CN109535421A - A kind of piperazine base carbon nitrogen polymer, Its Preparation Method And Use - Google Patents
A kind of piperazine base carbon nitrogen polymer, Its Preparation Method And Use Download PDFInfo
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- CN109535421A CN109535421A CN201811645199.8A CN201811645199A CN109535421A CN 109535421 A CN109535421 A CN 109535421A CN 201811645199 A CN201811645199 A CN 201811645199A CN 109535421 A CN109535421 A CN 109535421A
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- carbon nitrogen
- base carbon
- piperazine base
- nitrogen polymer
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- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 title claims abstract description 104
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229920000642 polymer Polymers 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000001699 photocatalysis Effects 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000007146 photocatalysis Methods 0.000 claims abstract description 12
- 241000894006 Bacteria Species 0.000 claims abstract description 11
- 230000002269 spontaneous effect Effects 0.000 claims abstract description 7
- 230000012010 growth Effects 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229920000877 Melamine resin Polymers 0.000 claims description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 230000006798 recombination Effects 0.000 abstract description 5
- 238000005215 recombination Methods 0.000 abstract description 5
- 239000004020 conductor Substances 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 104
- 230000000052 comparative effect Effects 0.000 description 75
- 238000006116 polymerization reaction Methods 0.000 description 21
- 238000004458 analytical method Methods 0.000 description 18
- 238000002329 infrared spectrum Methods 0.000 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 230000007547 defect Effects 0.000 description 6
- 238000013508 migration Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 238000004627 transmission electron microscopy Methods 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 125000004193 piperazinyl group Chemical group 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- -1 heptan Carbon nitrogen Chemical compound 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000000279 solid-state nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000003643 water by type 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
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The present invention relates to conductor photocatalysis material fields, and in particular to a kind of piperazine base carbon nitrogen polymer and preparation method thereof and the purposes as photochemical catalyst.The piperazine base carbon nitrogen polymer is the seven piperazines-triazine radical carbon nitrogen polymer of club shaped structure out by the seven piperazine spontaneous oriented growths of base carbon nitrogen polymer of lamellar structure.Piperazine base carbon nitrogen polymer Carrier recombination rate in the present invention is low, and rodlike structure can effectively capture luminous energy and bacterium, has excellent photocatalytic activity and stability, can be recycled, and has good actual application prospect.
Description
Technical field
The present invention relates to conductor photocatalysis material fields, and in particular to a kind of piperazine base carbon nitrogen polymer and preparation method thereof
With the purposes as photochemical catalyst.
Background technique
Using semiconductor light-catalyst processing environment contaminant problems increasingly by the favor of scientist.Photocatalysis is killed
Bacterium can be effective relative to now widely used ultraviolet light, ozone, disinfectant sterilization etc. as a kind of emerging sterilization technology
Prevent the introducing of ultraviolet light and toxic gas from causing to damage to human body and the formation of harmful by-products and to environment and human body
Harm.Meanwhile photo-catalyst using sunlight provide energy, have efficiently, wide spectrum, be not likely to produce drug resistance and secondary dirt
The advantages such as dye.But research at present and widely used P25 TiO2Because forbidden bandwidth it is wider can only by ultraviolet excitation,
But ultraviolet light only accounts for the part (less than 5%) of sunlight very little, while the recombination rate of higher photo-generated carrier is but also its amount
Sub- efficiency is very low.So sunlight and the higher visible light catalyst of carrier mobility can be made full use of by how obtaining
Have become an important field of research.
Current graphited C3N4(g-C3N4) be used as a kind of non-metal optical catalyst because preparation method is simple, raw material is honest and clean
Valence is easy to get, visible light absorbing and it is without secondary pollution and become research hotspot.But the g-C of this high polymerization degree3N4Surface it is living
Property site is less and Carrier recombination rate is high, quantum efficiency is lower.Meanwhile current most g-C3N4For lamellar structure, it is difficult to effectively
It absorbs sunlight and captures bacterium.The carbon nitrogen polymer of low polymerization degree can have due to the more active sites of surface exposure
Effect promotes photocatalytic activity.But, still more plain to the understanding of the growth control of oligomeric carbon nitrogen polymer at present, especially
The oligomeric carbon nitrogen polymer of the piperazine base of spontaneous stereospecfic polymerization therein is there is not yet related report.
Summary of the invention
It is rodlike out by the seven spontaneous oriented growth of piperazine base carbon nitrogen polymer of lamellar structure that the purpose of the present invention is to provide one kind
Seven piperazines-the triazine radical of structure is copolymerized carbon nitrogen polymer.
