CN113247869A - Preparation method of carbon nitride material, carbon nitride material prepared by preparation method and application of carbon nitride material - Google Patents
Preparation method of carbon nitride material, carbon nitride material prepared by preparation method and application of carbon nitride material Download PDFInfo
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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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary 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
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/305—Electrodes, e.g. test electrodes; Half-cells optically transparent or photoresponsive electrodes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
Abstract
The invention discloses a preparation method of a carbon nitride material, the prepared carbon nitride material and application thereof, wherein the preparation method comprises the following steps: calcining the precursor complex under inert atmosphere and high temperature to obtain a carbonized product; and (3) carrying out acid treatment on the obtained carbonized product, washing with deionized water, centrifuging and drying to obtain the carbon nitride nano material. The carbon nitride material prepared by the method is simple to operate, raw materials are easy to obtain, the prepared carbon nitride material is a novel carbon nitride material with a five-membered ring structure, the difficulty in thermodynamics and kinetics of the existing carbon nitride material prepared by taking five-membered ring carbon nitrogen micromolecules as a repeating unit is overcome, the energy band structure is very narrow, the carbon nitride material can respond to near infrared light, and the carbon nitride material can be effectively applied to the fields of photoelectrochemical biosensing and the like, especially in nontransparent biological sample photoelectrochemical biosensing.
Description
Technical Field
The invention relates to the technical field of material chemistry, in particular to a preparation method of a carbon nitride material, the prepared carbon nitride material and application thereof.
Background
Carbon nitride, as a novel metal-element-free graphite-like semiconductor material, shows a huge application prospect in the fields of micromolecules, solar energy-chemical energy conversion, photoelectric biosensing and the like due to the unique molecular/electronic structure and surface properties, and arouses extensive research interest of people. However, most of the carbon nitride materials reported at present have wide band gaps and only respond to ultraviolet light and part of visible light, so that the utilization rate of the carbon nitride materials to sunlight is limited; on the other hand, the application of the material in the fields of biosensing, infrared physiotherapy and the like is limited because the light with short wavelength (visible-ultraviolet light) has poor light penetration compared with the light with long wavelength. Therefore, the preparation of the carbon nitride material has important significance. However, the adjustment of the band structure of carbon nitride material still has great challenges, and the absorption and utilization of sunlight far do not meet the requirements of practical application. Therefore, it is of great significance to develop a new method for preparing carbon nitride materials with narrow band gaps and with an optical response range extending to the near-infrared light region.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a preparation method of a carbon nitride material, and the carbon nitride nano material with a five-membered ring structure with narrow band gap and near infrared response can be prepared by the method.
The invention also provides the carbon nitride material prepared by the preparation method and application thereof.
The technical scheme is as follows: in order to achieve the above object, the present invention provides a method for preparing a carbon nitride material, comprising the steps of:
(1) placing a precursor metal organic framework material in a crucible, and calcining under the inert atmosphere and high-temperature conditions to obtain a carbonized product;
(2) and (2) carrying out acid treatment on the carbonized product obtained in the step (1), washing with deionized water, centrifuging and drying to obtain the carbon nitride material.
Wherein the precursor is a complex prepared from one or more five-membered ring ligands and metal ions.
Wherein the five-membered ring ligand comprises 2-methylimidazole or 1-methylimidazole, and the metal ion comprises Zn2+Or Co2+。
Further, the complex comprises ZIF-2, ZIF-3, ZIF-4, ZIF-5, ZIF-6, ZIF-10, ZIF-64, ZIF-8, ZIF-67, ZIF-7, ZIF-9, ZIF-11 or ZIF-12.
Wherein the inert atmosphere in the step (1) is a nitrogen atmosphere or an argon atmosphere. The gas flow rate is 100 mL/min to 500 mL/min.
