CN109046420B - Preparation method of porous carbon nitride photocatalyst - Google Patents
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 39
- 239000000919 ceramic Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 239000002243 precursor Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
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- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- 238000005215 recombination Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the technical field of preparation of photocatalytic materials, and relates to a preparation method of a porous carbon nitride photocatalyst; the method comprises the following specific steps: (1) putting melamine into a ceramic crucible and heating the melamine to a certain temperature in a tube furnace to obtain a carbon nitride precursor; (2) collecting the obtained carbon nitride precursor, grinding, weighing a certain amount, and paving in a ceramic square boat; (3) placing the ark loaded with the carbon nitride precursor into a tubular furnace and calcining in pure oxygen atmosphere to obtain a porous carbon nitride material; the preparation method has the advantages that the preparation process is simple and easy to operate, and no corrosive chemical reagents such as a template agent, strong acid, strong alkali and the like are adopted, so that the preparation method is green and environment-friendly; the porous carbon nitride photocatalyst prepared by the method has the advantages that the specific surface area is increased, the good hydrogen production performance by photocatalytic water decomposition and the good photocurrent response capability are displayed, the used raw materials are cheap and easy to obtain, and the mass production is facilitated.
Description
Technical Field
The invention belongs to the technical field of preparation of photocatalytic materials, and particularly relates to a porous carbon nitride photocatalyst and a preparation method thereof.
Background
With the increase of population and the development of society, the consumption of human energy on the earth is larger and larger, and the current worldwide energy demand mainly comes from non-renewable fossil energy sources such as coal, petroleum, natural gas and the like. The reserve of fossil energy on the earth is very limited, and according to the current population growth rate and energy consumption rate, if a novel energy capable of replacing the fossil energy is not developed, people face a very severe energy crisis in the next decades. At the same time, the combustion of fossil fuels inevitably brings about environmental pollutants such as: SO (SO)x，NOxDust (PM), volatile organic pollutants and toxic heavy metal pollutants. Among them, the most serious is CO2The excessive discharge causes serious greenhouse effect, so that the global climate changes, and extreme weather such as high temperature, drought, rainstorm and the like frequently appears around the world. At present, the search for energy sources that can replace fossil fuels is becoming more urgent, and hydrogen energy is becoming an energy storage and use facility established at presentThe best alternative to fossil fuels is available.
The current sources of hydrogen are water gas shift, small molecule alkane molecule cracking, water electrolysis, etc., but all the hydrogen preparation methods are still based on the consumption of fossil energy, and can generate huge CO2The amount of emissions, which also limits the popularity of hydrogen energy to some extent. Compared with the conventional hydrogen production mode, the photocatalytic water splitting hydrogen production is an ideal hydrogen energy preparation method, the photocatalytic water splitting hydrogen production is a technical means of directly splitting water into hydrogen and oxygen by using sunlight through a photocatalyst, the sunlight does not need to consume any other energy as a driving source, zero emission of greenhouse gases is completely achieved, and the core of the photocatalytic technology is the design and preparation of a high-efficiency photocatalyst.
Graphite phase carbon nitride (g-C)3N4) The photocatalyst is a new visible light response type organic semiconductor photocatalyst in recent years, has the characteristics of proper energy band position, stable physical and chemical properties, abundant and easily-obtained preparation raw materials and the like, and can decompose water to produce hydrogen and oxygen under the irradiation of visible light; but block-shaped g-C3N4Has the defects of small specific surface area, poor conductivity, high photon-generated carrier recombination rate and the like. By mixing in blocks g-C3N4The carbon nitride material with a porous structure is prepared by medium pore forming, so that the specific surface area of the carbon nitride material can be effectively improved, the active sites can be increased, and the migration path of carriers can be shortened, thereby reducing the recombination rate of photo-generated electron-hole pairs and improving the photocatalytic activity.
However, the preparation of porous carbon nitride at present usually requires the preparation of SiO with regular morphology2As a hard template agent, the template is etched by hydrofluoric acid with strong corrosivity or bulk carbon nitride by strong acid and strong alkali, which undoubtedly increases the preparation cost and is not green and environment-friendly. Therefore, the research on the synthesis method of the porous carbon nitride, which is simple in operation and green and pollution-free in the synthesis process, is a hot spot and a focus in the research field of the carbon nitride material at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a manipulatorSimple operation, green synthesis process, mass production of porous carbon nitride photocatalyst without any template agent, strong acid, strong alkali and other corrosive chemical reagents, and effective solution of the existing block g-C3N4The material has the defects of small specific surface area, poor conductivity and high recombination rate of photon-generated carriers, so that the photocatalytic hydrogen production performance is effectively improved.