The present invention also provides a kind of preparation method of the piperazine base carbon nitrogen polymer of spontaneous stereospecfic polymerization simultaneously, and this method can be with
Obtain the piperazine base carbon nitrogen polymer that photo-catalyst activity significantly improves.
To realize that aforementioned invention purpose, a kind of technical solution that the present invention uses are as follows:
A kind of piperazine base carbon nitrogen polymer, the piperazine base carbon nitrogen polymer be by lamellar structure seven piperazine base carbon nitrogen polymers from
Send out oriented growth and the seven piperazines-triazine radical carbon nitrogen polymer of club shaped structure out.
Piperazine base carbon nitrogen polymer Carrier recombination rate in the present invention is low, and club shaped structure can effectively capture luminous energy and thin
Bacterium has excellent photocatalytic activity and stability, can be recycled, and has good actual application prospect.
Preferably, seven piperazine base carbon nitrogen polymers of the lamellar structure are with a thickness of 5-15 microns, carbon-nitrogen ratio 0.67；It is described
Seven piperazines-triazine radical carbon the nitrogen polymer of club shaped structure, the length is 10-20 microns, diameter is 50-75 nanometers.
Further, seven piperazine base carbon nitrogen polymer thickness of the lamellar structure are preferably 10 microns.
Further, the seven piperazines-triazine radical carbon nitrogen polymer of the club shaped structure, length is preferably 12~16 microns,
Diameter is preferably 55 nanometers.
Preferably, the preparation method of the piperazine base carbon nitrogen polymer, comprising:
Step 1: melamine sufficiently being dissolved with water, obtains suspension；
Step 2: roasting the suspension to obtain solid particle；
Step 3: grinding obtains catalyst after the solid particle is cooled to room temperature.
Preparation method very simple of the invention is convenient, raw materials used simple and easy to get, cheap, it is possible to prevente effectively from dirty
The by-product of metachromia generates, without secondary pollution in sterilization process, is also not required to additional energy supply.Using melamine as presoma, pass through
High-temperature roasting method is simple and quick to be prepared for piperazine base carbon nitrogen polymer.The above-mentioned water used of the present invention is preferably deionized water.
Preferably, the mass ratio that feeds intake of melamine and water is 3:2~8 in the step 1；The dissolution of melamine and water
Temperature is 15~75 DEG C；The dissolution time of melamine and water is preferably 10~50 minutes.
Further, in the step 1, the mass ratio that feeds intake of melamine and water is preferably 3:4,3:5,1:2, optimal
Choosing is 1:2, and in this proportional region, the content of prepared piperazine base carbon nitrogen polymer free from admixture or impurity is few.
Further, in the step 1, the solution temperature of melamine and water is preferably 15~30 DEG C, most preferably 25
℃.Control can obtain the piperazine base carbon nitrogen polymer of spontaneous stereospecfic polymerization in preferred range.
Further, in the step 1, the dissolution time of melamine and water is preferably 30 minutes.
Further, in the step 2, the suspension maturing temperature is 400~500 DEG C, and preferably maturing temperature is
450℃。
Further, in the step 2, the calcining time of the suspension is 2~6 hours, preferably 4 hours.
Further, in the step 2, the suspension roasting heating rate is 3~8 DEG C/min, preferably heating speed
Rate is 5 DEG C/min.
The present invention is prepared for the polymerization of piperazine base carbon nitrogen using melamine as presoma, by the way that high-temperature roasting method is simple and quick
Object.The carbon nitrogen polymer being prepared is compared to traditional C3N4, surface can expose more functional groups, chain section termination
There are apparent defects, increase the active site of catalyst, and in addition sheet can be effective with the rodlike nanostructure coexisted
Improve the separation of photo-generated carrier.In addition, the club shaped structure of carbon nitrogen oligomer can effectively capture luminous energy and bacterium in the present invention, both
The efficiency of light energy utilization can be improved, promote the conduction velocity of light induced electron, and can effectively contact with bacterium, enhancing photocatalysis is living
Property.
Preferably, the piperazine base carbon nitrogen polymer has photocatalytic activity in visible light wave range, can be used as photochemical catalyst, uses
In photo-catalyst.
According to piperazine base carbon nitrogen polymer prepared by the method for the present invention, carbon-nitrogen ratio is low, is the piperazine base carbon of spontaneous stereospecfic polymerization
Nitrogen polymer has excellent photocatalytic activity in visible light wave range.
The photo-catalyst process uses visible light, and the bacterium is Escherichia coli.
