CN110227533B - Preparation method of graphite-phase carbon nitride photocatalyst - Google Patents

Preparation method of graphite-phase carbon nitride photocatalyst Download PDF

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CN110227533B
CN110227533B CN201910603311.XA CN201910603311A CN110227533B CN 110227533 B CN110227533 B CN 110227533B CN 201910603311 A CN201910603311 A CN 201910603311A CN 110227533 B CN110227533 B CN 110227533B
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graphite
carbon nitride
phase carbon
photocatalyst
heat treatment
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CN110227533A (en
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张新宇
杨成武
秦家千
马明臻
刘日平
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Yanshan University
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    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
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    • 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
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    • C01B2203/02Processes for making hydrogen or synthesis gas
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    • C01B2203/0277Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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    • 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

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Abstract

The invention provides a graphite-phase carbon nitride photocatalyst and a preparation method and application thereof, belonging to the technical field of photocatalytic materials. The graphite-phase carbon nitride comprises graphite-phase carbon nitride and oxygen atoms doped in a crystal lattice of the graphite-phase carbon nitride, wherein the graphite-phase carbon nitride has cyano structure defects. The graphite-phase carbon nitride photocatalyst has high photocatalytic activity and high photocatalytic stability. The results of the examples show that when the catalyst is used for photocatalytic water decomposition hydrogen production, the graphite-phase carbon nitride photocatalyst provided by the invention has higher hydrogen production amount in the same time compared with the existing pure graphite-phase carbon nitride, and still maintains the original catalytic activity after eight cycles. The preparation method is simple and easy to operate.

