CN110142055A - Enhance the microwave irradiation method of graphite phase carbon nitride photocatalysis performance - Google Patents

Enhance the microwave irradiation method of graphite phase carbon nitride photocatalysis performance Download PDF

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Publication number
CN110142055A
CN110142055A CN201810142188.1A CN201810142188A CN110142055A CN 110142055 A CN110142055 A CN 110142055A CN 201810142188 A CN201810142188 A CN 201810142188A CN 110142055 A CN110142055 A CN 110142055A
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carbon nitride
phase carbon
graphite phase
microwave irradiation
minutes
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CN110142055B (en
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毛智勇
刘怡
王达健
唐义骅
陈静静
安娜
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Tju Binhai Industrial Research Institute Co ltd
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Tianjin University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • B01J35/39
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341Irradiation 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
    • B01J37/344Irradiation 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 electromagnetic wave energy
    • B01J37/346Irradiation 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 electromagnetic wave energy of microwave energy
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents

Abstract

The invention discloses a kind of microwave irradiation methods for enhancing graphite phase carbon nitride photocatalysis performance, the following steps are included: graphite phase carbon nitride is evenly spread in ethyl alcohol, obtain precursor ethanol mixture, by the precursor ethanol mixture microwave irradiation N minutes in micro-wave oven, obtain modified graphite phase carbon nitride, wherein, N=1~5, the power of microwave irradiation are 800~1000W;The ratio of the quality of the graphite phase carbon nitride and the volume of the ethyl alcohol is 5:(1~4).Microwave irradiation method of the invention can simply, efficiently improve the catalytic efficiency of graphite phase carbon nitride, achieve the effect that fast decoupled organic pollutant under radiation of visible light, and simple process, preparation process are pollution-free, it is significant to the Photocatalytic Performance Study of carbon nitride material.