Beneficial effect
Due to the implementation of above technical scheme, the present invention has the advantage that compared with prior art
1. preparation method very simple of the invention is convenient, raw materials used simple and easy to get, cheap, it is possible to prevente effectively from
The by-product of pollution generates, without secondary pollution in sterilization process, is also not required to additional energy supply.Prepared piperazine base carbon nitrogen polymer
Photochemical catalyst Carrier recombination rate is low, and club shaped structure can effectively capture luminous energy, has excellent photocatalytic activity and stability,
It can be recycled, there is good actual application prospect.
2. the present invention is prepared for the polymerization of piperazine base carbon nitrogen using melamine as presoma, by the way that high-temperature roasting method is simple and quick
Object.The carbon nitrogen polymer being prepared is compared to traditional C3N4, surface can expose more functional groups, chain section termination
There are apparent defects, increase the active site of catalyst, and in addition sheet can be effective with the rodlike nanostructure coexisted
Improve the separation of photo-generated carrier.In addition, the club shaped structure of carbon nitrogen oligomer can effectively capture luminous energy and bacterium in the present invention, both
The efficiency of light energy utilization can be improved, promote the conduction velocity of light induced electron, and can effectively contact with bacterium, enhancing photocatalysis is living
Property.
Detailed description of the invention
Invention is further described in detail with reference to the accompanying drawings and detailed description:
Fig. 1 a is X-ray diffraction (XRD) map of sample prepared by embodiment 1 and comparative example 1~2；
Fig. 1 b is X-ray diffraction (XRD) map of sample prepared by Examples 1 to 3；
Fig. 2 a is scanning electron microscope (SEM) photo of sample prepared by embodiment 1；
Fig. 2 b is the partial enlargement photo of Fig. 2 a；
Fig. 2 c is the partial enlargement photo of Fig. 2 b；
Fig. 2 d is scanning electron microscope (SEM) photo of sample prepared by comparative example 1；
Fig. 2 e is scanning electron microscope (SEM) photo of sample prepared by comparative example 2；
Fig. 2 f is scanning electron microscope (SEM) photo of sample prepared by embodiment 2；
Fig. 2 g is scanning electron microscope (SEM) photo of sample prepared by embodiment 3；
Fig. 3 a is high resolution transmission electron microscopy (TEM) photo of sample prepared by embodiment 1；
Fig. 3 b is the partial enlargement photo of Fig. 3 a；
Fig. 4 a is 13C solid-state nuclear magnetic resonance (13CNMR) carbon of embodiment 1, sample prepared by comparative example 1 and comparative example 2
Spectrogram；
Fig. 4 b is the fluorescence spectrum of sample prepared by embodiment 1 and comparative example 1；
Fig. 5 a is the infrared spectrum analysis of embodiment 1, sample prepared by comparative example 1 and comparative example 2；
Fig. 5 b is the infrared spectrum analysis of sample prepared by Examples 1 to 3；
Fig. 5 c is the infrared spectrum analysis of sample prepared by embodiment 6~8；
Fig. 6 a is the uv-visible absorption spectra of sample prepared by embodiment 1 and comparative example 1；
Fig. 6 b is the uv-visible absorption spectra of sample prepared by Examples 1 to 3；
Fig. 7 is the photocatalytic activity comparison of embodiment 1 and comparative example 1,2；
Fig. 8 is that the photocatalytic activity of Examples 1 to 3 compares；
Fig. 9 is that the photocatalytic activity of embodiment 1,4,5 compares；
Figure 10 is that the photocatalytic activity of embodiment 1,6~8 compares.
Specific embodiment
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The some embodiments recorded in invention, for those of ordinary skill in the art, without creative efforts,
It is also possible to obtain other drawings based on these drawings.
It is combined with specific embodiments below making further detailed, clear and complete description of how realizing, institute to the present invention
Column embodiment is only further described the present invention, not thereby limiting the invention:
Piperazine base carbon nitrogen polymer photochemical catalyst prepared by the present invention is by the following means to progress structural characterization: using
The composition of Vario EL cube type elemental analyser analysis sample；Using Rigaku D/Max-RB type X-ray diffractometer (XRD)
Carry out structural analysis；Using JEOL JSM-6380LV type scanning electron microscope (SEM) and use 2011 type high-resolution of JEOL TEM saturating
Penetrate the appearance structure of electron microscope (TEM) analysis sample；Using 600 type solid-state nuclear magnetic resonance spectrum of AvanceIII HD
(NMR) structure of sample is analyzed；Using 500 type spectrometer of Varian Cary-Eclipse to the solid catalyst sample of preparation
Carry out fluorescence spectrum test；Examination of infrared spectrum is carried out using PerkinElmer-Frontier；Using model UV-2450 type
Spectrophotometer carries out UV-vis DRS test.
