CN108654665A - A kind of ultra-thin carbon nitride photocatalyst and its preparation method and application - Google Patents
A kind of ultra-thin carbon nitride photocatalyst and its preparation method and application Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 43
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229960001259 diclofenac Drugs 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006471 dimerization reaction Methods 0.000 claims abstract description 26
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000015556 catabolic process Effects 0.000 claims abstract description 17
- 238000006731 degradation reaction Methods 0.000 claims abstract description 17
- 239000008236 heating water Substances 0.000 claims abstract description 13
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 13
- 239000012498 ultrapure water Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000005286 illumination Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 description 12
- 238000005303 weighing Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000007146 photocatalysis Methods 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 230000006798 recombination Effects 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000000730 antalgic agent Substances 0.000 description 1
- -1 anti-arthritic Substances 0.000 description 1
- 230000002456 anti-arthritic effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010026 decatizing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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 invention belongs to photochemical catalyst field, a kind of ultra-thin carbon nitride photocatalyst and its preparation method and application is disclosed.The carbon nitride photocatalyst is that ultra-pure water stirring is added after mixing cyanamid dimerization and ammonium chloride, carries out heating water bath so that cyanamid dimerization and ammonium chloride are completely dissolved, after being evaporated completely to water, calcined at 450~600 DEG C, after it is cooled to room temperature, it mills, sieving is made.The photochemical catalyst is the high-performance catalysis material for having high-ratio surface and low photo-generated carrier combined efficiency, and collaboration persulfate has higher degradation rate, and the Diclofenac in degradable water, degradation rate reach 88% or more under visible light illumination.
Description
Technical field
The invention belongs to photocatalyst technology fields, more particularly, to a kind of ultra-thin carbon nitride photocatalyst and its system
Preparation Method and application.
Background technology
Diclofenac is often by as anodyne, anti-arthritic, medicine for rheumatism and important outpatient service medicine.But traditional dirt
Water technology is poor to Diclofenac processing capacity so that it is usually detected in water environment.It is double present in environment
The fragrant acid of chlorine is very big to the ecosystem and human health damage.Therefore, develop removal of the efficient water technology to Diclofenac
It is significant.
Graphite phase carbon nitride (g-C3N4) rely on its lower energy gap (about 2.7eV) and special electronic structure,
Fabulous activity is shown in Photocatalytic Activity for Degradation organic pollution etc..However, graphite phase carbon nitride there is also with
Lower disadvantage：Specific surface area is low, the high recombination rate in light induced electron and hole pair, visible light-responded low, these disadvantages are largely
On affect the photocatalysis performance of graphite phase carbon nitride.
Invention content
In order to solve above-mentioned the shortcomings of the prior art and disadvantage, a kind of ultra-thin carbonitride (UCN) photochemical catalyst is provided,
The photochemical catalyst is the high-performance catalysis material for having high-ratio surface and low photo-generated carrier combined efficiency, cooperates with persulfate
(PDS) there is higher degradation rate, and under visible light illumination can be in efficient degradation water Diclofenac.
Another object of the present invention is to provide the preparation methods of the ultra-thin carbonitride of the above method (UCN) photochemical catalyst.
It is still another object of the present invention to provide the applications of above-mentioned ultra-thin carbonitride (UCN) photochemical catalyst.
The purpose of the present invention is realized by following technical proposals：
A kind of ultra-thin carbon nitride photocatalyst, the carbon nitride photocatalyst are added after mixing cyanamid dimerization and ammonium chloride
Entering ultra-pure water stirring, carries out heating water bath so that cyanamid dimerization and ammonium chloride are completely dissolved, until after water is evaporated completely, 450~
600 DEG C of calcinings, after it is cooled to room temperature, mill, and sieving is made.
Preferably, the mass ratio of the cyanamid dimerization and ammonium chloride is (2~4)：(13~16), the cyanamid dimerization and chlorine
The total volume ratio of the gross mass and ultra-pure water of changing ammonium is (3~4) g：(3~4) mL.
Preferably, the temperature of the heating water bath is 70~75 DEG C.
Preferably, the heating rate of the calcining is 2.5~3.75 DEG C/min, and the time of the calcining is 2~4h.
