CN107199045A - A kind of preparation method and applications of g C3N4 Cu2O composite catalysts - Google Patents
A kind of preparation method and applications of g C3N4 Cu2O composite catalysts Download PDFInfo
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- CN107199045A CN107199045A CN201710479746.9A CN201710479746A CN107199045A CN 107199045 A CN107199045 A CN 107199045A CN 201710479746 A CN201710479746 A CN 201710479746A CN 107199045 A CN107199045 A CN 107199045A
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims description 37
- 239000000725 suspension Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000002351 wastewater Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 239000012265 solid product Substances 0.000 claims abstract description 9
- 238000002604 ultrasonography Methods 0.000 claims abstract description 9
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims abstract description 8
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001291 vacuum drying Methods 0.000 claims abstract description 8
- 239000000811 xylitol Substances 0.000 claims abstract description 8
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims abstract description 8
- 229960002675 xylitol Drugs 0.000 claims abstract description 8
- 235000010447 xylitol Nutrition 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 230000005588 protonation Effects 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 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 claims description 20
- 229940012189 methyl orange Drugs 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 239000003344 environmental pollutant Substances 0.000 claims description 7
- 231100000719 pollutant Toxicity 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000002957 persistent organic pollutant Substances 0.000 claims description 4
- 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 claims description 4
- 229940043267 rhodamine b Drugs 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001454 anthracenes Chemical class 0.000 claims description 2
- 150000004056 anthraquinones Chemical class 0.000 claims description 2
- 230000001795 light effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- -1 quinone imides Chemical class 0.000 claims description 2
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 238000007146 photocatalysis Methods 0.000 abstract description 13
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000011941 photocatalyst Substances 0.000 description 10
- 238000013019 agitation Methods 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 230000009467 reduction Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229940112669 cuprous oxide Drugs 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002135 nanosheet 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
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 230000003313 weakening effect Effects 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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
It is a primary object of the present invention to provide a kind of g C3N4‑Cu2The preparation method and applications of O composite catalysts, the preparation method includes：The first solution is provided, first solution includes the Cu of dissolved state2+；The g C of protonation are added in first solution3N4, stirring, ultrasound, acquisition suspension；Xylitol is added into the suspension under stirring, regulation pH value stirs to obtain mixed liquor to 10 12；The mixed liquor is heated to 150 200 DEG C in high-pressure reaction vessel, the 35h of isothermal reaction 25 obtains reactant；The reactant separation of solid and liquid after cooling is obtained into solid product, cleaned, vacuum drying；The solid product is heated to 150 250 DEG C of holding constant temperature 1h 3h under gas shield, g C are made3N4‑Cu2O composite catalysts.The g C3N4‑Cu2O composite catalysts have stronger visible absorption ability, photocatalysis performance enhancing.The g C3N4‑Cu2The organic pollution that O composite catalysts can be used in treating wastewater through catalysis of connected under visible light action, degradation effect is significantly and relatively stable.
Description
Technical field
The invention belongs to water-treatment technology field, more particularly to a kind of g-C3N4-Cu2The preparation method of O composite catalysts and
It is applied.
Background technology
Photocatalitic Technique of Semiconductor is one of most possible method realized by sunshine and eliminate environmental pollution.To current
Untill, most research all focuses on TiO2, this is mainly due to TiO2With excellent chemical stability, anti-light corrosivity
Can, cheap price and the advantages of good Environmental compatibility and as most important catalysis material.However, TiO2Forbidden band is wide
Spend for 3.2eV, belong to wide band gap semiconducter, can only absorb and account for the ultraviolet light that solar spectrum 3%-5%, wavelength are less than 390nm, therefore
Limit its utilization to sunshine.In order to effectively utilize sunshine, finding efficient visible light type catalyst turns into development light
One vital task of catalysis technique.Cuprous oxide (Cu2O) as typical p-type semiconductor catalysis material, its forbidden band is wide to be situated between
Between 2.0-2.4eV, relative to the semi-conducting material of broad-band gap, the absorbable most of visible ray of cuprous oxide is more fully sharp
Use solar energy.In addition, cuprous oxide is nontoxic, preparing cost, low, environmental resistance is good, therefore Cu2O photocatalysis under visible light
Decomposition water and degradable organic pollutant are widely studied.However, photo-generate electron-hole pair is rapid compound so that Cu2O light
Catalytic efficiency has much room for improvement.