Piperazine base carbon nitrogen polymer described in the embodiment of the present invention kills the experimentation of Escherichia coli such as under visible light
Under: in 25 DEG C of waters bath with thermostatic control, 15mg photochemical catalyst is added in the Escherichia coli liquid that 15mL bacterial concentration is 0.1 (OD) and is mixed
Uniformly.Then it is irradiated by light source of 300W xenon lamp, and filters out light of the wavelength less than 420 nanometers and carry out light-catalyzed reaction, the time is
90 minutes.It takes 100uL solution to be uniformly applied in agar plates within every 30 minutes, is placed in 37 DEG C of incubators after cultivating 24 hours
Observation bacterium colony growing state simultaneously counts.In addition, will configure identical solution is put into progress antibacterial experiment, this solution conduct at dark
Control sample.Bacterial inactivation rate is higher, and i.e. to represent photocatalytic activity stronger, therefore photocatalytic activity is obtained by bacterial inactivation rate.
Embodiment 1
The present embodiment provides a kind of piperazine base carbon nitrogen polymers, are prepared by following steps:
15.0g melamine is weighed in crucible, 30mL distilled water is measured and is added in crucible, crucible is placed in 25 DEG C
Stirring 30 minutes, makes it after completely dissolution, roasts 4 hours in 450 DEG C and naturally cools to room after (heating rate is 5 DEG C/min)
Temperature, grinding collect and obtain white solid, which is piperazine base carbon nitrogen polymer.
Preparing obtained piperazine base carbon nitrogen polymer by embodiment 1 is the material that club shaped structure is grown in lamellar structure, stick
Shape length is about 20 microns, and diameter is 55 nanometers, carbon-nitrogen ratio 0.67, and has photocatalytic activity.
Elemental analysis result referring to table 1, wherein as it can be seen that sample carbon-nitrogen ratio prepared by embodiment 1 be 0.67, carbon-nitrogen ratio
Lower than theoretical C3N40.75, illustrate that the degree of polymerization of piperazine base carbon nitrogen polymer prepared by embodiment 1 is relatively low, but nitrogen content is high
In theoretical C3N4, illustrate the presence for having more nitrogen defect, it is living to improve photocatalysis to be conducive to improve the migration of photo-generated carrier
Property.
Fig. 1 a is X-ray diffraction (XRD) map of embodiment 1, sample prepared by comparative example 1 and comparative example 2, is such as schemed
It shown in 1a, shows that the diffraction maximum of sample prepared by embodiment 1 is similar to the diffraction maximum of melem, illustrates that the sample is that carbon nitrogen is low
Polymers can expose more active sites to improve photocatalytic activity.
Fig. 2 a is scanning electron microscope (SEM) photo of sample prepared by embodiment 1, and the partial enlargement that Fig. 2 b is Fig. 2 a shines
Piece, Fig. 2 c are the partial enlargement photo of Fig. 2 b, such as Fig. 2 a, shown in Fig. 2 b, Fig. 2 c, show that sample prepared by embodiment 1 is piece
The material of club shaped structure is grown in layer structure, rodlike length is about 20 microns.
Fig. 3 a is high resolution transmission electron microscopy (TEM) photo of sample prepared by embodiment 1, and Fig. 3 b is Fig. 3 a's
Partial enlargement photo shows that the rodlike diameter of sample prepared by embodiment 1 is 55 nanometers as shown in Figure 3a and Figure 3b shows.
Fig. 4 a is sample prepared by embodiment 1 and comparative example 1~213C solid-state nuclear magnetic resonance (13C NMR) carbon spectrogram,
As shown in fig. 4 a, from top to bottom, embodiment 1, comparative example 1, comparative example 2 are followed successively by13C solid-state nuclear magnetic resonance (13CNMR) carbon is composed
Figure.Fig. 4 a shows that sample prepared by embodiment 1 is carbon nitrogen polymer based on triazine structure, and the migration of chemical shift
Illustrate to be mixed with oxygen in structure.
Fig. 4 b is that the fluorescence spectrum of sample prepared by embodiment 1 and comparative example 1 illustrates 1 institute of embodiment as shown in Figure 4 b
The separative efficiency of the carrier of the sample of preparation is higher, and photocatalytic activity can be improved.
Fig. 5 a is the infrared spectrum analysis of embodiment 1, sample prepared by comparative example 1 and comparative example 2, as shown in Figure 5 a,
Show that sample prepared by embodiment 1 is the carbon nitrogen polymer for mixing oxygen, containing hydroxyl, C=O bond and singly-bound.