And (2) placing the precursor in the step (1) in an inert atmosphere for 0.5-1.5 hours, heating to a specific temperature of 500-700 ℃ at a speed of 2-20 ℃/min during the calcination at a high temperature, and keeping for 0.5-5 hours to perform a carbonization reaction. Preferably, the carbonization reaction is carried out by raising the temperature to a specific temperature of 600 ℃ at a rate of 2 ℃/min to 10 ℃/min and holding the temperature for 3 hours.
Wherein, the acid treatment process in the step (2) is to soak the black powdery carbonized product in concentrated hydrochloric acid for 10 to 24 hours.
Further, step (2) is washed to neutrality with deionized water, comprising: adding deionized water, performing ultrasonic treatment, centrifuging, collecting supernatant, measuring pH, and repeating the above steps until pH is close to 7 and unchanged.
Further, the centrifugal speed in the step (2) is 13000rpm, and the centrifugal time is 5-10 minutes; the drying condition is vacuum drying at 50-120 ℃.
The carbon nitride material prepared by the preparation method of the carbon nitride material has a five-membered ring basic unit and is a carbon nitride nano material with a five-membered ring structure.
The carbon nitride material prepared by the preparation method of the carbon nitride material is applied to photoelectrochemical sensing.
The carbon nitride material prepared by the preparation method of the carbon nitride material is applied to photoelectric biosensing of non-transparent biological samples.
The mechanism is as follows: the carbon-nitrogen material taking five-membered ring carbon-nitrogen micromolecules as repeating units is prepared at present, and the preparation method has the following thermodynamic and kinetic difficulties: the boiling point of such molecules is generally at 200 ℃ and it is difficult to reach the polymerization temperature at which the high polymers are formed (generally above 400 ℃); the five-membered ring has ring tension, and the high-temperature polymerization is easier to form a six-membered ring product. The design principle of the invention is that the ligand is stabilized in advance by the stabilizing effect of the coordination bond formed by the metal and the ligand in the complex, the polymerization is carried out at the temperature when the crystal is disintegrated, the coordination bond is opened at the time, the ligand in a high-activity free radical state is easy to carry out polymerization reaction, and simultaneously the thermodynamic and kinetic difficulties mentioned above are overcome. For example, FIG. 1 shows the thermogravimetric analysis of, for example, a metal organic framework material ZIF-8 and the ligand 2-methylimidazole constituting ZIF-8: 2-methylimidazole crystals stabilized by intermolecular forces are disintegrated at 185 ℃, while ZIF-8 crystals stabilized by coordinate bonds are remarkably disintegrated at 565 ℃. Thermogravimetric mass spectrometry analysis of FIG. 2 also provides sufficient evidence that the ligand 2-methylimidazole radical is released along with the demethylation of 2-methylimidazole to form imidazole radical and methane while the ZIF-8 crystals are disintegrated.
During the polymerization, the unpaired electrons present in the radicals cannot be completely eliminated by forming new chemical bonds, so that a large number of unpaired electrons are present in such carbon-nitrogen materials. C with the most studied six-membered ring as repeating unit3N4By contrast, electron paramagnetic resonance (FIG. 3) of the present invention demonstrates that the ratio of free electrons in a five-membered ring carbon nitride material to C is higher than that of C at the same mass3N4Two orders of magnitude higher. When a large number of unpaired electrons are present in the material, the molecular orbital splits into an alpha orbital and a beta orbital due to the reduced symmetry. Electrons in the beta orbital absorb infrared light with sufficient energy to make the transition, so that the value of the optical band gap of such materials can be reduced to about 1eV (C)3N4About 2.7 eV). FIG. 4 shows a six-membered ring carbon nitride material C3N4And photoelectric response of five-membered ring carbon nitride material: in the presence of exciting light>At 420nm, the photocurrent of the five-membered ring carbon nitride material is as high as C3N4More than 10 times of the total weight of the composition; and C at 808nm of excitation light3N4Since the infrared light cannot be absorbed, no photocurrent is observed, and the five-membered ring carbon nitride material still has a significant photoelectric response.