The content of the invention
For drawbacks described above of the prior art, it is a primary object of the present invention to provide a kind of g-C3N4-Cu2O is compound to be urged
The preparation method and applications of agent, the catalyst has stronger visible absorption ability, photocatalysis performance enhancing and phase
To relatively stable.
In order to achieve the above object, the present invention is adopted the following technical scheme that：A kind of g-C3N4-Cu2The system of O composite catalysts
Preparation Method, comprises the following steps：
The first solution is provided, first solution includes the Cu of dissolved state2+；
The g-C of protonation is added in first solution3N4, stirring, ultrasound, acquisition suspension；
Xylitol is added into the suspension under stirring, regulation pH value stirs to obtain mixed liquor to 10-12；
The mixed liquor is heated to 150-200 DEG C in high-pressure reaction vessel, isothermal reaction 25-35h is reacted
Thing；
The reactant separation of solid and liquid after cooling is obtained into solid product, cleaned, vacuum drying；
The solid product is heated to 150-250 DEG C of holding constant temperature 1h-3h under atmosphere protection, g-C is made3N4-Cu2O
Composite catalyst.
As it is further preferably, in the composite catalyst, the g-C3N4With Cu2O mass ratio is 1:1-1:5.
As further preferably, the pressure of the high-pressure reaction vessel is 0.5-0.8MPa.
As further preferably, the vacuum drying temperature is 50-70 DEG C, and drying time is 6-10h.
As further preferably, the atmosphere uses argon gas.
As further preferably, the rate of heat addition of the solid product is 2-3k/min.
It is used as further preferred, the g-C of the protonation3N4Preparation method include：It is in heating rate by dicyandiamide
It is warming up under conditions of 1-3K/min after 500-600 DEG C, calcines 3-5h, cooling, grinding obtains powder；Added in the powder
The concentrated sulfuric acid is mixed, stirring, and ultrasound obtains mixture；The mixture and water are mixed, milk-white coloured suspension is obtained, will
The milk-white coloured suspension centrifugation, washing and dry, the g-C after being acidified3N4；By the g-C after the acidifying3N4In 50-75
DEG C heat backflow 4-8h, suction filtration, washing and the dry g-C that must be protonated3N4。
As further preferably, the mixing time is 6-10h, the ultrasonic time is 1-3h.
A kind of g-C3N4-Cu2The application of O composite catalysts, the g-C3N4-Cu2O composite catalysts are made in radiation of visible light
With the organic pollution in lower treating wastewater through catalysis of connected.
As further preferably, the processing includes：
G-C is added in waste water3N4-Cu2O composite catalysts, stirring forms mixture；
The mixture is placed in the range of exposures of visible ray；
The g-C3N4-Cu2O composite catalysts and the organic pollution in visible ray co-treating wastewater.
It is used as further preferred, having comprising Anthraquinones, quinone imides, oxa anthracenes and azo in the waste water
One or more in organic pollutants.
As further preferably, the pollutant in the waste water is selected from reactive brilliant bule, methylene blue, rhodamine B, activity
Bright red and methyl orange.
As further preferably, the initial concentration of the Pollutants in Wastewater is 10-100mg/L.
It is used as further preferred, the g-C in the mixture3N4-Cu2The addition of O composite catalysts is 0.1-2g/
L。
The beneficial effects of the invention are as follows：The present invention study first the coupling between semi-conducting material by narrow band gap come
Promote Cu2O photocatalytic activities, g-C has been successfully prepared using hydrothermal reduction method3N4-Cu2O composite photo-catalysts, it is described compound
G-C in catalyst3N4And Cu2Closely growth together, forms g-C to O3N4-Cu2The heterojunction structure of O plane-plane contacts.Compare
In the g-C of pure phase3N4And Cu2O, g-C3N4-Cu2O composites have stronger visible absorption ability.g-C3N4-Cu2O is heterogeneous
Knot can preferably ensure that the photocatalysis performance of compound with mating structure, than single-phase g-C3N4Or Cu2O has larger
Raising.The present invention is using the g-C protonated3N4It obvious dispersiveness is occurred, form the bigger nano-sheet of specific surface area
Structure, so as to more fully contact Cu2O forms even closer heterojunction structure.
