CN104140097B - A kind of phosphorus doping Graphene and preparation method thereof - Google Patents
A kind of phosphorus doping Graphene and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of phosphorus doping Graphene and preparation method thereof, described preparation method includes: phosphorus source is heated to 300-1600 DEG C under non-oxidizing atmosphere with organic salt or the mixture with organic acid and salt, obtains the mixture of phosphorus doping Graphene and metal-oxide; Remove the metal-oxide in mixture, obtain phosphorus doping Graphene. The present invention, by heating phosphorus source and organic salt or the mixture with organic acid Yu salt in non-oxidizing atmosphere, utilizes organic salt carbonized graphite alkene, inorganic oxide nucleation and phosphorus source pyrolysis to produce the theory of active phosphorus, prepares phosphorus doping Graphene. The method have technique simple, with short production cycle, can the advantage such as original position doping, and the phosphorus doping Graphene prepared has the advantages that porous, specific surface area greatly, are not reunited, can be widely applied to the every field such as lithium ion battery, ultracapacitor, lead-acid battery, water process, electro-catalysis, photocatalysis.
Description
Technical field
The present invention relates to material with carbon element technical field, specifically a kind of phosphorus doping Graphene and preparation method thereof.
Background technology
Along with the exhaustion of petroleum resources, clean energy technology is increasingly subject to the concern of people. Lithium ion battery, ultracapacitor, fuel cell equal energy source convert and storage art has noticeable application potential. Advanced electrode material and catalyst are core and the development bottlenecks of this kind of energy device. In recent years, with the development of Graphene and energy device technology, Heteroatom doping Graphene becomes the study hotspot in these fields.
In prior art fewer about the report of phosphorus doping Graphene. Hou Yanglong et al. is by graphene oxide mixing triphenyl phosphorus through Overheating Treatment, and obtaining the phosphorus content in the Graphene of phosphorus doping is 1.81% (AdvancedMaterials, 201,25,4932-4937). In Chinese patent CN103495430A, by mixed oxidization graphite and phosphorous ionic liquid, through being thermally treated resulting in doped graphene. In above-mentioned technology, all need with graphene oxide for substrate, it is impossible to original position prepares phosphorus doping Graphene, and relates to multiple experimental procedure, complex process, inefficiency.
Summary of the invention
In order to make up above-mentioned the deficiencies in the prior art, the technical problem to be solved be to provide a kind of technique simple, can the phosphorus doping graphene preparation method of original position Doping Phosphorus.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is:
A kind of phosphorus doping graphene preparation method, including:
Phosphorus source is heated to 300-1600 DEG C with organic salt or the mixture with organic acid and salt under non-oxidizing atmosphere, obtains the mixture of phosphorus doping Graphene and metal-oxide;
Remove the metal-oxide in mixture, obtain phosphorus doping Graphene;
Wherein, phosphorus source is selected from one or more in elemental phosphorous, phosphate, phosphate compounds and phosphite ester compound;
Wherein, one or more in the alkyl soap that magnesium, calcium, strontium, barium, cobalt, nickel, manganese, ferrum, zinc, aluminum, indium or the citrate of bismuth, gluconate, tartrate, D-VB5 salt, threose acid salt, carbon number are 8-24 and oleate of described organic salt;
Wherein, one or more in the alkyl fatty acid that citric acid, gluconic acid, tartaric acid, D-VB5, threonic acid THREONIC ACID., carbon number are 8-24 and oleic acid of described organic acid;
Wherein, described salt is selected from one or more in magnesium, calcium, strontium, barium, cobalt, nickel, manganese, ferrum, zinc, aluminum, indium or the acetate of bismuth, nitrate, chlorate, Bromide and iodized salt.
The beneficial effects of the present invention is: technique is simple, with short production cycle, can original position Doping Phosphorus, the feature that phosphorus doping Graphene has porous, specific surface area is big prepared, can be applicable to the every field such as lithium ion battery, ultracapacitor, lead-acid battery, water process, electro-catalysis, photocatalysis.
Accompanying drawing explanation
Fig. 1 show the scanning electron microscope (SEM) photograph of the phosphorus doping Graphene of the embodiment of the present invention 1 preparation.
Detailed description of the invention
By describing the technology contents of the present invention, structural feature in detail, being realized purpose and effect, below in conjunction with embodiment and coordinate accompanying drawing to be explained in detail.