On the basis, the photoelectrode prepared by the five-membered ring carbon nitride material successfully realizes dynamic and real-time monitoring of the concentration of exogenous Ascorbic Acid (AA) in blood, which is the first realization of photoelectric detection in an opaque biological sample. Using the electrode shown in fig. 5, there was a significant increase in photocurrent with each addition of exogenous ascorbic acid.
The invention synthesizes the carbon nitride with the five-membered ring structure for the first time, the carbon nitride materials in the prior art are all six-membered rings as repeating units, and the direct synthesis of the carbon nitride with the five-membered ring structure is difficult, so the invention has a great breakthrough.
Has the advantages that: compared with the prior art, the invention has the following advantages:
the invention provides a brand new preparation method of a carbon nitride material, which has the advantages of simple and convenient preparation process, rich raw material sources and low cost, the prepared carbon nitride material is carbon nitride with a five-membered ring structure, has a very narrow energy band structure, has response to near infrared light, and is more beneficial to development of applications such as photoelectrochemical biosensing and the like, and the prepared carbon nitride material can be used for non-transparent biological sample photoelectrochemical biosensing.
Drawings
FIG. 1 is a thermogravimetric analysis of complex ZIF-8 and the ligand 2-methylimidazole constituting ZIF-8;
FIG. 2 is a thermogravimetric-mass spectrometric analysis of ZIF-8 for (a) methane, (b) imidazole free radical, and (c) 2-methylimidazole free radical;
FIG. 3 carbon nitride material C having six-membered rings3N4And electron paramagnetic resonance strength of the five-membered ring carbon nitride material;
FIG. 4 carbon nitride material C having six-membered rings3N4And five-membered ring carbon nitride materials are respectively provided in>Photoelectric response under 420nm and 808nm excitation light, supporting electricityThe electrolyte was 0.1M KCl, and the applied bias was-0.3V (vs Ag/AgCl electrode);
FIG. 5 shows the experimental electrodes, in which (a) shows an indium tin oxide electrode, (b) shows an indium tin oxide electrode modified by a carbon nitride material with five rings, (c) shows a photograph of the modified electrode coated with blood, and the experimental process adopts the system in the third photograph;
FIG. 6 shows the photoelectric response of five-membered ring carbon nitride material coated with blood under 808nm excitation light, with a bias of-0.5V (relative to the ITO electrode).
Detailed Description
The invention will be further described with reference to specific embodiments and the accompanying drawings.
The experimental methods described in the examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Wherein: commercial ZIF-8 (particle size 100-.
Commercial six-membered ring carbon nitride material C3N4Purchased from mclin, CAS: 143334-20-7, cat number: g862684, the purity is more than or equal to 95 percent.
Example 1
The preparation method of the carbon nitride material comprises the following specific operations:
(1) 30mg of commercial ZIF-8 (containing 2-methylimidazole, Zn)2+) Placing the crucible into a 30mL ceramic crucible, covering the crucible cover, then placing the crucible into a tube furnace, introducing nitrogen for 1 hour at a gas flow rate of 500 mL/min, heating to 600 ℃ at a speed of 5 ℃/min under the nitrogen atmosphere, keeping the temperature for 3 hours, and naturally cooling to room temperature to obtain black powder.
(2) Placing the black powder obtained in the step (1) into a sample bottle, dropwise adding 1ml of 38 wt% hydrochloric acid, and reacting for 24 hours.
(3) Adding the mixture obtained in the step (2) into deionized water for ultrasonic treatment, and centrifuging the obtained dispersion liquid at the rotating speed of 13000rpm for 10 minutes.
(4) And (4) pouring off the supernatant, taking the solid, and repeating the operation in the step (3) until the measured pH value of the supernatant is close to 7 and is unchanged, and finally, keeping the black solid.
(5) And (5) drying the black solid obtained in the step (4) in a vacuum drying oven at 110 ℃ for 12 hours to obtain the carbon nitride material with the nanometer size, namely the five-membered ring carbon nitride material.
