CN112892611A - Fish scale tubular carbon nitride and preparation method and application thereof - Google Patents
Fish scale tubular carbon nitride and preparation method and application thereof Download PDFInfo
- Publication number
- CN112892611A CN112892611A CN202110082165.8A CN202110082165A CN112892611A CN 112892611 A CN112892611 A CN 112892611A CN 202110082165 A CN202110082165 A CN 202110082165A CN 112892611 A CN112892611 A CN 112892611A
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- tubular carbon
- melamine
- fish scale
- trithiocyanuric acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 241000251468 Actinopterygii Species 0.000 claims abstract description 68
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 49
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 49
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 claims description 28
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims description 12
- 238000013032 photocatalytic reaction Methods 0.000 claims description 12
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 12
- 239000003242 anti bacterial agent Substances 0.000 claims description 9
- 229940088710 antibiotic agent Drugs 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000975 dye Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 230000003115 biocidal effect Effects 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 21
- 238000000926 separation method Methods 0.000 abstract description 12
- 230000031700 light absorption Effects 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 239000012876 carrier material Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 16
- 239000011148 porous material Substances 0.000 description 9
- 238000001338 self-assembly Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000006798 recombination Effects 0.000 description 7
- 238000005215 recombination Methods 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 230000002349 favourable effect Effects 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000007847 structural defect Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011197 physicochemical method Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- -1 trithiocyanuric acid compound Chemical class 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention discloses fish scale tubular carbon nitride and a preparation method and application thereof, wherein the preparation method of the fish scale tubular carbon nitride comprises the following steps: respectively dissolving melamine and trithiocyanuric acid in an organic solvent, mixing the obtained solutions, stirring, adding water into the obtained mixed solution, filtering, drying, and calcining the obtained mixture to obtain the fish scale tubular carbon nitride. The fish scale tubular carbon nitride prepared by the invention has the advantages of large specific surface area, strong visible light absorption capacity, high photoproduction electron-hole separation efficiency, high catalytic activity, good structural stability and the like, can be directly applied to the field of photocatalysis, can also be used as a carrier for constructing a composite heterojunction material with stable structure and good photocatalytic performance, and is a novel carrier material with excellent photocatalytic activity. The preparation method also has the advantages of simple process, convenient operation, mild reaction conditions, no need of complex equipment, low cost and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
Description
Technical Field
The invention relates to tubular carbon nitride and a preparation method and application thereof, in particular to fish scale tubular carbon nitride and a preparation method thereof and application of the fish scale tubular carbon nitride in removing organic pollutants in water.
Background
With the rapid development of economy, environmental and energy problems have become a problem which needs to be solved urgently today. Antibiotic drugs have been widely used, and their excessive use and incomplete metabolism make antibiotics often detected in natural water, sewage, soil and other environmental media, and these unmetabolized antibiotics are likely to affect the development of biological cells, the circulation of ecosystem and promote the propagation of drug-resistant pathogenic bacteria, thereby adversely affecting the ecological environment and human health. At present, common methods for removing antibiotics in water environments at home and abroad comprise a biological method, a physicochemical method, an electrochemical method and a filtration method. Although the biological method is low in cost, the required time is long, and the removal effect is interfered by multiple factors. The electrochemical method has high unit treatment cost for low-concentration pollutants, and is difficult to use on a large scale. Filtration simply transfers contaminants from one phase to the other and does not mineralize them into carbon dioxide and water. Photocatalytic degradation in physicochemical methods can be seen as an effective and environmentally friendly method. However, in the previous studies, the following problems still remain in the photocatalyst used for photocatalytic degradation: the method has the advantages of low light utilization efficiency, fast photoproduction electron-hole recombination, poor photocatalytic performance, poor stability and the like, and greatly limits the wide application of photocatalytic degradation due to a large number of defects of the photocatalyst.
A large number of materials have been found to have photocatalytic properties to date, which mainly include metal-based photocatalytic materials and non-metal-based photocatalytic materials. A carbon nitride-based photocatalytic material is widely used for research in the field of photocatalysts because it is inexpensive and has a good photoresponse. Carbon nitride Material (g-C)3N4) Is a typical carbon nitride-based photocatalytic material (g-C)3N4Energy gap of about 2.7eV), which has been widely used in the field of photocatalysis because of its low cost and good light-responsive property, however, g-C3N4The g-C is greatly limited by the problems of small specific surface area, easy recombination of photoproduction electrons and holes, weak visible light absorption capacity, weak photocatalytic performance and the like3N4The use of (1). In recent years, carbon nitride is continuously modified, including ion doping, heterojunction construction, morphology change and the like, wherein tubular carbon nitride obtained by the morphology change obtains some excellent properties due to the special morphology, for example, the tubular morphology is favorable for electrons to move along the tube axis direction. However, the surface of the existing tubular carbon nitride is planar and smooth, which is not beneficial to the stable loading of other heterojunction materials, so that it is difficult to construct a tubular carbon nitride-based heterojunction material with stable performance, and meanwhile, the existing tubular carbon nitride also has the disadvantages of non-uniform structure, unstable structure, small specific surface area, weak light absorption capability, easy recombination of photo-generated electrons and holes, poor photocatalytic performance and the like, and the existence of the disadvantages greatly limits the wide application of the tubular carbon nitride as a carrier material in constructing the heterojunction composite material, and is difficult to meet the requirements in the field of photocatalysis. In addition, no report on the preparation of the fish scale tubular carbon nitride is found so far.