Brief description of the drawings
Fig. 1 is g-C3N4、Cu2G-C in the embodiment of the present invention of O and different dopings3N4-Cu2The XRD of O composite catalysts
Figure.
Fig. 2 is pure phase g-C3N4、Cu2G-C in O and the embodiment of the present invention 13N4-Cu2The Fourier transformation of O composite catalysts
Infrared spectrum.
Fig. 3 A, 3B, 3C are respectively pure phase Cu2O、g-C3N4With g-C in the embodiment of the present invention 13N4-Cu2O(1:5) it is combined and urges
The SEM figures of agent.
Fig. 4 is in Vis, g-C3N4And Cu2The degraded situation schematic diagram of methyl orange in O various combination reaction system.
Fig. 5 is g-C of the embodiment of the present invention3N4-Cu2O composite catalysts (g-C3N4：Cu2O=1:5) under visible light to first
The circulation experiment result schematic diagram of base orange degraded.
Embodiment
The present invention is by providing a kind of g-C3N4-Cu2The preparation method and applications of O composite catalysts, solve existing light
The defect that catalyst treatment organic wastewater photocatalysis performance is poor, catalytic performance is unstable etc., g-C prepared by the present invention3N4-Cu2O
Composite photo-catalyst, with stronger visible absorption ability, photochemical catalyst catalytic performance and stability enhancing.
In order to solve drawbacks described above, the main thought of the embodiment of the present invention is：
G-C of the embodiment of the present invention3N4-Cu2The preparation method of O composite catalysts, comprises the following steps：
The first solution is provided, first solution includes the Cu of dissolved state2+；
The g-C of protonation is added in first solution3N4, stirring, ultrasound, acquisition suspension；
Xylitol is added into the suspension under stirring, regulation pH value stirs to obtain mixed liquor to 10-12；
The mixed liquor is heated to 150-200 DEG C in high-pressure reaction vessel, isothermal reaction 25-35h is reacted
Thing；
The reactant separation of solid and liquid after cooling is obtained into solid product, cleaned, vacuum drying；
The solid product is heated to 150-250 DEG C of holding constant temperature 1h-3h under atmosphere protection, g-C is made3N4-Cu2O
Composite catalyst.
Graphite phase carbon nitride (g-C3N4) it is a kind of typical n-type semiconductor, g-C3N4It is that a kind of bandwidth is about
2.7eV nonmetallic polymer-type photochemical catalyst, there is good absorbability to visible ray, and with preferable heat endurance,
Chemical stability and the pollution-free advantage such as cheap.This causes g-C3N4In the field such as light hydrogen production by water decomposition and degradable organic pollutant
Have wide practical use.However, monomer g-C3N4System of Detecting Surface Defects For Material is more, and the recombination rate of its photo-generate electron-hole is higher, leads
Cause photocatalysis performance poor.To solve these problems, researcher adopts a series of measures, for example containing transition metal element, prepares
Loose structure g-C3N4And semiconductors coupling etc..It is to reduce photo-generated carrier that kind of a semi-conducting material is combined into heterojunction structure
The available strategy of recombination rate.
