CN115254173A - Graphite phase carbon nitride photocatalyst and preparation method, system and application thereof - Google Patents
Graphite phase carbon nitride photocatalyst and preparation method, system and application thereof Download PDFInfo
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- CN115254173A CN115254173A CN202211049603.1A CN202211049603A CN115254173A CN 115254173 A CN115254173 A CN 115254173A CN 202211049603 A CN202211049603 A CN 202211049603A CN 115254173 A CN115254173 A CN 115254173A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 69
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
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- 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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- 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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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a graphite-phase carbon nitride photocatalyst and a preparation method, a system and application thereof. The invention carries out continuous rapid high-temperature hydrothermal modification on graphite-phase carbon nitride based on a continuous reaction system, the modification time is 25.2-50.3 s, and the test result of photocatalytic water decomposition hydrogen production shows that the activity is improved by 5.2 times compared with that before modification, and the invention has the advantages of short reaction time and good performance of graphite-phase carbon nitride photocatalyst.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by photocatalytic water decomposition, and particularly relates to a graphite-phase carbon nitride photocatalyst as well as a preparation method, a system and an application thereof.
Background
Graphite phase carbon nitride (g-C) 3 N 4 ) The photocatalyst has the advantages of good thermal/chemical stability, no toxicity, no pollution and the like, and is widely researched in the application fields of photocatalytic water decomposition, photocatalytic organic wastewater degradation, photocatalytic heavy metal ion reduction and the like. In g-C 3 N 4 In the application of removing organic pollutants, the pure g-C 3 N 4 Small specific surface area, low visible light utilization efficiency, low conductivity, high photocarrier recombination efficiency, few interface (light) reaction active sites, slow surface reaction kinetic speed, moderate oxidation capacity and low catalytic activity. Therefore, the compound needs to pass through the pair g-C 3 N 4 The photocatalytic performance of the photocatalyst is strengthened by targeted modification.
Among the numerous modification methods, on g-C 3 N 4 Performing a hydrothermal post-treatment is an efficient and green process. Wherein g-C 3 N 4 Dispersing in pure water, hydrothermal treating, and modifying to obtain modified g-C 3 N 4 Has more excellent photocatalytic activity mainly due to (1) a large increase in specific surface area; (2) g-C 3 N 4 The formation of carbon vacancies and nitrogen vacancies; (3) introduction of surface oxygen-containing functional groups. The above hydrothermal treatment is usually carried out in a sealed tetrafluoroethylene liner, the hydrothermal temperature is usually 100 to 190 ℃, the treatment time is usually 6 to 8 hours, and the higher the hydrothermal temperature is, the longer the treatment time is, the g-C 3 N 4 The lower the yield.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a graphite phase carbon nitride photocatalyst, and a preparation method, a system and an application thereof, aiming at the defects of the prior art. The rapid high-temperature hydrothermal reaction based on the continuous reaction system modifies the graphite-phase carbon nitride to obtain the graphite-phase carbon nitride photocatalyst, and has the advantages of short modification time, high reaction temperature, less graphite-phase carbon nitride decomposition and good photocatalyst performance.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a graphite phase carbon nitride photocatalyst comprises the following steps:
dispersing graphite-phase carbon nitride in water to obtain graphite-phase carbon nitride dispersion liquid;
adding the graphite-phase carbon nitride dispersion liquid and preheated water into a reaction zone, and reacting at 260-300 ℃ for 25.2-50.3 s to obtain the graphite-phase carbon nitride photocatalyst.
Further, in the graphite phase carbon nitride dispersion liquid, the use amount ratio of the graphite phase carbon nitride to water is 1-10 g:1mL.
Further, the volume flow ratio of the graphite-phase carbon nitride dispersion liquid to the preheated water is 1:4.
furthermore, the reaction pressure of the reaction zone is 15-25 MPa.
