CN108911524B - Preparation method of Cl-doped glucose carbon-based graphene - Google Patents
Preparation method of Cl-doped glucose carbon-based graphene Download PDFInfo
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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Abstract
The invention discloses a preparation method of Cl-doped glucose carbon-based graphene, which comprises the steps of mixing glucose and hydrochloric acid, stirring and decocting a mixed solution in an atmospheric environment until the viscosity of the solution is 1 multiplied by 105~1×106Centipoise, mixing deionized water, absolute ethyl alcohol and the decocted caramel solution in proportion, filtering, taking the filtrate as a precursor solution doped with Cl, and spin-coating the precursor solution doped with Cl on a quartz plate to prepare a spin-coating film; drying the spin-coated sheet at a constant temperature for 20-35 min, then placing the dried spin-coated sheet under a vacuum condition, and annealing at 600-800 ℃ for 20-24 h to obtain a Cl-doped glucose carbon-based graphene film; the method has the advantages of simple process, mild conditions, low cost, high efficiency and environmental protection, and the prepared graphene material has the advantages of controllable doping amount and large sample sheet diameter.
Description
Technical Field
The invention belongs to the technical field of nano graphene materials, and particularly relates to a preparation method of Cl-doped glucose carbon-based graphene.
Background
Graphene is a two-dimensional carbon material, has excellent electrical, thermal, mechanical and other properties, is widely concerned in various fields such as energy, electronic materials, biomedicine and environmental protection, and the low-cost and high-quality graphene raw material is a necessary condition for promoting the application development of the graphene raw material. The existing graphene preparation technology comprises a reduced graphene oxide method, a chemical vapor deposition method, an epitaxial growth method, a molecular self-assembly method and the like, wherein the chemical reduced graphene oxide method can realize large-scale production, but the prepared graphene has more defects and inevitably generates certain pollution, and a chemical reagent used for reduction also has certain safety problems, and is mainly used for producing a functional graphene material with functional groups at present.
At present, much research is also carried out on the preparation of doped graphene, and CN108163847A provides a preparation method of large-sheet-diameter graphene, which uses graphite as a main raw material and high-viscosity syrup as a main auxiliary agent, and prepares the large-sheet-diameter graphene in a mechanical stripping manner, but the graphene prepared by the method has poor performance and is easily polluted by the syrup auxiliary agent, so that the performance of intrinsic graphene is lost, and functional graphene with special functional groups cannot be obtained. CN107973293A and CN107662917A also provide methods for preparing graphene, which mainly utilize agglomerated graphene obtained by mechanical stripping of graphite to decompose graphene blocks by ultrasonic vibration, but the graphene blocks obtained by the mechanical stripping preparation methods are different in shape and difficult to standardize after decomposition, and have serious defects that graphene is difficult to separate from ultrasonic solvent.
Therefore, from the perspective of industrially preparing large-area functionalized graphene with excellent conductivity, the method for preparing functionalized graphene, which is simple, convenient and feasible, low in cost and capable of being produced in large scale, is developed, and has great market potential.
Disclosure of Invention
The invention provides a preparation method of Cl-doped glucose carbon-based graphene, and particularly relates to the processes of preparation of a Cl-doped precursor solution, preparation of a spin-coated sheet and annealing, and the preparation method comprises the following specific steps:
(1) mixing glucose and hydrochloric acid according to the atomic ratio of C in the glucose to Cl in the hydrochloric acid of 9-3: 1, stirring and decocting the mixed solution at 100-200 ℃ in an atmospheric environment until the viscosity of the solution is 1 x 105~1×106Centipoise, mixing deionized water, absolute ethyl alcohol and the decocted precursor solution according to the volume ratio of 1:1: 2-3, and filtering to obtain a filtrate, wherein the filtrate is the precursor solution doped with Cl;
(2) spin-coating the Cl-doped precursor solution prepared in the step (1) on a quartz plate, wherein the spin-coating parameters are as follows: precoating for 3s at the rotating speed of 1000-1500 r/s, and then spin-coating for 1min at the rotating speed of 2200-2800 r/s to prepare a spin coating film;
(3) and (3) drying the spin coating prepared in the step (2) in a constant temperature oven for 20-35 min, then placing the dried spin coating in a vacuum furnace, and annealing at 600-800 ℃ for 20-24 h under a vacuum condition to obtain the Cl-doped glucose carbon-based graphene.
The concentration of the hydrochloric acid in the step (1) is 1-2 mol/L.
