CN106140241A - The nanometer g C of oxonium ion surface regulation and control3n4organic photocatalyst and its preparation method and application - Google Patents
The nanometer g C of oxonium ion surface regulation and control3n4organic photocatalyst and its preparation method and application Download PDFInfo
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- CN106140241A CN106140241A CN201610466170.8A CN201610466170A CN106140241A CN 106140241 A CN106140241 A CN 106140241A CN 201610466170 A CN201610466170 A CN 201610466170A CN 106140241 A CN106140241 A CN 106140241A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 42
- -1 oxonium ion Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 230000004048 modification Effects 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims abstract description 3
- 239000002135 nanosheet Substances 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 40
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 17
- 229960002163 hydrogen peroxide Drugs 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000010301 surface-oxidation reaction Methods 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
- 230000000593 degrading effect Effects 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 150000002978 peroxides Chemical class 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 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
- 238000002474 experimental method Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000005286 illumination Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 14
- 239000007787 solid Substances 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 11
- 239000000725 suspension Substances 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution Methods 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
-
- 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—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses the nanometer g C of a kind of oxonium ion surface regulation and control3N4Organic photocatalyst and its preparation method and application.This visible light catalyst is with porous g C3N4Two dimension organic nano sheet is matrix, and by oxonium ion, it is carried out surface modification acquisition.The oxonium ion surface regulation and control nanometer g C that the present invention provides3N4In organic photocatalyst, catalyst surface oxonium ion substantially changes its crystal structure, electronic structure and photocatalytic activity so that the nanometer g C after oxidation3N4The photocatalytic activity of rhodamine B is significantly strengthened by material under visible light illumination.Experiment shows, the nano oxidized g C that the present invention provides3N4The visible light catalysis activity of catalyst is pure phase g C3N42.5～3.5 times of photocatalyst.Additionally, the preparation method of present invention offer and experiment condition are gentle, simple to operate, beneficially large-scale production.
Description
Technical field
The present invention relates to catalyst material technical field, particularly to nanometer g-C of a kind of oxonium ion surface regulation and control3N4Have
Machine photocatalyst and its preparation method and application.
Background technology
Photocatalyst is that a class can absorb sunlight, and utilizes solar energy to play the material of catalytic action.Existing respectively
Class photocatalyst can the difficult degradation harmful organic substance in degrading waste water and air in a mild condition, be to administer water body and air
The effective technology of organic pollution.Along with developing rapidly of China or even world industry field, all kinds of in water body and air have
The problem of environmental pollution that organic pollutants causes has become as the key issue of the primary human social solved in the whole world.
Developing effective environmental pollution treatment technology is one of main path solving current problem of environmental pollution.And utilize photocatalyst
Organic pollution in degraded environment solves the effective means of environmental pollution and energy crisis just.
Compare the semiconductor light-catalysts such as more traditional transition group metallic oxide, sulfide, nanometer g-C3N4Organic light is urged
Agent has higher chemical stability, good photoelectron performance and visible light-responded characteristic, is a kind of excellent organic half
Conductor.Due to g-C3N4Having layer structure, it is compared more traditional photocatalyst and has bigger specific surface area and more catalysis
Active sites；Due to g-C3N4Energy gap be 2.7eV, its conventional semiconductors photocatalyst (such as TiO that compares2Forbidden band width
Degree is 3.4eV for the energy gap of 3.2eV, ZnO) can significantly utilize the visible light part in sunlight.g-C3N4Without mixing
Organic pollution in the miscellaneous visible light part catalytic degradation environment that just can directly utilize in sunlight, at field of environment protection
Have broad application prospects.But, in actual catalytic applications, its most critical issue existed is that its photocatalytic activity compares
Low.Therefore, seek to prepare the g-C of high activity, low cost3N4The organic photocatalyst material of base nanometer has long-range market application
Prospect.And prepare oxonium ion surface regulation and control nanometer g-C by simple calcining-ultrasonic-oxygen absorption method3N4Organic photocatalyst material
Expect and be applied to organic matter degradation aspect to yet there are no relevant report so far.
Summary of the invention
It is an object of the invention to provide nanometer g-C of a kind of oxonium ion surface regulation and control3N4Organic photocatalyst material and
Preparation method and application, described oxonium ion surface regulation and control nanometer g-C3N4Organic photocatalyst material can increase photocatalyst
Active sites, improves the separation efficiency of photo-generated carrier, has higher visible light catalysis activity.