A system for preparing the graphite-phase carbon nitride photocatalyst comprises a material conveying system, a preheating system, a mixed reaction system and a cooling and recycling system; the material conveying system comprises a plunger pump and a advection pump, the mixing reaction system comprises a T-shaped three-way mixer and a reaction area, and the cooling recovery system comprises a sleeve-type heat exchanger, a back pressure valve and a collecting device;
the constant-flow pump is connected with the preheater, the plunger pump and the preheater are both connected with an inlet of a T-shaped three-way mixer, an outlet of the T-shaped three-way mixer is connected with an inlet of the reaction zone, and an outlet of the reaction zone is connected with the collecting device through a pipeline and a back pressure valve; the double pipe heat exchanger is arranged outside the pipeline.
A catalyst prepared according to the process as described above.
The application of the catalyst prepared according to the method in photocatalytic decomposition of water to prepare hydrogen.
Further, dispersing the photocatalyst in a triethanolamine solution, and adding Pt to prepare hydrogen; wherein the dosage ratio of the photocatalyst to the triethanolamine solution is 20mg:80mL, and the volume concentration of the triethanolamine solution is 10%.
Further, the amount of Pt added was 1% by weight of the photocatalyst.
Compared with the prior art, the invention has the following beneficial effects:
the continuous rapid high-temperature hydrothermal reaction of the invention modifies graphite-phase carbon nitride, the reaction time is 25.2-50.3 s, and the test result of the activity of the photocatalyst for photocatalytic water decomposition hydrogen production shows that the activity is improved by 5.2 times compared with that before modification, and the photocatalyst has the advantages of short reaction time and good performance of the graphite-phase carbon nitride photocatalyst. The reaction mechanism of the invention is as follows: in the continuous rapid high-temperature hydrothermal modification treatment process, the graphite-phase carbon nitride dispersion liquid is mixed with high-temperature and high-pressure water to reach the reaction temperature, and g-C is formed at the reaction temperature 3 N 4 Partial decomposition produces ammonia gas, water is partially converted into water vapor to form a solid-liquid three-phase system, and high-temperature and high-pressure fluid can realize g-C 3 N 4 The stripping and shearing of the photocatalyst increase the g-C 3 N 4 The number of pores and the specific surface area of the catalyst, the g-C is destroyed 3 N 4 A conjugated structure of (a). The invention utilizes the saturated vapor pressure, the thermal diffusion coefficient, the low density, the surface tension and the viscosity of the hydrothermal system under the conditions of high temperature and high pressure to modify the graphite-phase carbon nitride, thereby avoiding the problems of poor improvement effect of the graphite-phase carbon nitride, excessive decomposition of the graphite-phase carbon nitride and the like of the existing method. The preparation method disclosed by the invention is time-saving, simple to operate and easy to repeat, and has wide popularization and application values.
Furthermore, in the invention, the temperature of the graphite phase carbon nitride dispersion liquid is raised to 260-300 ℃ by mixing with high-temperature preheated water under the pressure of 19MPa, and the volume flow of the graphite phase carbon nitride dispersion liquid and the high-temperature preheated water is controlled, so that the reaction time is between 25.2-50.3 s, and the reaction time is shortened.
The system can realize the continuous reaction of the graphite-phase carbon nitride photocatalyst, improves the catalytic performance of the catalyst, and has simple structure and easy realization.
The catalyst has higher photocatalytic performance and can be applied to hydrogen production by photocatalytic water decomposition.
Drawings
FIG. 1 shows a continuous rapid high-temperature hydrothermal reaction system according to the present invention.
FIG. 2 is a graph comparing hydrogen production rate curves of the photocatalysts of example 1 and comparative example 1.
FIG. 3 is a bar graph showing hydrogen production activity of the photocatalysts of examples 1 to 4.
FIG. 4 is a histogram of normalized yields of example 1 and the photocatalysts of examples 7-10.
Fig. 5 is an XRD spectrum of the photocatalyst of example 1 and comparative example 1.