The design of most critical of the present invention is in that: by heating phosphorus source and organic salt or the mixture with organic acid and salt in non-oxidizing atmosphere; organic salt carbonized graphite alkene, inorganic oxide nucleation and phosphorus source pyrolysis is utilized to produce the theory of active phosphorus; prepare the original position phosphorus doping Graphene with advantages such as porous, specific surface area are big; the method technique is simple, with short production cycle, be produced on a large scale, and the phosphorus doping Graphene prepared can be applicable to the every field such as lithium ion battery, ultracapacitor, lead-acid battery, water process, electro-catalysis, photocatalysis.
Phosphorus doping graphene preparation method provided by the invention, including:
Phosphorus source is heated to 300-1600 DEG C with organic salt or the mixture with organic acid and salt under non-oxidizing atmosphere, obtains the mixture of phosphorus doping Graphene and metal-oxide;
Remove the metal-oxide in mixture, obtain phosphorus doping Graphene;
Wherein, phosphorus source is selected from one or more in elemental phosphorous, phosphate, phosphate compounds and phosphite ester compound;
Wherein, one or more in the alkyl soap that magnesium, calcium, strontium, barium, cobalt, nickel, manganese, ferrum, zinc, aluminum, indium or the citrate of bismuth, gluconate, tartrate, D-VB5 salt, threose acid salt, carbon number are 8-24 and oleate of described organic salt;
Wherein, one or more in the alkyl fatty acid that citric acid, gluconic acid, tartaric acid, D-VB5, threonic acid THREONIC ACID., carbon number are 8-24 and oleic acid of described organic acid;
Wherein, described salt is selected from one or more in magnesium, calcium, strontium, barium, cobalt, nickel, manganese, ferrum, zinc, aluminum, indium or the acetate of bismuth, nitrate, chlorate, Bromide and iodized salt.
The mechanism that the present invention prepares phosphorus doping Graphene is as follows:
In phosphorus source and rich carbon organic salt or the rich carbon organic acid mixed system with salt, rich carbon organic acid or rich carbon organic salt as carbon source in high temperature non-oxygenated property atmosphere, through pyrolysis, the metal oxide surface that carbon atom grows in position becomes nuclear rearrangement, reset the growth presenting two-dimensional directional according to oxide surface template, and seriality is good, thus obtaining the mixture of porous graphene and metal-oxide.Meanwhile, produce active phosphorus after phosphorus source pyrolysis, take part in the rearrangement process of carbon atom, it is achieved the growth of phosphorus original position doped graphene; And organic phosphorus compound is not only provided to active phosphorus, also provide for part carbon, it is achieved the growth of phosphorus original position doped graphene. Metal-oxide has the advantages that to be dissolved in acid, and therefore mixture is after pickling processes, can obtain pure phosphorus doping porous graphene.
From the above it can be seen that the beneficial effects of the present invention is:
Only need by heating phosphorus source and organic salt or the mixture with organic acid Yu salt in non-oxidizing atmosphere due to the present invention, the mixture of phosphorus doping Graphene and metal-oxide can be prepared, follow-up can remove the metal-oxide in mixture by the conventional impurity removal process such as wash liquid and obtain the phosphorus doping Graphene that purity is higher, therefore compared to existing technologies, it is simple that the present invention has technique, with short production cycle, can the advantage such as original position doping, and the phosphorus doping Graphene prepared has porous, the feature that specific surface area is big, can be widely applied to lithium ion battery, ultracapacitor, lead-acid battery, water processes, electro-catalysis, the every field such as photocatalysis.
Preferably, phosphorus source is selected from one or more in red phosphorus, diammonium phosphate, ammonium dihydrogen phosphate, phosphoric acid, phosphorous acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, NSC 6513, NSC 5284, tributyl phosphite, tricresyl phosphite monooctyl ester and triphenyl phosphite.
Preferably, the weight ratio of described organic acid and salt is 1: 9-9: 1.
Preferably, phosphorus source is 0.1: 100-1: 10 with the weight ratio of organic salt.
Preferably, phosphorus source is 0.1: 100-1: 10 with the weight ratio of organic acid and the mixture of salt.
Preferably, described non-oxidizing atmosphere is made up of one or more in nitrogen, argon, hydrogen and ammonia.
