CN107999110A - A kind of Lacking oxygen tungsten oxide/nitridation carbon composite photocatalyst and its preparation method and application - Google Patents
A kind of Lacking oxygen tungsten oxide/nitridation carbon composite photocatalyst and its preparation method and application Download PDFInfo
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- CN107999110A CN107999110A CN201711124824.XA CN201711124824A CN107999110A CN 107999110 A CN107999110 A CN 107999110A CN 201711124824 A CN201711124824 A CN 201711124824A CN 107999110 A CN107999110 A CN 107999110A
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- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 title claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000428 dust Substances 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 22
- 238000012545 processing Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 10
- 230000005588 protonation Effects 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 230000002045 lasting effect Effects 0.000 claims abstract description 3
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000010842 industrial wastewater Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 4
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- 239000004065 semiconductor Substances 0.000 abstract description 9
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 18
- 230000001699 photocatalysis Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 229910003091 WCl6 Inorganic materials 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 125000005909 ethyl alcohol group Chemical group 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002023 wood 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—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The present invention relates to a kind of Lacking oxygen tungsten oxide/nitridation carbon composite photocatalyst and its preparation method and application, the preparation method of the composite photo-catalyst is as follows：S1：Nitridation carbon dust is placed in hydrochloric acid solution and carries out protonation processing, filtering, washing, drying after lasting stirring；S2：The nitridation carbon dust for protonating processing is scattered in absolute ethyl alcohol or water and is ultrasonically treated, tungsten hexachloride is then added and carries out hydro-thermal reaction；S3：The product of hydro-thermal reaction and washing, drying, grinding are collected, up to the Lacking oxygen tungsten oxide/nitridation carbon composite photocatalyst.The present invention is with Lacking oxygen WO2.72Processing is doped to carbonitride as doped semiconductor, the Lacking oxygen structure of tungsten oxide can provide more avtive spots, while Lacking oxygen tungsten oxide/carbonitride in light-catalyzed reaction（WO2.72/C3N4）Composite material has the energy gap of bigger, there is broader response range to sunlight.
Description
Technical field
The present invention relates to photocatalysis technology field, and in particular, to a kind of Lacking oxygen tungsten oxide/carbonitride composite photocatalyst
Agent and its preparation method and application.
Background technology
The oxide of tungsten belongs to novel semiconductor material, has good photocatalytic activity, wherein WO2.72（That is W18O49）It is
The unique a kind of tungsten oxide with non-stoichiometric existing for pure state being currently known.Because oxygen present in its crystal structure is empty
Position defect, makes it have the properties such as the photochromic of uniqueness, near infrared absorption, photocatalysis.But WO2.72At present also in experiment
In the room stage, synthesis cost is higher, product poor controllability, in order to preferably promote the use of, also needs to seek a kind of of low cost, operation
Simple preparation method.Hongye Zhang et al. have successfully prepared the WO of Lacking oxygen using hydro-thermal method2.72, it is easy to operate,
To experimental facilities also without excessive requirement, there is very big application space.
C and N is two kinds of elements that reserves are most abundant on the earth, and polymer semiconductor's carbonitride that they are formed is also because of its ring
Protect, the property such as nontoxic, stability is good is as the visible light catalytic material to receive much concern in recent years.But the ratio of simple carbonitride
Surface area is smaller, and energy gap is larger, and the recombination rate of photo-generate electron-hole pair is higher, it is impossible to efficiently uses sunlight, the big day of one's doom
The raising of its photocatalysis efficiency and the development in photocatalysis field are made.In order to further improve the photocatalytic activity of carbonitride,
Semiconductor doping processing can be carried out to it.
Therefore, it is necessary to seek a kind of semi-conducting material of energy level band-gap, to carbonitride after doped semiconductor, show
Write the purpose for improving its photocatalysis performance.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of Lacking oxygen tungsten oxide/carbonitride complex light
Catalyst, the present invention is with Lacking oxygen WO2.72Processing, the Lacking oxygen knot of tungsten oxide are doped to carbonitride as doped semiconductor
Structure can provide more avtive spots, while Lacking oxygen tungsten oxide/carbonitride in light-catalyzed reaction（WO2.72/C3N4）It is compound
Material has the energy gap of bigger, there is broader response range to sunlight.