Thermogravimetric analysis of the complex ZIF-8 and the ligand 2-methylimidazole forming the ZIF-8 in the step (1) is shown in figure 1, according to the second derivative of mass to temperature, the ZIF-8 can be judged to be the initial position of the loss mass peak at 565 ℃, the crystal structure is presumed to begin to collapse at the temperature, and therefore the temperature is selected for carbonization. The thermogravimetric-mass spectrogram of fig. 2 shows the corresponding molecular weight of the generated five-membered ring small molecular fragments, confirms the five-membered ring carbon nitrogen small molecules generated in the decomposition process, and proves that the invention synthesizes carbon nitride with a five-membered ring structure, and the embodiment generates the five-membered ring small molecules at a proper carbonization temperature.
The black solid obtained in step (5) was tested using electron paramagnetic resonance apparatus (FIG. 3), and it was confirmed that carbon nitride material C, which has a ratio of free electrons to six-membered ring commercialized in the five-membered ring carbon nitride material prepared in example 1, was identical in quality3N4Two orders of magnitude higher, so that the value of the optical bandgap of such materials can be reduced by about 1eV (C)3N4About 2.7 eV). FIG. 4 shows a six-membered ring carbon nitride material C3N4And photoelectric response of five-membered ring carbon nitride material: in the presence of exciting light>At 420nm, the photocurrent of the five-membered ring carbon nitride material is as high as C3N4More than 10 times of the total weight of the composition; and C at 808nm of excitation light3N4Since the infrared light cannot be absorbed, no photocurrent is observed, and the five-membered ring carbon nitride material still has obvious photoelectric response, which shows that the five-membered ring carbon nitride of the invention has response to near infrared light.
The ITO modified by the five-membered ring carbon nitride material prepared in the embodiment 1 of the invention is used as a working electrode, and the other ITO electrode is used as a double-electrode system (figure 5) consisting of a counter/half reference electrode, so that the concentration of exogenous Ascorbic Acid (AA) in whole blood of a human body is increasedAnd dynamic and real-time monitoring is carried out. mu.L of blood (human whole blood) was dropped on the five-membered ring carbon nitride-modified ITO, and photoelectric sensing was performed in human whole blood, with a bias of-0.5V against Ag/AgCl (saturated KCl solution). Using the electrode of fig. 5, the photoelectric signal was collected under laser excitation by a 808nm laser. As shown in FIG. 6, the enhanced photocurrent was linearly dependent on the concentration of exogenous ascorbic acid, 20. mu.M per 100S, ranging from 20. mu.M to 180. mu.M, and the detection limit (3. sigma./S) was 15.5. mu.M, as compared with the blank control group to which no AA was added. In addition, the fitted straight line has excellent linear correlation (R)20.999), indicating high accuracy and reliability in continuous monitoring. This is the first successful application of photoelectric biosensing to non-transparent biological samples. Therefore, the five-membered ring carbon nitride prepared by the method is applied to organisms as a novel narrow-gap semiconductor, and has great potential in realizing dynamic and real-time photoelectric biosensing.
Example 2
(1) 30mg of commercial ZIF-7 (containing benzimidazole, Zn) was weighed2+) Placing the crucible into a 30mL ceramic crucible, covering the crucible cover, then placing the crucible into a tube furnace, introducing nitrogen for 0.5 hour at a gas flow rate of 200 mL/minute, continuing to heat to 610 ℃ at a speed of 2 ℃/minute under the nitrogen atmosphere, keeping the temperature for 0.5 hour, and naturally cooling to room temperature to obtain black powder.
(2) Placing the black powder obtained in the step (1) into a sample bottle, dropwise adding 1ml of 38 wt% hydrochloric acid, and reacting for 10 hours.
(3) Adding the mixture obtained in the step (2) into ionized water for ultrasonic treatment, and centrifuging the obtained dispersion liquid at the rotating speed of 5000rpm for 5 minutes.
(4) And (4) pouring off the supernatant, taking the solid, and repeating the operation in the step (3) until the measured pH value of the supernatant is close to 7 and is unchanged, and finally, keeping the black solid.