Preferably, owing to phosphorus doping Graphene is at high temperature easily oxidised with air contact, in order to avoid aoxidizing the problems such as the product purity caused and Quality Down, the present invention is when removing the metal-oxide in mixture, preferably employ in the following manner: when completely cutting off air and/or mixture temperature lower than 100 DEG C when adopt the mode of wash liquid to remove the metal-oxide in mixture, one or more in hydrochloric acid, nitric acid, acetic acid and oxalic acid of described washing liquid. It is furthermore preferred that one or both adopting in 37% concentrated hydrochloric acid and 30% acetic acid, pickling 4-8 hour under the temperature conditions of 40-60 DEG C. After having washed, can extremely dry to obtain highly purified phosphorus doping Graphene by sucking filtration further.
Preferably, the speed of described heating is 0.5-15 DEG C/min. When the rate of heat addition is too fast, the productivity of phosphorus doping Graphene is relatively low, and the excessively slow rate of heat addition, the production cycle of product can be greatly prolonged again. It is furthermore preferred that the speed of described heating is 2-10 DEG C/min.
Preferably, in order to improve the product quality of phosphorus doping Graphene, phosphorus source is incubated 1-6h after heating to 350-1600 DEG C under non-oxidizing atmosphere with organic salt or the mixture with organic acid Yu salt.
Experimental technique described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all commercially obtain.
Embodiment 1, weigh 5.55 grams of calcium stearates and 0.45 gram of triphenyl phosphate, put it in magnetic boat, then in argon, the ramp of 4 DEG C/min is pressed to 700 DEG C with tube furnace, heat 2 hours at 700 DEG C, obtain phosphorus doping Graphene and calcium oxide mixture, with 37% concentrated hydrochloric acid of 10 milliliters at 50 DEG C, wash 4 hours, sucking filtration, to dry, can obtain phosphorus doping Graphene.Through elementary analysis, the phosphorus content of this phosphorus doping Graphene is 6.1%.
Embodiment 2, weigh 2 grams of calcium citrates and 0.2 gram of trioctyl phosphate, put it in magnetic boat, then in nitrogen, the ramp of 2 DEG C/min is pressed to 600 DEG C with tube furnace, heat 2 hours at 600 DEG C, obtain phosphorus doping Graphene and calcium oxide mixture, with 37% concentrated hydrochloric acid of 10 milliliters at 50 DEG C, wash 4 hours, sucking filtration, to dry, can obtain phosphorus doping Graphene. Through elementary analysis, the phosphorus content of this phosphorus doping Graphene is 4.2%.
Embodiment 3, weigh 2 grams of Eighteen alkyl acid calcium and 0.9 gram of triphenyl phosphite, put it in magnetic boat, then in nitrogen, the ramp of 10 DEG C/min is pressed to 600 DEG C with tube furnace, heat 2 hours at 600 DEG C, obtain phosphorus doping Graphene and calcium oxide mixture, with 30% acetic acid of 10 milliliters at 50 DEG C, wash 4 hours, sucking filtration, to dry, can obtain phosphorus doping Graphene. Through elementary analysis, the phosphorus content of this phosphorus doping Graphene is 6.4%.
Embodiment 4, weigh 1 gram of zinc oleate and 0.4 gram of tricresyl phosphite monooctyl ester, put it in magnetic boat, then in argon and hydrogen mixed gas, the ramp of 5 DEG C/min is pressed to 800 DEG C with tube furnace, heat 2 hours at 800 DEG C, obtain phosphorus doping Graphene and zinc oxide mix, with 37% concentrated hydrochloric acid of 10 milliliters at 50 DEG C, wash 4 hours, sucking filtration, to dry, can obtain phosphorus doping Graphene. Through elementary analysis, the phosphorus content of this phosphorus doping Graphene is 5.6%.
Embodiment 5, weigh 1 gram of oleic acid, 1 gram of zinc acetate and 0.5 gram of tributyl phosphate, put it in magnetic boat, then in nitrogen, the ramp of 5 DEG C/min is pressed to 800 DEG C with tube furnace, heat 2 hours at 800 DEG C, obtain phosphorus doping Graphene and zinc oxide mix, with 29% strong aqua ammonia of 10 milliliters at 50 DEG C, wash 4 hours, sucking filtration, to dry, can obtain phosphorus doping Graphene. Through elementary analysis, the phosphorus content of this phosphorus doping Graphene is 5.9%.
Embodiment 6, weigh 1 gram of gluconic acid, 1 gram of calcium acetate and 0.6 gram of triphenyl phosphite, put it in magnetic boat, then in nitrogen, the ramp of 5 DEG C/min is pressed to 400 DEG C with tube furnace, heat 6 hours at 400 DEG C, obtain phosphorus doping Graphene and zinc oxide mix, with 37% concentrated hydrochloric acid of 10 milliliters at 50 DEG C, wash 4 hours, sucking filtration, to dry, can obtain phosphorus doping Graphene. Through elementary analysis, the phosphorus content of this phosphorus doping Graphene is 5.5%.