Another object of the present invention is to provide application of the above-mentioned composite photo-catalyst in photocatalytic degradation industrial wastewater.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of Lacking oxygen tungsten oxide/carbonitride（WO2.72/C3N4）Composite photo-catalyst, the preparation method of the composite photo-catalyst
It is as follows：
S1：Nitridation carbon dust is placed in hydrochloric acid solution and carries out protonation processing, filtering, washing, drying after lasting stirring；
S2：The nitridation carbon dust for protonating processing is scattered in absolute ethyl alcohol or water and is ultrasonically treated, then adds chlordene
Change tungsten and carry out hydro-thermal reaction；
S3：The product of hydro-thermal reaction and washing, drying, grinding are collected, is urged up to the Lacking oxygen tungsten oxide/carbonitride complex light
Agent；
Wherein, in S2, the temperature of the hydro-thermal reaction is 180~220 DEG C, and the reaction time is 10~15h；The carbonitride and six
The mass ratio of tungsten chloride is 1：0.398~3.965.
The present invention is with Lacking oxygen WO2.72Processing, the Lacking oxygen of tungsten oxide are doped to carbonitride as doped semiconductor
Structure can provide more avtive spots, while Lacking oxygen tungsten oxide/carbonitride in light-catalyzed reaction（WO2.72/C3N4）It is multiple
Condensation material has the energy gap of bigger, there is broader response range to sunlight.Therefore, Lacking oxygen oxidation provided by the invention
Tungsten/nitridation carbon composite photocatalyst has more excellent photocatalytic activity.
In the present invention, it is ultrasonically treated and is on the one hand to make carbonitride be uniformly dispersed, still further aspect is ultrasonically treated can
Further to increase carbon nitride layer spacing, tungsten oxide can also be made evenly to be supported on carbon nitride layer while increasing specific surface area
Between.
Preferably, in S2, the temperature of the hydro-thermal reaction is 195~205 DEG C, and the reaction time is 11~13h；The nitridation
The mass ratio of carbon and tungsten hexachloride is 1：0.398~1.985.
Preferably, in S2, the temperature of the hydro-thermal reaction is 200 DEG C, reaction time 12h；The carbonitride and chlordene
The mass ratio for changing tungsten is 1：0.99.
Preferably, in S1, the concentration of the hydrochloric acid solution is 5~8mol/L.It is further preferable that in S1, the hydrochloric acid is molten
The concentration of liquid is 6mol/L.
In the S1 of the present invention, the presoma for preparing the nitridation carbon dust is urea, thiocarbamide or melamine.By forerunner
Body is placed in ceramics crucible with cover, and calcination processing is carried out in Muffle furnace.Heating parameters in Muffle furnace are：Heating rate 1~3
DEG C/min, kept after being warming up to 550 DEG C 3~5 it is small when, then cooled to room temperature.
Preferably, in S1, time for persistently stirring for 24 it is small when more than.
Preferably, it is described dispersed for using being ultrasonically treated, sonication treatment time is 10~60min in S2.
Preferably, in S3, the drying be in vacuum drying chamber in dried under the conditions of 60 DEG C 5~12 it is small when until dry.
Application of the above-mentioned composite photo-catalyst in photocatalytic degradation industrial wastewater is also within protection scope of the present invention.
Compared with prior art, the present invention has the advantages that：
The present invention is with Lacking oxygen WO2.72Processing, the Lacking oxygen structure of tungsten oxide are doped to carbonitride as doped semiconductor
More avtive spots, while Lacking oxygen tungsten oxide/carbonitride can be provided in light-catalyzed reaction（WO2.72/C3N4）Composite wood
Energy gap of the material with bigger, has sunlight broader response range.The preparation of composite photo-catalyst provided by the invention
Technique is simple, repeatability is high, and preparation process can be completed without too high requirement, common lab to experimental instrument and equipment.
