CN108706559A - A kind of preparation method of graphite phase carbon nitride material - Google Patents

A kind of preparation method of graphite phase carbon nitride material Download PDF

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Publication number
CN108706559A
CN108706559A CN201810541402.0A CN201810541402A CN108706559A CN 108706559 A CN108706559 A CN 108706559A CN 201810541402 A CN201810541402 A CN 201810541402A CN 108706559 A CN108706559 A CN 108706559A
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carbon nitride
phase carbon
graphite phase
nitride material
infrared heating
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CN108706559B (en
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袁玉鹏
徐文涛
徐更生
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Anhui University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00Nitrogen; Compounds thereof
    • C01B21/06Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0605Binary compounds of nitrogen with carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • B01J35/39
    • B01J35/615
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042Decomposition of water
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The present invention provides a kind of preparation methods of graphite phase carbon nitride material, belong to photochemical catalyst field.The present invention includes the following steps:Infrared heating nitrogen-rich organic small molecule obtains graphite phase carbon nitride material, and the temperature of the infrared heating is 550~1200 DEG C, and the time of the infrared heating is 5~30min, and the heating rate of the infrared heating is 25~30 DEG C/s.The present invention prepares graphite phase carbon nitride material with realizing quick, efficient, temperature-controllable, and prepared graphite phase carbon nitride material has larger specific surface area and excellent photocatalysis performance.Embodiment statistics indicate that, graphite phase carbon nitride material produced by the present invention with wide spectrum respond, response range can reach nearly 600nm, and photochemical catalyzing H2-producing capacity is excellent.