(5) And (5) drying the black solid obtained in the step (4) in a vacuum drying oven at 110 ℃ for 12 hours to obtain the nano-sized carbon nitride material.
Example 3
(1) 30mg of commercial ZIF-67 (containing 2-methylimidazole, Co)2+) Is arranged at 30Putting the crucible into a mL ceramic crucible, covering the crucible cover, putting the crucible into a tube furnace at the gas flow rate of 200 mL/min, introducing nitrogen for 0.5 hour, continuously heating to 550 ℃ at the speed of 10 ℃/min in the nitrogen atmosphere, keeping the temperature for 1.5 hours, and naturally cooling to room temperature to obtain black powder.
(2) Placing the black powder obtained in the step (1) into a sample bottle, dropwise adding 1ml of 38 wt% hydrochloric acid, and reacting for 20 hours.
(3) Adding the mixture obtained in the step (2) into ionized water for ultrasonic treatment, and centrifuging the obtained dispersion liquid at the rotating speed of 13000rpm for 2 hours.
(4) And (4) pouring off the supernatant, taking the solid, and repeating the operation in the step (3) until the measured pH value of the supernatant is close to 7 and is unchanged, and finally, keeping the black solid.
(5) And (5) drying the black solid obtained in the step (4) in a vacuum drying oven at 110 ℃ for 12 hours to obtain the nano-sized carbon nitride material.
Example 4
(1) 30mg of commercial ZIF-2 (containing imidazole, Zn) was weighed2+) Placing the crucible into a 30mL ceramic crucible, covering the crucible cover, then placing the crucible into a tube furnace, introducing argon gas at the gas flow rate of 100 mL/min for 1.5 hours, continuing to heat to 500 ℃ at the speed of 2 ℃/min under the argon atmosphere, keeping the temperature for 5 hours, and naturally cooling to room temperature to obtain black powder.
(2) Placing the black powder obtained in the step (1) into a sample bottle, dropwise adding 1ml of 38 wt% hydrochloric acid, and reacting for 10 hours.
(3) Adding the mixture obtained in the step (2) into deionized water for ultrasonic treatment, and centrifuging the obtained dispersion liquid at the rotating speed of 13000rpm for 5 minutes.
(4) And (4) pouring off the supernatant, taking the solid, and repeating the operation in the step (3) until the measured pH value of the supernatant is close to 7 and is unchanged, and finally, keeping the black solid.
(5) And (5) drying the black solid obtained in the step (4) in a vacuum drying oven at 50 ℃ for 20 hours to obtain the nano-sized carbon nitride material.
Example 5
(1) 30mg of commercial ZIF-3 (containing imidazole, Zn) was weighed2+) Placing the mixture in a 30mL ceramic crucible and covering the crucibleAnd covering, placing the crucible in a tube furnace at a gas flow rate of 500 mL/min, introducing nitrogen for 1 hour, continuously heating to 700 ℃ at a speed of 20 ℃/min in the nitrogen atmosphere, keeping for 1.5 hours, and naturally cooling to room temperature to obtain black powder.
(2) Placing the black powder obtained in the step (1) into a sample bottle, dropwise adding 1ml of 38 wt% hydrochloric acid, and reacting for 15 hours.
(3) Adding the mixture obtained in the step (2) into deionized water for ultrasonic treatment, and centrifuging the obtained dispersion liquid at the rotating speed of 13000rpm for 10 minutes.
(4) And (4) pouring off the supernatant, taking the solid, and repeating the operation in the step (3) until the measured pH value of the supernatant is close to 7 and is unchanged, and finally, keeping the black solid.
(5) And (5) drying the black solid obtained in the step (4) in a vacuum drying oven at 120 ℃ for 10 hours to obtain the nano-sized carbon nitride material.
Comparative example 1
Comparative example 1 was prepared in the same manner as in example 1, except that: imidazole or 2-methylimidazole is directly used for heating polymerization, and can be completely volatilized at 200 ℃ due to low boiling point, so that the five-membered ring carbon nitride material cannot be obtained.