FIG. 6 is XPS high resolution spectra of C1s, N1s, O1s of CN-280/5-9 of example 1 and CN-30/5-9 of comparative example 1, and XPS survey spectra of CN-280/5-9. Wherein (a) is an XPS high-resolution spectrum for C1s of CN-280/5-9 of example 1 and CN-30/5-9 of comparative example 1, (b) is an XPS high-resolution spectrum for N1s of CN-280/5-9 of example 1 and CN-30/5-9 of comparative example 1, (C) is an XPS high-resolution spectrum for O1s of CN-280/5-9 of example 1 and CN-30/5-9 of comparative example 1, and (d) is an XPS full spectrum for CN-280/5-9 of example 1;
FIG. 7 is a schematic diagram of the mechanism of continuous rapid high-temperature hydrothermal modification of graphite-phase carbon nitride. Wherein (a) is a reaction system, (b) is an enlarged view of a circle in the diagram (a), (c) and (d) are schematic views of a delaminating action and a shearing action occurring at the circle in the diagram (b).
In the figure, 1 is a graphite phase carbon nitride dispersion liquid, 2 is water, 3 is a plunger pump, 4 is a advection pump, 5 is a preheater, 6 is a T-shaped three-way mixer, 7 is a reaction zone, 8 is a double-pipe heat exchanger, 9 is a back pressure valve, and 10 is a collecting device.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.
The invention discloses a preparation method of a graphite-phase carbon nitride photocatalyst for photocatalytic hydrogen production, which comprises the following steps: through a continuous reaction system, the graphite-phase carbon nitride dispersion liquid and high-temperature preheated water are mixed in a reaction section and undergo rapid high-temperature high-pressure hydrothermal reaction, and graphite-phase carbon nitride is subjected to continuous rapid high-temperature high-pressure hydrothermal post-treatment to obtain a more efficient graphite-phase carbon nitride photocatalyst.
Specifically, referring to fig. 1, the continuous reaction system includes: the system comprises a material conveying system, a preheating system, a mixing reaction system and a cooling recovery system. The material conveying system comprises a plunger pump 3 and a flat flow pump 4, the preheating system comprises a preheater 5, the mixing reaction system comprises a T-shaped three-way mixer 6 and a reaction area 7, and the cooling recovery system comprises a double-pipe heat exchanger 8, a back pressure valve 9 and a collecting device 10. The constant-flow pump 4 is connected with the preheater 5, the plunger pump 3 and the preheater 5 are both connected with an inlet of the T-shaped three-way mixer 6, an outlet of the T-shaped three-way mixer 6 is connected with an inlet of the reaction zone 7, an outlet of the reaction zone 7 is connected with the collecting device 10 through a pipeline and a back pressure valve 9, and a sleeve type heat exchanger 8 is arranged on the outer side of one section of pipeline. The reaction zone 7 is internally provided with an electric heating wire for heating.
Delivering graphite phase carbon nitride dispersion liquid 1 through an advection pump 3, delivering water 2 through a plunger pump 4, wherein the volume flow rate of the graphite phase carbon nitride dispersion liquid is (9-18) mL/min, and the volume flow rate ratio of the graphite phase carbon nitride dispersion liquid to the plunger pump is 1:4.
the water 2 delivered by the plunger pump 4 is heated to 300-340 ℃ after passing through the preheating system 5, and then enters the mixing reaction system to react with the graphite-phase carbon nitride. The purpose of preheating is to ensure the reaction temperature.
The graphite phase carbon nitride dispersion liquid and high-temperature preheating water are mixed in a T-shaped three-way mixer 6 and then flow into a reaction zone 7 to react, the reaction time is 25.2-50.3 s, the reaction temperature is 260-300 ℃, and the pressure is 15-25 MPa.
And cooling the high-temperature mixed liquid to normal temperature through a sleeve type heat exchanger 8, flowing through a back pressure valve 9, collecting, filtering and drying the high-temperature mixed liquid through a collecting device 10 to obtain a modified graphite-phase carbon nitride sample.