For achieving the above object, the present invention uses following technical proposals:
Nanometer g-C of the oxonium ion surface regulation and control of the present invention3N4Organic photocatalyst, is to use oxonium ion to porous g-
C3N4Organic nano sheet carries out surface modification and forms.Its preparation method comprises the following steps: with tripolycyanamide as raw material, at air
Middle calcining obtains pure phase g-C3N4Powder, then be added in hydrogenperoxide steam generator, sonicated after, centrifugal dry, it is thus achieved that oxygen
Ion surface regulation and control nanometer g-C3N4Organic photocatalyst.
Concrete committed step is as follows:
1) pure phase g-C3N4Preparation: with tripolycyanamide as raw material, in air 400～700 DEG C calcining 1～7h, control rise
Temperature speed is 0.1～5 DEG C/min, takes out, it is thus achieved that pure phase g-C after being cooled to room temperature3N4Powder；
2)g-C3N4The preparation of nanometer sheet and surface oxidation treatment: the g-C that will prepare3N4Powder adds mass fraction
In the hydrogenperoxide steam generator of 30% so that H2O2With g-C3N4Mol ratio be (200～1000): 1, with dilute hydrochloric acid or dilute hydrogen-oxygen
Change the pH value of sodium regulation mixed solution to 1～11；Afterwards this solution is placed in ultrasonic machine in 20～100 DEG C of supersound process 1-
10h, centrifugal, drying, it is thus achieved that nanometer g-C of oxonium ion surface regulation and control3N4Organic photocatalyst.
In technique scheme, step 1) described in calcining heat be preferably 500～600 DEG C, more preferably 550
℃。
Described heating rate is preferably 1～4 DEG C/min, more preferably 2 DEG C/min.
Step 2) in H2O2With g-C3N4Mol ratio be preferably (400～800): 1, more preferably (600～800): 1；
Preferred is 1～6 by described mixed solution pH regulator, more preferably 2.
The heating-up temperature of supersound process is 40 DEG C, and the process time is 10h.
Nanometer g-C of the oxonium ion surface regulation and control that said method prepares3N4Organic photocatalyst.
This photocatalyst applications is in degradable organic pollutant.
The present invention provides a kind of oxonium ion surface regulation and control nanometer g-C3N4The preparation of organic photocatalyst and application thereof.Ultrasonic
In oxidizing process, the oxonium ion in mixed solution and g-C3N4Nano-material surface combines and forms N-O key, the N-O key being newly formed
G-C will be changed to a certain extent3N4The bond distance of chemical bond and bond angle between surface atom, thus change g-C3N4The electronics knot on surface
Structure and catalytic active site.g-C3N4Surface oxidation makes oxonium ion surface regulation and control nanometer g-C that the present invention provides3N4Organic light is urged
The light induced electron of agent and the separation efficiency in hole are strengthened, and catalysis activity is significantly improved.Test result indicate that, this
Oxonium ion surface regulation and control nanometer g-C of bright offer3N4Rhodamine B, under the irradiation of visible ray, is gone degraded by organic photocatalyst
Rate compares pure phase nanometer g-C3N4Organic photocatalyst improves 2.5～3.5 times, is conducive to its answering in environment and energy field
With.
It addition, the method that the present invention provides can obtain oxonium ion surface regulation and control nanometer g-C under mild conditions3N4Have
Machine photocatalyst, and equipment is simple to operation, can be used for large-scale production.
The present invention compares with the composite photo-catalyst technology of preparing of existing routine, has the advantage that (1) this catalyst is
Pure organic materials, it is to avoid the use of magnesium-yttrium-transition metal；(2) preparation technology is simple.
Accompanying drawing explanation
Fig. 1 is the XRD figure of product prepared by the embodiment of the present invention；
Fig. 2 is the UV-vis spectrogram of product prepared by the embodiment of the present invention；
Fig. 3 is the FT-IR figure of product prepared by the embodiment of the present invention；
Fig. 4 is the TEM figure of product prepared by the embodiment of the present invention；
Fig. 5 is the high-resolution TEM figure of product prepared by the embodiment of the present invention；
Fig. 6 is the XPS figure of product prepared by the embodiment of the present invention.
