CN105597820B - The carbonitride of one species graphite-phase/tetracarboxylic phenyl porphyrin nano composite and preparation method thereof - Google Patents
The carbonitride of one species graphite-phase/tetracarboxylic phenyl porphyrin nano composite and preparation method thereof Download PDFInfo
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- CN105597820B CN105597820B CN201510983690.1A CN201510983690A CN105597820B CN 105597820 B CN105597820 B CN 105597820B CN 201510983690 A CN201510983690 A CN 201510983690A CN 105597820 B CN105597820 B CN 105597820B
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- 125000006158 tetracarboxylic acid group Chemical group 0.000 title claims abstract description 39
- QCWPXJXDPFRUGF-UHFFFAOYSA-N N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 Chemical compound N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 QCWPXJXDPFRUGF-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000012071 phase Substances 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000000498 ball milling Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 5
- 239000007790 solid phase Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 239000000428 dust Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 7
- 229940043267 rhodamine b Drugs 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000975 dye Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract 1
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 10
- 239000011049 pearl Substances 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical group [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The present invention provides the preparation method of carbonitride/tetracarboxylic phenyl porphyrin nano composite of a species graphite-phase, is obtained using solid-phase ball milling method.The present invention also provides carbonitride/application of the tetracarboxylic phenyl porphyrin nano composite in photocatalysis of above-mentioned class graphite-phase.The preparation method of the present invention is simple, and cost is low, easy to operate, while can significantly save the reaction time.The nano composite material of the present invention has the sensitivity and stability that preferable PhotoelectrochemicalProperties Properties, stronger photocatalysis performance are become reconciled, and plays the role of in terms of organic pollutant degradation and photocatalytic degradation of dye important.
Description
Technical field
The invention belongs to Electroanalytical Chemistry technical field, and in particular to the carbonitride of a species graphite-phase/tetracarboxylic phenyl
Porphyrin nano composite and preparation method thereof.
Background technology
With society and economic fast development, energy crisis and environmental degradation have turned into global urgent problem to be solved.
How to develop efficient, environmentally friendly, the inexpensive energy has become too impatient to wait.Solar energy is as a kind of preferable, efficient, reproducible
The energy is of interest by more researchers, so scientist works as the preparation of substantial amounts of Job engagement to photosensitive materials and utilization
In.And most of photosensitive materials are inorganic semiconductors, so Recent study person also partly leads in the new polymerization species of searching
Body.Polymer semiconductor class graphite phase carbon nitride (g-C3N4), because its unique semiconductor energy band structure and excellent chemistry are steady
It is qualitative, photocatalysis field is introduced in as a kind of visible-light photocatalyst of not metallic components, for photodissociation aquatic products hydrogen, production
Oxygen, the organic selectivity synthesis photocatalysis degradation organic contaminant of photocatalysis etc., causes the extensive concern of people, is primarily due to g-
C3N4It is not only cheap stable, meet basic demand of the people to photochemical catalyst, and be also equipped with the chemical group of polymer semiconductor
The features such as into band structure easy-regulating, it is considered to be photocatalysis research field, particularly catalysis material research field, be worth
A kind of excellent semi-conducting material of further investigation.But due to the material property of polymer, by g-C3N4As photochemical catalyst
It there is also some problems, as specific surface area is small, the exciton binding energy of generation photo-generated carrier is high, photo-generate electron-hole is compound tight
Weight quantum efficiency is low larger with energy gap and can not seriously constrain it in energy environment photocatalysis effectively using sunshine etc.
The large-scale promotion application in field.So in order to further improve the separation of the carrier of semiconductor, method one common at present
Be carried noble metal and metalloid such as：Silver, golden nanometer particle；Furthermore be exactly and other semiconductors carry out being compounded to form semiconductor it is different
Matter knot, main purpose are that electronics can be shifted quickly to show high catalytic performance after promoting electronics and hole separation.
The content of the invention
The invention discloses the carbonitride of a species graphite-phase/tetracarboxylic phenyl porphyrin nano composite and its preparation side
Method, and organic dyestuff is degraded with the material.
First purpose of the present invention is to provide carbonitride/tetracarboxylic phenyl porphyrin nano composite wood of a species graphite-phase
The preparation method of material, obtained using solid-phase ball milling method.
Preferably, it is that tetracarboxylic phenyl porphyrin, the nitridation carbon dust of class graphite-phase and ball milling pearl are put into ball milling together
In tank, stir what 30 ~ 50min was obtained under 300 ~ 400rpm rotating speed.
Preferably, the mass ratio of the carbonitride of the tetracarboxylic phenyl porphyrin and class graphite-phase is：1:20~1:25.
Preferably, the preparation method of the carbonitride of the class graphite-phase is：By melamine solid under air conditionses,
550 DEG C are warming up to, 4 ~ 4.5 hours is incubated, is down to room temperature, obtains the carbonitride of class graphite-phase.
Preferably, it is to be warming up to 550 DEG C with 4 ~ 5 DEG C/min of speed during heating.
Preferably, before the reaction of the carbonitride of tetracarboxylic phenyl porphyrin and class graphite-phase, it is further comprising the steps of：By class
After the carbonitride grinding of graphite-phase, ball milling pearl is added, 2 ~ 3h is stirred in ball grinder.
Second object of the present invention is to provide the nitrogen for the class graphite-phase being prepared using any of the above-described described method
Change carbon/tetracarboxylic phenyl porphyrin nano composite.
Carbonitride/tetracarboxylic phenyl porphyrin nano composite that third object of the present invention is to provide class graphite-phase exists
Application in photocatalysis.
Preferably, the carbonitride of class graphite-phase/tetracarboxylic phenyl porphyrin nano composite is coated in ITO conduction glass
On glass, place it in electrolytic cell, electrochemistry i-t curve tests are carried out under conditions of CHI900 and 150w xenon lamp；Survey
During examination, using three-electrode system, working electrode is filamentary silver, and reference electrode is silver silver chloride electrode, is platinum electrode to electrode, electrolysis
Matter is 0.35mol/LNa2S and 0.35mol/LNa2SO3, bias used is 0.1V, and the time of photoswitch is 10 seconds.
Carbonitride/tetracarboxylic phenyl porphyrin nano composite that fourth object of the present invention is to provide class graphite-phase exists
Application in organic pollutant degradation and photocatalytic degradation of dye.
The present invention is using successful by the method for class graphite phase carbon nitride and tetracarboxylic phenyl porphyrin solid phase mixing ball-milling method
Composite is prepared for, method is simple, and cost is low, easy to operate, while can significantly save the reaction time.By tetracarboxylic
, can be very because tetracarboxylic phenyl porphyrin is a kind of good photosensitizer after phenyl porphyrin and class graphite phase carbon nitride are compound
Good capture photon improves the efficiency of light energy utilization；In addition, both materials are also matching in level structure, tetracarboxylic phenyl porphin
Quinoline is a kind of p-type organic semiconductor, and the carbonitride of class graphite-phase is as a kind of n-type semiconductor, and the two compound can form different
Matter knot, the formation of hetero-junctions have beneficial to exciting the electronics inside lower material to shift in light, can reduce light induced electron and hole
It is compound, improve photocatalysis performance.The nano composite material of the present invention has preferable PhotoelectrochemicalProperties Properties, stronger photocatalytic
Can, while play the role of in terms of organic pollutant degradation and photocatalytic degradation of dye important.
Brief description of the drawings
Accompanying drawing is used for providing a further understanding of the present invention, and a part for constitution instruction, the reality with the present invention
Apply example to be used to explain the present invention together, be not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the g-C of the present invention3N4、g-C3N4The scanning electron microscope diagram of/TCPP nano composite materials；
Fig. 2 is the g-C of the present invention3N4、g-C3N4The infrared figure of/TCPP nano materials；
Fig. 3 is the g-C of the present invention3N4、g-C3N4The uv drses figure of/TCPP nano materials；
Fig. 4 is the g-C of the present invention3N4、g-C3N4The i-t curve figures of/TCPP nano materials.
Fig. 5 is the g-C of the present invention3N4、g-C3N4The degradation time figure of/TCPP nano materials for rhodamine B.
Embodiment
Following embodiment facilitates a better understanding of the present invention, but does not limit the present invention.Experiment in following embodiments
Method, it is conventional method unless otherwise specified.Test material used, is city unless otherwise specified in following embodiments
Sell.
The preparation method of carbonitride/tetracarboxylic phenyl porphyrin nano composite of the species graphite-phase of the present invention is：
（1）Weigh 5 ~ 10g melamine solid samples to be put into 25ml porcelain crucible, Muffle is put into after crucible is capped
In stove, under air conditionses, 550 DEG C are warming up to 4 ~ 5 DEG C/min of speed, and 4 ~ 4.5 hours are incubated at 550 DEG C, it
After be down to room temperature, take out crucible, obtain the carbonitride of class graphite-phase, be faint yellow solid；It is standby to be ground into powder；
（2）By step（1）The nitridation carbon dust of the class graphite-phase of preparation add 10 ~ 15 ball milling pearls in ball grinder with
300 ~ 400rpm rotating speed stirs 2 ~ 3h；
（3）Take out nitridation carbon dust, clean ball grinder after, by 10mg tetracarboxylic phenyl porphyrin, 200mg nitrogenize carbon dust and
10 ~ 15 ball milling pearls are put into ball grinder together, and 30 ~ 50min is stirred under 300 ~ 400rpm rotating speed, and obtained solid is
The carbonitride of class graphite-phase/tetracarboxylic phenyl porphyrin nano composite.
Ball mill used can be the ball mill of any model in the present invention, as long as it disclosure satisfy that the inventive method
It is required that.
Embodiment 1
The preparation method of carbonitride/tetracarboxylic phenyl porphyrin nano composite of the species graphite-phase of the present invention is：
（1）Weigh 5g melamine solid samples to be put into 25ml porcelain crucible, Muffle furnace is put into after crucible is capped
In, 550 DEG C are warming up to 4 DEG C/min of speed, and 4 hours are incubated at 550 DEG C, room temperature is down to afterwards, is taken out crucible, is obtained
It is faint yellow solid to the carbonitride of class graphite-phase；Whole process crucible is capped and obstructed any protective gas；It is ground into
Powder is standby；
（2）Weigh step（1）The nitridation carbon dust 0.2g of the class graphite-phase of preparation, 10 ball milling pearls are added with 400rpm's
Rotating speed stirs 2.5h；
（3）Take out nitridation carbon dust, clean ball grinder after, by 10mg tetracarboxylic phenyl porphyrin, 200mg nitrogenize carbon dust and
10 ball milling pearls are put into ball grinder together, and 40min is stirred under 300rpm rotating speed, and obtained solid is class graphite-phase
Carbonitride/tetracarboxylic phenyl porphyrin nano composite.
Fig. 1 is the g-C of the present invention3N4、g-C3N4The scanning electron microscope diagram of/TCPP nano composite materials；Wherein, A is schemed
For g-C3N4Scanning electron microscope diagram, figure B is g-C3N4The scanning electron microscope diagram of/TCPP nano composite materials.By scheming
1 can be seen that：The class graphite phase carbon nitride synthesized in A figures is laminar structured, and B figures are the electron microscopes of composite, can be with
Find out that TCPP is successfully compounded on carbonitride.
Fig. 2 is the g-C of the present invention3N4、g-C3N4The infrared figure of/TCPP nano composite materials；As seen from Figure 2：Class stone
The main appearance of black phase carbon nitride exists respectively：1200-1650 cm-1, the stretching vibration of the corresponding heterocycle for being C, N composition；3000
cm-1The peak of left and right be it is corresponding be N-H keys appearance, be corresponding to 809 or so peak triazine ring element appearance, from infrared figure
It can be seen that carbonitride is successfully prepared, and the appearance of nano composite material is almost similar with the appearance of carbonitride, only
It is Strength Changes, the amount for being primarily due to porphyrin is seldom compared with carbonitride.
Fig. 3 is the g-C of the present invention3N4、g-C3N4The uv drses figure of/TCPP nano materials；As seen from Figure 3：Phase
Than carbonitride, nano composite material substantially expands to the absorption region of light, on the one hand illustrates the successful preparation of nano composite material,
Secondly the absorption region to light can be increased by also illustrating the nano composite material of the present invention.
Embodiment 2
The preparation method of carbonitride/tetracarboxylic phenyl porphyrin nano composite of the species graphite-phase of the present invention is：
（1）Weigh 8g melamine solid samples to be put into 25ml porcelain crucible, Muffle furnace is put into after crucible is capped
In, 550 DEG C are warming up to 4 DEG C/min of speed, and 4.5 hours are incubated at 550 DEG C, room temperature is down to afterwards, takes out crucible,
The carbonitride of class graphite-phase is obtained, is faint yellow solid；Whole process crucible is capped and obstructed any protective gas；Ground
It is standby into powder；
（2）Weigh step（1）The nitridation carbon dust 0.2g of the class graphite-phase of preparation, 12 ball milling pearls are added with 350rpm's
Rotating speed stirs 2h；
（3）Take out nitridation carbon dust, clean ball grinder after, by 10mg tetracarboxylic phenyl porphyrin, 200mg nitrogenize carbon dust and
12 ball milling pearls are put into ball grinder together, and 50min is stirred under 350rpm rotating speed, and obtained solid is class graphite-phase
Carbonitride/tetracarboxylic phenyl porphyrin nano composite.
Embodiment 3
The preparation method of carbonitride/tetracarboxylic phenyl porphyrin nano composite of the species graphite-phase of the present invention is：
（1）Weigh 10g melamine solid samples to be put into 25ml porcelain crucible, Muffle furnace is put into after crucible is capped
In, 550 DEG C are warming up to 5 DEG C/min of speed, and 4 hours are incubated at 550 DEG C, room temperature is down to afterwards, is taken out crucible, is obtained
It is faint yellow solid to the carbonitride of class graphite-phase；Whole process crucible is capped and obstructed any protective gas；It is ground into
Powder is standby；
（2）Weigh step（1）The nitridation carbon dust 0.2g of the class graphite-phase of preparation, 15 ball milling pearls are added with 300rpm's
Rotating speed stirs 3h；
（3）Take out nitridation carbon dust, clean ball grinder after, by 10mg tetracarboxylic phenyl porphyrin, 200mg nitrogenize carbon dust and
15 ball milling pearls are put into ball grinder together, and 30min is stirred under 400rpm rotating speed, and obtained solid is class graphite-phase
Carbonitride/tetracarboxylic phenyl porphyrin nano composite.
Embodiment 4
（1）Carbonitride/tetracarboxylic phenyl porphyrin nano composite prepared by 4mg embodiment 1 is weighed, is added into
In 2ml distilled water, suspension is ultrasonically formed, the ITO electro-conductive glass cleaned up is added dropwise to using the method for drop coating
On；
（2）ITO electro-conductive glass after coating is placed in 60 DEG C of baking oven into dry 12h makes its dry tack free, then by ITO
Electro-conductive glass is put into porcelain boat, and 300 DEG C are warming up to 2 DEG C/min speed in tube furnace, and is incubated 2 hours at 300 DEG C,
Whole process is carried out under the protection of nitrogen.
（3）Electro-conductive glass is taken out, is placed it in electrolytic cell, electrification is carried out under conditions of CHI900 and 150w xenon lamp
Learn i-t curve tests；During test, using three-electrode system, working electrode is filamentary silver, and reference electrode is silver silver chloride electrode,
It is platinum electrode to electrode, electrolyte 0.35mol/LNa2S and 0.35mol/LNa2SO3, bias used is 0.1V, photoswitch
Time be 10 seconds；Test result is referring to Fig. 4.
As seen from Figure 4, close to twice of carbonitride, photoelectric current is more big also just to be said the photoelectric current of nano composite material
Mingguang City is reduced accordingly according to the probability of rear electron-hole recombinations, can also reflect nano composite material by photoelectric current size
Preparation can improve catalytic performance.
Embodiment 5
The application have selected rhodamine B as light degradation object, under light illumination under the conditions of by comparing two kinds of materials to sieve
Red bright B degradation time reflects the change of material catalytic performance.
（1）The concentration for preparing rhodamine B is that the placement of 10mg/L solution is stand-by, and the embodiment 1 for then weighing 20mg respectively is made
Standby carbonitride and carbonitride/tetracarboxylic phenyl porphyrin nano composite, are respectively put into the solution of rhodamine B；
（2）The irradiation of 150w xenon lamps is respectively adopted and carries out photocatalytic degradation experiment；
（3）Light application time took a sample to collect every ten minutes, is centrifuged and is determined with ultraviolet specrophotometer afterwards
The absorbance of solution.
（4）Collected receipt is mapped, schemed referring specifically to Fig. 5 A and B.
As seen from Figure 5, degraded of the carbonitride for rhodamine B takes around 70 minutes, and nano composite material pair
40min is only needed in the degraded of rhodamine B, it can be seen that the photocatalysis performance of nano composite material of the invention compares carbonitride
It is significantly improved.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., it should be included in the present invention's
Within protection domain.
Claims (7)
1. the carbonitride of class graphite-phase/application of the tetracarboxylic phenyl porphyrin nano composite in photocatalytic degradation of dye；
The carbonitride of the class graphite-phase/tetracarboxylic phenyl porphyrin nano composite is obtained using solid-phase ball milling method；Institute
It is rhodamine B to state dyestuff.
2. application according to claim 1, it is characterised in that：The carbonitride of the class graphite-phase/tetracarboxylic phenyl porphyrin
Nano composite material is to be put into tetracarboxylic phenyl porphyrin, the nitridation carbon dust of class graphite-phase and ball milling pearl in ball grinder together,
Stir what 30 ~ 50min was obtained under 300 ~ 400rpm rotating speed.
3. application according to claim 2, it is characterised in that：The carbonitride of the tetracarboxylic phenyl porphyrin and class graphite-phase
Mass ratio be：1:20~1:25.
4. the application according to Claims 2 or 3, it is characterised in that：The preparation method of the carbonitride of the class graphite-phase is：
By melamine solid under air conditionses, 550 DEG C are warming up to, 4 ~ 4.5 hours is incubated, is down to room temperature, obtains class graphite-phase
Carbonitride.
5. application according to claim 4, it is characterised in that：It is to be warming up to 550 with 4 ~ 5 DEG C/min of speed during heating
DEG C.
6. according to the application described in claim 2,3 or 5, it is characterised in that：In tetracarboxylic phenyl porphyrin and the nitrogen of class graphite-phase
It is further comprising the steps of before changing carbon reaction：After the carbonitride grinding of class graphite-phase, ball milling pearl is added, 2 are stirred in ball grinder
~3h。
7. application according to claim 4, it is characterised in that：It is anti-in the carbonitride of tetracarboxylic phenyl porphyrin and class graphite-phase
Ying Qian, it is further comprising the steps of：After the carbonitride grinding of class graphite-phase, ball milling pearl is added, 2 ~ 3h is stirred in ball grinder.
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