Description

Enhance the microwave irradiation method of graphite phase carbon nitride photocatalysis performance
Technical field
The invention belongs to catalysis material preparation and applied technical fields, and in particular to a kind of enhancing graphite phase carbon nitride light is urged Change the microwave irradiation method of performance.
Background technique
Modern society, environmental pollution increasingly become a very important problem, especially water pollution, live to people Cause very big harm.Traditionally many measures, such as emerging inorganic non-metallic are taken in order to handle contaminated water Catalysis, wherein graphite phase carbon nitride has the advantages that efficient, succinct, there is outstanding pollutant drop under the irradiation of visible light Solution ability.The stratiform packed structures of graphite phase carbon nitride are similar to graphite, and electronic band structure makes it have outstanding catalysis Performance, including photocatalysis degradation organic contaminant and photolysis water hydrogen.In order to by the catalytic performance of graphite phase carbon nitride into one Step improves, and the method being modified to it is also varied, including the common methods such as compound, doped metal ion, also changes including form The methods of become, be surface-treated.Although graphite phase carbon nitride is inorganic non-metallic catalyst of good performance at this stage, but it is urged Change the space that efficiency still has promotion.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of enhancing graphite phase carbon nitride photocatalysis performances Microwave irradiation method, which can simply, efficiently improve the catalytic efficiency of graphite phase carbon nitride.
It is a further object of the present invention to provide a kind of modified graphite phase carbon nitrides.
It is a further object of the present invention to provide a kind of microwave irradiation methods in enhancing graphite phase carbon nitride photocatalysis performance Application.
The present invention is achieved by the following technical solutions:
A kind of microwave irradiation method enhancing graphite phase carbon nitride photocatalysis performance, comprising the following steps:
Graphite phase carbon nitride is evenly spread in ethyl alcohol, precursor ethanol mixture is obtained, by the precursor ethanol Mixture obtains modified graphite phase carbon nitride microwave irradiation N minutes in micro-wave oven, wherein N=1~5, microwave The power of irradiation is 800~1000W;The ratio of the quality of the graphite phase carbon nitride and the volume of the ethyl alcohol is 5:(1~4).
In the above-mentioned technical solutions, the micro-wave oven is household microwave oven.
In the above-mentioned technical solutions, the unit of the quality is g, and the unit of the volume is L.
In the above-mentioned technical solutions, as the N > 1, N minutes of the microwave irradiation is divided into n times interruption and is carried out, often Microwave irradiation suspends after 1 minute, is further continued for carrying out after the precursor ethanol mixture cools to 20~25 DEG C of room temperature with the furnace Microwave irradiation, until whole microwave irradiation times reach N minutes.
In the above-mentioned technical solutions, the graphite phase carbon nitride the preparation method comprises the following steps: under air environment, by melamine Amine, urea, dicyanodiamine or thiocarbamide are warming up to 550~600 DEG C from 20~25 DEG C of room temperature and keep the temperature 2~3 hours, obtain the graphite Phase carbon nitride, wherein the rate of heating is 2~10 DEG C/min.
The modified graphite phase carbon nitride that above-mentioned microwave irradiation method obtains.
Application of the above-mentioned microwave irradiation method in enhancing graphite phase carbon nitride photocatalysis performance.
Application of the above-mentioned modified graphite phase carbon nitride in shortening the photocatalysis time.
In the above-mentioned technical solutions, by the modified graphite phase carbon nitride be added into dye solution and by visible light into Row irradiation, degrades after 10min, the surplus ratio of dyestuff is less than 20% in the dye solution;It is described when degradation is to 15min Dyestuff is degradable.
In the above-mentioned technical solutions, the dyestuff is rhodamine B, the quality and the dye of the modified graphite phase carbon nitride The ratio for expecting the concentration of solution is 0.1:20, and the unit of the quality is g, and the unit of the concentration is mg/L.
Compared to now possessing technology, microwave irradiation method of the invention can simply, efficiently improve graphite phase carbon nitride Catalytic efficiency, achieve the effect that fast decoupled organic pollutant under radiation of visible light, and simple process, preparation process are without dirt Dye, it is significant to the Photocatalytic Performance Study of carbon nitride material.
Detailed description of the invention
Fig. 1 is the XRD diffracting spectrum of graphite phase carbon nitride and modified graphite phase carbon nitride;
Fig. 2 is the FTIR spectrum of graphite phase carbon nitride and modified graphite phase carbon nitride;
Fig. 3 is the BET map of graphite phase carbon nitride and modified graphite phase carbon nitride;
Fig. 4 is the SEM and TEM of graphite phase carbon nitride and modified graphite phase carbon nitride;
Fig. 5 is the light degradation rhodamine B performance map of graphite phase carbon nitride and modified graphite phase carbon nitride.
Specific embodiment
