CN115724413A - g-C 3 N 4 Preparation method of self-assembled nitrogen vacancy powder - Google Patents
g-C 3 N 4 Preparation method of self-assembled nitrogen vacancy powder Download PDFInfo
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- CN115724413A CN115724413A CN202211523925.5A CN202211523925A CN115724413A CN 115724413 A CN115724413 A CN 115724413A CN 202211523925 A CN202211523925 A CN 202211523925A CN 115724413 A CN115724413 A CN 115724413A
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- citric acid
- dicyandiamide
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000000843 powder Substances 0.000 title claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 7
- 238000000137 annealing Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000004108 freeze drying Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
The invention discloses a g-C 3 N 4 A method for preparing self-assembled nitrogen vacancy powder, comprising the steps of: (1) Dissolving dicyandiamide and citric acid in deionized water, transferring the solution into a freeze dryer, and performing vacuum freeze drying to remove water to obtain a white powder product; (2) Annealing the product in a muffle furnace at 550 +/-25 ℃ for 2 +/-1 h at the heating rate of 10 +/-5 ℃/min, and grinding to obtain g-C 3 N 4 Self-assembling nitrogen vacancy powder. The mass ratio of dicyandiamide to citric acid is 100-300:1, its use in photocatalysis can obtain good effect.
Description
Technical Field
The present invention relates to g-C 3 N 4 Process for preparing self-assembled nitrogen vacancy powders, g-C prepared thereby 3 N 4 The self-assembled nitrogen vacancy powder can be used in the field of photocatalysis, for example, photocatalytic water decomposition hydrogen production, and belongs to the technical field of new materials.
Background
In recent years due to g-C 3 N 4 The advantages of high stability, simple preparation, proper band gap and the like are greatly concerned in the field of photocatalysis, but the further development of the photocatalysis material is limited by the limitations of poor light utilization rate, high carrier recombination rate and lower quantum efficiency. Nitrogen vacancies can compensate for these disadvantages, but the mainstream solution for introducing nitrogen vacancies at present is by secondary heat treatment of the photocatalyst in an oxidizing or reducing gas atmosphere. This process requires a large amount of energy to be consumed, and the secondary treatment process needs to be carried out in a flowing atmosphere, the formed waste gas is discharged to the environment and has certain harm to the environment, and the recovery treatment needs to consume additional energy. And the secondary treatment often requires high temperature conditions, which undoubtedly increases the possibility of danger.
CN201610885710.6 a g-C3N4 nanosheet with a monodisperse structure and a preparation method thereof. The g-C3N4 nano-sheet with a monodisperse structure has the size of 10-50nm, and has uniform particle distribution and no agglomeration phenomenon. The catalyst is prepared by a secondary calcination method under the condition of water vapor atmosphere, the preparation condition is mild, and the catalyst can be prepared in large quantities. The method is effectively applied to photocatalytic degradation of organic matters and hydrogen production by photolysis of water.
Disclosure of Invention
The invention aims to provide g-C rich in nitrogen vacancies 3 N 4 The object of the present invention is to provide a process for producing g-C 3 N 4 Use of self-assembled nitrogen vacancy powders, i.e. g-C 3 N 4 Self-assembled nitrogen vacancy powder is used for photocatalysis. Due to g-C 3 N 4 The self-assembled nitrogen vacancy powder can prolong visible light absorption, enlarge reaction surface area, adjust band gap, inhibit carrier recombination and improve charge separation efficiency, and vacancy defects are considered to be helpful to gasAdsorption and activation of bulk molecules, g-C 3 N 4 Self-assembled nitrogen vacancy powders are good photocatalytic materials. The photocatalyst is used for photocatalytic water decomposition to produce hydrogen, and good effects can be achieved.
The technical scheme of the invention is as follows: g-C 3 N 4 A method for preparing self-assembled nitrogen vacancy powder, comprising the steps of: (1) Dissolving dicyandiamide and citric acid in deionized water, transferring the solution into a freeze dryer, and performing vacuum freeze drying to remove water to obtain a white powder product; (2) Annealing the product in a muffle furnace at 550 +/-25 ℃ for 2 +/-1 h at the heating rate of 10 +/-5 ℃/min, and grinding to obtain g-C 3 N 4 Self-assembling nitrogen vacancy powder.
