CN110813351A - Preparation method of graphite phase carbon nitride catalyst - Google Patents
Preparation method of graphite phase carbon nitride catalyst Download PDFInfo
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- CN110813351A CN110813351A CN201911028006.9A CN201911028006A CN110813351A CN 110813351 A CN110813351 A CN 110813351A CN 201911028006 A CN201911028006 A CN 201911028006A CN 110813351 A CN110813351 A CN 110813351A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
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Abstract
The invention relates to a preparation method of a graphite-phase carbon nitride catalyst strengthened by biomass. The method comprises the following steps: 1) adding the precursor and the biomass into water according to a certain proportion, magnetically stirring, heating to 80 ℃, and evaporating until the water is evaporated to dryness to obtain a mixture. 2) And (2) putting the mixture obtained in the step (1) into a quartz crucible, sealing the quartz crucible by using aluminum foil paper, heating the quartz crucible to 500-800 ℃ under the nitrogen atmosphere, and continuously reacting for 2-24 hours to obtain the graphite-phase carbon nitride catalyst. The method uses the green cheap renewable biomass raw materials to strengthen the preparation of the graphite phase carbon nitride catalyst, and overcomes the defects that the performance of the graphite phase carbon nitride is improved by depending on precious metal deposition, semiconductor compounding and ion doping, the cost is high, the preparation process is complex, the large-scale preparation is difficult, and the like. When the graphite-phase carbon nitride is used for photocatalytic degradation of organic pollutants, the problems of low degradation rate, low degradation speed and the like are solved, and the defects of high cost and complex process in the traditional catalyst improvement method are overcome.
Description
Technical Field
The invention belongs to the field of chemical catalysis, and particularly relates to a preparation method of a graphite phase carbon nitride catalyst.
Background
Graphite phase carbon nitride (g)-C3N4) Is a visible light-responsive semiconductor photocatalyst prepared by thermal polymerization of precursors (urea, melamine, dicyandiamide, etc.) in which C, N atoms are sp atoms2The hybrid formation of highly delocalized pi conjugated system has good physical and chemical stability and energy band structure, and has wide application prospect in the fields of photocatalytic degradation of organic pollutants, photolysis of water to produce hydrogen, photo-reduction of carbon dioxide and the like.
At present, graphite phase carbon nitride (g-C)3N4) The main preparation methods comprise a high-temperature high-pressure solid phase method, a vapor deposition method, a solvothermal method and a high-temperature thermal polymerization method. But the currently available g-C3N4The problems of small specific surface area, easy combination of photo-generated electrons and vacancies, low visible light absorption utilization rate and the like exist in the photocatalysis process, and the practical application of the photocatalysis material is limited. In the prior published documents, noble metal deposition, ion doping, heterojunction composite construction with other semiconductors and other means are often adopted to modify the noble metal, but the cost is high, the flow is complex and the large-scale preparation is difficult.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a graphite phase carbon nitride catalyst, a biomass-enhanced preparation method and uses thereof. The method uses cheap, green and nontoxic biomass to assist in synthesizing the graphite-phase carbon nitride catalyst, can prepare the graphite-phase carbon nitride catalyst in an environment-friendly manner, and can overcome the defects that the performance of the traditional catalyst is enhanced by depending on noble metals and other semiconductors, the cost is high, the flow is complex, the large-scale preparation is difficult, and the like. When the catalyst is used for photocatalytic degradation of organic pollutants, the problems of low degradation rate, slow degradation rate, low utilization rate of visible light and the like in the prior art are improved.
The invention provides a preparation method of graphite phase carbon nitride, which comprises the following steps:
(1) adding the precursor and the biomass into water according to a certain proportion, magnetically stirring, heating to 80 ℃, and evaporating until the water is evaporated to dryness to obtain a mixture.
(2) And (2) putting the mixture obtained in the step (1) into a quartz crucible, sealing the quartz crucible by using aluminum foil paper, heating the quartz crucible to 500-800 ℃ under the nitrogen atmosphere, and continuously reacting for 2-24 hours to obtain the graphite-phase carbon nitride catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) the biomass used in the invention can be obtained from nature, and is green, nontoxic and cheap.
(2) The method is a method for preparing graphite-phase carbon nitride by biomass reinforcement, wherein in the method, the biomass can increase the nitrogen content on the surface of a catalyst and increase the crystallinity of an active crystal face in the process of precursor polymerization, and meanwhile, the forbidden bandwidth can be reduced and the absorption of visible light can be increased in the synthesis process. Meanwhile, the biomass can be gradually removed in the thermal polymerization process, and the template agent is used, so that the carbon nitride catalyst with high active sites is obtained.