Detailed description of the invention
In order to further appreciate that the present invention, below in conjunction with embodiment, the preferred embodiments of the invention are described, but
It is to should be appreciated that these describe simply as further illustrating the features and advantages of the present invention rather than limitation of the present invention.
The invention provides a kind of oxonium ion surface regulation and control nanometer g-C3N4The preparation method of organic photocatalyst, it may be assumed that with three
Poly cyanamid is raw material, and calcining obtains pure phase g-C in atmosphere3N4Powder, then be added in hydrogenperoxide steam generator, through ultrasonic place
After reason, centrifugal drying, it is thus achieved that oxonium ion surface regulation and control nanometer g-C3N4Organic photocatalyst.In such scheme, g-C3N4Ultrasonic
Oxidizing process is committed step prepared by the present invention, H2O2/g-C3N4The ratio of the two, pH value, the ultrasonic temperature of heating in mixed solution
Degree, ultrasonic duration are the essential condition affecting end product performance quality.
Oxidation g-C prepared by the present invention3N4Nanometer sheet energy gap is 2.60eV, and has one in the range of 600～800nm
Fixed absorbability, it is possible to significantly absorb visible ray, has the visible light catalytic performance of excellence.And aoxidize g-C3N4Have rich
Rich avtive spot and specific surface area, and can effectively suppress the compound of photo-generated carrier.Therefore, identical at experiment condition
Under conditions of, aoxidize g-C3N4Visible light catalytic effect is pure g-C3N42.5～3.5 times of nanometer sheet visible light catalytic effect.This
Outward, the oxidation g-C that prepared by the present invention3N4Effect stability during the use of nanometer sheet, without deactivation phenomenom.
Compared with prior art, the present invention is with cheap, nontoxic tripolycyanamide as raw material, it is not necessary to severe toxicity is former
Material, passes through H2O2Oxidation prepares oxidation g-C3N4Nanometer sheet.Meanwhile, the method technique is simple, low in raw material price, reduces
Production cost, it is easy to accomplish industrial applications.Visible light catalyst prepared by the present invention may not only be applied to water pollution control, and
And also have the biggest application potential in the aspects such as air pollution treatment, photolysis water hydrogen, solaode and catalytic carrier.
Illustrating below in conjunction with specific embodiment, the chemical reagent used in the embodiment of the present invention is commercial.
Embodiment 1
Weighing 10.0g tripolycyanamide to be placed in crucible, cover tightly and be placed in Muffle furnace calcining, calcining heat is 550 DEG C, calcining
Time is 5h, and room temperature is taken out and obtained pure phase g-C3N4.By pure for 100mg phase g-C3N4It is placed in beaker, and adds 30ml mass fraction
Being the hydrogen peroxide of 30%, adjust PH=2 with dilute hydrochloric acid, in ultrasonic machine, 40 DEG C of heating 10h, are centrifuged the suspension obtained, take
Go out supernatant, solid is placed in baking oven and is dried acquisition oxidation g-C3N4Nanometer sheet.
As it is shown in figure 1, implement the g-C of preparation for the present invention3N4XRD figure sheet, show preparation g-C3N4There is graphite-phase
Crystal formation.
As shown in a line in Fig. 2, implement the g-C of preparation for the present invention3N4Uv-visible absorption spectra, show preparation
g-C3N4Visible ray can be absorbed, and in the range of 600～800nm, have certain absorbability.
As shown in a line in Fig. 3, implement the g-C of preparation for the present invention3N4FTIR collection of illustrative plates, show preparation g-C3N4Have
Layer structure.
Fig. 4,5 for the present invention implement preparation g-C3N4TEM figure, show preparation g-C3N4For lamellar.
Fig. 6 is the g-C that the present invention implements preparation3N4XPS figure, show oxonium ion adsorb at g-C3N4Surface, Mole percent
Ratio about 5%.
Embodiment 2
Weighing 10.0g tripolycyanamide to be placed in crucible, cover tightly and be placed in Muffle furnace calcining, calcining heat is 550 DEG C, calcining
Time is 5h, and room temperature is taken out and obtained pure phase g-C3N4.By pure for 100mg phase g-C3N4It is placed in beaker, and adds 30ml mass fraction
Being the hydrogen peroxide of 30%, PH=7, in ultrasonic machine, 40 DEG C of heating 10h, are centrifuged the suspension obtained, and take out supernatant, will
Solid is placed in baking oven to be dried and obtains oxidation g-C3N4Nanometer sheet.
