 800 ℃ of calcining 6h, naturally cooling then.Get several microns to tens microns block decolorizing carbon, random pattern (Fig. 1).
Embodiment 1
The preparation of polyacrylonitrile emulsion is identical with Comparative Examples 1.Get an amount of white polypropylene nitrile powder and immerse in the PDDA solution, ultrasonic it is uniformly dispersed, leave standstill 15min, centrifugal, precipitation is distributed to titanium sulfate (Ti (SO
4)
2) in the solution (10mM, sulfuric acid is regulated pH=0.95), leaving standstill 15min, (1M pH=4), leaves standstill centrifugation behind the 1h to centrifugal back redispersion, and oven dry has promptly coated one deck phosphoric acid salt on polyacrylonitrile nano ball surface in sodium radio-phosphate,P-32 solution.To put into quartz boat after the grinding of the product after the oven dry, place tube furnace, 230 ℃ of calcining 2h in the air, the logical argon gas 4h in cooling back is to catch up with air to the greatest extent, temperature programming to 450 ℃ (speed be 4 ℃/min), this temperature lower calcination 4h, (speed is 4 ℃/min) calcining 6h to rise to 800 ℃ then, naturally cooling, carbonization productive rate 42%.To calcine after product and immerse in hydrofluoric acid and the vitriolic mixing solutions (volume ratio 4: 1), leave standstill 24h to remove the phosphoric acid salt coating.The products therefrom median size is 50nm.
Embodiment 2
Vinyl cyanide 6.2mL, Potassium Persulphate 0.1g, sodium lauryl sulphate 2g are dissolved in the 93.8mL water, stir down logical high purity nitrogen and after half an hour temperature is risen to 70 ℃, reaction 12h obtains white emulsion.Get white polypropylene nitrile powder after the lyophilize.Get an amount of white polypropylene nitrile powder and immerse in calcium chloride (10mM) solution, leave standstill 30min, product is distributed in yellow soda ash (1M) solution after centrifugal, leave standstill centrifugation behind the 1h, oven dry has promptly coated one deck lime carbonate on polyacrylonitrile nano ball surface.To put into quartz boat after the grinding of the product after the oven dry, place tube furnace, 280 ℃ of calcining 2h in the air, the logical argon gas 4h in cooling back is to catch up with air to the greatest extent, temperature programming to 450 ℃ (speed be 6 ℃/min), this temperature lower calcination 5h, (speed is 6 ℃/min) calcining 10h to rise to 1200 ℃ then, naturally cooling, carbonization productive rate 39%.To calcine after product and immerse in the hydrochloric acid soln (1M), leave standstill 5min to remove the lime carbonate coating.Products therefrom is a decolorizing carbon, and median size is 130nm.
Embodiment 3
Vinyl cyanide 3.7mL, Potassium Persulphate 0.1g, sodium lauryl sulphate 2g are dissolved in the 96.3mL water, stir down logical high purity nitrogen and after half an hour temperature is risen to 70 ℃, reaction 12h obtains white emulsion.Get the polyacrylonitrile white powder after the lyophilize.Get an amount of white polypropylene nitrile powder and immerse in cupric chloride 10 (mM) solution, leave standstill 30min, product is distributed in sodium phosphate (1M) solution after centrifugal, leave standstill centrifugation behind the 1h, oven dry has promptly coated one deck cupric phosphate on polyacrylonitrile nano ball surface.To put into quartz boat after the grinding of the product after the oven dry, place tube furnace, 200 ℃ of calcining 4h in the air, the logical argon gas 4h in cooling back is to catch up with air to the greatest extent, temperature programming to 450 ℃ (speed be 5 ℃/min), this temperature lower calcination 6h, rise to then 1000 ℃ (speed be 5 ℃/min) calcining 8h, naturally cooling.Product is a decolorizing carbon, and the carbonization productive rate is 40%.To calcine after product and immerse in the salpeter solution (1M), leave standstill 2h to remove the cupric phosphate coating.The products therefrom median size is 35nm.