Therefore, the fish scale tubular carbon nitride which has the advantages of large specific surface area, strong visible light absorption capacity, high photoproduction electron-hole separation efficiency, high catalytic activity and good structural stability, and the preparation method which is matched with the fish scale tubular carbon nitride and has the advantages of simple process, convenient operation, mild reaction condition, no need of complex equipment and low cost are obtained, and the method has very important significance for improving the application range of the tubular carbon nitride.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the fish scale tubular carbon nitride with large specific surface area, strong visible light absorption capacity, high photoproduction electron-hole separation efficiency, high catalytic activity and good structural stability, and also provides a preparation method of the fish scale tubular carbon nitride with simple process, convenient operation, mild reaction condition, no need of complex equipment and low cost and application of the fish scale tubular carbon nitride in removing organic pollutants in water.
In order to solve the technical problems, the invention adopts the technical scheme that:
a preparation method of fish scale tubular carbon nitride comprises the following steps:
s1, respectively dissolving melamine and trithiocyanuric acid in an organic solvent to obtain a melamine solution and a trithiocyanuric acid solution;
s2, mixing the melamine solution and the trithiocyanuric acid solution obtained in the step S1, and stirring to obtain a mixed solution of melamine and trithiocyanuric acid;
s3, adding water into the mixed solution of melamine and trithiocyanuric acid obtained in the step S2, filtering and drying to obtain a tubular mixture of melamine and trithiocyanuric acid;
s4, calcining the mixture of the tubular melamine and the cyanuric acid obtained in the step S3 to obtain the fish scale tubular carbon nitride.
In the step S1, the ratio of melamine to organic solvent is 1 g: 30 mL-50 mL; the ratio of the trithiocyanuric acid to the organic solvent is 1 g: 30 mL-50 mL; the organic solvent is at least one of ethanol, N-dimethylformamide and dimethyl sulfoxide.
In the step S2, the molar ratio of melamine to trithiocyanuric acid in the mixed solution of melamine and trithiocyanuric acid is 0.5-1.5: 1; the concentration of melamine in the mixed solution of melamine and trithiocyanuric acid is 0.05-0.15M; the stirring is carried out at the temperature of 20-80 ℃; the rotating speed of the stirring is 600 rpm; the stirring time is 1-4 h.
In the preparation method of the fish scale tubular carbon nitride, the volume ratio of the mixed solution of melamine and trithiocyanuric acid to water is 6-10: 5-20 in step S3 is further improved; the drying temperature is 70-80 ℃.
In the above method for preparing tubular carbon nitride of fish scales, further improvement, in step S4, the calcining is performed in a nitrogen atmosphere or an argon atmosphere; the heating rate in the calcining process is 2.3 ℃/min; the calcining temperature is 450-550 ℃; the calcining time is 2-4 h.
As a general technical concept, the invention also provides the fish scale tubular carbon nitride prepared by the preparation method.
As a general technical concept, the invention also provides application of the fish scale tubular carbon nitride in removing organic pollutants in water.
The application is further improved, and comprises the following steps: mixing the fish scale tubular carbon nitride with the water body containing organic pollutants, stirring, and carrying out photocatalytic reaction under the illumination condition to finish the removal of the organic pollutants in the water body.
The application is further improved, wherein the ratio of the fish scale tubular carbon nitride to the water body containing organic pollutants is 0.5-1 g: 1L; the organic pollutants in the water body containing the organic pollutants are antibiotics and/or dyes; the antibiotic is tetracycline hydrochloride; the initial concentration of the organic pollutants in the water body containing the organic pollutants is less than or equal to 20 mg/L.