The stirring in the step (1) is carried out at the rotating speed of 1500r/min for 30-40 min under the temperature of 1000-.
And (2) filtering in the step (1) by using a filter tip with the aperture of 0.1-0.3 mu m.
And (3) drying at 80-100 ℃.
The vacuum degree of the vacuum condition in the step (3) is 2 multiplied by 10-1Pa ~5×10-1Pa。
The invention has the beneficial effects that:
(1) the invention uses simple equipment and medicines for preparation; the process is easy to control and has strong repeatability; the preparation method is simple, convenient and safe, can be operated in a standardized way, and provides a good reference for large-scale preparation of other doped functionalized graphene.
(2) The graphene prepared by annealing the spin-coated sheet has controllable growth morphology and growth area, and the prepared graphene film has excellent performance, good surface appearance flatness, nano-level appearance, good conductivity and excellent performance, and can be directly used for photoelectric devices.
(3) The invention can better research the preparation method and the growth mechanism of the novel graphene and further research the performances of the differently doped graphene.
Drawings
Fig. 1 is a TEM image of Cl-doped glucose carbon-based graphene prepared in example 1;
fig. 2 is a raman spectrum of Cl-doped glucose carbon-based graphene prepared in example 1;
fig. 3 is a TEM image of Cl-doped glucose carbon-based graphene prepared in example 2;
fig. 4 is a raman spectrum of Cl-doped glucose carbon-based graphene prepared in example 2;
fig. 5 is a TEM image of Cl-doped glucose carbon-based graphene prepared in example 3;
fig. 6 is a raman spectrum of Cl-doped glucose carbon-based graphene prepared in example 3;
FIG. 7 is an absorption spectrum of Cl-doped glucose carbon-based graphene prepared in examples 1 to 3.
Detailed Description
The invention is further illustrated by the following examples and figures.
Example 1
A preparation method of Cl-doped glucose carbon-based graphene specifically relates to the processes of preparation of Cl-doped precursor solution, preparation of spin-coated sheet and annealing, and specifically comprises the following steps:
(1) mixing glucose and hydrochloric acid with concentration of 1mol/L according to atomic ratio of C in glucose and Cl in hydrochloric acid of 9:1, decocting the mixed solution at 100 deg.C under atmospheric environment until the solution viscosity is 1 × 105Stirring at the rotating speed of 1500r/min for 30min, stirring at the rotating speed of 800r/min for 30min along with the increase of the viscosity of the solution after decoction, stirring at the rotating speed of 300r/min until the stirring is finished, mixing deionized water, absolute ethyl alcohol and the caramel solution after decoction according to the volume ratio of 1:1:2, and filtering, wherein the filtering is carried out by using a filter tip with the aperture of 0.1 mu m, and the filtrate is a precursor solution doped with Cl;
(2) spin-coating the Cl-doped precursor solution prepared in the step (1) on a quartz plate, wherein the spin-coating parameters are as follows: precoating at a rotating speed of 1500r/s for 3s, and finally spin-coating at a rotating speed of 2800r/s for 1min to obtain a spin-coating film;
(3) drying the spin coating film prepared in the step (2) in a constant temperature oven at 80 ℃ for 35min, and then placing the dried spin coating film in a vacuum furnace with the vacuum degree of 2 multiplied by 10-1And (3) annealing at 800 ℃ for 20h under Pa vacuum condition to obtain the Cl-doped glucose carbon-based graphene.
Fig. 1 is a TEM image of Cl-doped glucose carbon-based graphene prepared in this example, and it can be seen that the film-forming quality of the doped graphene is good and the film-forming is thin; fig. 2 is a raman spectrum of the Cl-doped glucose carbon-based graphene prepared in this example, from which three graphene characteristic peaks, i.e., a D peak, a G peak, and a 2D peak, can be found, confirming that the annealed material is a graphene film; the diagonal surface resistance of the Cl-doped graphene sheet prepared in the embodiment is subjected to characterization test, the resistance is 3.5k omega, and the conductivity is good, which shows that the doped graphene film prepared by the invention can be further developed and used for electrodes of photoelectric devices.