(3) Compared with the traditional noble metal deposition, the method simplifies the preparation process of the catalyst, has low cost and simple operation, and is suitable for mass preparation.
(4) The method adopts the biomass to enhance and improve the photocatalytic activity of the graphite-phase carbon nitride, overcomes the defects of high cost, ion loss in the using process of the catalyst and the like caused by doping with other ions in the traditional method, meets the development requirement of green chemistry, and greatly improves the degradation rate of the biomass-enhanced carbon nitride catalyst on organic pollutants.
Drawings
FIG. 1 is a scanning electron micrograph of graphite-phase carbon nitride obtained in step (2) of example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of graphite-phase carbon nitride obtained in step (2) of example 2 of the present invention.
FIG. 3 is a scanning electron micrograph of graphite-phase carbon nitride obtained in step (2) of example 3 of the present invention.
FIG. 4 is a scanning mirror image of graphite-phase carbonitride obtained in step (2) of example 4 of the present invention.
FIG. 5 is a scanning mirror image of graphite-phase carbonitride obtained in step (2) of example 5 of the present invention.
FIG. 6 is a scanning mirror image of graphite-phase carbonitride obtained in step (2) of example 6 according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a preparation method of graphite-phase carbon nitride, which comprises the following steps:
(1) adding the precursor and the biomass into water according to a certain proportion, magnetically stirring, heating to 80 ℃, and evaporating until the water is evaporated to dryness to obtain a mixture.
(2) And (2) putting the mixture obtained in the step (1) into a quartz crucible, sealing the quartz crucible by using aluminum foil paper, heating the quartz crucible to 500-600 ℃ in a nitrogen atmosphere, and continuously reacting for 2-24 hours to obtain the graphite-phase carbon nitride catalyst.
In the invention, the biomass material contains C, N, H elements, can be well combined with the precursor, increases the nitrogen content on the surface of the carbon nitride, and is easy to remove after calcination without affecting the crystal structure of the catalyst.
Specifically, the biomass refers to: directly from an organism or an extract of an organism. Mainly comprises any one or more of corn straw, lignin, cellulose, hemicellulose, shrimp shell, crab shell, chitin, starch, alginic acid, silk, wool and wool keratin, for example, the following components: chitin, lignin, cellulose and cellulose, cellulose and hemicellulose, glucose and chitin, etc., preferably chitin.
In the present invention, the method for self-polymerizing the precursor at high temperature to form carbon nitride is the prior art, and the person skilled in the art can refer to the method disclosed in the prior art to prepare the carbon nitride, for example, according to the following method:
and (2) putting the precursor (such as urea) into a quartz crucible, sealing the quartz crucible by using aluminum foil paper, heating the quartz crucible to 500-800 ℃ under the nitrogen atmosphere, and heating and roasting the quartz crucible for 2-24 hours to obtain the graphite-phase carbon nitride catalyst.
As a preferred technical scheme of the method, the mixing mode in the step (1) is as follows: firstly, the biomass is placed in a container, then the mixed liquid of the biomass and water is added, and the ultrasonic treatment is carried out for 60 min.
Preferably, the precursor in step (1) comprises any one of urea, melamine, dicyandiamide, thiourea and monocyanide or a combination of at least two of the two (the formed precursor-biomass mixture is urea-chitin, urea-cellulose, urea-glucose and the like), and preferably urea.
Preferably, the mass ratio of the precursor to the biomass in the step (1) is 100: (0.01-10), for example, 100:0.02, 100:0.06, 100:0.2, 100:0.5, 100:0.7, 100:0.9, 100:1, 100: 10. 100:15, 100:20, etc. If the mass ratio is more than 100:20, the biomass content in the system is too high, the crystallinity of graphite phase carbon nitride is reduced, and the catalytic activity is reduced; if the mass ratio is less than 100:0.02, the biomass content is too low, and the carbon nitride is difficult to be correspondingly regulated and controlled. More preferably, the mass ratio of the precursor to the biomass is 100 (0.06-10).
Preferably, the heating rate in step (2) is 2 ℃/min to 15 ℃/min, such as 2 ℃/min, 5 ℃/min, 7 ℃/min, 10 ℃/min, 12 ℃/min, 15 ℃/min, preferably 10 ℃/min to 15 ℃/min.
Preferably, the heating temperature in step (2) is 500 to 600 ℃, for example, 500 ℃, 520 ℃, 530 ℃, 550 ℃, 560 ℃, 580 ℃, and the like, preferably 550 to 580 ℃.
Preferably, the roasting time in the step (2) is 2h to 12h, such as 2h, 3h, 5h, 6.5h, 7h, 7.5h, 8h and the like.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) adding the precursor and the biomass into water according to the proportion of 100 (0.06-10), performing ultrasonic treatment for 1h, performing magnetic stirring, heating to 80 ℃ until the water is evaporated to dryness, and thus obtaining a mixture.