The embodiment of the present invention is based on hydrothermal reduction method and high-temperature calcination by g-C3N4Grow into Cu2O surfaces are made
g-C3N4-Cu2O composite photo-catalysts.The sign of structure, pattern and optical property has been carried out to the photochemical catalyst of synthesis, and with first
Base orange waits as simulating pollution thing to have evaluated the photocatalytic degradation capability of composite catalyst.Test result indicates that g-C3N4And Cu2O
Two phase compositions coexist and with close contact interface, form g-C3N4-Cu2The heterojunction structure of O plane-plane contacts.Except this
Outside g-C3N4-Cu2O hetero-junctions can preferably ensure that the photocatalysis performance of compound with mating structure, than single-phase g-
C3N4Or Cu2O is greatly improved, and with good photochemical stability.Composite catalyst of the embodiment of the present invention is catalyzed
Overall improve of performance is attributed to that p-n junction hetero-junctions effectively facilitates the separation of electric charge, to suppress electron-hole compound and absorb light
The extension of wave-length coverage.
G-C of the embodiment of the present invention3N4-Cu2O composite catalysts can be in treating wastewater through catalysis of connected under radiation of visible light effect
Organic pollution.The embodiment of the present invention have studied catalyst of the embodiment of the present invention by taking methyl orange as an example is used for treating wastewater through catalysis of connected mistake
Cheng Shi, its degradation effect to organic pollution in water environment, but be not limited to the embodiment of the present invention and only methyl orange is risen
Effect, other pollutants of degrading can also reach the effect of similar catalytic degradation.
In order to which above and other purpose, feature and the advantage of the present invention can be become apparent, number cited below particularly is implemented
Example, to illustrate g-C of the present invention3N4-Cu2The preparation method and applications of O composite catalysts.
Embodiment 1
Raw material and reagent
Dicyanodiamine (C2H4N4), Salzburg vitriol (CuSO4·5H2O), sodium hydroxide (NaOH), hydrochloric acid (HCl) are
Analyze pure (AR), purchased from Chemical Reagent Co., Ltd., Sinopharm Group；Xylitol (C5H1205), methyl orange (C14H14N3NaO3S)
To analyze pure (AR), purchased from Shanghai Aladdin biochemical technology limited company.
Protonate g-C3N4Preparation
By dicyandiamide after being warming up to 550 DEG C under conditions of heating rate is 2K/min, 4h is calcined, cooling, grinding is obtained
Pale yellow powder；Concentrated sulfuric acid mixing is added in powder after grinding, stirring, ultrasound obtains mixture；By the mixture
Mixed with water, obtain milk-white coloured suspension, by milk-white coloured suspension centrifugation, washed and dry, after being acidified
g-C3N4；By the g-C after the acidifying3N4In 65 DEG C of heat backflow 6h, suction filtration, washing and dry g-C3N4。
g-C3N4-Cu2The preparation of O composite photo-catalysts
High-temperature calcination is aided with by g-C with hydrothermal reduction method3N4Grow into Cu2O surfaces, are comprised the following steps that：First in magnetic
By 1.25g CuSO under power stirring4·5H2O is added in 40mL deionized waters, when solution is changed into navy blue, is continued toward above-mentioned
G-C is added in solution3N4Ultrasonic 1h is further continued for after powder magnetic agitation 1h, and uniform suspension, wherein g-C is made3N4：Cu2O
Mass ratio be 1:5,1.5g xylitol, Zhi Houyong are and then added into above-mentioned suspension under conditions of magnetic agitation
After the pH that 1moL/L NaOH solutions adjust above-mentioned suspension is 12 or so, magnetic agitation 1h, above-mentioned mixed liquor is transferred to poly- four
The autoclave of PVF liner is heated to after 180 DEG C of isothermal reaction 30h, natural cooling after reactor is taken out, by liner
Sample suction filtration separate, flushed three times repeatedly with deionized water, 60 DEG C of dry 8h in vacuum drying chamber.Finally by gained
Sample argon gas protection under with 2.3k/min be heated to 200 DEG C holding constant temperature 2h, be made g-C3N4-Cu2O hetero-junctions.