Description

Preparation method of graphite-phase carbon nitride photocatalyst
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a graphite-phase carbon nitride photocatalyst and a preparation method and application thereof.
Background
The photocatalytic technology is a technology for converting solar energy into chemical energy by using a semiconductor material as a medium. The photocatalytic technology has many applications in the fields of energy conversion, air purification, water treatment, building materials and the like. But have limited their practical application due to some of the drawbacks of the semiconductor materials themselves.
Graphite-phase carbon nitride is a semiconductor material which is discovered in recent years and does not contain metal elements, has the advantages of good visible light catalytic activity, low cost and easiness in regulation, but has low visible light absorption capacity, large forbidden band width and poor catalytic stability, so that the photocatalytic performance is poor. Introduction of structural defects into carbon nitride is an effective method for increasing photocatalytic activity, and among them, cyano functional groups are the more effective defect to be studied. However, the photocatalytic performance of the modified carbon nitride under current research is still to be further improved.
Disclosure of Invention
The invention aims to provide a graphite-phase carbon nitride photocatalyst as well as a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a graphite-phase carbon nitride photocatalyst which comprises graphite-phase carbon nitride and oxygen atoms doped in a graphite-phase carbon nitride crystal lattice, wherein the graphite-phase carbon nitride has a cyano structure defect.
Preferably, the atomic percentage of oxygen atoms in the graphite-phase carbon nitride photocatalyst is 0.5-2 at.%.
The invention provides a preparation method of the graphite-phase carbon nitride photocatalyst in the scheme, which comprises the following steps: mixing urea and ascorbic acid, and carrying out heat treatment on the obtained mixture to obtain the graphite-phase carbon nitride photocatalyst.
Preferably, the mass ratio of the urea to the ascorbic acid is 50g (5-100) mg.
Preferably, the temperature of the heat treatment is 450-600 ℃.
Preferably, the time of the heat treatment is 1-3 h.
Preferably, the heat treatment is carried out at a temperature from room temperature to the heat treatment temperature, and the temperature rise rate is 2-30 ℃/min.
Preferably, the atmosphere of the heat treatment is an air atmosphere.
The invention provides an application of the graphite-phase carbon nitride photocatalyst prepared by the scheme or the preparation method in the scheme in photocatalytic hydrolysis hydrogen production.
The invention provides a graphite-phase carbon nitride photocatalyst which comprises graphite-phase carbon nitride and oxygen atoms doped in a graphite-phase carbon nitride crystal lattice, wherein the graphite-phase carbon nitride has a cyano structure defect. The graphite-phase carbon nitride photocatalyst has high photocatalytic activity and high photocatalytic stability. The results of the examples show that when the catalyst is used for photocatalytic water decomposition hydrogen production, the graphite-phase carbon nitride photocatalyst provided by the invention has higher hydrogen production amount in the same time compared with the existing pure graphite-phase carbon nitride, and still maintains the original catalytic activity after eight cycles.
The invention provides a preparation method of the graphite-phase carbon nitride photocatalyst, which is simple and easy to operate.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the photocatalyst prepared in example 1 of the present invention;
FIG. 2 is a Fourier transform infrared spectrum of the photocatalyst prepared in example 1 of the present invention and pure graphite phase carbon nitride;
FIG. 3 is a high resolution X-ray photoelectron Spectroscopy (XPS) of O1s for the photocatalyst prepared in example 1 of the present invention;
FIG. 4 is a diagram of hydrogen production by photo-decomposition of water with a photocatalyst and pure graphite-phase carbon nitride prepared in examples 1 to 4 of the present invention;
FIG. 5 is a photo-catalytic cycling test chart of the photocatalyst prepared in example 1 and pure graphite-phase carbon nitride.
Detailed Description
The invention provides a graphite-phase carbon nitride photocatalyst which comprises graphite-phase carbon nitride and oxygen atoms doped in a graphite-phase carbon nitride crystal lattice, wherein the graphite-phase carbon nitride has a cyano structure defect.
In the invention, the atomic percentage of oxygen atoms in the graphite-phase carbon nitride photocatalyst is preferably 0.5 to 2 at.%, more preferably 0.8 to 1.7 at.%, and most preferably 1.0 to 1.5 at.%. The atomic percent of oxygen atoms described herein is relative to the graphite phase carbon nitride photocatalyst, i.e., the total number of atoms of carbon, nitrogen, and oxygen. The oxygen atoms of the present invention are doped into the crystal lattice of the graphite phase carbon nitride, and more specifically occupy the lattice sites of the nitrogen atoms in the graphite phase carbon nitride.