Fig. 6 a is that the uv-visible absorption spectra of sample prepared by embodiment 1 and comparative example 1 shows as shown in Figure 6 a
Sample prepared by embodiment 1 is the club shaped structure gone out by sheet stereospecfic polymerization, is relatively had to the comparative example 1 of single lamellar structure
Stronger light absorption, improves the efficiency of light energy utilization, has facilitation to photocatalytic activity is promoted.
Fig. 7 is the photocatalytic activity comparison of embodiment 1 and comparative example 1,2；Fig. 8 is the photocatalytic activity of Examples 1 to 3
Comparison；Fig. 9 is that the photocatalytic activity of embodiment 1,4,5 compares；Figure 10 is that the photocatalytic activity of embodiment 1,6~8 compares.
As shown in Fig. 7-10, show that the present embodiment 1 has more preferably photocatalytic activity compared with other embodiments.
Comparative example 1
This example provides a kind of piperazine base carbon nitrogen polymer, is prepared by following steps:
15.0g melamine is weighed in crucible, is roasted 4 hours in 450 DEG C, (heating rate is 5 DEG C/min) and then certainly
It is so cooled to room temperature, white solid is collected in grinding, which is piperazine base carbon nitrogen polymer.
Preparing obtained piperazine base carbon nitrogen polymer carbon-nitrogen ratio by comparative example 1 is 0.66, is lamellar structure, and have
Certain photocatalytic activity.
Elemental analysis result is referring to table 1, wherein carbon-nitrogen ratio is low as it can be seen that sample carbon-nitrogen ratio prepared by comparative example 1 is 0.66
In theoretical C3N4, illustrate that the degree of polymerization of sample prepared by comparative example 1 is relatively low, and nitrogen content is higher than existing C3N4, explanation has
The presence of more nitrogen defect, the migration for being conducive to improve photo-generated carrier is to improve photocatalytic activity.
Fig. 1 aX x ray diffraction (XRD) map shows the diffraction maximum of sample and the diffraction maximum of melem prepared by comparative example 1
It is similar, illustrate that sample prepared by comparative example 1 is carbon nitrogen oligomer, more active sites can be exposed to improve photocatalysis
Activity.
Fig. 2 d is that scanning electron microscope (SEM) photo of sample prepared by comparative example 1 shows 1 institute of comparative example as shown in Figure 2 d
The sample of preparation is mainly lamellar structure.
Fig. 4 a13C solid-state nuclear magnetic resonance (13CNMR) carbon spectrogram shows that sample prepared by comparative example 1 is to be with triazine structure
The carbon nitrogen polymer on basis, and the migration of chemical shift illustrates to be mixed with oxygen in structure.
Fig. 4 b is fluorescence spectrum, illustrates that the separative efficiency of the carrier of sample prepared by comparative example 1 is lower, and photocatalysis is living
Property is weaker.
Fig. 5 a is infrared spectrum analysis, shows that sample prepared by comparative example 1 is the carbon nitrogen polymer for mixing oxygen, main oxygen
Functional group is hydroxyl.
Fig. 6 a is that the uv-visible absorption spectra of sample prepared by embodiment 1 and comparative example 1 shows as shown in Figure 6 a
The light absorption of piperazine base carbon nitrogen polymer is than going out club shaped structure by sheet stereospecfic polymerization prepared by the comparative example 1 of lamellar structure
Sample prepared by embodiment 1 is weak, and activity is lower.
Fig. 7 shows that sample prepared by this comparative example 1 has certain photocatalytic activity.
Fig. 4 b is the fluorescence spectrum of sample prepared by embodiment 1 and comparative example 1, as shown in Figure 4 b, prepared by embodiment 1
Sample carrier separative efficiency it is higher than comparative example 1.
Fig. 6 a is that the uv-visible absorption spectra of sample prepared by embodiment 1 and comparative example 1 shows as shown in Figure 6 a
Sample prepared by embodiment 1 has stronger light absorption compared with sample prepared by comparative example 1.
Comparative example 2
This example provides a kind of nitridation carbon polymer, is prepared by following steps:
15.0g melamine is weighed in crucible, 4 hours are roasted in 550 DEG C, and (heating rate is 5 DEG C/min), then certainly
It is so cooled to room temperature, white solid is collected in grinding, then obtains carbonitride.
Preparing obtained nitridation carbon polymer carbon-nitrogen ratio by comparative example 1 is 0.72, is lamellar structure, and photocatalysis
Activity is low.
For elemental analysis result referring to table 1, sample carbon-nitrogen ratio prepared by comparative example 2 is 0.72, is shown prepared by comparative example 2
Sample be high polymerization structure.
Fig. 1 aX x ray diffraction (XRD) map shows that sample prepared by this comparative example 2 is the C of high polymerization3N4。
Fig. 2 e is that sample prepared by comparative example 2 is scanning electron microscope (SEM) photo, shows sample prepared by this comparative example 2
For lamellar structure.