A continuous rapid high-temperature hydrothermal reaction is carried out in the reaction zone 7, specifically, the purpose of rapid temperature rise is achieved by mixing the graphite-phase carbon nitride dispersion liquid and high-temperature preheating water, and the reaction temperature is between 260 and 300 ℃; controlling the reaction time by controlling the volume flow (the volume flow unit is mL/min) of the graphite phase carbon nitride dispersion liquid and water, wherein the reaction time is between 25.2 and 50.3 s; in order to prevent the boiling of the water solution in the pipeline and the damage of the pipeline, the reaction pressure is controlled to be (15-25) MPa by adjusting a back pressure valve 9. Specifically, the reaction temperature can be 260 ℃, 280 ℃, 290 ℃ or 300 ℃; the volume flow ratio of the graphite phase carbon nitride dispersion liquid to the high-temperature preheated water is 1: the volume flow rate of the graphite phase carbon nitride dispersion may be 9mL/min, 12mL/min, 13.5mL/min, 15mL/min, or 18mL/min, corresponding to reaction times of 50.3s, 37.7s, 33.6s, 30.2s, and 25.2s, respectively. The treatment of the graphite phase carbon nitride at a temperature higher than the decomposition temperature of the graphite phase carbon nitride is carried out by continuous rapid high-temperature hydrothermal treatment, so that the graphite phase carbon nitride is modified on the premise of no decomposition, and the modified graphite phase carbon nitride is endowed with good photocatalytic activity.
Preferably, the mass volume ratio of the graphite phase carbon nitride to the dispersant (water) is (1-10): 1, the mass unit of the graphite phase carbon nitride is mg, the mass unit of the dispersing agent is mL, and the dispersing agent is water.
The invention changes a continuous reaction system, quickly heats the mixed graphite phase carbon nitride dispersion liquid and high-temperature preheated water, and quickly cools the mixed graphite phase carbon nitride dispersion liquid by designing a double-pipe heat exchanger, so that the reaction temperature is higher, and the time for heating and cooling is greatly reduced. And after reacting for tens of seconds in the cylindrical reactor, collecting and filtering the graphite-phase carbon nitride particles through a back pressure valve to finally obtain the modified graphite-phase carbon nitride particles.
The present invention will be described in detail with reference to the following examples, which are not intended to limit the present invention.
A series of graphite phase carbon nitride photocatalysts for sewage treatment are prepared according to the method disclosed by the invention, and the method is as follows.
Example 1
The embodiment provides a preparation method of a graphite-phase carbon nitride photocatalyst for photocatalytic hydrogen production, which comprises the following steps:
step one, dispersing 3g of graphite phase Carbon Nitride (CN) in 600mL of pure water to obtain graphite phase carbon nitride dispersion liquid 1;
placing the graphite-phase carbon nitride dispersion liquid in the step one into a storage bin;
pumping the graphite phase carbon nitride dispersion liquid at a volume flow of 9mL/min, and controlling the volume flow ratio of the graphite phase carbon nitride dispersion liquid to water to be 1:4, adjusting the back pressure valve 8 to make the pipeline pressure be 19MPa;
step four, adjusting the power of electric heating wires on the wall surfaces of the preheater 5 and the reaction zone 7, keeping the temperature of the mixed water 2 and the graphite-phase carbon nitride dispersion liquid 1 in the reaction zone 7 at 280 ℃, and allowing the sample to stay in the mixed water for 50.3 seconds and then to flow out of the reaction zone 7;
step five, cooling the system after the reaction in the step four by water through a sleeve type heat exchanger 8, performing suction filtration, washing and drying to obtain a graphite phase carbon nitride photocatalyst which is marked as CN-280/5-9; according to CN-T/c-m c ，CN-T/c-m c Wherein T represents the hydrothermal treatment temperature, c represents the dispersion concentration mg/mL, m c Represents the volume flow rate mL/min of the graphite phase carbon nitride dispersion.
Example 2
This example is the same as example 1 except that the temperature of water 2 in reaction zone 7 after mixing with graphite phase carbon nitride dispersion 1 was maintained at 260 ℃.
Example 3
This example is the same as example 1 except that the temperature of the reaction zone 7 after mixing of water 2 with the graphite-phase carbon nitride dispersion 1 was maintained at 290 ℃.
Example 4
This example is the same as example 1 except that the temperature of water 2 in reaction zone 7 after mixing with graphite phase carbon nitride dispersion 1 was maintained at 300 ℃.