Claims (10)
1. A method for preparing a carbon nitride material is characterized by comprising the following steps:
(1) calcining the precursor complex under inert atmosphere and high temperature to obtain a carbonized product;
(2) and (2) carrying out acid treatment on the carbonized product obtained in the step (1), removing impurities, washing with deionized water, centrifuging and drying to obtain the carbon nitride material.
2. The method for producing a carbon nitride material according to claim 1, wherein the precursor in the step (1) is a complex prepared from one or more five-membered ring ligands and a metal ion.
3. The method for producing a carbon nitride material according to claim 2, wherein the five-membered ring ligand comprises imidazole2-methylimidazole or benzimidazole, the metal ion including Zn2+Or Co2+。
4. The method for producing a carbon nitride material according to any one of claims 1 to 3, wherein the complex preferably comprises a metal organic framework material ZIF-2, ZIF-3, ZIF-4, ZIF-5, ZIF-6, ZIF-10, ZIF-64, ZIF-8, ZIF-67, ZIF-7, ZIF-9, ZIF-11 or ZIF-12.
5. The method for producing a carbon nitride material according to claim 1, wherein the inert atmosphere in the step (1) is a nitrogen atmosphere or an argon atmosphere.
6. The method for producing a carbon nitride material according to claim 1, wherein the precursor in the step (1) is placed in an inert atmosphere for 0.5 to 1.5 hours, and the calcination is performed at a high temperature of 500 to 700 ℃ at a rate of 2 to 20 ℃/min and is maintained for 0.5 to 5 hours.
7. The method for producing a carbon nitride material according to claim 1, wherein the acid treatment in the step (2) is carried out by immersing the carbonized product in concentrated hydrochloric acid for 10 to 24 hours.
8. A carbon nitride material produced by the method for producing a carbon nitride material according to claim 1, wherein the carbon nitride material has a five-membered ring basic unit.
9. The use of the carbon nitride material prepared by the method for preparing a carbon nitride material according to claim 1 in photoelectrochemical sensing.
10. The use of the carbon nitride material prepared by the method for preparing a carbon nitride material according to claim 1 in photoelectric biosensing of a non-transparent biological sample.
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| CN114231271A (en) * | 2021-12-13 | 2022-03-25 | 巢湖学院 | Preparation method of europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material |
| CN116443851A (en) * | 2023-05-06 | 2023-07-18 | 大连理工大学 | Method for preparing high-nitrogen-doped carbon material by molecular scale finite field pyrolysis and application |
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| CN106169381A (en) * | 2016-07-26 | 2016-11-30 | 北京工业大学 | A kind of synthetic method constructing the azotized carbon nano pipe with electrochemical capacitance performance based on ZIF 67 |
| CN107986247A (en) * | 2017-12-26 | 2018-05-04 | 佛山科学技术学院 | A kind of preparation method of graphite phase carbon nitride nanotube |
| KR20190032027A (en) * | 2017-09-19 | 2019-03-27 | 한국과학기술원 | Method for preparing hydrophobic metal organic framework-carbon nitride |
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| CN106169381A (en) * | 2016-07-26 | 2016-11-30 | 北京工业大学 | A kind of synthetic method constructing the azotized carbon nano pipe with electrochemical capacitance performance based on ZIF 67 |
| KR20190032027A (en) * | 2017-09-19 | 2019-03-27 | 한국과학기술원 | Method for preparing hydrophobic metal organic framework-carbon nitride |
| CN107986247A (en) * | 2017-12-26 | 2018-05-04 | 佛山科学技术学院 | A kind of preparation method of graphite phase carbon nitride nanotube |
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| CN114231271A (en) * | 2021-12-13 | 2022-03-25 | 巢湖学院 | Preparation method of europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material |
| CN116443851A (en) * | 2023-05-06 | 2023-07-18 | 大连理工大学 | Method for preparing high-nitrogen-doped carbon material by molecular scale finite field pyrolysis and application |
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