The preparation method of the ultra-thin carbon nitride photocatalyst, comprises the following specific steps that：
S1. cyanamid dimerization and ammonium chloride mixing are weighed, alumina crucible is transferred to, ultra-pure water is added；
S2. heating water bath is carried out, while being kept stirring state so that cyanamid dimerization and ammonium chloride are completely dissolved, until water is complete
Pressure decatizing is dry；
S3. it after water evaporation is dry, calcines at 450~600 DEG C, after it is cooled to room temperature, mills, be sieved, obtain ultra-thin
Carbon nitride photocatalyst.
Application of the ultra-thin carbon nitride photocatalyst in degradation Diclofenac field.
Ultra-thin carbonitride (UCN) photochemical catalyst is degraded the method for the application in Diclofenac field under visible light：
It is to weigh UCN catalyst described in 0.025g to be placed in quartzy photodissociation pipe, double chlorine that a concentration of 5mg/l of 25ml are first added thereto are fragrant
Acid solution adds the PDS solution of a concentration of 1~3mmol/L of 1ml.The use of 350W xenon lamps configuration 420nm optical filters is light source.
The amount of remaining Diclofenac in solution is measured after 30~150min of illumination using liquid chromatogram.
Graphite phase carbon nitride (g-C in the present invention3N4) by its lower energy gap (about 2.7eV) and special
Electronic structure shows fabulous activity in Photocatalytic Activity for Degradation organic pollution etc..However, its light-catalysed property
Can, light induced electron low by specific surface area and hole be easy the shortcomings of compound and seriously affected.Some researches show that by graphite
Phase carbon nitride (g-C3N4) Morphological control, be made two-dimensional ultrathin carbonitride (UCN), the thickness of the ultra-thin carbon nitride layer in the present invention
Degree is 2~4nm, molecular formula and graphite phase carbon nitride g-C3N4It is identical.On the one hand, since the grain size of UCN becomes smaller, specific surface face
Product increases, and adsorption efficiency improves, and becomes larger with the contact area of reaction substrate.On the other hand, since grain size becomes smaller, electronics is from body phase
The time for being diffused into surface shortens, and the probability of recombination in electronics and hole becomes smaller, to make photocatalysis efficiency improve.
In addition, persulfate (PDS) is added in the reaction system, the photocatalytic activity of UCN can be enhanced.With oxidisability
Oxo-anions free radical such as SO4 -·The ability that removal organic polluter is removed in ultra-thin carbonitride photocatalysis can be improved.Meanwhile photoproduction
Electronics is consumed by these anion, inhibits the compound of light induced electron and hole, its photocatalysis performance is made to be improved.
Compared with prior art, the invention has the advantages that：
1. the ultra-thin carbon nitride photocatalyst of the present invention is the high property for having specific surface and low photo-generated carrier combined efficiency
Can catalysis material, there is higher degradation rate with PDS synergistic effects, and under visible light illumination can be in efficient degradation water it is double
The fragrant acid of chlorine, degradation rate reach 88% or more.
2. the present invention increases the specific surface of graphite phase carbon nitride by the pattern of the ultra-thin carbon nitride photocatalyst of regulation and control
Product, adsorption efficiency improve, become larger with the contact area of reaction substrate, time of the electronics from bulk diffusion to surface shortens, electronics
Become smaller with the probability of recombination in hole, to improve the photocatalysis efficiency of ultra-thin carbonitride.
3. in the ultra-thin carbon nitride photocatalyst of the present invention, by cooperateing with PDS degradation Diclofenacs, PDS is in the condition for having light
Under can be excited to form the higher free radical of activity to be easier degradation DCF, can effectively reduce g-C3N4Photohole and electronics
Recombination rate, to strengthen the photocatalysis efficiency of ultra-thin carbonitride.
4. the present invention preparation method simple economy, can meet the requirement to economic cost, have higher application prospect with
Use value.
Description of the drawings
Fig. 1 is the TEM photos of the UCN in embodiment 1.
Fig. 2 is the g-C in comparative example 13N4TEM photos.
Fig. 3 is to recycle the degradation rate to Diclofenac three times under UCN/PDS reaction systems in embodiment 1.