In order to realize the purpose of the invention, the concrete steps are as follows:
(1) preparation of the Miller amine blocks: weighing melamine, placing the melamine in a ceramic crucible, and covering a crucible cover; then placing the crucible in a tubular furnace, introducing dry air, slowly heating to a certain temperature, stopping heating, keeping for a period of time, and cooling to obtain a white Meldrum amine block;
(2) grinding the Miller amine block material obtained in the step (1) to obtain a Miller amine powder material; then weighing the miller amine powder material, and uniformly spreading the miller amine powder material in a ceramic ark;
(3) and (3) placing the ceramic ark of the Miller amine powder material spread in the step (2) into a tubular furnace, introducing dry pure oxygen, raising the temperature to a certain temperature according to a certain temperature raising rate program, keeping the temperature for a period of time, and cooling to obtain the porous carbon nitride photocatalyst.
Preferably, the melamine is used in the step (1) in an amount of 1.0 to 8.0 g.
Preferably, the flow rate of the drying air in the step (1) is 100-400 mL/min.
Preferably, the slow temperature rise in the step (1) is 2-10 ℃/min.
Preferably, the temperature for stopping the temperature rise in the step (1) is 350-450 ℃, and the holding time is 1-12 h.
Preferably, the ratio of the mass of the miller amine powder material in the step (2) to the bottom area of the ceramic ark is 0.1-1.0g
：1050 mm2。
The flow rate of the dry pure oxygen in the step (3) is 100-400 mL/min.
And (3) slowly raising the temperature to 2-10 ℃/min.
The temperature for stopping the temperature rise in the step (3) is 500-600 ℃, and the holding time is 1-12 h.
Has the advantages that:
compared with the prior art for synthesizing porous carbon nitride, the method has the following obvious advantages: the preparation process is simple and easy to operate, no template agent, strong acid, strong alkali and other corrosive chemical reagents are adopted, and the porous carbon nitride photocatalyst can be obtained only by changing the precursor and the calcining atmosphere for synthesizing the carbon nitride material, so that the preparation method conforms to the sustainable development concept of environmental protection; the porous carbon nitride photocatalyst prepared by the invention shows obviously enhanced photocurrent response capability, the hydrogen activity of the photocatalyst for decomposing water under visible light irradiation can reach 6059.2 mmol/gh, and the quantum efficiency can reach 17%.
Drawings
FIG. 1 shows the blocks g-C thus prepared3N4And FT-IR spectrograms of the porous carbon nitride photocatalyst obtained at different temperatures.
Figure 2 is a TEM image of the 550 CN porous carbon nitride photocatalyst prepared in example 3.
Figure 3 SEM image of 550 CN porous carbon nitride photocatalyst prepared in example 3.
FIG. 4 shows the block g-C thus prepared3N4And XRD spectrograms of the porous carbon nitride photocatalyst obtained at different temperatures.
FIG. 5 shows the block g-C thus prepared3N4And BET spectrograms of the porous carbon nitride photocatalyst obtained at different temperatures.
FIG. 6 shows g-C under irradiation of visible light3N4And the hydrogen production activity of the synthesized porous carbon nitride photocatalyst.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments and drawings, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1:
the preparation method of the direct carbon nitride precursor of the melem comprises the following specific operations: 1.0g of melamine was weighed into a 20 mL ceramic crucible and the crucible lid was covered. And then placing the crucible into a tube furnace, raising the temperature to 350 ℃ at a temperature raising rate of 2 ℃/min in a dry air atmosphere with the flow rate of 100mL/min, keeping for 4h, and naturally cooling to room temperature to prepare a white melem block. And then placing the calcined miller amine block material into an agate mortar for fully grinding to obtain the miller amine powder material. Then 0.50 g of the Miller amine powder material is weighed and evenly spread to the bottom with the area of 1050mm2Ceramic ark (size 21 x 50 x 15 mm). And then, placing the tiled melem powder material into a tube furnace again, carrying out programmed heating to 500 ℃ at the heating rate of 4 ℃/min under the dry pure oxygen atmosphere with the flow rate of 100mL/min, keeping the temperature for 1 h, and naturally cooling to room temperature to prepare the porous carbon nitride photocatalyst, which is named as 500-CN.