In the above application, further improvement, the stirring is performed under dark conditions; the rotating speed of the stirring is 500-800 rpm; the stirring time is 30 min; the light source adopted in the photocatalytic reaction is a xenon lamp, and the optical power is 45-50W; the photocatalytic reaction is carried out under the stirring condition with the rotating speed of 500 rpm-800 rpm; the temperature of the photocatalytic reaction is 25-35 ℃; the time of the photocatalytic reaction is 30-120 min.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a preparation method of fish scale tubular carbon nitride, which takes melamine and trithiocyanuric acid as raw materials, the melamine and the trithiocyanuric acid are fully dissolved in an organic solvent, then the solution of the melamine and the trithiocyanuric acid is mixed to form a tubular self-assembly aggregate through self-assembly, the melamine and the trithiocyanuric acid are fully dissolved in the organic solvent, the self-assembly between the melamine and the trithiocyanuric acid is more thorough and uniform, the tubular self-assembly aggregate is precipitated by water, which can not be realized by other solvents, and finally the tubular self-assembly aggregate is calcined, the self-assembly of the aggregate is more thorough and uniform, the trithiocyanuric acid is sensitive to temperature and has low melting point (305 ℃), so the aggregate is melted in the calcination and temperature rise process, and meanwhile, the combination of edge effect is weaker in a force field within a certain range, and the movement between molecules can be caused, thereby forming a fish scale structure, and simultaneously, melamine and cyanuric acid are decomposed along with the rising of the calcining temperature to generate a large amount of gas, such as H2S and NH3Resulting in pore structure and defects on the surface of the self-assembled aggregate, thereby preparing the flake tubular carbon nitride. Compared with the conventional tubular carbon nitride, the fish scale tubular carbon nitride prepared by the method has the following advantages: the surfaces of the fish scale tubular carbon nitride consist of fish scales, have rough surface appearance and rich pore structures, have a large number of structural defects, can effectively improve the band gap structure, and are beneficial to greatly improving the photocatalytic performance; the fish scale tubular carbon nitride has stronger visible light absorption capacity, can improve the energy band structure,the crystal region of the carbon nitride is better protected, and the excellent photoelectrochemical property is ensured, so that the separation efficiency of photoproduction electrons and holes can be accelerated, the recombination of the photoproduction electrons and the holes is reduced, and the photocatalysis activity is better; the fish scale tubular carbon nitride has a more stable structure, is not easy to break, and is favorable for directional transfer and separation of operation electrons, thereby being more favorable for improving the photocatalytic performance. The fish scale tubular carbon nitride prepared by the invention has the advantages of large specific surface area, strong visible light absorption capacity, high photoproduction electron-hole separation efficiency, high catalytic activity, good structural stability and the like, can be directly applied to the field of photocatalysis as a catalyst material, can also be used as a carrier of other materials for constructing a composite heterojunction material with stable structure and good photocatalytic performance, and is a novel carrier material with excellent photocatalytic activity. Meanwhile, the preparation method provided by the invention has the advantages of simple process, convenience in operation, mild reaction conditions, no need of complex equipment, low cost and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
(2) The invention provides application of fish scale tubular carbon nitride in removing organic pollutants in water, and the organic pollutants in the water can be effectively removed by mixing the fish scale tubular carbon nitride with the water containing the organic pollutants for a photocatalytic reaction. The method for removing the organic pollutants in the water body by using the fish scale tubular carbon nitride can quickly and efficiently degrade various types of organic pollutants (such as antibiotics and dyes) in the water body by using the fish scale tubular carbon nitride to carry out photocatalytic degradation on the organic pollutants, has the advantages of simple process, low treatment cost, high treatment efficiency, good removal effect, high safety, no secondary pollution and the like, particularly can realize the efficient removal of the antibiotics in the water body, and has good practical application prospect.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 shows a fish scale obtained in example 1 of the present inventionSheet tubular carbon nitride (FTCN)so) Tubular Melamine and Trithiocyanic acid mixture (CNS-1), Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) Wherein (A) is CNS-1 and (B) is TCNiso(C) and (D) are FTCNso。
FIG. 2 shows the Flake Tubular Carbonitrides (FTCN) obtained in example 1 of the present inventionso) Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) A TEM image of (a).
FIG. 3 shows the Flake Tubular Carbonitrides (FTCN) obtained in example 1 of the present inventionso) Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) And raw carbon nitride (g-C)3N4) XRD pattern of (a).
FIG. 4 shows the Flake Tubular Carbonitrides (FTCN) obtained in example 1 of the present inventionso) Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) And raw carbon nitride (g-C)3N4) N of (A)2Adsorption-removal of attached figure.
FIG. 5 shows the Flake Tubular Carbonitrides (FTCN) obtained in example 1 of the present inventionso) And raw carbon nitride (g-C)3N4) XPS spectra of (A).
FIG. 6 shows the Flake Tubular Carbonitrides (FTCN) obtained in example 1 of the present inventionso) Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) And raw carbon nitride (g-C)3N4) Ultraviolet-visible diffuse reflectance spectrum of (a).
FIG. 7 shows the Flake Tubular Carbonitrides (FTCN) obtained in example 1 of the present inventionso) Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) And raw carbon nitride (g-C)3N4) Spectrum of photoelectrochemical properties of (a).
FIG. 8 shows the Flake Tubular Carbonitrides (FTCN) in example 2 of the present inventionso) Tubular Carbon Nitride (TCN)iso) And raw carbon nitride (g-C)3N4) The degradation effect of the tetracycline hydrochloride is shown.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The starting materials and equipment used in the following examples are commercially available. In the examples of the present invention, unless otherwise specified, the adopted process is a conventional process, the adopted equipment is conventional equipment, and the obtained data are average values of three or more repeated experiments.
Example 1
A preparation method of fish scale tubular carbon nitride comprises the following steps:
(1) 1.08g of melamine and 1.41g of trithiocyanuric acid were added to 50mL of dimethyl sulfoxide, respectively, to obtain a melamine solution and a trithiocyanuric acid solution.