Specific implementation mode
The content further illustrated the present invention with reference to specific embodiment, but should not be construed as limiting the invention.
Raw material and instrument employed in following embodiment are commercially available；Wherein photochemical reactor is that rotation photochemistry is anti-
Device (Xujiang Electromechanical Plant, Nanjing, China) XPA-7, lamp source is answered to be the xenon long-arc lamp (Xujiang Electromechanical Plant, Nanjing, China) of 350W and filtered configured with 420nm
Mating plate.
Embodiment 1
The preparation of UCN photochemical catalysts：15ml is added in alumina crucible in accurate 2g cyanamid dimerizations and the 13g ammonium chlorides of weighing
Ultra-pure water, heating water bath (keep 75 DEG C), while stirring so that cyanamid dimerization and ammonium chloride are completely dissolved, water evaporation does it
Afterwards, capping is transferred in Muffle furnace, is risen to 600 DEG C with 2.5 DEG C/min heating rates and is kept temperature 4h, after being cooled to room temperature
Mill and obtained after filtering the UCN powder of yellow.
Comparative example 1
g-C3N4The preparation of photochemical catalyst：2g cyanamid dimerizations accurately are weighed in alumina crucible, and the ultra-pure water of 15ml is added,
Heating water bath (is kept for 75 DEG C), while stirring and cyanamid dimerization and ammonium chloride are completely dissolved, after water evaporation is dry, capping transfer
Into Muffle furnace, rises to 600 DEG C with 2.5 DEG C/min heating rates and keep temperature 4h, mill and filter after being cooled to room temperature
The g-C of yellow is obtained afterwards3N4Powder.
By the g-C of the UCN of embodiment 1 and comparative example 13N4Tem analysis is carried out respectively, and Fig. 1 is the UCN's in embodiment 1
TEM photos, Fig. 2 are the g-C in comparative example 13N4TEM photos.From fig. 1, it can be seen that UCN has two-dimensional ultrathin structure, surface has more
A stomata, this is because caused by ammonium chloride resolves into gas under high temperature, as shown in Figure 2, the g-C of comparative example 13N4Structure be
The thick-layer stacking provisions of thick-layer.
By the g-C of the UCN of embodiment 1 and comparative example 13N4Carry out BET analyses respectively, by specific surface area/pore-size distribution and
The specific surface area that pore analysis instrument (SA3100, the U.S.) measures UCN is 45.231m2/ g, g-C3N4Specific surface area be
14.236m2/ g, the experimental result are coincide with TEM test results.This is because large specific surface area is capable of providing more absorption
Site and active site, adsorption efficiency improve, become larger with the contact area of reaction substrate, electronics from bulk diffusion to surface when
Between shorten, the probability of recombination in electronics and hole becomes smaller, to improve the photocatalysis efficiency of UCN.
Embodiment 2
The preparation of UCN photochemical catalysts：20ml is added in alumina crucible in accurate 4g cyanamid dimerizations and the 16g ammonium chlorides of weighing
Ultra-pure water, heating water bath (keep 70 DEG C), while stirring so that cyanamid dimerization and ammonium chloride are completely dissolved, water evaporation does it
Afterwards, capping is transferred in Muffle furnace, is risen to 450 DEG C with 3.75 DEG C/min heating rates and is kept temperature 2h, is cooled to room temperature
The UCN powder of yellow is obtained after milling and filter afterwards.
Embodiment 3
The preparation of UCN photochemical catalysts：23ml is added in alumina crucible in accurate 4g cyanamid dimerizations and the 13g ammonium chlorides of weighing
Ultra-pure water, heating water bath (keep 75 DEG C), while stirring so that cyanamid dimerization and ammonium chloride are completely dissolved, water evaporation does it
Afterwards, capping is transferred in Muffle furnace, is risen to 600 DEG C with 3.75 DEG C/min heating rates and is kept temperature 2h, is cooled to room temperature
The UCN powder of yellow is obtained after milling and filter afterwards.