Comparative example 1
This comparative example is the same as example 1 except that the electric heating wires on the wall surfaces of the preheater 5 and the reaction zone 7 were in a non-energized state, and the experiment was carried out at room temperature of 30 ℃.
Example 5
The embodiment provides a preparation method of a graphite-phase carbon nitride photocatalyst for photocatalytic hydrogen production, which comprises the following steps:
step one, dispersing 0.6g of graphite phase Carbon Nitride (CN) in 600mL of pure water to obtain a graphite phase carbon nitride dispersion liquid;
placing the graphite-phase carbon nitride dispersion liquid in the step one into a storage bin;
pumping the graphite phase carbon nitride dispersion liquid at a volume flow of 9mL/min, and controlling the volume flow ratio of the graphite phase carbon nitride dispersion liquid to water to be 1:4, adjusting the back pressure valve 9 to make the pipeline pressure 19MPa;
step four, adjusting the power of electric heating wires on the wall surfaces of the preheater 5 and the reaction zone 7, keeping the temperature of the mixed water 2 and the graphite-phase carbon nitride dispersion liquid 1 in the reaction zone 7 at 280 ℃, and allowing the sample to stay in the mixed water for 50.3 seconds and then to flow out of the reaction zone 7;
and step five, cooling the system after the reaction in step four by water through a sleeve type heat exchanger 8, performing suction filtration, washing and drying to obtain the graphite phase carbon nitride photocatalyst which is marked as CN-280/1-9.
Example 6
The embodiment provides a preparation method of a graphite-phase carbon nitride photocatalyst for photocatalytic hydrogen production, which comprises the following steps:
step one, dispersing 6g of graphite phase Carbon Nitride (CN) in 600mL of pure water to obtain graphite phase carbon nitride dispersion liquid;
step two, placing the graphite-phase carbon nitride dispersion liquid obtained in the step one into a storage bin;
pumping the graphite phase carbon nitride dispersion liquid at a volume flow of 9mL/min, and controlling the volume flow ratio of the graphite phase carbon nitride dispersion liquid to water to be 1:4, adjusting the back pressure valve to enable the pipeline pressure to be 19MPa;
step four, adjusting the power of electric heating wires on the wall surfaces of the preheater 5 and the reaction zone 7, keeping the temperature of the mixed water 2 and the graphite-phase carbon nitride dispersion liquid 1 in the reaction zone 7 at 280 ℃, and allowing the sample to stay in the mixed water for 50.3 seconds and then to flow out of the reaction zone 7;
and step five, cooling the system after the reaction in step four by water through a sleeve type heat exchanger, performing suction filtration, washing and drying to obtain the graphite-phase carbon nitride photocatalyst which is marked as CN-280/10-9.
Example 7
The embodiment provides a preparation method of a graphite-phase carbon nitride photocatalyst for photocatalytic hydrogen production, which comprises the following steps:
step one, dispersing 3g of graphite phase Carbon Nitride (CN) in 600mL of pure water to obtain graphite phase carbon nitride dispersion liquid;
placing the graphite-phase carbon nitride dispersion liquid in the step one into a storage bin;
pumping the graphite phase carbon nitride dispersion liquid at a volume flow rate of 12mL/min, and controlling the volume flow rate ratio of the graphite phase carbon nitride dispersion liquid to water to be 1:4, adjusting the back pressure valve to make the pipeline pressure 19MPa;
step four, adjusting the power of electric heating wires on the wall surfaces of the preheater 5 and the reaction zone 7, so that the temperature of the mixed water 2 and the graphite-phase carbon nitride dispersion liquid 1 in the reaction zone 7 is kept at 300 ℃, and the sample stays in the mixed water for 37.7 seconds and then flows out of the reaction zone 7;
and step five, cooling the system after the reaction in step four by water through a sleeve type heat exchanger, performing suction filtration, washing and drying to obtain the graphite-phase carbon nitride photocatalyst which is marked as CN-280/5-12.