(2) And (2) mixing the melamine solution and the trithiocyanuric acid solution obtained in the step (1), and magnetically stirring at 600rpm for 4h at the temperature of 30 ℃ to obtain a yellow mixed solution of melamine and trithiocyanuric acid.
(3) And (3) adding 100mL of water into 100mL of the mixed solution of the yellow melamine and the trithiocyanuric acid obtained in the step (2), separating out yellow precipitate, filtering, drying the obtained precipitate at 80 ℃, and grinding to obtain a tubular mixture of the melamine and the trithiocyanuric acid, wherein the mixture is marked as CNS-1.
(4) Placing 1.25g of the tubular mixture of melamine and trithiocyanuric acid obtained in the step (3) in a tubular furnace, heating to 550 ℃ at a heating rate of 2.3 ℃/min in a nitrogen atmosphere, and maintaining for 4h to obtain the fish scale tubular carbon nitride, which is marked as FTCNso。
Comparative example 1
Tubular Carbon Nitride (TCN)iso) The preparation method comprises the following steps:
(1) adding 1.01g of melamine and 1.41g of trithiocyanuric acid into 80mL of 50% ethanol solution, mixing, carrying out self-assembly under stirring, then keeping at 100 ℃ for 6h for hydrothermal reaction, filtering and drying after the reaction to obtain the tubular melamine/trithiocyanuric acid compound.
(2) 1.25g of the tubular melamine/trithiocyanuric acid compound obtained in step (1) was placed in a tube furnace and heated at a rate of 2.3 ℃/min under a nitrogen atmosphere to a temperature ofCalcining at 550 ℃ for 4h, and drying to obtain tubular carbon nitride which is marked as TCNiso。
FIG. 1 shows the Flake Tubular Carbonitrides (FTCN) obtained in example 1 of the present inventionso) Tubular Melamine and Trithiocyanic acid mixture (CNS-1), Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) Wherein (A) is CNS-1 and (B) is TCNiso(C) and (D) are FTCNso. As can be seen from FIG. 1, the Flake Tubular Carbon Nitride (FTCN) prepared in the present inventionso) The surface of (2) is very rough, a large number of nano pores exist on the surface, the existence of a large number of pores causes the fish scale tubular carbon nitride to have a large number of structural defects, and meanwhile, the fish scale tubular carbon nitride (FTCN) can be obviously seenso) Is a tubular structure, the surface of which is composed of fish scales, and the size of the fish scales is 100 nm. In addition, as shown in FIG. 1, the carbon nitride (FTCN) is tubular with fish scalesso) In marked contrast, the Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) The surfaces of the fish-shaped fish bodies are smooth and have no fish scale structures. In addition, as can be seen from the scanning electron microscope characterization result of the tubular melamine and trithiocyanuric acid mixture (CNS-1) prepared by the invention, the surface of the tubular melamine and trithiocyanuric acid mixture (CNS-1) is smoother.
FIG. 2 shows the Flake Tubular Carbonitrides (FTCN) obtained in example 1 of the present inventionso) Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) A TEM image of (a). As can be seen from FIG. 2, the Flake Tubular Carbon Nitride (FTCN) prepared in example 1 of the present inventionso) Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) All are tubular structures.
FIG. 3 shows the Flake Tubular Carbonitrides (FTCN) obtained in example 1 of the present inventionso) Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) And raw carbon nitride (g-C)3N4) XRD pattern of (a). In the present invention, the original carbon nitride (g-C)3N4) Is prepared by a conventional preparation method. As can be seen from FIG. 3, the fish scale is tubular carbon nitride (FTCN)so) There are two distinct diffraction peaks in total, with the peak at 13.2 ° (100) corresponding to the in-plane structural stacking of the triazine units, and at 27.4 ° (002)) The other peak at (a) corresponds to the interlayer stacking of aromatic units. It is worth emphasizing that the completely dissolved self-assembled prepared FTCNsoIntact retention of g-C3N4Crystal structure of (a), and insufficiently dissolved self-assembled prepared TCNisoMiddle g-C3N4Due to the fact that melamine and trithiocyanuric acid are sufficiently dissolved in an organic solvent in the preparation method of the present invention, the self-assembly between melamine and trithiocyanuric acid is more thorough and uniform. More importantly, fish scale tubular carbon nitride (FTCN)so) The ordered structure inside is beneficial to enhancing the photocatalytic activity.
FIG. 4 shows the Flake Tubular Carbonitrides (FTCN) obtained in example 1 of the present inventionso) Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) And raw carbon nitride (g-C)3N4) N of (A)2Adsorption-removal of attached figure. From FIG. 4, it can be seen that N is the number2The pore structure and specific surface area of the material were studied by adsorption-desorption, and the results showed that all samples were typical type III isotherms, indicating that all samples had a mesoporous structure. The results of analyzing the pore size distribution and the specific surface area by using the BJH adsorption method and the BET method respectively show that g-C3N4And TCNisoFewer mesopores in the middle, and FTCNsoWith a large number of mesopores of about 30 nm. Furthermore, FTCNsoRatio g-C3N4And TCNisoHas a larger specific surface area, which is associated with a rich population of pores. The invention relates to fish scale tubular carbon nitride (FTCN)so) Has rich pore structure and larger specific surface area, can provide more catalytic active sites, can promote the adsorption of pollutants, and is favorable for improving the photocatalytic activity.