Fig. 4 a13C solid-state nuclear magnetic resonance (13CNMR) carbon spectrogram shows that sample prepared by comparative example 2 is to be with piperazine structure in heptan
The carbon nitrogen polymer of the high polymerization on basis.
Fig. 5 a infrared spectrum analysis spectrogram shows that sample prepared by comparative example 2 is the nitridation carbon polymer of high polymerization, nothing
Apparent oxide structure.
Fig. 7 shows the photocatalytic activity of sample prepared by this comparative example 2 significantly lower than embodiment 1.
Table 1
Table 1 is the elemental analysis result of piperazine base carbon nitrogen polymer prepared by embodiment 1 and comparative example 1~2.
As shown in Table 1, product carbon-nitrogen ratio prepared by comparative example 2 is 0.72, shows product prepared by comparative example 2 for height
The structure of polymerization.Product carbon-nitrogen ratio prepared by embodiment 1 and comparative example 1 is respectively 0.67,0.66, and carbon-nitrogen ratio is lower than comparative example
Product prepared by 2 illustrates that embodiment 1 and the degree of polymerization of product prepared by comparative example 1 are relatively low, but nitrogen content is higher than comparative example
Product prepared by 2 illustrates that product prepared by embodiment 1 and comparative example 1 has the presence of more nitrogen defect, is conducive to improve light
The migration of raw carrier is to improve photocatalytic activity.
Fig. 1 a is X-ray diffraction (XRD) map of sample prepared by embodiment 1 and comparative example 1~2, such as Fig. 1 a institute
Show, from top to bottom, be followed successively by embodiment 1, comparative example 1, sample prepared by comparative example 2 X-ray diffraction (XRD) map.Figure
1a shows that embodiment 1 is similar to the diffraction maximum of melem to the diffraction maximum of sample prepared by comparative example 1, illustrate embodiment 1 with
Sample prepared by comparative example 1 is carbon nitrogen oligomer, and sample prepared by comparative example 2 is the structure of high polymerization.
Fig. 4 a is sample prepared by embodiment 1 and comparative example 1~213C solid-state nuclear magnetic resonance (13C NMR) carbon spectrogram,
As shown in fig. 4 a, from top to bottom, embodiment 1, comparative example 1, comparative example 2 are followed successively by13C solid-state nuclear magnetic resonance (13CNMR) carbon is composed
Figure.Fig. 4 a shows that sample prepared by embodiment 1 and comparative example 1 is the carbon nitrogen polymer based on triazine structure, and chemical
The migration of displacement illustrates to be mixed with oxygen in structure, and sample prepared by comparative example 2 is the high polymerization based on piperazine structure in heptan
Carbon nitrogen polymer.
Fig. 5 a is the infrared spectrum analysis spectrogram of embodiment 1, sample prepared by comparative example 1 and comparative example 2, such as Fig. 5 a institute
Show, from top to bottom, is followed successively by the infrared spectrum analysis spectrogram of embodiment 1, comparative example 1 and comparative example 2.Fig. 5 a shows embodiment 1
It is the carbon nitrogen polymer for mixing oxygen with sample prepared by comparative example 1, sample prepared by comparative example 2 is the nitridation carbon poly of high polymerization
Object is closed, without apparent oxide structure.
Fig. 7 is the photocatalytic activity comparison of embodiment 1 and comparative example 1,2, as shown in fig. 7, embodiment 1 has strongest light
Catalytic activity.
Embodiment 2
Calcining time is changed to 2 hours, remaining preparation process is the same as embodiment 1.
Fig. 1 b is X-ray diffraction (XRD) map of sample prepared by Examples 1 to 3, and as shown in Figure 1 b, display is implemented
The diffraction maximum of sample prepared by example 2 and the diffraction maximum of melem are similar, illustrate that the sample is oligomeric carbon nitrogen photochemical catalyst.
Fig. 2 f is that scanning electron microscope (SEM) photo of sample prepared by embodiment 2 shows 2 institute of embodiment as shown in figure 2f
The sample of preparation is the material that club shaped structure is grown in lamellar structure, but rodlike length is shorter, is about 5 microns.
Carbon-oxygen bond is also mixed in sample prepared by the bright embodiment 2 in infrared spectrum analysis spectrogram surface in Fig. 5 b.
Fig. 6 b is that the uv-visible absorption spectra of sample prepared by Examples 1 to 3 shows embodiment as shown in Figure 6 b
The photon absorbing intensity of sample prepared by 2 is lower.
Fig. 8 shows that sample prepared by the present embodiment 2 has certain photocatalytic activity.