Example 8
The embodiment provides a preparation method of a graphite-phase carbon nitride photocatalyst for photocatalytic hydrogen production, which comprises the following steps:
step one, dispersing 3g of graphite phase Carbon Nitride (CN) in 600mL of pure water to obtain graphite phase carbon nitride dispersion liquid;
step two, placing the graphite-phase carbon nitride dispersion liquid obtained in the step one into a storage bin;
pumping the graphite-phase carbon nitride dispersion liquid at a volume flow rate of 13.5mL/min, and controlling the volume flow rate ratio of the graphite-phase carbon nitride dispersion liquid to water to be 1:4, adjusting the back pressure valve to enable the pipeline pressure to be 19MPa;
step four, adjusting the power of electric heating wires on the wall surfaces of the preheater 5 and the reaction zone 7, keeping the temperature of the mixed water 2 and the graphite-phase carbon nitride dispersion liquid 1 in the reaction zone 7 at 300 ℃, and allowing the sample to stay in the mixed water for 33.6 seconds and then to flow out of the reaction zone 7;
and step five, cooling the system after the reaction in step four by water through a sleeve type heat exchanger, performing suction filtration, washing and drying to obtain the graphite-phase carbon nitride photocatalyst which is marked as CN-280/5-13.5.
Example 9
The embodiment provides a preparation method of a graphite-phase carbon nitride photocatalyst for photocatalytic hydrogen production, which comprises the following steps:
step one, dispersing 3g of graphite phase Carbon Nitride (CN) in 600mL of pure water to obtain graphite phase carbon nitride dispersion liquid;
placing the graphite-phase carbon nitride dispersion liquid in the step one into a storage bin;
pumping the graphite phase carbon nitride dispersion liquid at a volume flow rate of 15mL/min, and controlling the volume flow rate ratio of the graphite phase carbon nitride dispersion liquid to water to be 1:4, adjusting the back pressure valve to make the pipeline pressure 19MPa;
step four, adjusting the power of electric heating wires on the wall surfaces of the preheater 5 and the reaction zone 7, keeping the temperature of the mixture of the water 2 and the graphite-phase carbon nitride dispersion liquid 1 in the reaction zone 7 at 300 ℃, and allowing the sample to stay in the mixture for 30.2 seconds and then flow out of the reaction zone 7;
and step five, after the reaction in the step four, performing water cooling, suction filtration, washing and drying on the system through a sleeve type heat exchanger to obtain graphite-phase carbon nitride photocatalysis which is marked as CN-280/5-15.
Example 10
The embodiment provides a preparation method of a graphite-phase carbon nitride photocatalyst for photocatalytic hydrogen production, which comprises the following steps:
step one, dispersing 3g of graphite phase Carbon Nitride (CN) in 600mL of pure water to obtain graphite phase carbon nitride dispersion liquid;
placing the graphite-phase carbon nitride dispersion liquid in the step one into a storage bin;
pumping the graphite phase carbon nitride dispersion liquid at a volume flow rate of 18mL/min, and controlling the volume flow rate ratio of the graphite phase carbon nitride dispersion liquid to water to be 1:4, adjusting the back pressure valve to make the pipeline pressure 19MPa;
step four, adjusting the power of electric heating wires on the wall surfaces of the preheater 5 and the reaction zone 7, keeping the temperature of the mixed water 2 and the graphite-phase carbon nitride dispersion liquid 1 in the reaction zone 7 at 300 ℃, and allowing the sample to stay in the mixed water for 25.2 seconds and then flow out of the reaction zone 7;
and step five, cooling the system after the reaction in step four by water through a sleeve type heat exchanger, performing suction filtration, washing and drying to obtain the graphite-phase carbon nitride photocatalyst which is marked as CN-280/5-18.