FIG. 5 shows the Flake Tubular Carbonitrides (FTCN) obtained in example 1 of the present inventionso) And raw carbon nitride (g-C)3N4) XPS spectra of (A). As can be seen from FIG. 5, the fish scale is tubular carbon nitride (FTCN)so) Almost no sulfur element, which shows that the function of the trithiocyanuric acid is to frame the skeleton, generate holes and defects, but not introduce S element doping.
FIG. 6 shows the present inventionScale tubular carbon nitride (FTCN) prepared in EXAMPLE 1so) Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) And raw carbon nitride (g-C)3N4) Ultraviolet-visible diffuse reflectance spectrum of (a). As can be seen from FIG. 6, all samples exhibited strong ultraviolet absorption (. lamda.) (in the above range)<420nm) but clearly different from VSL (λ)>420nm) (fig. 6A). FTCNsoThe VSL absorption performance of the material is slightly stronger than that of TCNisoAnd g-C3N4This is due to the special structure formed by sufficient self-assembly. Meanwhile, the band gap structure of the material is analyzed, and g-C calculated through UV-vis DRS data is obtained3N4、TCNisoAnd FTCNsoThe band gaps of (a) are 2.72eV, 2.68eV and 2.64eV, respectively (fig. 6B). On the other hand, g-C was obtained by XPS3N4、TCNisoAnd the valence bands of FTCNso are 1.98eV, 1.93eV, and 1.71eV, respectively. From the band gap and the valence band, g-C can be calculated3N4、TCNisoAnd the conduction band of FTCNso were 0.74eV, 0.75eV, and 0.93eV, in that order (fig. 6C). It can be seen that upon excitation under VSL radiation, the FTCNsoSemiconductors can generate electrons and holes.
After analyzing FTCNsoAfter the bandgap structure of the semiconductor is known, the potential energy (. O) between the semiconductor and active oxygen is measured2-OH) to further analyze the ability of the material to generate reactive oxygen species. Deriving FTCN according to position information of valence band and conduction bandsoAbility to generate an active ingredient. FTCNsoHas an edge potential greater than O2/·O2 -Potential (-0.33eV), which results in FTCNsoThe electron on CB of (2) participates in O2Reduction to O2 -The process of (1). Due to FTCNsoThe semiconductor material can generate O2-O and2 -is to generate H2O2Thus resulting in an FTCNsoHeterojunction composite materials capable of producing H2O2. However, FTCNsoValence edge potential ratios of OH-/. OH (2.40eV) and H2The more negative potential of O/. OH (2.72eV) results in it not having the ability to generate. OH directly. Based on the fact that OH cannot be directly generatedIndeed, OH has a weaker effect in the degradation process. The relevant reaction return is as follows:
FTCNso+VSL→FTCNso(e-/h+) (1)
h++OH-→·OH (2)
·OOH+H++e-→H2O2 (5)
H2O2+e-→·OH+OH- (6)
FIG. 7 shows the Flake Tubular Carbonitrides (FTCN) obtained in example 1 of the present inventionso) Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) And raw carbon nitride (g-C)3N4) Spectrum of photoelectrochemical properties of (a). In FIG. 7, (A) is a photoelectric flow chart, (B) is a transient PL spectrum, and (C) is an EIS spectrum. As can be seen from FIG. 7, the FTCNsoThe best photocurrent intensity is shown, which indicates that the heterojunction material has the best e-h + separation efficiency and photocurrent response. This is probably due to fish scale tubular carbon nitride (FTCN) as a result of photocurrentso) There are structural defects and ordered tubular structures. In addition, the solid state steady state PL spectrum was used to determine the separation efficiency of the photogenerated carriers (fig. 7B). Based on g-C3N4The photocatalyst of (2) has a distinct absorption peak near 465nm, and at the same time, the PL spectrum of the modified sample has a certain red shift, which further confirms that the band gap has changed.
For a good photocatalyst, not only the combination of electrons and holes needs to be suppressed, but also the transfer of electrons and holes must be accelerated. The transfer of electrons is measured by electrochemical impedance EIS, FIG. 7C, FTCNsoThe radian of the heterojunction compound is smaller than that of electric arcs of other prepared samples, which shows that the carrier migration resistance of the heterojunction compound is lower, and the photocatalytic activity is favorably improved. In short, according to the photoelectrochemical results, the heterojunction composite material has the highest e-h + separation and transfer efficiency, and is beneficial to improving the photocatalytic performance. In addition, the steady state PL was used to visually observe the electron-hole recombination time (fig. 7B). FTCNsoHas a longer average decay time, which indicates FTCNsoIt is possible to effectively accelerate the transfer of photo-generated charges and effectively suppress charge recombination.