Embodiment 3
Calcining time is changed to 6 hours, remaining preparation process is the same as embodiment 1.
Fig. 1 bX x ray diffraction (XRD) map shows that sample prepared by the present embodiment 3 is oligomeric carbon-nitrogen material.
Fig. 2 g is that scanning electron microscope (SEM) photo of sample prepared by embodiment 3 shows 3 institute of embodiment as shown in Figure 2 g
The sample of preparation is club shaped structure.
Fig. 5 b infrared spectrum analysis figure illustrates to be mixed with carbon-oxygen bond in sample prepared by embodiment 3, increases oxygen defect,
Catalytic activity can be improved.
Fig. 6 b uv-visible absorption spectra shows that the photon absorbing intensity of sample prepared by embodiment 3 is stronger.
Fig. 8 shows that sample prepared by the present embodiment 3 has certain photocatalytic activity.
Fig. 1 b be Examples 1 to 3 prepared by sample X-ray diffraction (XRD) map, as shown in Figure 1 b, on to
Under, be followed successively by embodiment 1, embodiment 2, sample prepared by embodiment 3 X-ray diffraction (XRD) map, show embodiment 1
The diffraction maximum of sample prepared by~3 and the diffraction maximum of melem are similar, and illustrate sample prepared by Examples 1 to 3 is
Carbon nitrogen oligomer.
Fig. 5 b is the infrared spectrum analysis spectrogram of sample prepared by Examples 1 to 3, as shown in Figure 5 b, from top to bottom, according to
The secondary infrared spectrum analysis spectrogram for sample prepared by embodiment 1, embodiment 2, embodiment 3, shows that Examples 1 to 3 is made
Carbon-oxygen bond is mixed in standby sample structure.
Fig. 6 b is the uv-visible absorption spectra of sample prepared by Examples 1 to 3, shows the light absorption of embodiment 2
Intensity is lower, so corresponding photocatalytic activity is weaker.
Fig. 8 is that the photocatalytic activity of Examples 1 to 3 compares, and shows that embodiment 1 compared with embodiment 2~3 there is best light to urge
Change activity.
Embodiment 4
Maturing temperature is changed to 400 DEG C, for remaining preparation process with embodiment 1, Fig. 9 shows sample prepared by the present embodiment 4
Product have certain photocatalytic activity.
Embodiment 5
Maturing temperature is changed to 500 DEG C, for remaining preparation process with embodiment 1, Fig. 9 shows sample prepared by the present embodiment 5
Product have certain photocatalytic activity.
Fig. 9 is that the photocatalytic activity of embodiment 1,4,5 compares, and shows that embodiment 1 compared with embodiment 4~5 there is best light to urge
Change activity.
Embodiment 6
Amount of water is changed to 10mL, for remaining preparation process with embodiment 1, Fig. 5 c is sample prepared by embodiment 6~8
Infrared spectrum analysis show that there are carbon-oxygen bonds in the structure of sample prepared by embodiment 6 as shown in Figure 5 c；Figure 10 shows
Sample prepared by the present embodiment 6 has certain photocatalytic activity.
Embodiment 7
Amount of water is changed to 20mL, remaining preparation process is the same as embodiment 1, the bright embodiment 7 of Fig. 5 c infrared spectrum analysis chart
There are carbon-oxygen bonds in the structure of prepared sample；Figure 10 shows that sample prepared by the present embodiment 7 has certain photocatalysis
Activity.
Embodiment 8
Amount of water is changed to 40mL, remaining preparation process is the same as embodiment 1, the bright embodiment 8 of Fig. 5 c infrared spectrum analysis chart
There are carbon-oxygen bonds in the structure of prepared sample；Figure 10 shows that the present embodiment 8 and embodiment 1 are living with similar photocatalysis
Property.
Fig. 5 c is the infrared spectrum analysis figure of sample prepared by embodiment 6~8, is shown prepared by embodiment 6~8
There is carbon-oxygen bond in sample structure.
Figure 10 is that the photocatalytic activity of embodiment 1,6~8 compares, and shows that embodiment 1 has best light compared with embodiment 6~8
Catalytic activity.
It should be noted that above-described embodiment can be freely combined as needed.The above is only of the invention preferred
Embodiment, it is noted that for those skilled in the art, in the premise for not departing from the principle of the invention
Under, several improvements and modifications can also be made, these modifications and embellishments should also be considered as the scope of protection of the present invention.
Claims (9)
1. a kind of piperazine base carbon nitrogen polymer, it is characterised in that:
Seven piperazines-triazine radical carbon the nitrogen of the club shaped structure gone out by the seven piperazine spontaneous oriented growths of base carbon nitrogen polymer of lamellar structure gathers
Close object.