Embodiment 2
Protonate g-C3N4Preparation
By dicyandiamide after being warming up to 500 DEG C under conditions of heating rate is 1K/min, 5h is calcined, cooling, grinding is obtained
Pale yellow powder；Concentrated sulfuric acid mixing is added in powder after grinding, stirring, ultrasound obtains mixture；By the mixture
Mixed with water, obtain milk-white coloured suspension, by milk-white coloured suspension centrifugation, washed and dry, after being acidified
g-C3N4；By the g-C after the acidifying3N4In 50 DEG C of heat backflow 8h, suction filtration, washing and dry g-C3N4。
g-C3N4-Cu2The preparation of O composite photo-catalysts
High-temperature calcination is aided with by g-C with hydrothermal reduction method3N4Grow into Cu2O surfaces, are comprised the following steps that：First in magnetic
By 1.25g CuSO under power stirring4·5H2O is added in 40mL deionized waters, when solution is changed into navy blue, is continued toward above-mentioned
G-C is added in solution3N4Ultrasonic 2h is further continued for after powder magnetic agitation 2h, and uniform suspension, wherein g-C is made3N4：Cu2O
Mass ratio be 3:5,1.5g xylitol, Zhi Houyong are and then added into above-mentioned suspension under conditions of magnetic agitation
After the pH that 1moL/L NaOH solutions adjust above-mentioned suspension is 10 or so, magnetic agitation 2h, above-mentioned mixed liquor is transferred to poly- four
The autoclave of PVF liner is heated to after 150 DEG C of isothermal reaction 35h, natural cooling after reactor is taken out, by liner
Sample suction filtration separate, flushed three times repeatedly with deionized water, 70 DEG C of dry 6h in vacuum drying chamber.Finally by gained
Sample argon gas protection under with 3k/min be heated to 250 DEG C holding constant temperature 1h, be made g-C3N4-Cu2O hetero-junctions.
Embodiment 3
Protonate g-C3N4Preparation
By dicyandiamide after being warming up to 600 DEG C under conditions of heating rate is 3K/min, 3h is calcined, cooling, grinding is obtained
Pale yellow powder；Concentrated sulfuric acid mixing is added in powder after grinding, stirring, ultrasound obtains mixture；By the mixture
Mixed with water, obtain milk-white coloured suspension, by milk-white coloured suspension centrifugation, washed and dry, after being acidified
g-C3N4；By the g-C after the acidifying3N4In 75 DEG C of heat backflow 4h, suction filtration, washing and dry g-C3N4。
g-C3N4-Cu2The preparation of O composite photo-catalysts
High-temperature calcination is aided with by g-C with hydrothermal reduction method3N4Grow into Cu2O surfaces, are comprised the following steps that：First in magnetic
By 1.25g CuSO under power stirring4·5H2O is added in 40mL deionized waters, when solution is changed into navy blue, is continued toward above-mentioned
G-C is added in solution3N4Ultrasonic 3h is further continued for after powder magnetic agitation 3h, and uniform suspension, wherein g-C is made3N4：Cu2O
Mass ratio be 1:1,1.5g xylitol, Zhi Houyong are and then added into above-mentioned suspension under conditions of magnetic agitation
After the pH that 1moL/L NaOH solutions adjust above-mentioned suspension is 12 or so, magnetic agitation 2h, above-mentioned mixed liquor is transferred to poly- four
The autoclave of PVF liner is heated to after 200 DEG C of isothermal reaction 25h, natural cooling after reactor is taken out, by liner
Sample suction filtration separate, flushed three times repeatedly with deionized water, 50 DEG C of dry 10h in vacuum drying chamber.Finally by institute
The sample obtained is heated to 150 DEG C of holding constant temperature 3h under argon gas protection with 1k/min, and g-C is made3N4-Cu2O hetero-junctions.
Raw material and reagent used are similar to Example 1 in 2-3 preparation methods of the embodiment of the present invention.
g-C3N4-Cu2The sign of O composite catalysts
The crystal thing of powder particle is characterized with x-ray powder diffraction instrument (XPert Pro, Dutch Panalytical companies)
Phase, x-ray source is Cu K alpha rays, and the 059nm of λ=0.154, scanning range is 8 °~80 °, and operating voltage is 40kV.With in Fu
The infrared spectrum of leaf transformation infrared spectrometer (Thermo Nexus 470, NICOLET companies of the U.S.) determination sample, KBr tablettings.