As shown in c line in Fig. 2, the g-C prepared for the present embodiment3N4Uv-visible absorption spectra, show preparation g-
C3N4Visible ray can be absorbed, it is seen that light abstraction width is up to 600nm.
Embodiment 3
Weighing 10.0g tripolycyanamide to be placed in crucible, cover tightly and be placed in Muffle furnace calcining, calcining heat is 550 DEG C, calcining
Time is 5h, and room temperature is taken out and obtained pure phase g-C3N4.By pure for 100mg phase g-C3N4It is placed in beaker, and adds 30ml mass fraction
Being the hydrogen peroxide of 30%, adjust PH=4 with dilute hydrochloric acid, in ultrasonic machine, 40 DEG C of heating 10h, are centrifuged the suspension obtained, take
Go out supernatant, solid is placed in baking oven and is dried acquisition oxidation g-C3N4Nanometer sheet.
As shown in b line in Fig. 2, the g-C prepared for the present embodiment3N4Uv-visible absorption spectra, show preparation g-
C3N4Visible ray can be absorbed, and in the range of 600～800nm, have certain absorbability.
Embodiment 4
Weighing 10.0g tripolycyanamide to be placed in crucible, cover tightly and be placed in Muffle furnace calcining, calcining heat is 550 DEG C, calcining
Time is 5h, and room temperature is taken out and obtained pure phase g-C3N4.By pure for 100mg phase g-C3N4It is placed in beaker, and adds 30ml mass fraction
Be the hydrogen peroxide of 30%, adjust PH=11 with dilute sodium hydroxide, 40 DEG C of heating 10h in ultrasonic machine, by the suspension that obtains from
The heart, takes out supernatant, is placed in baking oven by solid and is dried acquisition oxidation g-C3N4Nanometer sheet.
As shown in b line in Fig. 3, implement the g-C of preparation for the present invention3N4FTIR collection of illustrative plates, show preparation g-C3N4Have
Layer structure.
Embodiment 5
Weighing 10.0g tripolycyanamide to be placed in crucible, cover tightly and be placed in Muffle furnace calcining, calcining heat is 550 DEG C, calcining
Time is 5h, and room temperature is taken out and obtained pure phase g-C3N4.By pure for 100mg phase g-C3N4It is placed in beaker, and adds 30ml mass fraction
Being the hydrogen peroxide of 30%, adjust PH=2 with dilute hydrochloric acid, in ultrasonic machine, 20 DEG C of heating 10h, are centrifuged the suspension obtained, take
Go out supernatant, solid is placed in baking oven and is dried acquisition oxidation g-C3N4Nanometer sheet.
As shown in c line in Fig. 3, implement the g-C of preparation for the present invention3N4FTIR collection of illustrative plates, show preparation g-C3N4Have
Layer structure.
Embodiment 6
Weighing 10.0g tripolycyanamide to be placed in crucible, cover tightly and be placed in Muffle furnace calcining, calcining heat is 550 DEG C, calcining
Time is 5h, and room temperature is taken out and obtained pure phase g-C3N4.By pure for 100mg phase g-C3N4It is placed in beaker, and adds 30ml mass fraction
Being the hydrogen peroxide of 30%, adjust PH=2 with dilute hydrochloric acid, in ultrasonic machine, 60 DEG C of heating 10h, are centrifuged the suspension obtained, take
Go out supernatant, solid is placed in baking oven and is dried acquisition oxidation g-C3N4Nanometer sheet.
Embodiment 7
Weighing 10.0g tripolycyanamide to be placed in crucible, cover tightly and be placed in Muffle furnace calcining, calcining heat is 550 DEG C, calcining
Time is 5h, and room temperature is taken out and obtained pure phase g-C3N4.By pure for 100mg phase g-C3N4It is placed in beaker, and adds 30ml mass fraction
Being the hydrogen peroxide of 30%, adjust PH=2 with dilute hydrochloric acid, in ultrasonic machine, 80 DEG C of heating 10h, are centrifuged the suspension obtained, take
Go out supernatant, solid is placed in baking oven and is dried acquisition oxidation g-C3N4Nanometer sheet.