As can be seen from fig. 1 to 7, the flake tubular carbon nitride prepared in the present invention has the following advantages compared to the conventional tubular carbon nitride: the surfaces of the fish scale tubular carbon nitride consist of fish scales, have rough surface appearance and rich pore structures, have a large number of structural defects, can effectively improve the band gap structure, and are beneficial to greatly improving the photocatalytic performance; the fish scale tubular carbon nitride has stronger visible light absorption capacity, can improve an energy band structure, better protects a crystal region of the carbon nitride, and ensures excellent photoelectrochemical performance, so that the separation efficiency of photoproduction electrons and holes can be accelerated, the recombination of the photoproduction electrons and the holes is reduced, and the fish scale tubular carbon nitride has better photocatalytic activity; the fish scale tubular carbon nitride has a more stable structure, is not easy to break, and is favorable for directional transfer and separation of operation electrons, thereby being more favorable for improving the photocatalytic performance. Therefore, the fish scale tubular carbon nitride prepared by the method has the advantages of large specific surface area, strong visible light absorption capacity, high photoproduction electron-hole separation efficiency, high catalytic activity, good structural stability and the like, can be directly applied to the field of photocatalysis as a catalyst material, can also be used as a carrier of other materials for constructing a composite heterojunction material with stable structure and good photocatalytic performance, and is a novel carrier material with excellent photocatalytic activity.
Example 2
The application of fish scale tubular carbon nitride in removing organic pollutants in water body, in particular to the application of fish scale tubular carbon nitride in removing tetracycline hydrochloride in water body by catalysis, which comprises the following steps:
the fish scale tubular carbon nitride (FTCN) obtained in example 1 was takenso) Tubular Carbon Nitride (TCN) prepared in comparative example 1iso) And raw carbon nitride (g-C)3N4) Respectively adding 25mg of the tetracycline hydrochloride (TCH) solution into 50mL of 10mg/L tetracycline hydrochloride (TCH) solution, uniformly mixing, adsorbing the tetracycline hydrochloride under the conditions of 30 ℃ and 600rpm, and reaching adsorption equilibrium after 30 min; placing the mixed solution after reaching the adsorption balance in a xenon lamp (lambda)>420nm), carrying out a photocatalytic reaction for 30min at the temperature of 30 ℃ and the rpm of 600, and finishing the TCH treatment.
FIG. 8 shows the Flake Tubular Carbonitrides (FTCN) in example 2 of the present inventionso) Tubular Carbon Nitride (TCN)iso) And raw carbon nitride (g-C)3N4) The degradation effect of the tetracycline hydrochloride is shown. As can be seen from FIG. 8, the FTCNsoThe photocatalytic activity of the photocatalyst is obviously higher than that of TCNisoAnd g-C3N4They are arranged in the order of FTCNso>TCNiso>g-C3N4Wherein FTCNso、TCNisoAnd g-C3N4The degradation efficiency of tetracycline hydrochloride is 70.5 percent, 57.3 percent and 23 percent in sequence, which shows that the fish scale tubular carbon nitride (FTCN) prepared by the inventionso) Has better photocatalytic activity and can remove organic pollutants in water more effectively.
Therefore, the method for removing the organic pollutants in the water body by using the fish scale tubular carbon nitride can quickly and efficiently degrade the organic pollutants of different types (such as antibiotics and dyes) in the water body by using the fish scale tubular carbon nitride to carry out photocatalytic degradation on the organic pollutants, has the advantages of simple process, low treatment cost, high treatment efficiency, good removal effect, high safety, no secondary pollution and the like, particularly can realize the efficient removal of the antibiotics in the water body, and has good practical application prospect.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. The preparation method of the fish scale tubular carbon nitride is characterized by comprising the following steps:
s1, respectively dissolving melamine and trithiocyanuric acid in an organic solvent to obtain a melamine solution and a trithiocyanuric acid solution;
s2, mixing the melamine solution and the trithiocyanuric acid solution obtained in the step S1, and stirring to obtain a mixed solution of melamine and trithiocyanuric acid;
s3, adding water into the mixed solution of melamine and trithiocyanuric acid obtained in the step S2, filtering and drying to obtain a tubular mixture of melamine and trithiocyanuric acid;
s4, calcining the mixture of the tubular melamine and the cyanuric acid obtained in the step S3 to obtain the fish scale tubular carbon nitride.
2. The method for preparing tubular carbon nitride with fish scales according to claim 1, wherein in step S1, the ratio of melamine to organic solvent is 1 g: 30 mL-50 mL; the ratio of the trithiocyanuric acid to the organic solvent is 1 g: 30 mL-50 mL; the organic solvent is at least one of ethanol, N-dimethylformamide and dimethyl sulfoxide.