Example 2
A preparation method of Cl-doped glucose carbon-based graphene specifically relates to the processes of preparation of Cl-doped precursor solution, preparation of spin-coated sheet and annealing, and specifically comprises the following steps:
(1) according to glucoseMixing glucose and hydrochloric acid with concentration of 1.5mol/L at atomic ratio of C to Cl in hydrochloric acid of 5:1, decocting the mixed solution at 150 deg.C under atmospheric environment until the solution viscosity is 1 × 106Stirring at a rotating speed of 1200r/min for 35min, stirring at a rotating speed of 600r/min for 35min along with the increase of the viscosity of the solution after decoction, stirring at a rotating speed of 300r/min until the stirring is finished, mixing deionized water, absolute ethyl alcohol and the decocted caramel solution according to a volume ratio of 1:1:2.5, and filtering, wherein the filtering is carried out by using a filter tip with the aperture of 0.2 mu m, and the filtrate is a precursor solution doped with Cl;
(2) spin-coating the Cl-doped precursor solution prepared in the step (1) on a quartz plate, wherein the spin-coating parameters are as follows: precoating at a rotating speed of 1200r/s for 3s, and finally spin-coating at a rotating speed of 2500r/s for 1min to prepare a spin-coating film;
(3) drying the spin coating film prepared in the step (2) in a constant temperature oven at 90 ℃ for 30min, and then placing the dried spin coating film in a vacuum furnace with the vacuum degree of 3 multiplied by 10-1And (3) annealing at 750 ℃ for 22h under Pa vacuum condition to obtain the Cl-doped glucose carbon-based graphene.
Fig. 3 is a TEM image of Cl-doped glucose carbon-based graphene prepared in this example, and it can be seen that the film-forming quality of the doped graphene is good, and the film layer is thicker than that of example 1; fig. 4 is a raman spectrum of the Cl-doped glucose carbon-based graphene prepared in this embodiment, and from the raman spectrum, three characteristic peaks of graphene, namely a D peak, a G peak, and a 2D peak, can be found, and it is confirmed that a substance obtained by annealing is a graphene film, and a diagonal surface resistance of the Cl-doped graphene sheet prepared in this embodiment is subjected to a characterization test, and the resistance is 3k Ω, and the conductivity is good, which indicates that the doped graphene film prepared in the present invention can be further developed and used for an electrode of a photoelectric device.
Example 3
A preparation method of Cl-doped glucose carbon-based graphene specifically relates to the processes of preparation of Cl-doped precursor solution, preparation of spin-coated sheet and annealing, and specifically comprises the following steps:
(1) mixing glucose at an atomic ratio of C in glucose to Cl in hydrochloric acid of 3:1Mixing glucose with hydrochloric acid with concentration of 2mol/L, decocting the mixed solution at 200 deg.C under atmospheric environment until the viscosity of the solution is 1 × 106Stirring at a rotating speed of 1000r/min for 40min, increasing the viscosity of the solution after decoction, stirring at a rotating speed of 500r/min for 40min, stirring at a rotating speed of 300r/min until the stirring is finished, mixing deionized water, absolute ethyl alcohol and the decocted caramel solution according to a volume ratio of 1:1:3, and filtering, wherein the filtering is performed by using a filter tip with a pore diameter of 0.3 mu m, and the filtrate is a precursor solution doped with Cl;
(2) spin-coating the Cl-doped precursor solution prepared in the step (1) on a quartz plate, wherein the spin-coating parameters are as follows: precoating for 3s at the rotating speed of 1000r/s, and finally spin-coating for 1min at the rotating speed of 2200r/s to prepare a spin-coating film;
(3) drying the spin coating film prepared in the step (2) in a constant temperature oven at 100 ℃ for 20min, and then placing the dried spin coating film in a vacuum furnace with the vacuum degree of 5 multiplied by 10-1And (3) annealing at 600 ℃ for 24h under Pa vacuum condition to obtain the Cl-doped glucose carbon-based graphene.
Fig. 5 is a TEM image of Cl-doped glucose carbon-based graphene prepared in this example, and it can be seen that the film-forming quality of the doped graphene is good, and the film layer is thicker than that in example 2; fig. 6 is a raman spectrum of the Cl-doped glucose carbon-based graphene prepared in this example, from which three graphene characteristic peaks, i.e., a D peak, a G peak, and a 2D peak, can be found, confirming that the annealed material is a graphene film; the diagonal surface resistance of the Cl-doped graphene sheet prepared in the embodiment is subjected to characterization test, the resistance is 2k omega, and the conductivity is good, which shows that the doped graphene film prepared by the invention can be further developed and used for electrodes of photoelectric devices.
Fig. 7 is an absorption spectrum of Cl-doped glucose carbon-based graphene prepared in examples 1 to 3, and it can be seen from the absorption spectrum that all Cl-doped glucose carbon-based graphene prepared in examples 1 to 3 have an absorption peak, and it is confirmed that Cl doping changes an absorption band gap of graphene, and due to a film thickness, light absorption of example 3 is the best, which illustrates that the doped graphene thin film prepared in the present invention can be further developed into a focal plane for a photoelectric device.