Description

A kind of preparation method of graphite phase carbon nitride material
Technical field
The present invention relates to photocatalyst technology field more particularly to a kind of preparation methods of graphite phase carbon nitride material.
Background technology
In the past few decades, since limited fossil fuel resource constantly consumes that have caused many energy short on the earth A series of problems, such as scarce and environmental pollution, the self-examination and concern of the mankind are caused.Cleaning is found, the sustainable energy used becomes The mankind current most important things, and solar energy and Hydrogen Energy are then inexhaustible, nexhaustible, graphite phase carbon nitride material (g- C3N4) as a kind of photocatalyst material of rich nitrogen, luminous energy can be absorbed and water decomposition is generated into hydrogen, have raw material inexpensively easy , environmental-friendly, high thermostabilization and the advantages that chemical stability, gradually attract people's attention.
It is closed by hydro-thermal predominantly using the small molecule of rich nitrogen as presoma the existing preparation side of graphite phase carbon nitride material It is prepared at techniques such as, high temperature hot polymerizations, required time a few hours are even longer by tens hours, and fabrication processing is cumbersome, consumption Time is long, energy is more, and inefficiency is unfavorable for industrialized production, and improved method is by micro-wave oven Microwave-assisted firing Carbon nitride material is prepared, has reached and has prepared carbon nitride material within the time (5~20 minutes) quickly, but microwave heating Temperature is uncontrollable, can not monitor and be controlled preparation in real time, it is larger to result in the contingency tested every time.
Invention content
In consideration of it, the purpose of the present invention is to provide a kind of preparation method of graphite phase carbon nitride material, realize quickly, Efficiently, graphite phase carbon nitride material is prepared to temperature-controllable.
In order to achieve the above-mentioned object of the invention, the present invention provides following technical scheme:
A kind of preparation method of graphite phase carbon nitride material, includes the following steps:
Infrared heating nitrogen-rich organic small molecule, obtains graphite phase carbon nitride material, and the temperature of the infrared heating is 550~ 1200 DEG C, the time of the infrared heating is 5~30min, and the heating rate of the infrared heating is 25~30 DEG C/s.
Preferably, the nitrogen-rich organic small organic molecule is urea, melamine, thiocarbamide or dicyanodiamine.
Preferably, the temperature of the infrared heating is 600~900 DEG C.
Preferably, the temperature of the infrared heating is 700 DEG C.
Preferably, the time of the infrared heating is 10~20min.
Preferably, the device of the infrared heating is the infrared stoves that are rapidly heated of RPT.
Preferably, the nitrogen-rich organic small molecule is placed in alumina crucible.
Preferably, the light source of the infrared heating is infrared lamp.
The present invention provides a kind of preparation methods of graphite phase carbon nitride material, include the following steps:Infrared heating richness nitrogen Organic molecule obtains graphite phase carbon nitride material, and the temperature of the infrared heating is 550~1200 DEG C, the infrared heating Time be 5~30min, the heating rate of the infrared heating is 25~30 DEG C/s.The present invention realizes quick, efficient, warm Degree controllably prepares graphite phase carbon nitride material, and prepared graphite phase carbon nitride material has larger specific surface area, high Up to 131.14m2/ g and excellent photocatalysis performance.Embodiment statistics indicate that, graphite phase carbon nitride material produced by the present invention It is responded with wide spectrum, response range can reach nearly 600nm, and photochemical catalyzing H2-producing capacity is excellent, and hydrogen-producing speed is 73.57μmol/h。
Description of the drawings
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the X ray diffracting spectrum of graphite phase carbon nitride material prepared by embodiment 1;
Fig. 2 is the infared spectrum of graphite phase carbon nitride material prepared by embodiment 1;
Fig. 3 is the abosrption spectrogram of 1 gained graphite phase carbon nitride material of embodiment;
Fig. 4 is the photocatalytic hydrogen production by water decomposition performance curve of 1 gained graphite phase carbon nitride material of embodiment;
Fig. 5 is the X ray diffracting spectrum of 2 gained graphite phase carbon nitride material of embodiment;
Fig. 6 is the infared spectrum of graphite phase carbon nitride material prepared by embodiment 2;
Fig. 7 is the abosrption spectrogram of 2 gained graphite phase carbon nitride material of embodiment;
Fig. 8 is the photocatalytic hydrogen production by water decomposition performance curve of 2 gained graphite phase carbon nitride material of embodiment;
Fig. 9 is the X ray diffracting spectrum of 3 gained graphite phase carbon nitride material of embodiment;
Figure 10 is the abosrption spectrogram of graphite phase carbon nitride material prepared by embodiment 3;
Figure 11 is the X ray diffracting spectrum of 4 gained graphite phase carbon nitride material of embodiment;
Figure 12 is the abosrption spectrogram of graphite phase carbon nitride material prepared by embodiment 4;
Figure 13 is the X ray diffracting spectrum of 5 gained graphite phase carbon nitride material of embodiment;
Figure 14 is the abosrption spectrogram of graphite phase carbon nitride material prepared by embodiment 5.
Specific implementation mode
The present invention provides a kind of preparation methods of graphite phase carbon nitride material, include the following steps:
Infrared heating nitrogen-rich organic small molecule, obtains graphite phase carbon nitride material, and the temperature of the infrared heating is 550~ 1200 DEG C, the time of the infrared heating is 5~30min, and the heating rate of the infrared heating is 25~30 DEG C/s.
In the present invention, the nitrogen-rich organic small organic molecule is preferably urea, melamine, thiocarbamide or dicyan two Amine.The present invention does not have special restriction to the source of the nitrogen-rich organic small molecule, using city well known to those skilled in the art Sell commodity.
In the present invention, the temperature of the infrared heating is preferably 600~900 DEG C, more preferably 700 DEG C.
In the present invention, the time of the infrared heating is preferably 10~20min.
In the present invention, the device of the infrared heating is preferably the infrared stoves that are rapidly heated of RPT.In the present invention, described The infrared stoves that are rapidly heated of RPT are preferably the infrared stoves that are rapidly heated of commercially available RPT.
In the present invention, the nitrogen-rich organic small molecule is preferably disposed in alumina crucible.
In the present invention, preferably further include obtaining infrared heating product cooled to room temperature after the completion of the infrared heating To graphite phase carbon nitride material.
In the present invention, the light source of the infrared heating is infrared lamp.
The preparation method of graphite phase carbon nitride material provided by the invention is described in detail with reference to embodiment, But they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Weigh 10g urea, be put into 20mL alumina crucibles, cover crucible cover, be put into infrared heating furnace, respectively with 600 DEG C, 625 DEG C, 650 DEG C, 675 DEG C, 700 DEG C are heating temperature, carry out heating 20min, are just made to five groups not after cooled Synthermal graphite phase carbon nitride material;
The X ray diffracting spectrum of the graphite phase carbon nitride material prepared in the present embodiment is as shown in Figure 1, illustrate the material prepared Material is graphite phase carbon nitride.
The infrared spectrogram of prepared graphite phase carbon nitride material is as shown in Fig. 2, illustrate the material prepared in the present embodiment Material is graphite phase carbon nitride material.
The abosrption spectrogram of prepared graphite phase carbon nitride material is as shown in figure 3, illustrate the stone prepared in the present embodiment There are black phase carbon nitride material wide spectrum absorbent properties, response range can reach nearly 600nm.
In the present embodiment prepared graphite phase carbon nitride material material photocatalytic hydrogen production by water decomposition performance as shown in figure 4, Photochemical catalyzing concrete operation step:The sample for weighing 10mg preparations, is put into photo catalysis reactor, and 20mL 10% is added Triethanolamine aqueous solution as sacrifice agent, the Pt of 0.5wt% is added as co-catalyst, using 300W xenon lamp (equipped with λ >= The optical filter of 420nm) under conditions of carry out photocatalysis hydrogen production experiment, Fig. 4 illustrate prepare graphite phase carbon nitride material material have Preferable photocatalysis performance.
Embodiment 2
10g urea is weighed, is put into 20mL alumina crucibles, covers crucible cover, is put into that RPT is infrared to be rapidly heated in stove, Respectively using 5min, 10min, 15min, 20min as heating time, heating temperature is 700 DEG C, and four groups of differences are just obtained after cooled The graphite phase carbon nitride material material of heating time;
The X ray diffracting spectrum of the graphite phase carbon nitride material material prepared in the present embodiment is as shown in figure 5, illustrate preparation Material is graphite phase carbon nitride.
The infrared spectrogram of prepared graphite phase carbon nitride material material is as shown in fig. 6, illustrate preparation in the present embodiment Material is graphite phase carbon nitride material material.
The abosrption spectrogram of prepared graphite phase carbon nitride material material is as shown in fig. 7, illustrate preparation in the present embodiment Graphite phase carbon nitride material material has wide spectrum absorbent properties, and as shown in Figure 7, light abstraction width is by 700 DEG C of 5min's of heating 440nm has widened the 660nm of 700 DEG C of 20min of heating, illustrates that the graphite phase carbon nitride material prepared has wide spectrum absorbability Energy.
The photocatalytic hydrogen production by water decomposition performance test of prepared graphite phase carbon nitride material material is as implemented in the present embodiment Example 1, the results are shown in Figure 8, illustrates that the graphite phase carbon nitride material material prepared has preferable photocatalysis performance.
The specific surface area of graphite phase carbon nitride material made from Examples 1 to 2 is tested, the results are shown in Table 1, by Table 1 is as can be seen that graphite phase carbon nitride material specific surface area produced by the present invention is big.
The specific surface area of graphite phase carbon nitride material made from 1 Examples 1 to 2 of table
The specific surface area of graphite phase carbon nitride material made from Examples 1 to 2 is tested, the results are shown in Table 2, by Watch 2 has excellent photocatalytic hydrogen production by water decomposition as can be seen that graphite phase carbon nitride material hydrogen-producing speed produced by the present invention is fast Performance.
The hydrogen-producing speed of graphite phase carbon nitride material made from 2 Examples 1 to 2 of table
Embodiment 3
10g melamines are weighed, is put into 20mL alumina crucibles, covers crucible cover, are put into the infrared stoves that are rapidly heated of RPT In, using 20min as heating time, heating temperature is 700 DEG C, and graphite phase carbon nitride material material is just obtained after cooled;
The XRD diffracting spectrums of prepared graphite phase carbon nitride material material are as shown in figure 9, prepared by explanation in the present embodiment Material be graphite phase carbon nitride.
The abosrption spectrogram of prepared graphite phase carbon nitride material material is as shown in Figure 10 in the present embodiment, illustrates preparation Graphite phase carbon nitride material material has wide spectrum absorbent properties.
Embodiment 4
10g thiocarbamides are weighed, is put into 20mL alumina crucibles, covers crucible cover, are put into that RPT is infrared to be rapidly heated in stove, Using 20min as heating time, heating temperature is 700 DEG C, and graphite phase carbon nitride material material is just obtained after cooled;
The XRD diffracting spectrums of prepared graphite phase carbon nitride material material are as shown in figure 11 in the present embodiment, illustrate made Standby material is graphite phase carbon nitride.
The abosrption spectrogram of prepared graphite phase carbon nitride material material is as shown in figure 12 in the present embodiment, illustrates preparation Graphite phase carbon nitride material material has wide spectrum absorbent properties.
Embodiment 5
10g dicyanodiamines are weighed, is put into 20mL alumina crucibles, covers crucible cover, are put into the infrared stoves that are rapidly heated of RPT In, using 20min as heating time, heating temperature is 700 DEG C, and graphite phase carbon nitride material material is just obtained after cooled;
The XRD diffracting spectrums of prepared graphite phase carbon nitride material material are as shown in figure 13 in the present embodiment, illustrate made Standby material is graphite phase carbon nitride.
The abosrption spectrogram of prepared graphite phase carbon nitride material material is as shown in figure 14 in the present embodiment, illustrates preparation Graphite phase carbon nitride material material has wide spectrum absorbent properties.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (8)