Embodiment 4
The preparation of UCN photochemical catalysts：15ml is added in alumina crucible in accurate 2g cyanamid dimerizations and the 13g ammonium chlorides of weighing
Ultra-pure water, heating water bath (keep 75 DEG C), while stirring so that cyanamid dimerization and ammonium chloride are completely dissolved, water evaporation does it
Afterwards, capping is transferred in Muffle furnace, is risen to 500 DEG C with 2.5 DEG C/min heating rates and is kept temperature 4h, after being cooled to room temperature
Mill and obtained after filtering the UCN powder of yellow.
Embodiment 5
The preparation of UCN photochemical catalysts：Accurate 2g cyanamid dimerizations and the 16g ammonium chlorides of weighing is added in alumina crucible
The ultra-pure water of 13.5ml, heating water bath (is kept for 75 DEG C), while stirring and cyanamid dimerization and ammonium chloride are completely dissolved, water evaporation
After dry, capping is transferred in Muffle furnace, is risen to 500 DEG C with 2.5 DEG C/min heating rates and is kept temperature 4h, is cooled to room
The UCN powder of yellow is obtained after milling and filter after temperature.
Embodiment 6
Applications of the UCN catalyst collaboration PDS of the present invention in Diclofenac wastewater treatment, includes the following steps：
1. configuring the diclofenac solution of a concentration of 5mg/L of 25ml, UCN photochemical catalysts made from 25mg embodiments 1 are added,
Ultrasonic 5min, which is placed in photochemical reactor, is protected from light absorption 0.5h.
2. configuring the PDS solution of a concentration of 1mmol/L of 1ml, it is added in the above-mentioned solution obtained by step 1；
3. using 350W xenon lamps configuration 420nm optical filters as light-catalyzed reaction light source, solution takes out in illumination 150min,
The hypo solution that the 40mmol/L of 1ml is added immediately is quenched, and uses the remaining double chlorine of liquid chromatogram measuring solution
The concentration C of fragrant acid.According to formula P=(C0- C) * 100% removal rate for calculating Diclofenac, wherein C0For the first of Diclofenac
Beginning concentration, the results are shown in Table 1.
4. weighing UCN obtained in 25mg embodiments 1, step 1 and step 3 are repeated, obtains catalyst UCN to Diclofenac
Removal rate.
5. weighing g-C obtained in 25mg comparative examples 13N4, step 1-3 is repeated, catalyst g-C is obtained3N4PDS pairs of collaboration
The removal rate of Diclofenac.
6. weighing g-C obtained in 25mg comparative examples 13N4, step 1 and step 3 are repeated, catalyst g-C is obtained3N4To double
The removal rate of the fragrant acid of chlorine.
7. configuring the diclofenac solution of a concentration of 5mg/L of 25ml, ultrasonic 5min, which is placed in photochemical reactor, to be protected from light
0.5h is adsorbed, the PDS solution of a concentration of 1mmol/L of 1ml is reconfigured, is added in diclofenac solution, step 3 is repeated and obtains PDS
To the removal rate of Diclofenac.
1 different catalysts system of table catalytic degradation Diclofenac in visible light
Embodiment 7
A kind of applications of the UCN catalyst collaboration PDS of the present invention in Diclofenac wastewater treatment, includes the following steps：
1. configuring the diclofenac solution of a concentration of 5mg/L of 25ml, UCN photochemical catalysts made from 25mg implementations 1 are added, surpass
Sound 5min, which is placed in photochemical reactor, is protected from light absorption 0.5h.
2. configuring the PDS solution of a concentration of 3mmol/L of 1ml, it is added in the above-mentioned solution obtained by step 1；
3. this application configures 420nm optical filters as light-catalyzed reaction light source using 350W xenon lamps, solution is in illumination
150min taking-ups are added a certain amount of hypo solution and are quenched immediately, and remaining double using liquid chromatogram measuring solution
The concentration C of the fragrant acid of chlorine.According to formula P=(C0- C) * 100% removal rate for calculating Diclofenac, wherein C0For Diclofenac
Initial concentration.The results are shown in Table 2.
4. weighing UCN obtained in 25mg embodiments 1, step 1 and step 3 are repeated, obtains catalyst UCN to Diclofenac
Removal rate.