In order to enable those skilled in the art to better understand the present invention/scheme of the invention, it is with reference to the accompanying drawing and specific real It applies example and further illustrates technical solution of the present invention.
In a specific embodiment of the invention, urea CO (NH2)2It buys from Hengshan Mountain chemical industry, rhodamine B (RhB) C28H37ClN2O3It buys from Tianjin good fortune morning chemical reagent factory, ethyl alcohol C2H6O is bought from Hengshan Mountain chemical industry, and the purity of mentioned reagent is equal It is pure to analyze.
Micro-wave oven is household microwave oven, and concrete model is the KD21C, AN (B) of beauty;
The test equipment and model of XRD are as follows: x-ray powder diffraction instrument, RINT Ultima- III, Japanese Rigaku are public Department;
The test equipment and model of SEM are as follows: scanning electron microscope, S-4800, Japanese Hitachi company;
The test equipment and model of TEM are as follows: high-resolution-ration transmission electric-lens instrument, JEM-6700F, Japanese Hitachi company;
The test equipment and model of FTIR spectrum are as follows: Fourier infrared spectrograph, WQE-410, Bruker company, the U.S.;
The test equipment and model of BET map are as follows: Full-automatic physical chemical adsorption instrument, AUTOSORB-1, U.S. Kang Ta Company;
The test equipment and model of light degradation rhodamine B performance map are as follows: ultraviolet-uisible spectrophotometer, TU-1901, north Jing Puxi all purpose instrument Co., Ltd;The test method of light degradation rhodamine B performance map is as follows: configuration concentration 20mg/ The rhodamine B solution of L takes 100ml rhodamine B solution as simulating pollution object, takes sample to be tested (graphite phase carbon nitride and modification Graphite phase carbon nitride) it 0.1g and is put into simulating pollution object, it carries out shading dark treatment (beaker is wrapped with tinfoil), by magnetic Power stirs 40min, reach first sampling after adsorption equilibrium it is primary (sampling about 7ml upper solution, at this time 0) irradiation time is set as, Start to test, i.e., is irradiated (while magnetic agitation) by visible light (>=420nm), illumination 30min terminates, wherein every 5min sampling is primary, and 7 samples (1 time including 6 times in test process and before testing) will be taken to be centrifuged respectively, take upper layer clear Clear its ultravioletvisible absorption all-wave scanning spectra of liquid testing, data are the absorbance of rhodamine B at 554nm.With testing In 6 samples taken in journey the absorbance of (remaining) rhodamine B respectively with rhodamine B in 1 samples taken before test Absorbance (i.e. initial soln) compare, the as surplus ratio of dyestuff.
Rhodamine B or methyl orange can be used in graphite phase carbon nitride and the organic pollutant of modified graphite phase carbon nitride degradation To simulate.
Embodiment 1
A kind of microwave irradiation method enhancing graphite phase carbon nitride photocatalysis performance, comprising the following steps:
The graphite phase carbon nitride of pale yellow powder shape is evenly spread in ethyl alcohol, precursor ethanol mixture is obtained, it will Precursor ethanol mixture microwave irradiation 4 minutes in micro-wave oven, obtain modified graphite phase carbon nitride, wherein 4 minutes Microwave irradiation, which is divided into 4 interruptions, to carry out, and every microwave irradiation suspends after 1 minute, cools to room with the furnace to precursor ethanol mixture It is further continued for carrying out microwave irradiation after 20~25 DEG C of temperature, until whole microwave irradiation times reach 4 minutes;The power of microwave irradiation is 800W;The quality of graphite phase carbon nitride is 0.5g, and the volume of ethyl alcohol is 200mL.
Wherein, graphite phase carbon nitride the preparation method comprises the following steps: the urea as presoma is fitted into corundum crucible, in air Under environment, crucible is placed in Muffle furnace, so that urea is warming up to 550 DEG C from 20~25 DEG C of room temperature and keeps the temperature 3 hours, obtain graphite-phase Carbonitride, wherein the rate of heating is 10 DEG C/min.
Fig. 1 is that the XRD diffracting spectrum of graphite phase carbon nitride and modified graphite phase carbon nitride changes as seen from the figure in embodiment 1 Property graphite phase carbon nitride be carbonitride, wherein MT-g-C3N4For modified graphite phase carbon nitride, g-C3N4For graphite phase carbon nitride.
Fig. 2 is the FTIR spectrum of graphite phase carbon nitride and modified graphite phase carbon nitride in embodiment 1, wherein MT-g-C3N4 For modified graphite phase carbon nitride, g-C3N4For graphite phase carbon nitride.As seen from the figure, the modified graphite phase nitrogen after microwave treatment The absorbance for changing-OH group of carbon improves, and the graphite phase carbon nitride the adsorbed hydroxyl content after showing microwave treatment increases.
Fig. 3 is the BET map of graphite phase carbon nitride and modified graphite phase carbon nitride in embodiment 1, wherein MT-g-C3N4For Modified graphite phase carbon nitride, g-C3N4For graphite phase carbon nitride.As seen from the figure, the modified graphite after microwave treatment mutually nitrogenizes The specific surface area and porosity of carbon is all promoted, and specific surface area is by 66.7m2/ g (graphite phase carbon nitride) is promoted to 72.5m2/g (modified graphite phase carbon nitride).