The invention provides a preparation method of the graphite phase carbon nitride catalyst in the scheme, which comprises the following steps: mixing urea and ascorbic acid, and carrying out heat treatment on the obtained mixture to obtain the graphite-phase carbon nitride photocatalyst.
The invention mixes urea and ascorbic acid to obtain a mixture.
In the invention, the mass ratio of the urea to the ascorbic acid is preferably 50g (5-100) mg, more preferably 50g (10-70) mg, and most preferably 50g:30 mg. The source of the urea and ascorbic acid is not particularly required in the present invention, and commercially available products well known to those skilled in the art may be used. The invention has no special requirements on the mixing mode, and any mode can be used for uniformly mixing the two.
After the mixture is obtained, the invention carries out heat treatment on the mixture to obtain the graphite phase carbon nitride photocatalyst.
In the invention, the temperature of the heat treatment is preferably 450-600 ℃, and more preferably 500 ℃; the time of the heat treatment is preferably 1-3 h, and more preferably 2 h; the atmosphere of the heat treatment is preferably an air atmosphere. The heat treatment time refers to the holding time after the heat treatment temperature is reached. According to the invention, the temperature is preferably raised from room temperature to the heat treatment temperature, and the rate of temperature rise is preferably 2-30 ℃/min, and more preferably 10-20 ℃/min. The invention preferably puts the mixture into a porcelain ark for heat treatment. The invention does not require any particular equipment for the heat treatment, which in a particular embodiment of the invention is preferably carried out in a muffle furnace.
The invention utilizes diketogulonic acid generated by the thermal decomposition of ascorbic acid to influence the thermal polymerization process of urea, and finally obtains the graphite-phase carbon nitride photocatalyst with the structure.
After the heat treatment, the heat-treated product is preferably cooled to room temperature along with the furnace to obtain the graphite-phase carbon nitride photocatalyst.
The invention provides an application of the graphite-phase carbon nitride photocatalyst prepared by the scheme or the preparation method in the scheme in photocatalytic water decomposition hydrogen production. The invention has no special requirement on the source of water, and can be river water, seawater and the like. The conditions for the application of the present invention are not particularly limited, and the conditions for the application well known in the art may be used.
The following will explain the graphite phase carbon nitride photocatalyst provided by the present invention and its preparation method and application in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
And (2) uniformly mixing 50g of urea and 30mg of ascorbic acid, pouring the mixture into an alumina porcelain square boat, putting the porcelain square boat into a muffle furnace, heating the porcelain square boat from room temperature to 500 ℃ at the heating rate of 10 ℃/min, preserving heat for 2 hours, and then cooling the porcelain square boat to the room temperature along with the furnace to obtain the graphite-phase carbon nitride photocatalyst.
FIG. 1 is an X-ray diffraction pattern (XRD) of the graphite phase carbon nitride photocatalyst prepared in example 1; as can be seen from FIG. 1, the photocatalyst prepared in the present invention maintains the original structure and properties of pure carbon nitride;
FIG. 2 is a Fourier transform Infrared Spectroscopy (FTIR) plot of the graphite phase carbon nitride photocatalyst prepared in example 1 and pure graphite phase carbon nitride; as can be seen from FIG. 2, the presence of a cyano peak in the photocatalyst according to the present invention, but not in the pure graphite-phase carbon nitride, indicates that the graphite-phase carbon nitride prepared according to the present invention has cyano structural defects.
FIG. 3 is a high resolution X-ray photoelectron Spectroscopy (XPS) of O1s for the graphite-phase carbon nitride photocatalyst prepared in example 1 of the present invention; as can be seen from fig. 3, oxygen atoms were doped into the crystal lattice of graphite-phase carbon nitride, and as can be seen from fig. 3, the atomic percent of oxygen atoms was 1.42 at.%.
Example 2
And (2) uniformly mixing 50g of urea and 5mg of ascorbic acid, pouring the mixture into an alumina porcelain square boat, putting the porcelain square boat into a muffle furnace, heating the porcelain square boat from room temperature to 450 ℃ at the heating rate of 2 ℃/min, preserving heat for 1h, and then cooling the porcelain square boat to the room temperature along with the furnace to obtain the graphite-phase carbon nitride photocatalyst.
Example 3
And (2) uniformly mixing 50g of urea and 50mg of ascorbic acid, pouring the mixture into an alumina porcelain square boat, putting the porcelain square boat into a muffle furnace, heating the porcelain square boat from room temperature to 550 ℃ at the heating rate of 20 ℃/min, preserving heat for 2 hours, and then cooling the porcelain square boat to the room temperature along with the furnace to obtain the graphite-phase carbon nitride photocatalyst.