5. weighing g-C obtained in 25mg comparative examples 13N4, step 1-3 is repeated, catalyst g-C is obtained3N4PDS pairs of collaboration
The removal rate of Diclofenac.
6. weighing g-C obtained in 25mg comparative examples 13N4, step 1 and step 3 are repeated, catalyst g-C is obtained3N4To double
The removal rate of the fragrant acid of chlorine.
7. configuring the diclofenac solution of a concentration of 5mg/L of 25ml, ultrasonic 5min, which is placed in photochemical reactor, to be protected from light
0.5h is adsorbed, the PDS solution of a concentration of 3mmol/L of 1ml is reconfigured, is added in diclofenac solution, step (3) is repeated and obtains
Removal rates of the PDS to Diclofenac.
UCN, UCN+PDS, g-C after reaction 150min3N4、g-C3N4+ PDS, PDS light reaction systems remove Diclofenac
Except rate, as shown in table 2.As shown in Table 2, UCN ratios g-C3N4Photocatalysis efficiency higher, it is double and due to the synergistic effect of PDS
The degradation efficiency of the fragrant acid of chlorine significantly increases, and improves the photocatalysis efficiency of UCN.
2 different catalysts system visible light photocatalytic degradation Diclofenac of table
Embodiment 8
UCN photochemical catalysts after being reacted in embodiment 1 are filtered, and using washing three times, methanol is washed one time, it
It is placed in 60 DEG C of baking ovens and is dried overnight.The UCN photochemical catalysts after 25mg reacting dryings are weighed, step 1- in embodiment 4 is repeated
3, removal rates of the UCN photochemical catalysts collaboration PDS to Diclofenac after calculating cycle twice.It repeats experiment to carry out 3 times altogether, detection
UCN photochemical catalysts cooperate with PDS to the removal rate of Diclofenac after 3 cyclic tests, and the results are shown in Figure 3.Fig. 3 is embodiment 1
In UCN photochemical catalysts recycle 3 collaboration PDS to the degradation rates of Diclofenac.From the figure 3, it may be seen that in the 3rd cyclic test,
UCN photochemical catalysts collaboration PDS still can reach 82.9% to the removal rate of Diclofenac, illustrate the UCN photochemical catalysts tool of the present invention
Standby good photocatalysis stability.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitute, combination and simplify,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (6)
1. a kind of ultra-thin carbon nitride photocatalyst, which is characterized in that the carbon nitride photocatalyst is by cyanamid dimerization and chlorination
Ultra-pure water stirring is added after ammonium mixing, carries out heating water bath so that cyanamid dimerization and ammonium chloride are completely dissolved, until water is evaporated completely
Afterwards, it calcines at 450~600 DEG C, after it is cooled to room temperature, mills, sieving is made.
2. ultra-thin carbon nitride photocatalyst according to claim 1, which is characterized in that the cyanamid dimerization and ammonium chloride
Mass ratio is (2~4)：(13~16), the total volume ratio of the gross mass and ultra-pure water of the cyanamid dimerization and ammonium chloride be (3~
4)g：(3~4) mL.
3. ultra-thin carbon nitride photocatalyst according to claim 1, which is characterized in that the temperature of the heating water bath is 70
~75 DEG C.
4. ultra-thin carbon nitride photocatalyst according to claim 1, which is characterized in that the heating rate of the calcining is
2.5~3.75 DEG C/min, the time of the calcining is 2~4h.
5. according to the preparation method of the ultra-thin carbon nitride photocatalyst of claim 1-4 any one of them, which is characterized in that including
Following specific steps：
S1. cyanamid dimerization and ammonium chloride mixing are weighed, alumina crucible is transferred to, ultra-pure water is added；
S2. heating water bath is carried out, while being kept stirring state so that cyanamid dimerization and ammonium chloride are completely dissolved, until water steams completely
It is dry；
S3. it after water evaporation is dry, calcines at 450~600 DEG C, after it is cooled to room temperature, mills, be sieved, obtain ultra-thin nitridation
Carbon photochemical catalyst.
6. application of the ultra-thin carbon nitride photocatalyst of claim 1-4 any one of them in degradation Diclofenac field.
Priority Applications (1)
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