1. a kind of preparation method of graphite phase carbon nitride material, includes the following steps:
Infrared heating nitrogen-rich organic small molecule obtains graphite phase carbon nitride material, and the temperature of the infrared heating is 550~1200 DEG C, the time of the infrared heating is 5~30min, and the heating rate of the infrared heating is 25~30 DEG C/s.
2. preparation method according to claim 1, which is characterized in that the nitrogen-rich organic small organic molecule be urea, Melamine, thiocarbamide or dicyanodiamine.
3. preparation method according to claim 1, which is characterized in that the temperature of the infrared heating is 600~900 DEG C.
4. preparation method according to claim 3, which is characterized in that the temperature of the infrared heating is 700 DEG C.
5. preparation method according to claim 1 or 3, which is characterized in that the time of the infrared heating be 10~ 20min。
6. preparation method according to claim 1, which is characterized in that the device of the infrared heating is RPT infrared quickly Heating furnace.
7. preparation method according to claim 1, which is characterized in that the nitrogen-rich organic small molecule is placed in alumina crucible In.
8. preparation method according to claim 1, which is characterized in that the light source of the infrared heating is infrared lamp.
CN201810541402.0A 2018-05-30 2018-05-30 Preparation method of graphite phase carbon nitride material Expired - Fee Related CN108706559B (en)