Brief description of the drawings
Fig. 1 is the WO that various embodiments of the present invention provide2.72/C3N4The XRD test charts of composite photo-catalyst；
Fig. 2 is the WO that various embodiments of the present invention provide2.72/C3N4The drop for the industrial wastewater that composite photo-catalyst simulates methyl orange
Solve design sketch；
Fig. 3 is the WO that each comparative example of the present invention provides2.72/C3N4The drop for the industrial wastewater that composite photo-catalyst simulates methyl orange
Solve design sketch.
Embodiment
Further illustrate the present invention below in conjunction with specific embodiments and the drawings, but embodiment the present invention is not done it is any
The restriction of form.Unless stated otherwise, the reagent of the invention used, method and apparatus is the art conventional reagent, methods
And equipment.
Unless stated otherwise, agents useful for same and material of the present invention are purchased in market.
Embodiment 1
A kind of Lacking oxygen tungsten oxide/nitridation carbon composite photocatalyst, it is described（WO2.72/C3N4）The preparation method of composite photo-catalyst
It is as follows：
（1）Weigh 20g urea to be placed in ceramics crucible with cover, protected after being warming up to 550 DEG C in Muffle furnace with the speed of 2 DEG C/min
Hold 4 it is small when, cooled to room temperature obtain nitridation carbon dust；The nitridation carbon dust 0.5g prepared is taken to be dispersed in 500ml concentration
For in the hydrochloric acid of 6M, persistently stir 24 it is small when after nitridation carbon dust is collected by centrifugation, three times and dried with deionized water washing；
（2）Weigh 0.1g protonation carbonitrides to be dispersed in 75ml absolute ethyl alcohols and be ultrasonically treated 10min, add
0.0398gWCl6（The mass ratio of carbonitride and WCl6 are 1:0.398）；It is placed in autoclave, 200 DEG C of hydro-thermal process 12h；
（3）Will（2）Hydro-thermal process product is washed three times after being cooled to room temperature, and 60 DEG C of vacuum drying 10h obtain WO2.72：C3N4Quality
Than the composite photo-catalyst for 0.2（It is named as WOCN1）.
Embodiment 2
A kind of Lacking oxygen tungsten oxide/nitridation carbon composite photocatalyst, it is described（WO2.72/C3N4）The preparation method of composite photo-catalyst
It is as follows：
（1）Weigh 20g urea to be placed in ceramics crucible with cover, protected after being warming up to 550 DEG C in Muffle furnace with the speed of 2 DEG C/min
Hold 3 it is small when, cooled to room temperature obtain nitridation carbon dust；The nitridation carbon dust 0.5g prepared is taken to be dispersed in 500ml concentration
For in the hydrochloric acid of 5M, persistently stir 24 it is small when after nitridation carbon dust is collected by centrifugation, three times and dried with deionized water washing；
（2）Weigh 0.1g protonation carbonitrides to be dispersed in 75ml absolute ethyl alcohols and be ultrasonically treated 10min, add 0.099gWCl6
（The mass ratio of carbonitride and WCl6 are 1:0.99）；It is placed in autoclave, 180 DEG C of hydro-thermal process 15h；
（3）Will（2）Hydro-thermal process product is washed three times after being cooled to room temperature, and 60 DEG C of vacuum drying 10h obtain WO2.72：C3N4Quality
Than the composite photo-catalyst for 0.5（It is named as WOCN2）.