Example 2:
the preparation method of the direct carbon nitride precursor of the melem comprises the following specific operations: 6.0 g of melamine was weighed into a 50 mL ceramic crucible and the crucible lid was covered. And then placing the crucible into a tube furnace, raising the temperature to 390 ℃ at a heating rate of 5 ℃/min in a dry air atmosphere with the flow rate of 200 mL/min, keeping the temperature for 6 h, and naturally cooling the crucible to room temperature to prepare a white melem block. And then placing the calcined miller amine block material into an agate mortar for fully grinding to obtain the miller amine powder material. Then 0.30 g of the Miller amine powder material is weighed and evenly spread to the bottom with the area of 1050mm2Ceramic ark (size 21 x 50 x 15 mm). And then placing the tiled melem powder material into a tube furnace again, carrying out temperature programmed heating to 520 ℃ at a heating rate of 5 ℃/min under a dry pure oxygen atmosphere with the flow rate of 300 mL/min, keeping the temperature for 12h, and naturally cooling to room temperature to prepare the porous carbon nitride photocatalyst which is named as 520-CN.
Example 3:
preparation of direct carbon nitride precursor melemThe following is done: 2.0 g of melamine was weighed into a 20 mL ceramic crucible and the crucible lid was covered. And then placing the crucible into a tube furnace, raising the temperature to 390 ℃ at a heating rate of 5 ℃/min in a dry air atmosphere with the flow rate of 300 mL/min, keeping the temperature for 4h, and naturally cooling the crucible to room temperature to prepare a white melem block. And then placing the calcined miller amine block material into an agate mortar for fully grinding to obtain the miller amine powder material. Then 0.50 g of the Miller amine powder material is weighed and evenly spread to the bottom with the area of 1050mm2Ceramic ark (size 21 x 50 x 15 mm). And then placing the tiled melem powder material into a tube furnace again, carrying out temperature programmed heating to 550 ℃ at a heating rate of 5 ℃/min under a dry pure oxygen atmosphere with the flow rate of 300 mL/min, keeping the temperature for 6 h, and naturally cooling to room temperature to prepare the porous carbon nitride photocatalyst, which is named as 550-CN.
Example 4:
the preparation method of the direct carbon nitride precursor of the melem comprises the following specific operations: 8.0 g of melamine was weighed into a 100mL ceramic crucible and the crucible lid was covered. And then placing the crucible into a tube furnace, raising the temperature to 450 ℃ in a drying air atmosphere with the flow rate of 400mL/min at the temperature raising rate of 8 ℃/min, keeping for 8 h, and naturally cooling to room temperature to prepare a white melem block. And then placing the calcined miller amine block material into an agate mortar for fully grinding to obtain the miller amine powder material. Then 0.50 g of the Miller amine powder material is weighed and evenly spread to the bottom with the area of 1050mm2In a ceramic ark (size 21 x 50 x 15 mm); and then placing the tiled melem powder material into a tube furnace again, carrying out temperature programmed heating to 600 ℃ at the heating rate of 2 ℃/min under the dry pure oxygen atmosphere with the flow rate of 200 mL/min, keeping the temperature for 4h, and naturally cooling to room temperature to prepare the porous carbon nitride photocatalyst, which is named as 600-CN.
Example 5:
block g-C3N4The preparation method specifically comprises the following steps: weighing 2.0 g of melamine, placing the melamine in a 20 mL ceramic crucible, and covering a crucible cover; then placing the crucible in the tube typeIn the furnace, the temperature is programmed to 550 ℃ at the heating rate of 5 ℃/min under the dry air atmosphere with the flow rate of 300 mL/min, and after the temperature is kept for 4 hours, the furnace is naturally cooled to the room temperature to prepare a light yellow block g-C3N4Material, named g-C3N4。
FT-IR, TEM, XRD, BET characterization of the catalyst is shown in FIGS. 1, 2, 3, and 4.
FIG. 1: from the FT-IR spectrum, the prepared material is 808 cm-1Has characteristic peak of triazine structure, and is 1242, 1322, 1412, 1563 and 1634 cm-1And a stretching vibration peak corresponding to C-N isomerism is also shown, which indicates that the prepared material is carbon nitride.
FIG. 2: the microstructure of the carbon nitride obtained by calcination with the precursor and calcination atmosphere changed was found to be porous by TEM analysis.
FIG. 3: the prepared porous carbon nitride monolithic microstructure was found to be sponge-like by SEM analysis.
FIG. 4: the porous carbon nitride material obtained at different temperatures was found to have diffraction peaks similar to those of bulk carbon nitride by XRD analysis, again indicating that the internal molecular structure of the porous carbon nitride remains intact.
FIG. 5: BET tests show that the specific surface area of porous carbon nitride is significantly increased compared to bulk carbon nitride, where bulk g-C3N4Specific surface areas of 500 CN, 520 CN, 550 CN and 600CN were 1.9 cm2/g、22.1 cm2/g、 28.9 cm2/g、39.6 cm2/g、24.7 cm2(ii) in terms of/g. The porous carbon nitride obtained at 550 ℃ has the largest specific surface area.