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN111153390A (en) * 2020-01-19 2020-05-15 安徽大学 Mesoporous graphite-phase carbon nitride material and preparation method and application thereof
JP2020152609A (en) * 2019-03-20 2020-09-24 株式会社日本触媒 Method for producing graphitic carbon nitride and novel graphitic carbon nitride
CN112452683A (en) * 2020-10-19 2021-03-09 赵梓俨 Infrared antibacterial coating and preparation method thereof
CN113060710A (en) * 2021-03-19 2021-07-02 内蒙古科技大学 Method for extracting graphite-phase carbon nitride from coal gangue
CN114904550A (en) * 2022-05-18 2022-08-16 安徽大学 Method for efficiently preparing melamine self-assembled supramolecular material
CN115025803A (en) * 2022-06-29 2022-09-09 安徽大学 Cyano-modified carbon nitride and preparation method and application thereof

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020152609A (en) * 2019-03-20 2020-09-24 株式会社日本触媒 Method for producing graphitic carbon nitride and novel graphitic carbon nitride
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CN111153390B (en) * 2020-01-19 2022-04-08 安徽大学 Mesoporous graphite-phase carbon nitride material and preparation method and application thereof
CN112452683A (en) * 2020-10-19 2021-03-09 赵梓俨 Infrared antibacterial coating and preparation method thereof
CN113060710A (en) * 2021-03-19 2021-07-02 内蒙古科技大学 Method for extracting graphite-phase carbon nitride from coal gangue
CN114904550A (en) * 2022-05-18 2022-08-16 安徽大学 Method for efficiently preparing melamine self-assembled supramolecular material
CN114904550B (en) * 2022-05-18 2024-03-19 安徽大学 Method for preparing melamine self-assembled supermolecular material
CN115025803A (en) * 2022-06-29 2022-09-09 安徽大学 Cyano-modified carbon nitride and preparation method and application thereof
CN115025803B (en) * 2022-06-29 2024-01-09 安徽大学 Cyano modified carbon nitride and preparation method and application thereof

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