3. The method for preparing fish scale tubular carbon nitride according to claim 1 or 2, wherein in step S2, the molar ratio of melamine to trithiocyanuric acid in the mixed solution of melamine and trithiocyanuric acid is 0.5-1.5: 1; the concentration of melamine in the mixed solution of melamine and trithiocyanuric acid is 0.05-0.15M; the stirring is carried out at the temperature of 20-80 ℃; the rotating speed of the stirring is 600 rpm; the stirring time is 1-4 h.
4. The method for preparing tubular carbon nitride with fish scales according to claim 1 or 2, wherein in step S3, the volume ratio of the mixed solution of melamine and trithiocyanuric acid to water is 6-10: 5-20; the drying temperature is 70-80 ℃.
5. The method for producing tubular carbon nitride for fish scales according to claim 1 or 2, wherein in step S4, the calcination is performed in a nitrogen atmosphere or an argon atmosphere; the heating rate in the calcining process is 2.3 ℃/min; the calcining temperature is 450-550 ℃; the calcining time is 2-4 h.
6. A fish scale tubular carbon nitride, which is prepared by the preparation method of any one of claims 1 to 5.
7. Use of the flake tubular carbon nitride of claim 6 for removing organic contaminants from a body of water.
8. Use according to claim 7, characterized in that it comprises the following steps: mixing the fish scale tubular carbon nitride with the water body containing organic pollutants, stirring, and carrying out photocatalytic reaction under the illumination condition to finish the removal of the organic pollutants in the water body.
9. The use of claim 8, wherein the ratio of the fish scale tubular carbon nitride to the water containing organic pollutants is 0.5 g-1 g: 1L; the organic pollutants in the water body containing the organic pollutants are antibiotics and/or dyes; the antibiotic is tetracycline hydrochloride; the initial concentration of the organic pollutants in the water body containing the organic pollutants is less than or equal to 20 mg/L.
10. Use according to claim 8 or 9, characterized in that the stirring is carried out in dark conditions; the rotating speed of the stirring is 500-800 rpm; the stirring time is 30 min; the light source adopted in the photocatalytic reaction is a xenon lamp, and the optical power is 45-50W; the photocatalytic reaction is carried out under the stirring condition with the rotating speed of 500 rpm-800 rpm; the temperature of the photocatalytic reaction is 25-35 ℃; the time of the photocatalytic reaction is 30-120 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110082165.8A CN112892611B (en) | 2021-01-21 | 2021-01-21 | Fish scale tubular carbon nitride and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110082165.8A CN112892611B (en) | 2021-01-21 | 2021-01-21 | Fish scale tubular carbon nitride and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112892611A true CN112892611A (en) | 2021-06-04 |
| CN112892611B CN112892611B (en) | 2022-07-26 |
Family
ID=76117429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110082165.8A Active CN112892611B (en) | 2021-01-21 | 2021-01-21 | Fish scale tubular carbon nitride and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112892611B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114558600A (en) * | 2022-01-20 | 2022-05-31 | 南京林业大学 | Mixed-dimension S-doped g-C3N4Base van der waals heterojunction photocatalyst and preparation method and application thereof |
| CN114984990A (en) * | 2022-05-16 | 2022-09-02 | 湖南大学 | Tubular carbon nitride-based Schottky heterojunction photocatalyst and preparation method and application thereof |
| CN115254172A (en) * | 2022-08-29 | 2022-11-01 | 江苏科技大学 | Vesicular g-C 3 N 4 Photocatalyst and preparation method thereof |
| CN115254149A (en) * | 2022-05-16 | 2022-11-01 | 湖南大学 | Floatable carbon nitride based piezoelectric light catalyst, preparation method and application thereof |
| CN115301267A (en) * | 2021-09-08 | 2022-11-08 | 南京工业大学 | Porous tubular carbon nitride catalyst suitable for visible light catalysis and preparation method and application thereof |
| CN115672370A (en) * | 2022-10-25 | 2023-02-03 | 哈尔滨工业大学 | Preparation method of tubular carbon nitride for visible light catalytic degradation of micropollutants in water |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111185216A (en) * | 2020-01-19 | 2020-05-22 | 湖南大隆环境科技有限公司 | Hollow tubular sulfur-doped carbon nitride/graphite-phase carbon nitride homojunction photocatalyst and preparation method and application thereof |
-
2021
- 2021-01-21 CN CN202110082165.8A patent/CN112892611B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111185216A (en) * | 2020-01-19 | 2020-05-22 | 湖南大隆环境科技有限公司 | Hollow tubular sulfur-doped carbon nitride/graphite-phase carbon nitride homojunction photocatalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| YOUNG-SI JUN ET AL: ""3-D Macroscopic Assemblies of Low Dimensional Carbon Nitrides for Enhanced Hydrogen Evolution"", 《ANGEW.CHEMIE》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115301267A (en) * | 2021-09-08 | 2022-11-08 | 南京工业大学 | Porous tubular carbon nitride catalyst suitable for visible light catalysis and preparation method and application thereof |