Embodiment 7, weigh 2 grams of manganese citrates and 0.6 gram of NSC 6513, put it in magnetic boat, then in nitrogen, the ramp of 5 DEG C/min is pressed to 1200 DEG C with tube furnace, heat 2 hours at 1200 DEG C, obtaining phosphorus doping Graphene and manganese monoxide mixture, the acetic acid with the 30% of 10 milliliters, at 50 DEG C, washs 4 hours, sucking filtration, to dry, can obtain phosphorus doping Graphene. Through elementary analysis, the phosphorus content of this phosphorus doping Graphene is 6.35%.
Embodiment 8, weigh 2 grams of calcium citrates, 3 grams of calcium stearates and 0.25 gram of trioctyl phosphate, put it in magnetic boat, then in nitrogen, the ramp of 2 DEG C/min is pressed to 850 DEG C with tube furnace, heat 4 hours at 850 DEG C, obtain phosphorus doping Graphene and calcium oxide mixture, with 37% concentrated hydrochloric acid of 10 milliliters at 50 DEG C, wash 4 hours, sucking filtration, to dry, can obtain phosphorus doping Graphene. Through elementary analysis, the phosphorus content of this phosphorus doping Graphene is 4.3%.
Embodiment 9, weigh 2 grams of calcium citrates, 3 grams of calcium stearates and 0.2 gram of ammonium dihydrogen phosphate, put it in magnetic boat, then in nitrogen, the ramp of 2 DEG C/min is pressed to 900 DEG C with tube furnace, heat 2 hours at 900 DEG C, obtain phosphorus doping Graphene and calcium oxide mixture, with 37% concentrated hydrochloric acid of 10 milliliters at 50 DEG C, wash 4 hours, sucking filtration, to dry, can obtain phosphorus doping Graphene. Through elementary analysis, the phosphorus content of this phosphorus doping Graphene is 4.2%.
Embodiment 10, weigh 4 grams of calcium stearates and 0.3 gram of diammonium phosphate, put it in magnetic boat, then in nitrogen, the ramp of 2 DEG C/min is pressed to 600 DEG C with tube furnace, heat 2 hours at 600 DEG C, obtain phosphorus doping Graphene and calcium oxide mixture, with 37% concentrated hydrochloric acid of 10 milliliters at 50 DEG C, wash 4 hours, sucking filtration, to dry, can obtain phosphorus doping Graphene. Through elementary analysis, the phosphorus content of this phosphorus doping Graphene is 4.1%.
Embodiment 11, weigh 4 grams of oleic acid, 4 grams of manganese acetates and 0.3 gram of red phosphorus, put it in magnetic boat, then in nitrogen, the ramp of 2 DEG C/min is pressed to 600 DEG C with tube furnace, heat 2 hours at 600 DEG C, obtain phosphorus doping Graphene and manganese monoxide mixture, with 37% concentrated hydrochloric acid of 10 milliliters at 50 DEG C, wash 4 hours, sucking filtration, to dry, can obtain phosphorus doping Graphene. Through elementary analysis, the phosphorus content of this phosphorus doping Graphene is 0.8%.
Embodiment 12, weigh 4 grams of stearic acid, 0.4 gram of zinc nitrate and 0.3 gram of diammonium phosphate, put it in magnetic boat, then in nitrogen, the ramp of 2 DEG C/min is pressed to 600 DEG C with tube furnace, heat 2 hours at 600 DEG C, obtain phosphorus doping Graphene and calcium oxide mixture, with 37% concentrated hydrochloric acid of 10 milliliters at 50 DEG C, wash 4 hours, sucking filtration, to dry, can obtain phosphorus doping Graphene. Through elementary analysis, the phosphorus content of this phosphorus doping Graphene is 4.5%.
Embodiment 13, weigh 0.4 gram of oleic acid, 4 grams of barium iodides and 0.1 gram of diammonium phosphate, put it in magnetic boat, then in nitrogen, the ramp of 2 DEG C/min is pressed to 600 DEG C with tube furnace, heat 2 hours at 600 DEG C, obtain phosphorus doping Graphene and calcium oxide mixture, with 37% concentrated hydrochloric acid of 10 milliliters at 50 DEG C, wash 4 hours, sucking filtration, to dry, can obtain phosphorus doping Graphene. Through elementary analysis, the phosphorus content of this phosphorus doping Graphene is 6.0%.