FIG. 6 is a graph showing the activity of a porous carbon nitride photocatalyst in photocatalytic decomposition of water to produce hydrogen, as can be seen in comparison to the bulk g-C3N4The hydrogen production activity of the porous carbon nitride is obviously improved, wherein the block g-C3N4The hydrogen production amounts of 500 CN, 520 CN, 550 CN and 600CN are 463.3 mmol/gh, 1897.9 mmol/gh, 3929.8 mmol/gh, 6059.2 mmol/gh and 1449.9 mmol/gh respectively; the porous carbon nitride obtained at 550 ℃ has the highest hydrogen production activityAnd the quantum efficiency is about 17%.
Claims (7)
1. A preparation method of a porous carbon nitride photocatalyst is characterized by comprising the following steps:
(1) preparation of the Miller amine blocks: weighing melamine, placing the melamine in a ceramic crucible, covering the crucible cover, placing the ceramic crucible in a tube furnace, introducing dry air, slowly heating to a certain temperature, stopping heating, keeping for a period of time, and cooling to obtain a Melamine block; the temperature for stopping temperature rise is 350-450 ℃, and the holding time is 1-12 h;
(2) grinding the Miller amine block obtained in the step (1) to obtain a Miller amine powder material; weighing a miller amine powder material, and flatly paving the miller amine powder material in a ceramic ark;
(3) and (3) putting the ceramic ark containing the miller amine powder material in the step (2) into a tube furnace, introducing dry pure oxygen, slowly heating to a certain temperature, keeping for a period of time, and cooling to obtain the porous carbon nitride photocatalyst.
2. The method as claimed in claim 1, wherein the flow rate of the drying air in step (1) is 100-400 mL/min.
3. The method for preparing a porous carbon nitride photocatalyst according to claim 1, wherein the slow temperature rise in step (1) is 2-10 ℃/min.
4. The method for preparing a porous carbon nitride photocatalyst according to claim 1, wherein the ratio of the mass of the miller amine powder material in the step (2) to the bottom area of the ceramic canoe is 0.1-1.0 g: 1050mm2。
5. The method as claimed in claim 1, wherein the flow rate of the dry pure oxygen in step (3) is 100-400 mL/min.
6. The method for preparing a porous carbon nitride photocatalyst according to claim 1, wherein the slow temperature rise in the step (3) is 2-10 ℃/min.
7. The method as claimed in claim 1, wherein the temperature for stopping the temperature increase in step (3) is 500-600 ℃, and the holding time is 1-12 h.
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| CN110124733A (en) * | 2019-04-30 | 2019-08-16 | 江苏大学 | A kind of conjugated polymer photochemical catalyst and preparation method and application |
| CN110327960A (en) * | 2019-06-27 | 2019-10-15 | 华南师范大学 | A kind of porous laminar carbonitride of alkali metal modified and its preparation method and application |
| CN111232939B (en) * | 2020-01-17 | 2023-06-09 | 南京工业大学 | Preparation of g-C with easier stripping by stereo molecule embedding 3 N 4 Is a method of (2) |
| CN112495412A (en) * | 2020-10-30 | 2021-03-16 | 江苏大学 | Porous thin-layer graphite phase carbon nitride and preparation method and application thereof |
| CN113321818A (en) * | 2021-05-11 | 2021-08-31 | 中山大学 | Composite hydrogel and preparation method and application thereof |
| CN114984997B (en) * | 2022-07-15 | 2023-03-14 | 西安交通大学 | Three-dimensional porous carbon nitride based Zn monatomic photocatalyst, preparation method and application |
| CN115178288B (en) * | 2022-08-01 | 2024-01-30 | 陕西科技大学 | Ni-Ni 2 P/g-C 3 N 4 Photocatalyst and preparation method thereof |
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| KR100866311B1 (en) * | 2007-04-16 | 2008-11-03 | 고려대학교 산학협력단 | Method for preparing n-rich nanoporous graphitic carbon nitride structure |
| WO2016027042A1 (en) * | 2014-08-21 | 2016-02-25 | The University Of Liverpool | Two-dimensional carbon nitride material and method of preparation |
| CN104310321A (en) * | 2014-09-15 | 2015-01-28 | 浙江大学 | Preparation method of porous g-C3N4 semi-conducting material |
| CN107297217B (en) * | 2017-06-01 | 2020-04-28 | 西安交通大学 | Porous thin-layer graphite-phase carbon nitride-supported platinum photocatalyst and preparation method and application thereof |
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