(2) And (2) putting the mixture obtained in the step (1) into a quartz crucible, sealing the quartz crucible by using aluminum foil paper, heating the mixture to 550-580 ℃ at the heating rate of 10-15 ℃/min in the nitrogen atmosphere, and continuously reacting for 2-12 h to obtain the graphite-phase carbon nitride catalyst.
The following examples illustrate the preparation of the carbon nitride catalyst. The compounds in the following examples can be prepared directly according to the existing methods, but of course, in other examples, they can be directly commercially available, and are not limited thereto.
Example 1
Preparing a graphite-phase carbon nitride catalyst:
(1) weighing 10g of urea and 0.006g of chitin, placing in a 250mL beaker, adding 100mL of water, performing ultrasonic treatment for 60min, magnetically stirring and heating to 80 ℃ until the water is evaporated to dryness to obtain a mixture.
(2) And (2) filling the mixture obtained in the step (1) into a quartz crucible, sealing the quartz crucible by using aluminum foil paper, heating the quartz crucible to 550 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, and continuing to react for 2 hours to obtain the faint yellow graphite phase carbon nitride catalyst.
Example 2
Preparing a graphite-phase carbon nitride catalyst:
(1) weighing 10g of urea and 0.006g of lignin, placing the urea and the lignin in a 250mL beaker, adding 100mL of water, carrying out ultrasonic treatment for 60min, and then heating to 80 ℃ under magnetic stirring until the water is evaporated to dryness to obtain a mixture.
(2) And (2) filling the mixture obtained in the step (1) into a quartz crucible, sealing the quartz crucible by using aluminum foil paper, heating the quartz crucible to 550 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, and continuing to react for 2 hours to obtain the yellow graphite phase carbon nitride catalyst.
Example 3
Preparing a graphite-phase carbon nitride catalyst:
(1) weighing 10g of urea and 0.006g of cellulose, placing the urea and the cellulose in a 250mL beaker, adding 100mL of water, carrying out ultrasonic treatment for 60min, and then heating the mixture to 80 ℃ under magnetic stirring until the water is evaporated to dryness to obtain a mixture.
(2) And (2) filling the mixture obtained in the step (1) into a quartz crucible, sealing the quartz crucible by using aluminum foil paper, heating the quartz crucible to 550 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, and continuing to react for 2 hours to obtain the faint yellow graphite phase carbon nitride catalyst.
Example 4
The preparation method and conditions were the same as in example 1, except that:
the addition amounts of the urea and the chitin are respectively adjusted to 10g and 0.001 g.
Adjusting the heating rate of the step (2) to be 15 ℃/min;
regulating the temperature of the step (2) to 500 ℃ and continuing the reaction for 2 h.
Example 5
The preparation method and conditions were the same as in example 1, except that:
the addition amounts of the urea and the chitin are respectively adjusted to 10g and 1 g.
Adjusting the heating rate of the step (2) to be 12 ℃/min;
regulating the temperature of the step (2) to 570 ℃, and continuing the reaction for 8 h.
Example 6
The preparation method and conditions were the same as in example 1, except that:
the addition amounts of the urea and the chitin are respectively adjusted to 10g and 1.5 g.
Adjusting the heating rate of the step (2) to be 13 ℃/min;
regulating the temperature of the step (2) to 580 ℃, and continuing the reaction for 12 h.
Example 7
The preparation method and conditions were the same as in example 1, except that:
the adding amount of the urea and the chitin is adjusted to 10g and 2g respectively.
Adjusting the heating rate of the step (2) to be 15 ℃/min;
regulating the temperature of the step (2) to 600 ℃ and continuing the reaction for 24 h.
Comparative example 1
Weighing 10g of urea, placing the urea in a 250mL beaker, adding 100mL of water, carrying out ultrasonic treatment for 60min, and then carrying out magnetic stirring and heating to 80 ℃ until the water is evaporated to dryness to obtain a mixture.
And (3) putting the obtained mixture into a quartz crucible, sealing the quartz crucible by using aluminum foil paper, heating the quartz crucible to 550 ℃ at the heating rate of 10 ℃/min in the nitrogen atmosphere, and continuously reacting for 2 hours to obtain the graphite-phase carbon nitride catalyst.
FIG. 1 is a scanning electron micrograph of graphite-phase carbon nitride obtained in step (2) of example 1 of the present invention. FIG. 2 is a scanning electron micrograph of graphite-phase carbon nitride obtained in step (2) of example 2 of the present invention. FIG. 3 is a scanning electron micrograph of graphite-phase carbon nitride obtained in step (2) of example 3 of the present invention. FIG. 4 is a scanning electron micrograph of the obtained graphite-phase carbon nitride in step (2) of example 4 of the present invention. FIG. 5 is a scanning electron micrograph of the obtained graphite-phase carbon nitride of example 5 of the present invention, step (2).