Example 11
The embodiment provides a preparation method of a graphite-phase carbon nitride photocatalyst for photocatalytic hydrogen production, which comprises the following steps:
step one, dispersing 2g of graphite phase Carbon Nitride (CN) in 600mL of pure water to obtain graphite phase carbon nitride dispersion liquid;
placing the graphite-phase carbon nitride dispersion liquid in the step one into a storage bin;
pumping the graphite phase carbon nitride dispersion liquid at a volume flow rate of 10mL/min, and controlling the volume flow rate ratio of the graphite phase carbon nitride dispersion liquid to water to be 1:4, adjusting the back pressure valve to enable the pipeline pressure to be 15MPa;
step four, adjusting the power of electric heating wires on the wall surfaces of the preheater 5 and the reaction zone 7, keeping the temperature of the mixed water 2 and the graphite-phase carbon nitride dispersion liquid 1 in the reaction zone 7 at 270 ℃, and allowing the sample to stay in the mixed water for 45.3 seconds and then to flow out of the reaction zone 7;
and step five, cooling the system after the reaction in the step four by water through a sleeve type heat exchanger, performing suction filtration, washing and drying to obtain the graphite-phase carbon nitride photocatalyst.
Example 12
The embodiment provides a preparation method of a graphite-phase carbon nitride photocatalyst for photocatalytic hydrogen production, which comprises the following steps:
step one, dispersing 4g of graphite phase Carbon Nitride (CN) in 600mL of pure water to obtain graphite phase carbon nitride dispersion liquid;
placing the graphite-phase carbon nitride dispersion liquid in the step one into a storage bin;
pumping the graphite phase carbon nitride dispersion liquid at a volume flow rate of 16mL/min, and controlling the volume flow rate ratio of the graphite phase carbon nitride dispersion liquid to water to be 1:4, adjusting the back pressure valve to enable the pipeline pressure to be 25MPa;
step four, adjusting the power of the electric heating wires on the wall surfaces of the preheater 5 and the reaction zone 7, so that the temperature of the mixed water 2 and the graphite-phase carbon nitride dispersion liquid 1 in the reaction zone 7 is kept at 300 ℃, and the sample stays in the mixed water for 28.3 seconds and then flows out of the reaction zone 7;
and step five, cooling the system after the reaction in step four by water through a sleeve type heat exchanger, performing suction filtration, washing and drying to obtain the graphite-phase carbon nitride photocatalyst.
Performance evaluation:
FIG. 1 is a schematic view of a continuous rapid high-temperature hydrothermal reaction system from which all of the photocatalysts of the examples and comparative examples of the present invention were prepared.
FIG. 2 is a graph comparing the hydrogen production rate curves of the photocatalysts of example 1 and comparative example 1, wherein the photocatalytic hydrogen production by water decomposition test method comprises: 20mg of photocatalyst is dispersed in 80mL of 10vol% triethanolamine solution, and Pt (1 wt% of photocatalyst) is added as a cocatalyst to detect the hydrogen production amount in the photocatalytic system. As can be seen from FIG. 2, with respect to pure g-C 3 N 4 (namely the raw material CN corresponds to the reaction temperature of 30 ℃), the photocatalyst of the invention has obviously improved average photocatalytic hydrogen production rate and obviously improved activity.
FIG. 3 is a bar graph showing hydrogen production activity of the photocatalysts of examples 1 to 4, under the same test conditions as those in FIG. 2. As can be seen from FIG. 3, the hydrogen production activity of the samples treated at 260 deg.C, 280 deg.C, 290 deg.C and 300 deg.C was higher than that of the photocatalyst of comparative example 1, and the photocatalyst performance was higher.
Fig. 4 is a histogram of normalized yield of the photocatalysts of examples 1 and 7-10, and it can be seen from fig. 4 that the yield of the product is significantly improved with the increase of the flow rate.
FIG. 5 shows XRD spectra of the photocatalysts of example 1 and comparative example 1. According to FIG. 5, XRD spectra of CN-280/5 and CN-30/5 are substantially consistent, which indicates that the structure of graphite phase carbon nitride is not changed during the hydrothermal reaction.