Embodiment 3
A kind of Lacking oxygen tungsten oxide/nitridation carbon composite photocatalyst, it is described（WO2.72/C3N4）The preparation method of composite photo-catalyst
It is as follows：
（1）Weigh 20g urea to be placed in ceramics crucible with cover, protected after being warming up to 550 DEG C in Muffle furnace with the speed of 2 DEG C/min
Hold 3 it is small when, cooled to room temperature obtain nitridation carbon dust；The nitridation carbon dust 0.5g prepared is taken to be dispersed in 500ml concentration
For in the hydrochloric acid of 7M, persistently stir 24 it is small when after nitridation carbon dust is collected by centrifugation, three times and dried with deionized water washing；
（2）Weigh 0.1g protonation carbonitrides to be dispersed in 75ml absolute ethyl alcohols and be ultrasonically treated 10min, add
0.1985gWCl6（Carbonitride and WCl6Mass ratio be 1:1.985）；It is placed in autoclave, 220 DEG C of hydro-thermal process 10h；
（3）Will（2）Hydro-thermal process product is washed three times after being cooled to room temperature, and 60 DEG C of vacuum drying 10h obtain WO2.72：C3N4Quality
Than the composite photo-catalyst for 1.0（It is named as WOCN3）.
Embodiment 4
A kind of Lacking oxygen tungsten oxide/nitridation carbon composite photocatalyst, it is described（WO2.72/C3N4）The preparation method of composite photo-catalyst
It is as follows：
（1）Weigh 20g urea to be placed in ceramics crucible with cover, protected after being warming up to 550 DEG C in Muffle furnace with the speed of 2 DEG C/min
Hold 4 it is small when, cooled to room temperature obtain nitridation carbon dust；The nitridation carbon dust 0.5g prepared is taken to be dispersed in 500ml concentration
For in the hydrochloric acid of 6M, persistently stir 24 it is small when after nitridation carbon dust is collected by centrifugation, three times and dried with deionized water washing；
（2）Weigh 0.1g protonation carbonitrides to be dispersed in 75ml absolute ethyl alcohols and be ultrasonically treated 10min, add
0.3965gWCl6（The mass ratio of carbonitride and WCl6 are 1:3.965）；It is placed in autoclave, 195 DEG C of hydro-thermal process 13h；
（3）Will（2）Hydro-thermal process product is washed three times after being cooled to room temperature, and 60 DEG C of vacuum drying 10h obtain WO2.72：C3N4Quality
Than the composite photo-catalyst for 2.0.
Comparative example 1
Step is removed in this comparative example（1）The middle sulfuric acid solution for selecting same concentrations is substituted outside hydrochloric acid solution, other raw materials and system
Preparation Method is same as Example 1.The composite photo-catalyst that this comparative example is prepared is named as WOCN4.
Comparative example 2
Step is removed in this comparative example（2）In hydrothermal temperature be outside 150 DEG C, other raw materials and preparation method with embodiment 1
It is identical.The composite photo-catalyst that this comparative example is prepared is named as WOCN5.
Comparative example 3
Step is removed in this comparative example（2）In hydrothermal conditions be outside 5h, other raw materials and preparation method with embodiment 1
It is identical.The composite photo-catalyst that this comparative example is prepared is named as WOCN6.
Comparative example 4
Step is removed in this comparative example（2）In the dosage of tungsten chloride be outside 0.5949g, other raw materials and preparation method with reality
It is identical to apply example 1.The composite photo-catalyst that this comparative example is prepared is named as WOCN7.
Fig. 1 is the XRD test charts for the composite photo-catalyst that various embodiments of the present invention are prepared, as shown in Figure 1, at 23 °
With 27 ° at occur WO respectively2.72And C3N4Characteristic peak.
Fig. 2 and Fig. 3 is the WO that various embodiments of the present invention are prepared2.72/C3N4Composite photo-catalyst and comparative example and
The degradation effect figure for the industrial wastewater that pure carbon nitride photocatalyst simulates methyl orange.The experiment number of embodiment 1,2,3 from Fig. 2
According to can be seen that simple Lacking oxygen WO2.72Under visible light illumination to methyl orange almost without Photocatalytic activity；
WO2.72/C3N4Composite photo-catalyst is relative to simple C3N4, its catalytic activity is significantly improved.