The mass ratio of dicyandiamide to citric acid is 100-300:1.
dissolving dicyandiamide and citric acid in deionized water, and stirring at 40 + -15 deg.C for more than 10min to disperse uniformly.
The water in the solution was removed by freeze drying under vacuum using freeze drying.
Annealing the dried product at 550 + -25 deg.C for 2 + -1 hr with a heating rate of 10 + -5 deg.C/min, and grinding to obtain g-C 3 N 4 Self-assembled nitrogen vacancy powder, which can achieve good effect when used for photocatalysis.
The invention has the beneficial effects that: the method prepares g-C without secondary treatment 3 N 4 Self-assembling nitrogen-vacancy powder, the method comprising using two water-soluble compounds, dicyandiamide and citric acid, in a mass ratio of 200:1 into water, vacuum freeze drying to obtain white precursor powder, annealing at proper temperature and grinding to obtain g-C 3 N 4 Self-assembling nitrogen vacancy powder. This method does not require a subsequent heat treatment process. The key of the method is that two water-soluble compounds, namely dicyandiamide and citric acid, are used simultaneously. Meanwhile, dicyandiamide and citric acid are added into the aqueous solution, and a precursor is obtained through vacuum freeze drying, so that the method is simple and convenient in step. The other raw material, citric acid, is cheap, stable and nontoxic. All in oneAnnealing the precursor to obtain g-C 3 N 4 Self-assembled nitrogen vacancy powders, such nitrogen vacancy structures being highly beneficial for photocatalysis.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a product of an embodiment of the present invention. The addition amounts of citric acid are respectively as follows: CA-CN12 of 12mg, CA-CN10 of 10mg, CA-CN8 of 8mg, CA-CN6 of 6mg and CA-CN0 of 0mg. By contrast, BCN is g-C obtained directly by solid phase sintering of dicyandiamide 3 N 4 . From the figure, g-C can be seen 3 N 4 The basic crystal structure of (a) is preserved.
FIG. 2 is a Scanning Electron Microscope (SEM) image of a product of an embodiment of the invention.
FIG. 3 is a Transmission Electron Microscope (TEM) image of a product of an embodiment of the invention.
FIG. 4 is a chart of the UV-VIS absorption spectrum of a product of an embodiment of the present invention.
FIG. 5 shows photocatalytic water splitting to generate H after the product of the present example supports promoter Pt 2 Activity of (2). CA-CN12, CA-CN10, CA-CN8, CA-CN6 and CA-CN0 respectively correspond to the addition of citric acid of 12mg, 10mg, 8mg, 6mg and 0mg, and BCN is directly obtained by solid-phase sintering dicyandiamide. BCN is the comparative sample without nitrogen vacancies, CA-CN10 is the best performing sample; CA-CN0, 6, 8, 10, 12 refers to the amount of additive through which nitrogen vacancies are introduced.
Detailed Description
(1) Dispersing 2g of dicyandiamide and 10mg of citric acid in 40ml of deionized water, and stirring at 40 ℃ until the dicyandiamide and the citric acid are completely dissolved to form a colorless transparent solution;
(2) Transferring the solution into a freeze dryer for vacuum freeze drying to remove water to obtain a white powder product;
(3) Annealing the product in a muffle furnace at 550 ℃ for 2 hours at a heating rate of 10 ℃/min. The obtained block sample is ground in agate mortar to obtain a powder sample, and the powder sample can obtain a good effect when being used for photocatalysis.
The product was analyzed using X-ray light diffraction (XRD), scanning Electron Microscope (SEM), transmission Electron Microscope (TEM), and ultraviolet visible absorption spectroscopy.
Fig. 1 is an XRD pattern of products with different amounts of citric acid added, which are: the content of CA-CN12 was 12mg, that of CA-CN10 was 10mg, that of CA-CN8 was 8mg, that of CA-CN6 was 6mg, that of CA-CN0 was 0mg, and that of BCN was directly obtained by solid-phase sintering of dicyandiamide. FIG. 1 shows that the basic crystal structure of g-C3N4 is unchanged.