The pattern and distribution of particles situation of mirror (SEM) observation sample are shown using Japanese JEOL JSM-6380-LA types scanning electron.
Fig. 1 is g-C3N4、Cu2O and different doping (g-C3N4：Cu2O=1：1、3:5、1:5) g-C3N4-Cu2O is combined
The XRD of system sample, wherein single-phase g-C3N4Sample is in the characteristic peak difference that the θ of the angle of diffraction 2 is at 27.38 ° and 13.04 ° two
Corresponding to g-C3N4(002) and (100) crystal face in (JCPDS 87-1526) card, this also just illustrates have in synthetic sample
The presence of three-S- 5-triazine units.The θ of the angle of diffraction 2 be 27.38 ° place highest peak be by cyclic aromatic thing interlayer accumulate form
, when by g-C3N4And Cu2O is carried out after being combined according to different dopings, with Cu2The continuous increase of O dopings, g-C3N4's
The two feature peak intensities are constantly weakening.This is probably because Cu2O successes are in g-C3N4Surface is deposited.In g-C3N4-Cu2O
The θ of the angle of diffraction 2 is in composite sample:One is at 29.582 °, 36.441 °, 42.328 °, 61.406 °, 73.556 °, 77.414 ° six
Row are sharp and narrow then to correspond to Cu2110,111,200,220,311,222 crystal faces in O (JCPDS 65-3288), show
Cu2O crystallinity is preferable.The g-C of all pure phases3N4And Cu2O characteristic peaks are all detected in composite sample, are illustrated
g-C3N4-Cu2O compound systems are mainly by middle g-C3N4And Cu2The phase compositions of O two.
As shown in Fig. 2 as FTIR spectrum go further research discuss the embodiment of the present invention 1 obtained by sample change
Learn composition information.In the Cu of pure phase2In O infrared spectrograms, positioned at 630cm-1It is the stretching vibration of Cu-O keys that the peak at place is corresponding
Result.And in the g-C of pure phase3N4In sample, what three main absorption regions can be eliminated detects, wherein
3000-3500nm-1The broad peak at place is the flexible of O-H keys in N-H keys stretching vibration peak and physical absorption water, secondly in 1200-
1700nm-1High-amplitude wave move absorption region, its characteristic peak is respectively in 1240,1320,1407,1567 and 1640cm-1, belong to typical case
CN heterocyclic compounds stretching vibration peak in 808cm-1The absworption peak at place corresponds to s-triazine ring flexural vibrations, and is mixed in difference
The g-C of miscellaneous ratio3N4-Cu2With g-C in O composites3N4Doping is continuously increased, its corresponding g-C3N4Feature inhale
Receiving peak is also gradually strengthening, and in the composite sample of all different doping ratios, pure phase g-C3N4And Cu2O characteristic peaks are deposited
, so that show the presence of two kinds of semi-conducting materials in composite catalyst of the embodiment of the present invention, the test result one with above-mentioned XRD
Cause.
Fig. 3 A, 3B, 3C are respectively pure phase Cu2O、g-C3N4With g-C in the embodiment of the present invention 13N4-Cu2O(1:5) it is combined and urges
The SEM figures of agent.As shown in Figure 3 B it is freshly synthesized out pure phase g-C3N4Sample shows obvious dispersiveness, and works as g-
C3N4And Cu2After O adulterates according to a certain percentage, by Fig. 3 C, we can be found that g-C3N4With three-dimensional hexagram Cu2O is close
Grow together, so as to form the hetero-junctions of plane-plane contact.