From above-mentioned Comparative Examples and embodiment to recently, unsaturated group-CN takes place crosslinked and causes carbonized product to be agglomerated into piece when polyacrylonitrile nano ball surface coated inorganic salt deposit can be avoided the polyacrylonitrile high-temperature calcination, thereby generates nano carbon microsphere.Can shrink during the carbonization of polyacrylonitrile nano carbon ball, so that the nano carbon microsphere particle diameter that generates is compared polyacrylonitrile is smaller.
Claims (6)
1. one kind is the method that presoma is produced Nano carbon balls with the polyacrylonitrile, and this method comprises the steps:
(1) letex polymerization: monomer vinyl cyanide, emulsifying agent, initiator are dissolved in the distilled water, stir logical nitrogen down, be warming up to 60～80 ℃ after air eliminates, reaction 2～15h gets white emulsion; Lyophilize obtains white powder, is the polyacrylonitrile latex nanometer ball of particle diameter 35～270nm;
(2) coating of inorganic salt: get step (1) gained white polypropylene nitrile powder, immerse in the inorganic salt A solution, leave standstill 5～30min behind the ultra-sonic dispersion, centrifugal; Throw out is distributed in the inorganic salt B solution, here the inorganic salt that the replacement(metathesis)reaction generation is coated on polyacrylonitrile nano ball surface can take place in inorganic salt A and inorganic salt B, leave standstill centrifugation behind 30～80min, use distilled water wash, and oven dry, coated the inorganic salt that the replacement(metathesis)reaction generation takes place by inorganic salt A and inorganic salt B on polyacrylonitrile nano ball surface; Wherein, inorganic salt A uses titanium sulfate, calcium chloride or cupric chloride; Inorganic salt B uses yellow soda ash, sodium phosphate or potassiumphosphate, inorganic salt B strength of solution 1～2M;
(3) high-temperature calcination: the product grinding that step (2) is obtained is placed in the quartz boat, 200～300 ℃ of preoxidation 1～5h in the air, the logical rare gas element in cooling back is caught up with most air, is warming up to 400～1200 ℃ under inert atmosphere, and calcining 1～24h makes the carbonization of polyacrylonitrile nano ball;
(4) removal of inorganic salt: step (3) products therefrom is placed acid solution, leave standstill 1～36h to remove the inorganic salt coating layer.
2. method according to claim 1, wherein used emulsifying agent is sodium lauryl sulphate, sodium laurylsulfonate, polyoxyethylene nine ethers or sim alkylphenol Soxylat A 25-7 in the step (1).
3. method according to claim 1, wherein used initiator is Potassium Persulphate, ammonium persulphate or Diisopropyl azodicarboxylate in the step (1).
4. method according to claim 1, wherein monomer concentration described in the step (1) is 2～9%w/v, initiator concentration 0.02～0.5%w/v, emulsifier concentration 0.2～0.5%w/v.
5. method according to claim 1, wherein employing segmented program heating mode is crossed in the calcining carbonization in step (3): the speed with 4-6 ℃/min is warming up to 400-800 ℃ earlier, calcined 1-8 hour, and be warming up to 800-1200 ℃ with 4-6 ℃/min speed again, calcined 1-16 hour.
6. method according to claim 1 wherein in step (4), is removed inorganic salt and is adopted hydrochloric acid, nitric acid, dilute sulphuric acid, hydrofluoric acid or hydrofluoric acid and vitriolic mixing solutions, and soak time is 1～24 hour.
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| CN105314614A (en) * | 2014-06-04 | 2016-02-10 | 北京化工大学 | Nitrogen-doped porous carbon nanotube material and its preparation method and use in super capacitor electrode |
| CN107188155A (en) * | 2017-06-05 | 2017-09-22 | 安徽大学 | A kind of preparation method of nitrogen-doped nanometer porous carbon ball |
| CN107311144B (en) * | 2017-08-03 | 2019-12-03 | 安徽大学 | A kind of preparation method of nitrogen-doped nanometer Porous hollow carbon ball |
| CN110790257B (en) * | 2019-11-22 | 2021-09-28 | 中国矿业大学 | Modulation method for nano carbon material morphology structure transformation based on crystallization induction |
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