As can be seen from figures 1-6, the graphite-phase carbon nitride catalyst lamella strengthened by using the biomass is increased, which is beneficial to improving the crystallinity and further improving the photocatalytic performance.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (4)
1. A method for preparing a graphite-phase carbon nitride catalyst, comprising the steps of:
(1) adding the precursor and the biomass into water according to a certain proportion, magnetically stirring, heating to 80 ℃, and evaporating until the water is evaporated to dryness to obtain a mixture;
(2) and (2) putting the mixture obtained in the step (1) into a quartz crucible, sealing the quartz crucible by using aluminum foil paper, heating the quartz crucible to 500-800 ℃ under the nitrogen atmosphere, and continuously reacting for 2-24 hours to obtain the graphite-phase carbon nitride catalyst.
2. The method according to claim 1, wherein the precursor combined with the biomass is selected from any one of urea, melamine, dicyandiamide, thiourea and cyanamide or a combination of at least two thereof.
3. The method of claim 1, wherein the biomass is selected from any one or more of straw, lignin, cellulose, hemicellulose, shrimp shell, crab shell, chitin, starch, alginic acid, wool, silk, and combinations thereof.
4. The method according to claim 1, characterized in that the mass ratio of the precursor to biomass is 100: (0.01-20).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111944355A (en) * | 2020-07-17 | 2020-11-17 | 河海大学 | Preparation method, preparation and application of fluorocarbon coating modifier |
| CN112023973A (en) * | 2020-09-10 | 2020-12-04 | 北京科技大学 | g-C with high photocatalytic efficiency3N4And method for preparing the same |
| CN112142022A (en) * | 2020-09-16 | 2020-12-29 | 复旦大学 | Preparation method of wide-spectral-response mesoporous carbon nitride |
| CN113186655A (en) * | 2021-04-06 | 2021-07-30 | 北京理工大学 | Nano carbon nitride fiber film and preparation method thereof |
| CN116586096A (en) * | 2023-05-26 | 2023-08-15 | 昆明理工大学 | Carbon nitride modified biochar material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120065052A1 (en) * | 2010-09-14 | 2012-03-15 | Basf Se | Process for producing a carbon-comprising support |
| CN105618102A (en) * | 2015-09-21 | 2016-06-01 | 江苏华天通纳米科技有限公司 | Carbon nitride photocatalyst with carbon nano-particles embedded in platy structures |
| CN106179444A (en) * | 2016-06-29 | 2016-12-07 | 陶雪芬 | A kind of preparation method of activated carbon supported carbon doping graphite phase carbon nitride |
| CN108940344A (en) * | 2018-07-26 | 2018-12-07 | 湖南大学 | Modified graphite phase carbon nitride photochemical catalyst and its preparation method and application |
-
2019
- 2019-10-28 CN CN201911028006.9A patent/CN110813351A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120065052A1 (en) * | 2010-09-14 | 2012-03-15 | Basf Se | Process for producing a carbon-comprising support |
| CN105618102A (en) * | 2015-09-21 | 2016-06-01 | 江苏华天通纳米科技有限公司 | Carbon nitride photocatalyst with carbon nano-particles embedded in platy structures |
| CN106179444A (en) * | 2016-06-29 | 2016-12-07 | 陶雪芬 | A kind of preparation method of activated carbon supported carbon doping graphite phase carbon nitride |
| CN108940344A (en) * | 2018-07-26 | 2018-12-07 | 湖南大学 | Modified graphite phase carbon nitride photochemical catalyst and its preparation method and application |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111944355A (en) * | 2020-07-17 | 2020-11-17 | 河海大学 | Preparation method, preparation and application of fluorocarbon coating modifier |
| CN111944355B (en) * | 2020-07-17 | 2022-07-15 | 河海大学 | Preparation method, preparation and application of fluorocarbon coating modifier |
| CN112023973A (en) * | 2020-09-10 | 2020-12-04 | 北京科技大学 | g-C with high photocatalytic efficiency3N4And method for preparing the same |
| CN112142022A (en) * | 2020-09-16 | 2020-12-29 | 复旦大学 | Preparation method of wide-spectral-response mesoporous carbon nitride |
| CN113186655A (en) * | 2021-04-06 | 2021-07-30 | 北京理工大学 | Nano carbon nitride fiber film and preparation method thereof |
| CN116586096A (en) * | 2023-05-26 | 2023-08-15 | 昆明理工大学 | Carbon nitride modified biochar material and preparation method thereof |
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