In order to obtain visible ray of embodiment of the present invention collaboration g-C3N4-Cu2O composite catalysts handle the effect of waste water, to reality
Applying the following a series of experiments of the progress of the composite catalyst prepared by example is proved：
1、g-C3N4-Cu2The research of O photocatalysis performance
Photocatalytic degradation experiment is using self-designed L ED lamps as light source, and a set of cups outer layer is by condensed water to ensure that photocatalysis is anti-
It should carry out at a constant temperature.By 10mg/L of concentration, volume be that 50mL rhodamine B (RhB) or methyl orange MO solution do target drop
Thing is solved, the dosage of catalyst is 0.025g.The absorption stirring 30min under first dark unglazed environment before light-catalyzed reaction,
To ensure to reach adsorption equilibrium, sampled at regular intervals once after turning on light, per sub-sampling 1.2mL, reaction time 30min.Take
With 0.45 μm of water system syringe membrane filtration after sample, a small amount of catalyst remained in sample is removed, oiling 0.1mL ethanol is placed in
Centrifuge tube, absorbance (the maximum absorption wavelength λ=554nm, or in wave-length coverage of filtrate is detected using ultraviolet-visual spectrometer
200-700nm carries out full wavelength scanner).With the degradation rate C/C of pollutant0Characterize the photocatalysis performance of composite catalyst.
In order to evaluate the photocatalysis performance of synthesized catalyst, under visible light illumination, methyl orange (MO) solution is made
Photocatalytic degradation experiment is carried out for the pollutant of simulation.Pass through the g-C prepared to the embodiment of the present invention 1 under different systems3N4-
Cu2Discussions of the O to MO degraded situation, as a result as shown in Figure 4, it has been found that in the control experiment of photochemical catalyst is not added with, MO
It is hardly degraded, this shows MO quite stables, so as to eliminate the possibility that MO occurs from degradation process.As single-phase g-C3N4
And Cu2After O is added, although have certain facilitation to MO degraded, but 30min to MO degraded also less than 20%,
And by g-C3N4And Cu2(mass ratio 1 after O is compound：5) after addition system, there is significant facilitation to MO degrading activity,
30min just degradable 84% MO.These results show g-C3N4-Cu2Single-phase photocatalytic system of the O/Vis systems compared to it
Degraded to MO is more efficient.
2、g-C3N4-Cu2The research of O stability
The stability of solid photocatalysts is extremely important in solid-liquid reaction.In order to test g-C3N4-Cu2O catalysis
The stability of performance, each reacted catalyst is collected again to be re-added in circular response next time.Such as Fig. 5
Shown, reaction 30min is basically unchanged to MO degradation rate after circulating 6 times, and catalyst stability is high.
Technical scheme in above-mentioned the embodiment of the present application, at least has the following technical effect that or advantage：
(1) present invention studies the coupling between the semi-conducting material by narrow band gap to promote Cu first2O photocatalysis is lived
Property, it has been successfully prepared g-C using hydrothermal reduction method3N4-Cu2O composite photo-catalysts, the composite catalyst g-C3N4And Cu2O
Closely growth together, forms g-C3N4-Cu2The heterojunction structure of O plane-plane contacts.Compared to the g-C of pure phase3N4With
Cu2O, g-C3N4-Cu2O composites have stronger visible absorption ability.g-C3N4-Cu2O hetero-junctions preferably can band
Distribution structure ensures that the photocatalysis performance of compound, than single-phase g-C3N4Or Cu2O is greatly improved.
(2) present invention is using the g-C protonated3N4, it obvious dispersiveness is occurred, form that specific surface area is bigger to be received
Rice laminated structure, so as to more fully contact Cu2O forms even closer heterojunction structure.
(3) present invention assesses composite photo-catalyst photocatalytic activity by visible light exposure degraded object test, as a result
Show g-C3N4-Cu2Degraded of the O/Vis systems compared to its single-phase photocatalytic system to pollutant is more efficient.
(4) g-C of the present invention3N4And Cu2The p-n junction heterojunction structure formed between O is stable, composite photocatalyst after circulating 6 times
Agent does not occur obvious inactivation, with good photochemical stability.
, but those skilled in the art once know basic creation although preferred embodiments of the present invention have been described
Property concept, then can make other change and modification to these embodiments.So, appended claims are intended to be construed to include excellent
Select embodiment and fall into having altered and changing for the scope of the invention.Obviously, those skilled in the art can be to the present invention
Carry out various changes and modification without departing from the spirit and scope of the present invention.So, if these modifications and variations of the present invention
Belong within the scope of the claims in the present invention and its equivalent technologies, then the present invention is also intended to exist comprising these changes and modification
It is interior.