If change the hydrochloric acid used in protonation processing procedure into sulphur it can be seen from the experimental result of comparative example in Fig. 31
Acid, other conditions are constant, and obtained product photocatalytic activity is less than simple carbonitride, do not play and improve light-catalysed purpose；
Change temperature or the processing time in water-heat process it can be seen from the experimental result of comparative example 2 and comparative example 3, also do not have equally
Obtain preferable photocatalytic degradation effect；It is opposite when tungsten oxide and carbonitride it can be seen from the experimental result of comparative example 4
When mass ratio is improper, the catalytic activity of composite photo-catalyst has declined on the contrary, hence it is evident that less than simple carbonitride.Thus may be used
See, in the present invention, the mass ratio of carbonitride and tungsten chloride, the temperature and time of hydro-thermal process and protonation handle the acid selected
Solution can all influence the photocatalytic activity of composite photo-catalyst.
Above-described embodiment, has carried out the purpose of the present invention, technical solution and beneficial effect further
Describe in detail, it should be understood that the foregoing is merely the embodiment of the present invention, be not intended to limit the present invention
Protection domain, within the spirit and principles of the invention, any modification, equivalent substitution, improvement and etc. done, should all include
Within protection scope of the present invention.
Claims (10)
- A kind of 1. Lacking oxygen tungsten oxide/nitridation carbon composite photocatalyst, it is characterised in that the preparation side of the composite photo-catalyst Method is as follows：S1：Nitridation carbon dust is placed in hydrochloric acid solution and carries out protonation processing, filtering, washing, drying after lasting stirring；S2：The nitridation carbon dust for protonating processing is scattered in absolute ethyl alcohol or water and is ultrasonically treated, then adds chlordene Change tungsten and carry out hydro-thermal reaction；S3：The product of hydro-thermal reaction and washing, drying, grinding are collected, is urged up to the Lacking oxygen tungsten oxide/carbonitride complex light Agent；Wherein, in S2, the temperature of the hydro-thermal reaction is 180~220 DEG C, and the reaction time is 10~15h；The carbonitride and six The mass ratio of tungsten chloride is 1：0.398~3.965.
- 2. composite photo-catalyst according to claim 1, it is characterised in that in S2, the temperature of the hydro-thermal reaction for 195~ 205 DEG C, the reaction time is 11~13h；The mass ratio of the carbonitride and tungsten hexachloride is 1：0.398~1.985.
- 3. composite photo-catalyst according to claim 2, it is characterised in that in S2, the temperature of the hydro-thermal reaction is 200 DEG C, reaction time 12h；The mass ratio of the carbonitride and tungsten hexachloride is 1：0.99.
- 4. composite photo-catalyst according to claim 1, it is characterised in that in S1, the nitridation carbon dust and hydrochloric acid solution Mixed liquor in, the mass concentration of carbonitride is 0.1~100g/L.
- 5. composite photo-catalyst according to claim 4, it is characterised in that the mixing of the nitridation carbon dust and hydrochloric acid solution In liquid, the mass concentration of carbonitride is 1~10g/L.
- 6. composite photo-catalyst according to claim 1, it is characterised in that in S1, the concentration of the hydrochloric acid solution for 5~ 8mol/L。
- 7. composite photo-catalyst according to claim 6, it is characterised in that in S1, the concentration of the hydrochloric acid solution is 6mol/ L。
- 8. composite photo-catalyst according to claim 1, it is characterised in that in S1, prepare the forerunner of the nitridation carbon dust Body is urea, thiocarbamide or melamine.
- 9. composite photo-catalyst according to claim 1, it is characterised in that in S2, it is described it is dispersed be using ultrasound at Reason, sonication treatment time is 10~60min.
- 10. application of any composite photo-catalyst of claim 1~9 in photocatalytic degradation industrial wastewater.
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| CN111408397A (en) * | 2020-03-30 | 2020-07-14 | 浙江工商大学 | Modified carbon nitride and tungsten oxide coupled p-n type heterojunction composite material and preparation method and application thereof |
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| CN111715267A (en) * | 2020-07-22 | 2020-09-29 | 陕西科技大学 | Carbon nitride/bismuth oxychloride/tungsten oxide heterojunction photocatalyst and preparation method and application thereof |
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