Example 4
And (2) uniformly mixing 50g of urea and 100mg of ascorbic acid, pouring the mixture into an alumina porcelain square boat, putting the porcelain square boat into a muffle furnace, heating the porcelain square boat from room temperature to 600 ℃ at the heating rate of 30 ℃/min, preserving heat for 3 hours, and then cooling the porcelain square boat to the room temperature along with the furnace to obtain the graphite-phase carbon nitride photocatalyst.
The graphite-phase carbon nitride photocatalyst prepared in examples 2 to 4 was characterized, and the results were similar to those in example 1, and all showed that the obtained graphite-phase carbon nitride photocatalyst had cyano defects and oxygen atoms were incorporated into the crystal lattice of graphite-phase carbon nitride.
Application of photocatalyst
The photocatalyst prepared in the embodiment 1-4 and the pure graphite phase carbon nitride are used for testing the hydrogen production performance by photocatalytic water decomposition:
the test conditions were: A300W xenon lamp is used as a light source, 50mg of photocatalyst, 8mL of triethanolamine is used as a hole trapping agent, 4mL of chloroplatinic acid (1mg/mL) is used as a cocatalyst, and 68mL of water is used.
Fig. 4 is a diagram of hydrogen production by photocatalytic decomposition of water by photocatalyst and pure graphite-phase carbon nitride prepared in embodiments 1 to 4 of the present invention, wherein carbon nitride in fig. 4 refers to pure graphite-phase carbon nitride, and examples 1 to 4 are, in order, embodiments 1 to 4, and the data in the diagram is shown in table 1.
TABLE 1 photocatalyst prepared in examples 1 to 4 and pure graphite phase carbon nitride yield of 5h
Case(s) Hydrogen production (mmol/g) in 5h
Example 1 6.7
Example 2 4.7
Example 3 4.4
Example 4 3.9
Pure graphite phase carbon nitride 2.1
Note: mmol/g in Table 1 refers to the amount of hydrogen produced per g of photocatalyst that catalyzes the decomposition of water.
As can be seen from fig. 4 and table 1, the graphite phase carbon nitride photocatalyst provided by the present invention has a higher hydrogen production rate in the same time than that of the conventional pure graphite phase carbon nitride, which indicates that the graphite phase carbon nitride photocatalyst provided by the present invention has a higher photocatalytic activity.
The graphite phase carbon nitride photocatalyst prepared in example 1 and pure graphite phase carbon nitride were subjected to cycle testing under the same conditions as above, each 5h cycle was one cycle, the photocatalyst was directly recovered after each cycle and used for the next cycle of testing, and 8 cycles were performed in total, and the results are shown in fig. 5, where carbon nitride in fig. 5 refers to pure graphite phase carbon nitride, and the specific data are shown in table 2.
TABLE 2 Hydrogen production by cycle test (unit: mmol/g)
Figure GDA0002471284110000051
Fig. 5 and table 2 show that the graphite-phase carbon nitride photocatalyst of example 1 still maintains the original catalytic activity after eight cycles of testing, while the pure graphite-phase carbon nitride photocatalyst of the unmodified sample has reduced catalytic activity, i.e., the catalyst provided by the present invention has higher photocatalytic activity and photocatalytic stability.
The graphite-phase carbon nitride photocatalyst prepared in the embodiments 2 to 4 was subjected to a cycle test under the same test conditions as above, and a cycle was set every 5 hours, and the results show that the graphite-phase carbon nitride photocatalyst of the embodiments 2 to 4 still maintains the original catalytic activity after eight cycles of the test.
From the above embodiments, the present invention provides a graphite phase carbon nitride photocatalyst and a preparation method thereof, and the graphite phase carbon nitride photocatalyst prepared by the present invention has higher photocatalytic activity and photocatalytic stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (4)

1. A preparation method of a graphite phase carbon nitride photocatalyst comprises the following steps: mixing urea and ascorbic acid, and carrying out heat treatment on the obtained mixture to obtain a graphite-phase carbon nitride photocatalyst; the temperature of the heat treatment is 450-600 ℃; the heat treatment time is 1-3 h;
the graphite-phase carbon nitride photocatalyst comprises graphite-phase carbon nitride and oxygen atoms doped in a graphite-phase carbon nitride crystal lattice, wherein the graphite-phase carbon nitride has a cyano structure defect.
2. The preparation method according to claim 1, wherein the mass ratio of the urea to the ascorbic acid is 50g (5-100) mg.
3. The method according to claim 1, wherein the heat treatment is carried out at a rate of 2 to 30 ℃/min from room temperature to the heat treatment temperature.
4. The production method according to claim 1, wherein an atmosphere of the heat treatment is an air atmosphere.
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