2. a kind of piperazine base carbon nitrogen polymer according to claim 1, it is characterised in that:
Seven piperazine base carbon nitrogen polymers of the lamellar structure are with a thickness of 5-15 microns, carbon-nitrogen ratio 0.67；
Seven piperazines-triazine radical carbon the nitrogen polymer of the club shaped structure, the length is 10-20 microns, diameter is 50-75 nanometers.
3. a kind of piperazine base carbon nitrogen polymer according to claim 1 or 2, it is characterised in that:
Seven piperazine base carbon nitrogen polymers of the lamellar structure are with a thickness of 10 microns；
Seven piperazines-triazine radical carbon the nitrogen polymer of the club shaped structure, the length is 12~16 microns, diameter is 55 nanometers.
4. a kind of preparation method of piperazine base carbon nitrogen polymer according to any one of claims 1 to 3, feature exist
In, comprising:
Step 1: melamine sufficiently being dissolved with water, obtains suspension；
Step 2: roasting the suspension to obtain solid particle；
Step 3: grinding obtains piperazine base carbon nitrogen polymer after the solid particle is cooled to room temperature.
5. the preparation method of piperazine base carbon nitrogen polymer according to claim 4, it is characterised in that:
In the step 1, the mass ratio that feeds intake of melamine and water is 3:2~8；The solution temperature of melamine and water be 15~
75℃；The dissolution time of melamine and water is 10~50 minutes.
6. the preparation method of piperazine base carbon nitrogen polymer according to claim 4 or 5, it is characterised in that:
In the step 1, the mass ratio that feeds intake of melamine and water is 1:2；The solution temperature of melamine and water is 25 DEG C；Three
The dissolution time of poly cyanamid and water is 30 minutes.
7. the preparation method of piperazine base carbon nitrogen polymer according to claim 4, it is characterised in that:
In the step 2, the suspension maturing temperature is 400~500 DEG C；The suspension calcining time is 2~6 hours；
The suspension roasting heating rate is 3~8 DEG C/min.
8. the preparation method of piperazine base carbon nitrogen polymer according to claim 4 or 7, it is characterised in that:
In the step 2, the suspension maturing temperature is 450 DEG C；The suspension calcining time is 4 hours；It is described suspended
It is 5 DEG C/min that liquid, which roasts heating rate,.
9. a kind of purposes of piperazine base carbon nitrogen polymer according to claim 1, it is characterised in that:
The piperazine base carbon nitrogen polymer has photocatalytic activity in visible light wave range, can be used as photochemical catalyst, kills for photocatalysis
Bacterium.
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| CN110368893A (en) * | 2019-08-22 | 2019-10-25 | 扬州大学 | Graphite phase carbon nitride composite material and preparation method and purposes |
| CN113644228A (en) * | 2021-08-12 | 2021-11-12 | 暨南大学 | Potassium ion battery carbon-nitrogen-based polymer negative electrode material and preparation method and application thereof |
| CN114956016A (en) * | 2022-05-24 | 2022-08-30 | 南京林业大学 | Preparation method of triazine-heptazine-based carbon nitride and triazine-heptazine-based carbon nitride |
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| CN108786886A (en) * | 2018-06-20 | 2018-11-13 | 上海师范大学 | Rodlike oligomeric carbonitride of one kind and the preparation method and application thereof |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Non-Patent Citations (2)
| Title |
|---|
| JUNWEI FU ET AL: "Hierarchical Porous O-Doped g-C3N4 with Enhanced Photocatalytic CO2 Reduction Activity", 《SMALL》 * |
| S.C.YAN ET AL: "Photodegradation performance of g-C3N4 fabricated by directly heating", 《LANGMUIR》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110368893A (en) * | 2019-08-22 | 2019-10-25 | 扬州大学 | Graphite phase carbon nitride composite material and preparation method and purposes |
| CN110368893B (en) * | 2019-08-22 | 2022-11-08 | 扬州大学 | Graphite phase carbon nitride composite material and preparation method and application thereof |
| CN113644228A (en) * | 2021-08-12 | 2021-11-12 | 暨南大学 | Potassium ion battery carbon-nitrogen-based polymer negative electrode material and preparation method and application thereof |
| CN114956016A (en) * | 2022-05-24 | 2022-08-30 | 南京林业大学 | Preparation method of triazine-heptazine-based carbon nitride and triazine-heptazine-based carbon nitride |
| CN114956016B (en) * | 2022-05-24 | 2023-10-24 | 南京林业大学 | Preparation method of triazine-heptazinyl carbon nitride and triazine-heptazinyl carbon nitride |
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