Fig. 4 is SEM the and TEM map of graphite phase carbon nitride and modified graphite phase carbon nitride in embodiment 1, wherein Fig. 4 It (a) is the SEM of graphite phase carbon nitride, Fig. 4 (b) is the SEM of modified graphite phase carbon nitride, and Fig. 4 (c) is graphite phase carbon nitride TEM, Fig. 4 (d) are the TEM of modified graphite phase carbon nitride.As seen from the figure, modified graphite phase carbon nitride lamellar structure become thinner and It is loose porous.
EDX elemental analysis shows g-C3N4The C/N molar ratio and O content of (C/N=1.40, O=1.40at%) are lower than MT- g-C3N4(C/N=1.51, O=3.25at%), shows MT-g-C3N4Nitrogen is likely to form in (modified graphite phase carbon nitride) skeleton Vacancy defect or microwave bombardment may cause C-NH2Conversion of the end group to C-OH group.
Embodiment 2
A kind of microwave irradiation method enhancing graphite phase carbon nitride photocatalysis performance, comprising the following steps:
The graphite phase carbon nitride of pale yellow powder shape is evenly spread in ethyl alcohol, precursor ethanol mixture is obtained, it will Precursor ethanol mixture microwave irradiation 3 minutes in micro-wave oven, obtain modified graphite phase carbon nitride, wherein 3 minutes Microwave irradiation, which is divided into 3 interruptions, to carry out, and every microwave irradiation suspends after 1 minute, cools to room with the furnace to precursor ethanol mixture It is further continued for carrying out microwave irradiation after 20~25 DEG C of temperature, until whole microwave irradiation times reach 3 minutes;The power of microwave irradiation is 800W;The quality of graphite phase carbon nitride is 0.5g, and the volume of ethyl alcohol is 200mL.
Wherein, the preparation method of graphite phase carbon nitride is thermal polycondensation process, specifically: urea is fitted into corundum crucible, Under air environment, crucible is placed in Muffle furnace, so that urea is warming up to 550 DEG C from 20~25 DEG C of room temperature and keeps the temperature 3 hours, obtain stone Black phase carbon nitride, wherein the rate of heating is 10 DEG C/min.
Embodiment 3
A kind of microwave irradiation method enhancing graphite phase carbon nitride photocatalysis performance, comprising the following steps:
The graphite phase carbon nitride of pale yellow powder shape is evenly spread in ethyl alcohol, precursor ethanol mixture is obtained, it will Precursor ethanol mixture microwave irradiation 5 minutes in micro-wave oven, obtain modified graphite phase carbon nitride, wherein 5 minutes Microwave irradiation, which is divided into 5 interruptions, to carry out, and each microwave irradiation suspends after 1 minute, cools to the furnace to precursor ethanol mixture It is further continued for carrying out microwave irradiation after 20~25 DEG C of room temperature, until whole microwave irradiation times reach 5 minutes;The power of microwave irradiation For 800W;The quality of graphite phase carbon nitride is 0.5g, and the volume of ethyl alcohol is 200mL.
Wherein, graphite phase carbon nitride the preparation method comprises the following steps: urea is fitted into corundum crucible, under air environment, by earthenware Crucible is placed in Muffle furnace, so that urea is warming up to 550 DEG C from 20~25 DEG C of room temperature and is kept the temperature 3 hours, obtains graphite phase carbon nitride, In, the rate of heating is 10 DEG C/min.
Fig. 5 is the light degradation rhodamine B performance map of graphite phase carbon nitride and modified graphite phase carbon nitride in Examples 1 to 3 (visible light source being replaced with the xenon lamp with 420nm edge filter, organic pollutant is rhodamine B), wherein curve 1 is absorption Blank control is balanced, i.e., sample made from embodiment 1, not illumination, it was demonstrated that other curve dyestuffs disappear are added in rhodamine B solution Failure fruit is generated by degradation, and non-adsorbed.Curve 2 is the light degradation rhodamine B performance map of graphite phase carbon nitride, and curve 3 is The light degradation rhodamine B performance map for the modified graphite phase carbon nitride that embodiment 2 obtains, curve 4 are the modification stone that embodiment 1 obtains The light degradation rhodamine B performance map of black phase carbon nitride, curve 5 are the light degradation for the modified graphite phase carbon nitride that embodiment 3 obtains Rhodamine B performance map.As seen from the figure, compared to graphite phase carbon nitride, modified graphite phase carbon nitride the disposal efficiency is obviously improved, And the disposal efficiency highest of the modified graphite phase carbon nitride by 4 minutes microwave irradiations, using modified stone made from embodiment 1 When black phase carbon nitride degradation 10min, the surplus ratio of dyestuff (rhodamine B) is less than 20% (before starting illumination in solution The amount of the substance of rhodamine B), when 15min, is degradable.Other embodiments sample, degradable dyestuff at least want 20min, former Beginning graphite phase carbon nitride is even more to need 30min that could complete to degrade.Microwave irradiation improves the separative efficiency of photo-generated carrier, promotees The absorption of organic pollutant, respond on into surface.
Illustrative description is done to the present invention/invention above, it should which explanation is not departing from core of the invention In the case of, any simple deformation, modification or other skilled in the art can not spend being equal for creative work to replace It changes and each falls within the present invention/invention protection scope.