Claims (5)
1. A preparation method of Cl-doped glucose carbon-based graphene is characterized by comprising the following specific steps:
(1) mixing glucose and hydrochloric acid according to the atomic ratio of C in the glucose to Cl in the hydrochloric acid of 9-3: 1, stirring and decocting the mixed solution at 100-200 ℃ in an atmospheric environment until the viscosity of the solution is 1 x 105~1×106Centipoise, mixing deionized water, absolute ethyl alcohol and the decocted caramel solution according to the volume ratio of 1:1: 2-3, and filtering to obtain a filtrate, namely a precursor solution doped with Cl;
(2) spin-coating the Cl-doped precursor solution prepared in the step (1) on a quartz plate, wherein the spin-coating parameters are as follows: precoating for 3s at the rotating speed of 1000-1500 r/s, and then spin-coating for 1min at the rotating speed of 2200-2800 r/s to prepare a spin coating film;
(3) drying the spin-coated sheet prepared in the step (2) at a constant temperature for 20-35 min, then placing the dried spin-coated sheet under a vacuum condition, and annealing at 600-800 ℃ for 20-24 h to obtain a Cl-doped glucose carbon-based graphene film;
in the step (1), the stirring is carried out at a rotation speed of 1000-.
2. The method for preparing Cl-doped glucose carbon-based graphene according to claim 1, wherein the concentration of the hydrochloric acid in the step (1) is 1-2 mol/L.
3. The method for preparing Cl-doped glucose carbon-based graphene according to claim 1, wherein the filtering in the step (1) is performed by using a filter tip with a pore size of 0.1-0.3 μm.
4. The method for preparing Cl-doped glucose carbon-based graphene according to claim 1, wherein the drying temperature in the step (3) is 80-100 ℃.
5. The method for preparing Cl-doped glucose carbon-based graphene according to claim 1, wherein the degree of vacuum in the vacuum condition in the step (3) is 2 x 10-1Pa~5×10-1Pa。
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009231810A (en) * | 2008-02-26 | 2009-10-08 | Denso Corp | Semiconductor carbon film, semiconductor device, and method of manufacturing semiconductor carbon film |
| CN103359727A (en) * | 2013-07-24 | 2013-10-23 | 云南师范大学 | Preparation method of oxygen and chlorine co-doped graphene quantum dots |
| CN104294584A (en) * | 2014-09-29 | 2015-01-21 | 黄勇 | Fabric with doped-type graphene coating and preparation process of fabric |
| CN106587022A (en) * | 2016-12-21 | 2017-04-26 | 昆明物理研究所 | Preparation method of sodium-doped multilayer graphene |
| CN106587023A (en) * | 2016-12-21 | 2017-04-26 | 昆明物理研究所 | Method for preparation of semiconductor type sulfur-doped graphene film |
| CN106601591A (en) * | 2016-12-21 | 2017-04-26 | 昆明物理研究所 | Preparation method of chlorine-doped multilayer graphene film |
| CN108314005A (en) * | 2018-03-27 | 2018-07-24 | 广西师范大学 | A kind of method and its device preparing chlorine doped graphene quantum dot |
-
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009231810A (en) * | 2008-02-26 | 2009-10-08 | Denso Corp | Semiconductor carbon film, semiconductor device, and method of manufacturing semiconductor carbon film |
| CN103359727A (en) * | 2013-07-24 | 2013-10-23 | 云南师范大学 | Preparation method of oxygen and chlorine co-doped graphene quantum dots |
| CN104294584A (en) * | 2014-09-29 | 2015-01-21 | 黄勇 | Fabric with doped-type graphene coating and preparation process of fabric |
| CN106587022A (en) * | 2016-12-21 | 2017-04-26 | 昆明物理研究所 | Preparation method of sodium-doped multilayer graphene |
| CN106587023A (en) * | 2016-12-21 | 2017-04-26 | 昆明物理研究所 | Method for preparation of semiconductor type sulfur-doped graphene film |
| CN106601591A (en) * | 2016-12-21 | 2017-04-26 | 昆明物理研究所 | Preparation method of chlorine-doped multilayer graphene film |
| CN108314005A (en) * | 2018-03-27 | 2018-07-24 | 广西师范大学 | A kind of method and its device preparing chlorine doped graphene quantum dot |
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