Embodiment 8
Weighing 10.0g tripolycyanamide to be placed in crucible, cover tightly and be placed in Muffle furnace calcining, calcining heat is 550 DEG C, calcining
Time is 5h, and room temperature is taken out and obtained pure phase g-C3N4.By pure for 100mg phase g-C3N4It is placed in beaker, and adds 30ml mass fraction
Being the hydrogen peroxide of 30%, adjust PH=2 with dilute hydrochloric acid, in ultrasonic machine, 40 DEG C of heating 5h, are centrifuged the suspension obtained, and take out
Supernatant, is placed in solid in baking oven and is dried acquisition oxidation g-C3N4Nanometer sheet.
Embodiment 9
Weighing 10.0g tripolycyanamide to be placed in crucible, cover tightly and be placed in Muffle furnace calcining, calcining heat is 550 DEG C, calcining
Time is 5h, and room temperature is taken out and obtained pure phase g-C3N4.By pure for 100mg phase g-C3N4It is placed in beaker, and adds 10ml mass fraction
Being the hydrogen peroxide of 30%, adjust PH=2 with dilute hydrochloric acid, in ultrasonic machine, 80 DEG C of heating 10h, are centrifuged the suspension obtained, take
Go out supernatant, solid is placed in baking oven and is dried acquisition oxidation g-C3N4Nanometer sheet.
Embodiment 10
Weighing 10.0g tripolycyanamide to be placed in crucible, cover tightly and be placed in Muffle furnace calcining, calcining heat is 550 DEG C, calcining
Time is 5h, and room temperature is taken out and obtained pure phase g-C3N4.By pure for 100mg phase g-C3N4It is placed in beaker, and adds 20ml mass fraction
Being the hydrogen peroxide of 30%, adjust PH=2 with dilute hydrochloric acid, in ultrasonic machine, 40 DEG C of heating 10h, are centrifuged the suspension obtained, take
Go out supernatant, solid is placed in baking oven and is dried acquisition oxidation g-C3N4Nanometer sheet.
Embodiment 11
Weighing 10.0g tripolycyanamide to be placed in crucible, cover tightly and be placed in Muffle furnace calcining, calcining heat is 550 DEG C, calcining
Time is 5h, and room temperature is taken out and obtained pure phase g-C3N4.By pure for 100mg phase g-C3N4It is placed in beaker, and adds 40ml mass fraction
Being the hydrogen peroxide of 30%, adjust PH=2 with dilute hydrochloric acid, in ultrasonic machine, 40 DEG C of heating 10h, are centrifuged the suspension obtained, take
Go out supernatant, solid is placed in baking oven and is dried acquisition oxidation g-C3N4Nanometer sheet.
The visible light catalyst prepared embodiment 1～11 respectively carries out active testing, and target contaminant is typical case
Water pollutant rhodamine B:
Experiment condition is as follows: the initial concentration of rhodamine B solution is 10mg/L, and volume is 100mL, and the consumption of catalyst is
0.1g, light source uses power to be the xenon lamp of 500W, and by the optical filter filtering ultraviolet light of 400nm.Will before light-catalyzed reaction
Catalyst and rhodamine B solution are sufficiently stirred for 30 minutes under dark room conditions, then start light-catalyzed reaction.Rhodamine B solution
Concentration is measured by ultraviolet-visible spectrophotometer with the change of light application time.The pure phase prepared for presoma with tripolycyanamide
g-C3N4On the basis of the visible light catalysis activity of organic photocatalyst 1, then test result is as shown in table 1.
The results of property of the visible light catalyst that table 1 embodiment 1～11 prepares
A kind of oxonium ion surface regulation and control nanometer g-C above present invention provided3N4The preparation of organic photocatalyst and application thereof
Being described in detail, principle and the embodiment of the present invention are set forth by specific case used herein, above reality
The explanation executing example is only intended to help to understand method and the core concept thereof of the present invention, it is noted that for the art
For those of ordinary skill, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out some improvement and regulation and control,
These improve and regulate and control to also fall in the protection domain of the claims in the present invention.
Claims (9)
1. nanometer g-C of oxonium ion surface regulation and control3N4Organic photocatalyst, it is characterised in that described photocatalyst is to adopt
With oxonium ion to porous g-C3N4Two dimension organic nano sheet carries out surface modification and forms.