FIG. 2 is a Scanning Electron Microscope (SEM) image of a product of an embodiment of the invention.
FIG. 3 is a Transmission Electron Microscope (TEM) image of a product of an embodiment of the invention.
FIG. 4 is a graph of the UV-VIS absorption spectrum of a product according to an embodiment of the present invention, and the band gap of the product is 2.60eV.
Application example
g-C prepared as in the examples 3 N 4 The self-assembled nitrogen vacancy powder photocatalyst is used for photocatalytic water decomposition to produce hydrogen, and specifically comprises the following steps: 50mg of the photocatalyst was dispersed in an aqueous solution of triethanolamine (15 vol%, pH = 11.0), and the volume of the reaction system was 250ml. Then, 3% wt of Pt as a promoter was photo-deposited in situ on the photocatalyst surface. The visible light source adopts a 300W xenon lamp provided with a 420nm cutoff filter. Before the light irradiation, the reaction device is vacuumized for a plurality of times to remove air. The reaction apparatus was kept at about 10 ℃ by connecting cooling water. A certain amount of gas is taken out from the system at certain intervals and injected into a gas chromatograph through an air inlet device to analyze generated H 2 The amount of (c).
The obtained H2 amount versus time is shown in FIG. 5. The result shows that the g-C3N4 self-assembled nitrogen vacancy powder has the activity of photocatalytic water decomposition to produce hydrogen.
Claims (3)
1. g-C 3 N 4 The preparation method of the self-assembled nitrogen vacancy powder is characterized by comprising the following steps: (1) Dissolving dicyandiamide and citric acid in deionized water, transferring the solution into a freeze dryer, and performing vacuum freeze drying to remove water to obtain a white powder product; (2) Annealing the product in a muffle furnace at 550 +/-25 DEG C2 +/-1 hour, the heating rate is 10 +/-5 ℃/min, and g-C is obtained after grinding 3 N 4 Self-assembling nitrogen vacancy powder;
the mass ratio of dicyandiamide to citric acid is 100-300:1.
2. the method of preparing g-C3N4 self-assembled nitrogen-vacancy powder of claim 1, wherein: dissolving dicyandiamide and citric acid in deionized water, and stirring at 40 + -15 deg.C for more than 10min to disperse uniformly.
3. A process for the preparation of g-C3N4 self-assembled nitrogen-vacancy powder as claimed in claim 1 or 2, wherein: freeze drying is adopted, and water is removed by vacuum freeze drying.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110270361A (en) * | 2019-06-26 | 2019-09-24 | 南京润科环境有限公司 | A kind of multiphase carbon doping g-C3N4Composite photo-catalyst and its preparation method and application |
| CN111151286A (en) * | 2020-01-16 | 2020-05-15 | 南京理工大学 | g-C containing nitrogen vacancy3N4Preparation method of/C composite material |
| US20200282384A1 (en) * | 2019-03-05 | 2020-09-10 | Soochow University | Phosphorus-doped tubular carbon nitride micro-nano material and application thereof in catalytic treatment of exhaust gas |
| CN114671417A (en) * | 2022-04-26 | 2022-06-28 | 山西大学 | Preparation method and application of nitrogen vacancy type carbon nitride with high specific surface area |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20200282384A1 (en) * | 2019-03-05 | 2020-09-10 | Soochow University | Phosphorus-doped tubular carbon nitride micro-nano material and application thereof in catalytic treatment of exhaust gas |
| CN110270361A (en) * | 2019-06-26 | 2019-09-24 | 南京润科环境有限公司 | A kind of multiphase carbon doping g-C3N4Composite photo-catalyst and its preparation method and application |
| CN111151286A (en) * | 2020-01-16 | 2020-05-15 | 南京理工大学 | g-C containing nitrogen vacancy3N4Preparation method of/C composite material |
| CN114671417A (en) * | 2022-04-26 | 2022-06-28 | 山西大学 | Preparation method and application of nitrogen vacancy type carbon nitride with high specific surface area |
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