Claims (10)

1. a kind of microwave irradiation method for enhancing graphite phase carbon nitride photocatalysis performance, which comprises the following steps:
Graphite phase carbon nitride is evenly spread in ethyl alcohol, precursor ethanol mixture is obtained, the precursor ethanol is mixed Object obtains modified graphite phase carbon nitride microwave irradiation N minutes in micro-wave oven, wherein N=1~5, microwave irradiation Power be 800~1000W;The ratio of the quality of the graphite phase carbon nitride and the volume of the ethyl alcohol is 5:(1~4).
2. microwave irradiation method according to claim 1, which is characterized in that the preparation method of the graphite phase carbon nitride Are as follows: under air environment, melamine, urea, dicyanodiamine or thiocarbamide are warming up to 550~600 DEG C from 20~25 DEG C of room temperature Heat preservation 2~3 hours, obtains the graphite phase carbon nitride, wherein the rate of heating is 2~10 DEG C/min.
3. microwave irradiation method according to claim 2, which is characterized in that micro- by described N minutes as the N > 1 Amplitude is carried out according to n times interruption is divided into, and every microwave irradiation suspends after 1 minute, cools to the furnace to the precursor ethanol mixture It is further continued for carrying out microwave irradiation after 20~25 DEG C of room temperature, until whole microwave irradiation times reach N minutes.
4. microwave irradiation method according to claim 3, which is characterized in that the unit of the quality is g, the volume Unit is L.
5. microwave irradiation method according to claim 4, which is characterized in that the micro-wave oven is household microwave oven.
6. the modified graphite phase carbon nitride that microwave irradiation method as claimed in claim 1 or 2 obtains.
7. modified graphite phase carbon nitride according to claim 6, which is characterized in that as the N > 1, by described N minutes Microwave irradiation, which is divided into n times interruption, to carry out, and every microwave irradiation suspends after 1 minute, to the precursor ethanol mixture furnace cooling It is further continued for carrying out microwave irradiation after to 20~25 DEG C of room temperature, until whole microwave irradiation times reach N minutes.
8. modified graphite phase carbon nitride according to claim 7, which is characterized in that the suction of the modified graphite phase carbon nitride The mean values of attached rate are 72.5m2/g。
9. microwave irradiation method is in enhancing graphite phase carbon nitride photocatalysis performance as described in any one of Claims 1 to 5 Application.
10. application as claimed in claim 9, which is characterized in that being added the modified graphite phase carbon nitride to dye solution In and be irradiated by visible light, degrade after 10min, the surplus ratio of dyestuff is less than 20% in the dye solution;Work as degradation When to 15min, the dyestuff is degradable.
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Cited By (1)

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