| CN114558600A (en) * | 2022-01-20 | 2022-05-31 | 南京林业大学 | Mixed-dimension S-doped g-C3N4Base van der waals heterojunction photocatalyst and preparation method and application thereof |
| CN114558600B (en) * | 2022-01-20 | 2023-10-20 | 南京林业大学 | Mixed dimension S doped g-C 3 N 4 Base van der Waals heterojunction photocatalyst, preparation method and application thereof |
| CN114984990A (en) * | 2022-05-16 | 2022-09-02 | 湖南大学 | Tubular carbon nitride-based Schottky heterojunction photocatalyst and preparation method and application thereof |
| CN115254149A (en) * | 2022-05-16 | 2022-11-01 | 湖南大学 | Floatable carbon nitride based piezoelectric light catalyst, preparation method and application thereof |
| CN115254172A (en) * | 2022-08-29 | 2022-11-01 | 江苏科技大学 | Vesicular g-C 3 N 4 Photocatalyst and preparation method thereof |
| CN115254172B (en) * | 2022-08-29 | 2023-12-19 | 江苏科技大学 | Vesicle-shaped g-C 3 N 4 Photocatalyst and preparation method thereof |
| CN115672370A (en) * | 2022-10-25 | 2023-02-03 | 哈尔滨工业大学 | Preparation method of tubular carbon nitride for visible light catalytic degradation of micropollutants in water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112892611B (en) | 2022-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112892611B (en) | Fish scale tubular carbon nitride and preparation method and application thereof | |
| Hou et al. | Variable dimensional structure and interface design of g-C3N4/BiOI composites with oxygen vacancy for improving visible-light photocatalytic properties | |
| Wang et al. | Template-free synthesis of oxygen-containing ultrathin porous carbon quantum dots/gC 3 N 4 with superior photocatalytic activity for PPCPs remediation | |
| Zhang et al. | Constructing of Z-scheme 3D g-C3N4-ZnO@ graphene aerogel heterojunctions for high-efficient adsorption and photodegradation of organic pollutants | |
| Zhang et al. | Formation of Mo2C/hollow tubular g-C3N4 hybrids with favorable charge transfer channels for excellent visible-light-photocatalytic performance | |
| CN112916035B (en) | Fish scale tubular carbon nitride composite heterojunction photocatalyst and preparation method and application thereof | |
| Du et al. | Construction and application of BiOCl/Cu-doped Bi2S3 composites for highly efficient photocatalytic degradation of ciprofloxacin | |
| Shi et al. | Stable, metal-free, visible-light-driven photocatalyst for efficient removal of pollutants: mechanism of action | |
| CN108816268B (en) | Composite photocatalytic nanomaterial and preparation method thereof, and pollutant degradation method | |
| Zhu et al. | All-solid-state Z-scheme heterostructures of 1T/2H-MoS2 nanosheets coupled V-doped hierarchical TiO2 spheres for enhanced photocatalytic activity | |
| Wang et al. | A facile synthesis of nano-layer structured g-C3N4 with efficient organic degradation and hydrogen evolution using a MDN energetic material as the starting precursor | |
| CN110201698A (en) | A kind of preparation method of polynary nonmetal doping carbon nitride photocatalyst | |
| Liu et al. | Codoped rutile TiO2 as a new photocatalyst for visible light irradiation | |
| CN113318764A (en) | Preparation method and application of nitrogen defect/boron doped tubular carbon nitride photocatalyst | |
| CN101711988A (en) | NaBiO3/BiOCl heterojunction photocatalyst and preparation method thereof | |
| Peng et al. | Construction of a Z-scheme gC 3 N 4/NBGO/BiVO 4 heterostructure with visible-light driven photocatalytic degradation of tetracycline: efficiency, reaction pathway and mechanism | |
| Zhang et al. | Synthesis of highly porous g-C3N4 nanotubes for efficient photocatalytic degradation of sulfamethoxazole | |
| CN110560119A (en) | Preparation and application of potassium-doped inverse opal carbon nitride photocatalyst | |
| Zhang et al. | In situ fabrication of type II 3D hierarchical flower-like BiOBr/Bi3O4Br heterojunction with improved photocatalytic activity | |
| CN112958061A (en) | Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2Photocatalyst and preparation method thereof | |
| CN111036272B (en) | C3N4/LaVO4Composite photocatalyst and preparation method thereof | |
| Wei et al. | A stable and efficient La-doped MIL-53 (Al)/ZnO photocatalyst for sulfamethazine degradation | |
| Plubphon et al. | Rapid preparation of g-C3N4/Bi2O2CO3 composites and their enhanced photocatalytic performance | |
| Sun et al. | Ammonia-dependent synthesis of (BiO) 2OHCl@ Bi24O31Cl10 heterostructures with enhanced visible-light induced photocatalytic activities on levofloxacin removal | |
| Berekute et al. | Novel visible-light-active Pg-CN-based α-Bi2O3/WO3 ternary photocatalysts with a dual Z-scheme heterostructure for the efficient decomposition of refractory ultraviolet filters and environmental hormones: Benzophenones |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |