CN110215929A - A kind of preparation method of the carbonitride of a large amount of negative electrical charges of surface band - Google Patents
A kind of preparation method of the carbonitride of a large amount of negative electrical charges of surface band Download PDFInfo
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- CN110215929A CN110215929A CN201910480390.XA CN201910480390A CN110215929A CN 110215929 A CN110215929 A CN 110215929A CN 201910480390 A CN201910480390 A CN 201910480390A CN 110215929 A CN110215929 A CN 110215929A
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- 238000002360 preparation method Methods 0.000 title claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 239000011780 sodium chloride Substances 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 230000002195 synergetic effect Effects 0.000 claims abstract description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 239000010431 corundum Substances 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- -1 alkali metal cation Chemical class 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000005030 aluminium foil Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Inorganic materials [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims 2
- 206010068150 Acoustic shock Diseases 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000009826 distribution Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910001414 potassium ion Inorganic materials 0.000 claims 1
- 235000009518 sodium iodide Nutrition 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 claims 1
- 238000012719 thermal polymerization Methods 0.000 claims 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [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 abstract description 5
- 229940043267 rhodamine b Drugs 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 239000000084 colloidal system Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 238000005286 illumination Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 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
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
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
-
- B01J35/39—
-
- B01J35/613—
-
- 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
- C02F2101/38—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
Abstract
The present invention calcines 2h under 550 DEG C of nitrogen atmospheres and is modified to carbonitride using NaCl, KI, body phase graphite phase carbon nitride and a small amount of deionized water as raw material.Modified carbonitride can be separated into colloid in water, have obvious lattice structure, and the introducing of a small amount of water makes its surface contain more polyhydroxy, form a large amount of negative electrical charge in nitridation carbon surface, be easy the reactant of Liquidity limit type.In addition, the order degree of carbonitride is improved due to the synergistic effect of NaCl and KI, and the surface texture of high-sequential can reduce the easily compound defect sites of electron hole pair, effectively enhance electric charge transfer, promote photocatalysis efficiency.Prepared modified nitridation carbon surface has a large amount of negative electrical charge in the present invention, there is the separating capacity of excellent light induced electron and hole.It is used for photocatalytic degradation rhodamine B, only rhodamine B can be decomposed 88% by 10min, be a kind of excellent photocatalytic degradation material.Attached drawing: the Zeta potential curve of modified carbonitride.
Description
Technical field
The present invention relates to a kind of preparation methods of the carbonitride with a large amount of negative electrical charges of fuse salt surface modification, belong to material
With catalytic science field.Modified nitridation carbon surface contains a large amount of negative electrical charge, is easy the reaction that absorption has cationic
Object.The carbonitride based photocatalyst of this method preparation is without precious metal, at low cost, easy to operate, can be mass, solves nitrogen
Change carbon in the application limitation of photocatalysis field, there is highly important application value.
Background technique
g-C3N4It is a kind of carbon material emerging in recent years, there is unique planar structure, good electricity, optics and object
Physicochemical property, and preparation process is simple, cost is relatively low.With known semiconductor light-catalyst such as TiO2, CdS etc. compare, g-
C3N4With corrosion-resistant, chemical stability is good, band structure is easy to regulate and control, it is seen that the features such as optical response range is wide, class graphene
Structure is conducive to electronics transfer transmission.The metal-doped electronic structure that can modify carbonitride, enhances visible light-responded ability
With the efficiency of transmission of electronics.Alkali metal ion such as Li in chloride+, Na+And K+After entering carbonitride molecular structure, not
With the dispersion that can cause carrier in space in molecular layer.By sodium chloride, potassium iodide in conjunction with body phase graphite phase carbon nitride, pass through
The synergistic effect of sodium chloride and potassium iodide mixture introduces new defect group and metal ion during the reaction, makes product
With better dissolubility, bigger specific surface area, the visible light absorption capacity of extension and more efficient light induced electron and hole
Separating capacity, and then extend its application in photocatalysis oxidation reaction.
Although ideal stratiform g-C3N4With huge theoretical specific surface area, but due to the stacking of polymeric layer, preparation
Body phase g-C3N4Material typically exhibits low-down specific surface area, and that there are electron-hole recombinations is fast and visible light-responded
The disadvantages of weak；The method that this patent uses surface salt modification makes to nitrogenize carbon surface with more negative electrical charges, to make have sun
The reactant of ionic is easier to be adsorbed onto nitridation carbon surface, it is small to compensate for carbonitride specific surface area itself, it is not easy to reaction
The shortcomings that object is adsorbed, and then promote the progress of reaction.Sodium chloride and the modified synergic of potassium iodide also make to nitrogenize carbon surface layer
Interior introducing ionizable metal salt, specific surface area increases, light induced electron and hole separation, transmission and transfer ability enhance, catalytic activity
It is promoted.It finally applies it in the degradation of photocatalysis rhodamine B, modified nitridation carbon activity has been significantly improved.
Summary of the invention
1. the present invention is to design a kind of preparation method of the carbonitride of a large amount of negative electrical charges of surface band, with sodium chloride, potassium iodide,
Body phase graphite phase carbon nitride and a small amount of deionized water are raw material, and two hours are calcined under 550 DEG C of nitrogen atmospheres to carbonitride
It is modified, modified nitridation carbon surface contains a large amount of negative electrical charge, and Zeta potential value reaches -45.5mV, and minor amount of water adds
Enter to make the surface CN a large amount of hydroxyl occur, to keep carbonitride more hydrophilic；It is characterized in that the selection and preparation process of raw material:
2. (1) weighs dicyandiamide 10g, it is fully ground with mortar, is then laid in the bottom of quartz boat, is wrapped up with aluminium foil
It is put into tubular heater；
(2).N230min is replaced, the oxygen in pipe is driven away.Start heating device, is heated up with the heating rate of 2.3 DEG C/min
To 550 DEG C, constant temperature 4h is maintained, then Temperature fall, is cooled to room temperature taking-up；
(3) weigh reaction after sample 600mg, add deionized water 0.2mL, added after being fully ground 600mg KI and
600mg NaCl, is fully ground, and makes to be uniformly mixed, and is then deposited in the centre of corundum boat and is placed in tubular heater；
(4).N230min is replaced, the oxygen in pipe is driven away.Start heating device, is warming up to the heating rate of 5 DEG C/min
550 DEG C, constant temperature 2h is maintained, then Temperature fall, is cooled to room temperature taking-up；
(5) sample obtained in the previous step is dissolved into deionized water by, carries out 20min in the ultrasonic vibration instrument of 40kHz
Ultrasonic vibration effect, unreacted salt is removed by being repeatedly centrifuged；
(6) solid after centrifugation is dried at 60 DEG C, obtains the carbonitride that surface has a large amount of negative electrical charges.
Detailed description of the invention
Fig. 1: Na-K-CN transmission electron microscope (TEM)；It can be seen that there is apparent lattice fringe in modified carbonitride；
Table 1: the specific surface area value of embodiment 1 and the made modified carbonitride of comparative example 1, example 2, example 3, example 4, it can be seen that single
The CN-2h of modified obtained its specific surface area of catalyst and direct reheating 2h of one sodium chloride and potassium iodide does not have the area Tai great
Not, and with CN it compares and also only promotes micro specific surface area.And the Na-K-CN that sodium chloride and potassium iodide act synergistically its
Specific surface area reaches 97.85m2/ g is promoted compared to CN close to 10 times.
Fig. 2: the X ray diffracting spectrum (XRD) of embodiment 1 and the made modified carbonitride of comparative example 1, example 2, example 3, example 4, it can
To find out that Na-K-CN changes the crystal plane structure of CN, diffracted intensity is caused to become smaller；This fits like a glove with the result that TEM is seen.
Fig. 3: the Fourier transform infrared spectroscopy of embodiment 1 and the made modified carbonitride of comparative example 1, example 2, example 3, example 4
(FT-IR), it can be seen that all samples all have the characteristic peak of carbonitride, 810cm-1Triazine ring breathing vibration peak and
1200-1650cm-1Three s-triazine rings stretching vibration peak.2400-3650cm-1Broad absorption band show material surface exist
Hydroxyl, absorption water and terminal amino group.Compared to CN, the modified carbonitride of salt is in 2178cm-1There is a new absorption in place
Peak, this is the absorption peak of terminal cyano group (C ≡ N), illustrates that alkali metal haloid destroys CN structural unit.
Fig. 4: the total spectrogram of XPS of embodiment 1 and the made modified carbonitride of comparative example 2, example 3, example 4, it can be found that Na-CN has
There is apparent Na 1s signal, K-CN has apparent K 2p signal, and Na-K-CN has the signal of Na 1s and K 2p simultaneously, and
Cl 2p and I the 3d spectrum of each sample occur without signal peak.
Table 2: embodiment 1 and the made modified carbonitride of comparative example 2, example 3, example 4, can by the content of the XPS each element measured
With see in the modified sample of alkali metal salt alkali metal element content in 4-5atm.%, and halogen element content less than
0.4atm.%.Therefore, content of halide ions can ignore completely.
Fig. 5: the uv-visible absorption spectra of embodiment 1 and the made modified carbonitride of comparative example 1, example 2, example 3, example 4, it can
Optical absorption to find out Na-K-CN is whole to visible light region red shift, greatly improves the extinction energy in visible-range
Power；
Fig. 6: the fluorescence emission spectrum of embodiment 1 and comparative example 1, example 2, example 3 and the made modified carbonitride of example 4 can be seen
The photoluminescence intensity of Na-K-CN significantly declines out, illustrates that the separating capacity in light induced electron and hole improves；
Fig. 7: the photoelectric respone curve of embodiment 1 and the made modified carbonitride of comparative example 1, it can be seen that the light of Na-K-CN
Electroresponse degree is obviously enhanced, and illustrates that Na-K-CN has the light induced electron of enhancing and the separating capacity in hole；
Fig. 8: the electrochemical impedance spectroscopy (EIS) of embodiment 1 and the made modified carbonitride of comparative example 1, it can be seen that Na-K-CN
The decline of electronics transfer resistance it is obvious, hence it is evident that improve the charge transmission and separating capacity of CN；
Fig. 9: the Zeta potential curve of embodiment 1 and the made modified carbonitride of comparative example 1, it can be found that Na-K-CN
Zeta potential value is -45.5mV, and-the 25.2mV compared to CN deviates 20.3mV to the left.So big elecrtonegativity shows the material
With good dispersion performance, the very strong Na-K-CN of elecrtonegativity can be easy to inhale by the effect of Electrostatic Absorption in RhB solution
RhB cation is enclosed, this hole that Na-K-CN is generated under illumination condition is easier to react with RhB.
Figure 10: the Raman spectrum of embodiment 1 and the made modified carbonitride of comparative example 1 under 325nm excitation, in Na-K-CN
There is also the electric charge transfers between three s-triazine rings and alkali metal cation, this makes hole more readily migrate into photochemical catalyst
Surface, to improve the reaction probability of the RhB cation of hole and absorption.
Figure 11: the photocatalytic degradation RhB of embodiment 1 and the made modified carbonitride of comparative example 1, example 2, example 3, example 4 conversion
Rate changes over time curve, it can be seen that relative to CN, K-CN and CN-2h, the Photocatalytic activity of Na-K-CN is significantly
It improves, rate of photocatalytic oxidation promotion is exceedingly fast, and the conversion ratio of RhB is up to reachable after 88%, 30min after photocatalytic degradation 10min
98%.
Specific embodiment
Carry out enumeration technical characterstic of the invention below in conjunction with specific embodiment.
Embodiment 1
600mg body phase CN is added into deionized water 0.2mL and 600mg chlorination according to the main flow method in embodiment 1
Sodium and 600mg potassium iodide ground and mixed in mortar are uniform, are then placed in corundum boat, in N in tube furnace2The protection of atmosphere
Under with the heating rate of 5 DEG C/min be warming up to 550 DEG C, keep 2h, gained is yellow green product.It is scattered in deionized water
In, ultrasonic 15min is then centrifuged for for several times to remove unreacted salt.It is primary rear dry with dehydrated alcohol centrifugation, obtain yellow green
Solid Na-K-CN.For photocatalytic degradation RhB, by the illumination of 30min, degradation efficiency 97.93%.
Comparative example 1
10g dicyandiamide is weighed, is fully ground with mortar, then uniform tiling is put into quartz boat, and by quartz boat
In tubular heater.N230min is replaced, the oxygen in pipe is driven away.After 30min, start heating device, with the liter of 2.3 DEG C/min
Warm rate is warming up to 550 DEG C, maintains constant temperature 4h, then Temperature fall, is cooled to room temperature taking-up.Flaxen blocks of solid is ground
Mill, obtains body phase CN.Taking the solid sample of 20mg to be dissolved in 50mL concentration in photocatalytic degradation RhB experiment is 5mgL-1Luo Dan
In the aqueous solution of bright B (RhB), by the illumination of 30min, there is 27.61% substrate to be degraded.
Comparative example 2
Add deionized water 0.2mL ground and mixed equal 600mg body phase CN according to the main flow method in embodiment 1
It is even, it is placed in quartz boat, nitrogen a few minutes is led in tube furnace, oxygen therein are drained, then in N2In atmosphere with 5 DEG C/
The speed of min is warming up to 550 DEG C of progress high temperature pyrolysis.Pyrolysis time 2h, blocks of solid is ground, and obtains CN-2h.It is urged for light
Change degradation RhB, by the illumination of 30min, degradation efficiency 46.58%.
Comparative example 3
600mg body phase CN is added into deionized water 0.2mL and 1200mg according to the main flow method in embodiment 1
NaCl ground and mixed in mortar is uniform, is then placed in corundum boat, in N in tube furnace2With 5 DEG C/min under the protection of atmosphere
Heating rate be warming up to 550 DEG C, keep 2h, gained is brown color product.It is scattered in deionized water, ultrasonic 15min,
It is then centrifuged for for several times to remove unreacted salt.Primary rear dry, the obtained yellow solid Na-CN with dehydrated alcohol centrifugation.With
Carry out photocatalytic degradation RhB, by the illumination of 30min, degradation efficiency 18.55%.
Comparative example 4
600mg body phase CN is added into deionized water 0.2mL and 1200mg KI according to the main flow method in embodiment 1
Ground and mixed is uniform in mortar, is then placed in corundum boat, in N in tube furnace2With the liter of 5 DEG C/min under the protection of atmosphere
Warm speed is warming up to 550 DEG C, keeps 2h, and gained is brown-green product.It is scattered in deionized water, ultrasonic 15min, then
Centrifugation is for several times to remove unreacted salt.It is primary rear dry with dehydrated alcohol centrifugation, obtain brown-green solid K-CN.It is urged for light
Change degradation RhB, by the illumination of 30min, degradation efficiency 40.28%.
Comparative example 5
According to the photocatalytic degradation RhB main flow method in embodiment 1, using different catalysts, in dark no light
Under the conditions of pass through 30min, RhB is undegraded.
Comparative example 6
According to the photocatalytic degradation RhB main flow method in embodiment 1, catalyst is not used, by 30min illumination,
RhB is undegraded.
Invention effect
1. modified nitridation carbon surface has a large amount of negative electrical charge, the Zeta potential value of Na-K-CN is -45.5mV, phase
20.3mV is deviated to the left than the -25.2mV in CN.In addition, the high elecrtonegativity of modified carbonitride makes it have good dispersibility
Can, the colloidal solution of a large amount of negative electrical charge carbonitrides of prepared surface band is with good stability, and standing three months will not go out
Existing coagulation phenomenon.
2. adulterate different haloids, the specific surface area difference of the carbonitride of acquisition is larger.The specific surface area of CN is
10.1m2·g-1；The specific surface area of Na-CN is 12.4m2·g-1, promoted compared to CN specific surface area and little；The ratio table of K-CN
Area is 13.0m2·g-1, promoted compared to CN specific surface area and little；The specific surface area of Na-K-CN is 97.9m2·g-1, it is
9 times of CN specific surface area are more.