2. prepare oxonium ion surface as claimed in claim 1 regulation and control nanometer g-C3N4The method of organic photocatalyst, its feature exists
In, comprising the following steps: with tripolycyanamide as raw material, calcining obtains pure phase g-C in atmosphere3N4Powder, then it is added into peroxide
Change in hydrogen solution, sonicated after, centrifugal dry, it is thus achieved that oxonium ion surface regulation and control nanometer g-C3N4Organic photocatalyst.
3. regulation and control nanometer g-C in oxonium ion surface as claimed in claim 23N4The preparation method of organic photocatalyst, its feature exists
In, specifically include following steps:
1) pure phase g-C3N4Preparation: with tripolycyanamide as raw material, in air 400～700 DEG C calcining 1～7h, control heat up speed
Rate is 0.1～5 DEG C/min, takes out, it is thus achieved that pure phase g-C after being cooled to room temperature3N4Powder；
2)g-C3N4The preparation of nanometer sheet and surface oxidation treatment: the g-C that will prepare3N4It is 30% that powder adds mass fraction
In hydrogenperoxide steam generator so that hydrogen peroxide and g-C3N4Mol ratio be (200～1000): 1, by dilute hydrochloric acid or dilute hydroxide
The pH value of sodium regulation mixed solution is to 1～11；This solution is placed in ultrasonic machine in 20～100 DEG C of supersound process 1-10h afterwards,
Centrifugal, drying, it is thus achieved that nanometer g-C of oxonium ion surface regulation and control3N4Organic photocatalyst.
Oxonium ion surface the most according to claim 3 regulation and control nanometer g-C3N4The preparation method of organic photocatalyst, its feature
Be, step 1) described in calcining heat be 550 DEG C.
Oxonium ion surface the most according to claim 3 regulation and control nanometer g-C3N4The preparation method of organic photocatalyst, its feature
Be, step 1) described in heating rate be 2 DEG C/min.
Oxonium ion surface the most according to claim 3 regulation and control nanometer g-C3N4The preparation method of organic photocatalyst, its feature
Be, step 2) in H2O2With g-C3N4Mol ratio be (600～800): 1, and be 2 by described mixed solution pH regulator.
Oxonium ion surface the most according to claim 3 regulation and control nanometer g-C3N4The preparation method of organic photocatalyst, its feature
Be, step 2) in the heating-up temperature of supersound process be 40 DEG C, the process time is 10h.
8. nanometer g-C of oxonium ion surface regulation and control3N4Organic photocatalyst, it is characterised in that by such as claim 2-7
Method described in any one prepares.
9. nanometer g-C of oxonium ion surface as claimed in claim 8 regulation and control3N4Organic photocatalyst applications is in organic dirt of degrading
Dye thing.
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| CN110801856A (en) * | 2019-11-25 | 2020-02-18 | 兰州大学 | Synthesis and application of graphite-phase carbon nitride-ammonium tungsten bronze composite photocatalyst |
| CN112079409A (en) * | 2020-09-14 | 2020-12-15 | 西南石油大学 | Method and device for shielding dye sensitization phenomenon in photocatalytic dye degradation by light filtering method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106914266A (en) * | 2017-03-06 | 2017-07-04 | 南方科技大学 | A kind of g C of fast degradation pollutant3N4Composite photo-catalyst and preparation method thereof |
| CN106914266B (en) * | 2017-03-06 | 2020-09-08 | 南方科技大学 | g-C for fast degrading pollutant3N4Composite photocatalyst and preparation method thereof |
| CN106955727A (en) * | 2017-04-14 | 2017-07-18 | 中国石油大学(华东) | The g C that a kind of surface is modified3N4Preparation |
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| CN107649168A (en) * | 2017-11-09 | 2018-02-02 | 江苏省环境科学研究院 | The method of bisphenol-A and its catalyst used in a kind of photocatalytic degradation water |
| CN107649168B (en) * | 2017-11-09 | 2020-04-03 | 江苏省环境科学研究院 | Method for degrading bisphenol A in water through photocatalysis and catalyst used by method |
| CN110801856A (en) * | 2019-11-25 | 2020-02-18 | 兰州大学 | Synthesis and application of graphite-phase carbon nitride-ammonium tungsten bronze composite photocatalyst |
| CN112079409A (en) * | 2020-09-14 | 2020-12-15 | 西南石油大学 | Method and device for shielding dye sensitization phenomenon in photocatalytic dye degradation by light filtering method |
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