The phosphorus doping Graphene prepared by above-described embodiment 1-13, carries out electron-microscope scanning, and the scanning electron microscope (SEM) photograph obtained can refer to shown in Fig. 1. As shown in Figure 1 it can be seen that the phosphorus doping Graphene that the present invention finally prepares presents vesicular texture.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every equivalent structure utilizing description of the present invention and accompanying drawing content to make or equivalence flow process conversion; or directly or indirectly it is used in other relevant technical fields, all in like manner include in the scope of patent protection of the present invention.
Claims (9)
1. a phosphorus doping graphene preparation method, it is characterised in that including:
Phosphorus source is heated to 300-1600 DEG C with organic salt or the mixture with organic acid and salt under non-oxidizing atmosphere, obtains the mixture of phosphorus doping Graphene and metal-oxide;
Remove the metal-oxide in mixture, obtain phosphorus doping Graphene;
Wherein, phosphorus source is selected from one or more in elemental phosphorous, phosphate, phosphate compounds and phosphite ester compound;
Wherein, one or more in the alkyl soap that magnesium, calcium, strontium, barium, cobalt, nickel, manganese, ferrum, zinc, aluminum, indium or the citrate of bismuth, gluconate, tartrate, D-VB5 salt, threose acid salt, carbon number are 8-24 and oleate of described organic salt;
Wherein, one or more in the alkyl fatty acid that citric acid, gluconic acid, tartaric acid, D-VB5, threonic acid THREONIC ACID., carbon number are 8-24 and oleic acid of described organic acid;
Wherein, described salt is selected from one or more in magnesium, calcium, strontium, barium, cobalt, nickel, manganese, ferrum, zinc, aluminum, indium or the acetate of bismuth, nitrate, chlorate, Bromide and iodized salt.
2. phosphorus doping graphene preparation method according to claim 1, it is characterised in that: phosphorus source is selected from one or more in red phosphorus, diammonium phosphate, ammonium dihydrogen phosphate, phosphoric acid, phosphorous acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, NSC 6513, NSC 5284, tributyl phosphite, tricresyl phosphite monooctyl ester and triphenyl phosphite.
3. phosphorus doping graphene preparation method according to claim 1, it is characterised in that: phosphorus source is incubated 1-6h after heating to 350-1600 DEG C under non-oxidizing atmosphere with organic salt or the mixture with organic acid and salt.
4. phosphorus doping graphene preparation method according to claim 1, it is characterized in that: when completely cutting off air and/or mixture temperature lower than 100 DEG C when adopt the mode of wash liquid to remove the metal-oxide in mixture, one or more in hydrochloric acid, nitric acid, acetic acid and oxalic acid of described washing liquid.
5. phosphorus doping graphene preparation method according to claim 1, it is characterised in that: described non-oxidizing atmosphere is made up of one or more in nitrogen, argon, hydrogen and ammonia.
6. phosphorus doping graphene preparation method according to claim 1, it is characterised in that: the speed of described heating is 0.5-15 DEG C/min.
7. phosphorus doping graphene preparation method according to claim 1, it is characterised in that: the weight ratio of described organic acid and salt is 1: 9-9: 1.
8. phosphorus doping graphene preparation method according to claim 1, it is characterised in that: the weight ratio of phosphorus source and organic salt is 0.1: 100-1: 10.
9. phosphorus doping graphene preparation method according to claim 1, it is characterised in that: the weight ratio of the mixture of phosphorus source and organic acid and salt is 0.1: 100-1: 10.
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| CN104860291A (en) * | 2015-05-07 | 2015-08-26 | 常州大学 | Preparation method of phosphorus doped graphene sheet |
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| 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 |
| CN109772394B (en) * | 2019-01-16 | 2022-04-15 | 盐城工学院 | Phosphorus-doped carbon/cuprous oxide composite catalyst and preparation method and application thereof |
| JP7338993B2 (en) * | 2019-03-06 | 2023-09-05 | 株式会社クラレ | Porous carbon and method for producing porous carbon |
| CN113582165A (en) * | 2021-07-21 | 2021-11-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of phosphorus atom doped graphene nanocomposite |
| CN115112260A (en) * | 2022-06-20 | 2022-09-27 | 陕西科技大学 | Purple phosphorus alkene/graphene temperature-sensitive sensor and preparation method thereof |
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