3. from the point of view of the effect of photocatalytic degradation RhB there is the catalytic effect of reaction in the modified carbonitride sample of difference
Biggish difference.The carbonitride of a large amount of negative electrical charges of surface band has good catalysis to imitate in photocatalytic degradation rhodamine B is tested
Fruit, the conversion ratio of rhodamine B is up to up to 98%, compared to body phase carbon nitride, degradation effect is obtained after 88%, 30min after 10min
Very big promotion is arrived.
Claims (6)
1. a kind of preparation method of the carbonitride of a large amount of negative electrical charges of surface band, with sodium chloride, potassium iodide, body phase graphite phase carbon nitride
It is raw material with a small amount of deionized water, two hours of calcining are modified carbonitride under 550 DEG C of nitrogen atmospheres, modified
Nitridation carbon surface contains a large amount of negative electrical charge, and Zeta potential value reaches -45.5mV, and it is a large amount of that the surface CN occurs in the addition of minor amount of water
Hydroxyl, to keep carbonitride more hydrophilic；It is characterized in that the selection and preparation process of raw material:
(1) weighs dicyandiamide 10g, is fully ground with mortar, is then laid in the bottom of quartz boat, is put into pipe with aluminium foil package
In formula heating furnace；
(2).N230min is replaced, the oxygen in pipe is driven away.Start heating device, is warming up to 550 with the heating rate of 2.3 DEG C/min
DEG C, constant temperature 4h is maintained, then Temperature fall, is cooled to room temperature taking-up；
(3) weighs the sample 600mg after reaction, adds deionized water 0.2mL, 600mg KI and 600mg are added after being fully ground
NaCl is fully ground, and makes to be uniformly mixed, and is then deposited in the centre of corundum boat and is placed in tubular heater；
(4).N230min is replaced, the oxygen in pipe is driven away.Start heating device, is warming up to 550 with the heating rate of 5 DEG C/min
DEG C, constant temperature 2h is maintained, then Temperature fall, is cooled to room temperature taking-up；
(5) sample obtained in the previous step is dissolved into deionized water by, and the super of 20min is carried out in the ultrasonic vibration instrument of 40kHz
The acoustic shock effect of swinging, unreacted salt is removed by being repeatedly centrifuged；
(6) solid after centrifugation is dried at 60 DEG C, obtains the carbonitride that surface has a large amount of negative electrical charges.
2. a kind of preparation method of the carbonitride of a large amount of negative electrical charges of surface band according to claim 1, it is characterised in that: with
Sodium chloride, potassium iodide, body phase graphite phase carbon nitride and a small amount of deionized water are raw material, prepare a kind of table by a step thermal polymerization method
The carbonitride of a large amount of negative electrical charges of face band.
3. a kind of preparation method of the carbonitride of a large amount of negative electrical charges of surface band according to claim 1, it is characterised in that: anti-
Heating rate control makes raw material, not because temperature heating is too fast, lead to raw material in pre-heat phase in 2-15 DEG C/min during answering
Uneven heating is even；Not because of the slow influence production efficiency that heated up.
4. a kind of preparation method of the carbonitride of a large amount of negative electrical charges of surface band according to claim 1, it is characterised in that: body
For the mass ratio of phase graphite phase carbon nitride and salt in 1:1 to 1:5, this can make body phase graphite phase carbon nitride very little because of salt amount
And cause to be modified unevenly, yield will not be caused too low because of salt amount too greatly and to body phase graphite phase carbon nitride overetch.
5. a kind of preparation method of the carbonitride of a large amount of negative electrical charges of surface band according to claim 1, it is characterised in that: chlorine
Change sodium and potassium iodide with mass ratio 1:3 to 3:1, makes carbonitride surface coordination Na+Ion and K+Ion, alkali metal cation draw
Enter the Cloud Distribution for changing nitridation carbon surface, the synergistic effect of sodium chloride and potassium iodide has modified carbonitride more
Big specific surface area and excellent photochemical properties.
6. a kind of preparation method of the carbonitride of a large amount of negative electrical charges of surface band according to claim 1, it is characterised in that: micro-
The addition of amount water makes the surface of carbonitride a large amount of hydroxyl occur, keeps carbonitride more hydrophilic, the additional amount of water is strict controlled in
600mg graphite phase carbon nitride corresponds to 0.1~0.2mL deionized water, and can be amplified with equal proportion.
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