In FIG. 6, (a) to (C) are XPS high-resolution spectra of C1s, N1s and O1s of CN-280/5 of example 1 and CN-30/5 of comparative example 1 in this order, and in FIG. 6, (d) is CN-28 of example 1XPS survey spectrum 0/5. As can be seen from the high resolution spectrum, g-C 3 N 4 The binding energy position of each functional group has no obvious movement and no new peak appears, which indicates that the continuous rapid high-temperature hydrothermal modification does not introduce new functional groups into the photocatalyst. Meanwhile, as can be seen from fig. 6 (b), the peak area of C = N-C/N- (C) 3 of the sample MCN-280/5 of example 1 is larger than that of MCN-30/5, which indicates that the number of the bridge structure N- (C) 3 of the heptazine ring is somewhat reduced as the hydrothermal modification proceeds, which may be caused by the shearing action of the high-temperature high-pressure fluid on the g-C3N4 photocatalyst by the continuous rapid high-temperature hydrothermal modification treatment. As shown in FIG. 6 (d), no impurity peak other than O, N, C appeared in CN-280/5, indicating that the influence of the constituent elements (Fe, cr, ni, etc.) on the sample due to corrosion of the stainless steel pipe can be excluded under this condition.
In FIG. 7, (a), (b), (c) and (d) are schematic diagrams of the mechanism of continuous rapid high-temperature hydrothermal modification of graphite-phase carbon nitride. As can be seen from FIG. 7, during the continuous rapid high temperature hydrothermal modification treatment, the graphite phase carbon nitride dispersion is mixed with high temperature and high pressure water to reach a set temperature at which g-C is formed 3 N 4 Partial decomposition produces ammonia gas, water is partially converted into water vapor to form a solid-liquid-gas three-phase system, and the high-temperature high-pressure fluid can realize the g-C pair 3 N 4 The stripping and shearing of the photocatalyst increase the g-C 3 N 4 The number of pores and the specific surface area of the catalyst, and the destruction of g-C 3 N 4 A conjugated structure of (a).
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (9)
1. A preparation method of a graphite-phase carbon nitride photocatalyst is characterized by comprising the following steps:
dispersing graphite-phase carbon nitride in water to obtain graphite-phase carbon nitride dispersion liquid;
adding the graphite-phase carbon nitride dispersion liquid and preheated water into a reaction zone, and reacting at 260-300 ℃ for 25.2-50.3 s to obtain the graphite-phase carbon nitride photocatalyst.
2. The method for preparing a graphite-phase carbon nitride photocatalyst according to claim 1, wherein the amount ratio of the graphite-phase carbon nitride to water in the graphite-phase carbon nitride dispersion is 1 to 10g:1mL.
3. The method of claim 1, wherein the volume flow ratio of the graphite phase carbon nitride dispersion to the preheated water is 1:4.
4. the method of claim 1, wherein the reaction pressure in the reaction zone is 15 to 25MPa.
5. A system for preparing the graphite-phase carbon nitride photocatalyst of claim 1, comprising a material delivery system, a preheating system, a mixing reaction system, and a cooling recovery system; the material conveying system comprises a plunger pump (3) and a advection pump (4), the mixed reaction system comprises a T-shaped three-way mixer (6) and a reaction zone (7), and the cooling recovery system comprises a sleeve-type heat exchanger (8), a back pressure valve (9) and a collecting device (10);
the constant-flow pump (4) is connected with the preheater (5), the plunger pump (3) and the preheater (5) are both connected with the inlet of the T-shaped three-way mixer (6), the outlet of the T-shaped three-way mixer (6) is connected with the inlet of the reaction zone (7), and the outlet of the reaction zone (7) is connected with the collecting device (10) through a pipeline and a back pressure valve (9); the double pipe heat exchanger (8) is arranged outside the pipeline.
6. A catalyst prepared according to the method of any one of claims 1 to 4.
7. Use of a catalyst prepared according to any one of claims 1 to 4 in the photocatalytic decomposition of water to produce hydrogen.
8. The use of claim 7, wherein the photocatalyst is dispersed in a triethanolamine solution, and Pt is added to produce hydrogen; wherein the dosage ratio of the photocatalyst to the triethanolamine solution is 20mg:80mL, and the volume concentration of the triethanolamine solution is 10%.
9. Use according to claim 8, wherein Pt is added in an amount of 1% by weight of the photocatalyst.
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