Claims (10)
1. a kind of g-C3N4-Cu2The preparation method of O composite catalysts, it is characterised in that：Methods described comprises the following steps：
The first solution is provided, first solution includes the Cu of dissolved state2+；
The g-C of protonation is added in first solution3N4, stirring, ultrasound, acquisition suspension；
Xylitol is added into the suspension under stirring, regulation pH value stirs to obtain mixed liquor to 10-12；
The mixed liquor is heated to 150-200 DEG C in high-pressure reaction vessel, isothermal reaction 25-35h obtains reactant；
The reactant separation of solid and liquid after cooling is obtained into solid product, cleaned, vacuum drying；
The solid product is heated to 150-250 DEG C of holding constant temperature 1h-3h under atmosphere protection, g-C is made3N4-Cu2O is combined
Catalyst.
2. g-C according to claim 13N4-Cu2The preparation method of O composite catalysts, it is characterised in that：Described be combined is urged
In agent, the g-C3N4With Cu2O mass ratio is 1:1-1:5.
3. g-C according to claim 13N4-Cu2The preparation method of O composite catalysts, it is characterised in that：The solid production
The rate of heat addition of thing is 2-3k/min.
4. g-C according to claim 13N4-Cu2The preparation method of O composite catalysts, it is characterised in that：The protonation
G-C3N4Preparation method include：By dicyandiamide after being warming up to 500-600 DEG C under conditions of heating rate is 1-3K/min,
3-5h is calcined, cooling, grinding obtains powder；Concentrated sulfuric acid mixing is added in the powder, stirring, ultrasound obtains mixture；Will
The mixture is mixed with water, obtains milk-white coloured suspension, and the milk-white coloured suspension is centrifuged, wash and dried, is obtained
G-C after to acidifying3N4；By the g-C after the acidifying3N4In 50-75 DEG C of heat backflow 4-8h, suction filtration, washing and dry proton
The g-C of change3N4。
5. g-C according to claim 43N4-Cu2The preparation method of O composite catalysts, it is characterised in that：During the stirring
Between be 6-10h, the ultrasonic time be 1-3h.
6. the g-C as described in claim any one of 1-53N4-Cu2The application of O composite catalysts, it is characterised in that：The g-
C3N4-Cu2Organic pollution of the O composite catalysts under radiation of visible light effect in treating wastewater through catalysis of connected.
7. g-C according to claim 63N4-Cu2The application of O composite catalysts, it is characterised in that：The processing includes：
G-C is added in waste water3N4-Cu2O composite catalysts, stirring forms mixture；
The mixture is placed in the range of exposures of visible ray；
The g-C3N4-Cu2O composite catalysts and the organic pollution in visible ray co-treating wastewater.
8. g-C according to claim 63N4-Cu2The application of O composite catalysts, it is characterised in that：Included in the waste water
One or more in Anthraquinones, quinone imides, the organic pollution of oxa anthracenes and azo.
9. g-C according to claim 83N4-Cu2The application of O composite catalysts, it is characterised in that：In the organic wastewater
Pollutant be selected from reactive brilliant bule, methylene blue, rhodamine B, reactive brilliant red and methyl orange.
10. g-C according to claim 73N4-Cu2The application of O composite catalysts, it is characterised in that：Have in the waste water
The initial concentration of organic pollutants is 10-100mg/L；G-C in the mixture3N4-Cu2The addition of O composite catalysts is
0.1-2g/L。
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Inventor after: Li Dongya Inventor after: Xia Dongsheng Inventor after: Xu Haiming Inventor after: Liao Wei Inventor after: Zuo Shiyu Inventor after: Cao Gang Inventor after: Yuan Xiangjuan Inventor after: Sun Lei Inventor before: Li Dongya Inventor before: Xia Dongsheng Inventor before: Xu Haiming Inventor before: Liao Wei Inventor before: Zuo Shiyu Inventor before: Cao Gang Inventor before: Yuan Xiangjuan Inventor before: Sun Lei |
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Application publication date: 20170926 |