CN112337476B - Copper tungstate/copper bismuthate composite photocatalyst and preparation method thereof - Google Patents
Copper tungstate/copper bismuthate composite photocatalyst and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 7
- 229910052802 copper Inorganic materials 0.000 title claims description 7
- 239000010949 copper Substances 0.000 title claims description 7
- OQFRENMCLHGPRB-UHFFFAOYSA-N copper;dioxido(dioxo)tungsten Chemical compound [Cu+2].[O-][W]([O-])(=O)=O OQFRENMCLHGPRB-UHFFFAOYSA-N 0.000 title description 5
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000004570 mortar (masonry) Substances 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 7
- 238000005406 washing Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000001782 photodegradation Methods 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 230000004298 light response Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229960004989 tetracycline hydrochloride Drugs 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
- C02F2101/38—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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- 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
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to CuWO 4 /CuBi 2 O 4 A preparation method of a composite photocatalyst belongs to the technical field of photocatalysis. The composite photocatalyst has strong visible light response capability, has high-efficiency photodegradation activity in the process of eliminating photocatalytic organic pollutants, and is a photocatalyst material with great application potential. The preparation method of the composite photocatalyst mainly comprises the following steps: cuWO 4 And CuBi 2 O 4 Preparing a precursor; fully mixing the two prepared precursors according to a certain proportion, and preparing CuWO by adopting a pyrolysis mixed precursor method 4 /CuBi 2 O 4 A composite photocatalyst is provided. The composite photocatalyst is simple to prepare and suitable for mass production; the required raw materials are rich, the cost is low, and the method has good application prospect in the field of environment.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and relates to copper tungstate CuWO 4 Copper bismuthate CuBi 2 O 4 A composite photocatalyst and a preparation method thereof, in particular to CuWO with high-efficiency visible light catalytic activity and high stability 4 /CuBi 2 O 4 A composite photocatalyst and a preparation method thereof.
Background
Solar energy has the advantages of cleanness, no pollution, high energy and renewable utilization, and is one of the important choices of human beings for dealing with environmental pollution and energy shortage at present. The photocatalysis can convert solar energy into storable chemical energy by utilizing a photocatalyst, has the characteristics of environmental friendliness, low cost, mild reaction and the like, and is a novel technical means with great application potential. At present, the photocatalysis technology is widely applied to two fields of energy and environment, such as hydrogen production by photolysis of water, photocatalytic reduction of carbon dioxide, air purification, water pollution treatment and the like. In the process of photocatalytic reaction, when a photocatalyst absorbs light, a photon-generated carrier is generated, and the recombination of electrons and holes greatly influences the activity of the photocatalyst. The pn junction composite photocatalyst forms a pn junction at an interface, so that dipole layers with positive and negative space charges arranged at two sides are formed at the interface of two semiconductors, and a built-in electric field pointing from an n-type photocatalyst to the p-type photocatalyst is constructed, so that electrons and holes migrate to the opposite direction, the separation efficiency of electron-hole pairs is greatly improved, and the method becomes an important means for improving the catalytic efficiency of the photocatalyst.
CuBi 2 O 4 The p-type narrow band gap semiconductor is a spinel-structured p-type narrow band gap semiconductor, has the forbidden band width of about 1.5-1.8 eV, has special magnetic, dielectric and photoelectric properties, good photo-thermal stability, high conduction band position (-0.6 eV), and strong reducibility of photo-generated electrons. Single-component CuBi 2 O 4 Poor conductivity, resulting in low carrier mobility (10) -3 cm 2 V -1 S -1 ) And the diffusion length is short (10-50 nm), the recombination of photogenerated holes and electrons is serious, and the overall catalytic efficiency is low. Therefore, how to effectively regulate and control CuBi 2 O 4 Carrier transmission is to construct CuBi with high activity 2 O 4 The photocatalyst needs to solve the core problem. n-type CuWO 4 The photocatalyst is a typical oxidation type photocatalyst, has a proper band gap, has strong visible light absorption capacity, is relatively deep in valence band, and has strong oxidation and mineralization capacities. In the invention, copper tungstate is loaded on the surface of copper bismuthate in situ by a simple heat treatment decomposition precursor method, the synergistic effect of the two components is fully exerted by the construction of the compound, and the separation of photon-generated carriers is effectively promoted by utilizing the pn junction between the copper tungstate and the copper bismuthate, so that the photocatalytic activity is obviously improved. Compared with the traditional hydrothermal in-situ growth, the preparation method avoids the generation of a byproduct, namely bismuth tungstate in other conventional preparation methods, and is suitable for large-scale industrial production of CuWO 4 /CuBi 2 O 4 A preparation method of a composite photocatalyst.
Disclosure of Invention
The invention aims to provide CuWO 4 /CuBi 2 O 4 The invention relates to a composite photocatalyst and a preparation method thereof, and the purpose of the invention is realized by the following technical steps:
(1)CuBi 2 O 4 preparing a precursor: dissolving copper nitrate, bismuth nitrate and sodium hydroxide (preferably, the molar ratio is 1 2 O 4 And (3) precursor.
(2)CuWO 4 Preparing a precursor: preparing inorganic copper salt solution and tungsten source solution, slowly dripping the tungsten source solution into the copper salt solution, stirring for liquid phase reaction, centrifuging, and drying in the air at room temperature to obtain CuWO 4 And (3) precursor. The molar ratio of copper to tungsten in the mixed solution is 1.
(3)CuWO 4 /CuBi 2 O 4 Preparing a composite photocatalyst: weighing a certain amount of CuWO 4 Precursor and CuBi 2 O 4 Grinding and mixing the precursor by a mortar or ball milling and mixing the precursor, and then carrying out pyrolysis reaction, specifically preparing CuWO under the conditions that the temperature of the precursor mixture is 400-500 ℃, the heating rate is 1-10 ℃/min and the calcination time is 0.5-10h 4 /CuBi 2 O 4 A composite photocatalyst. By regulating CuWO 4 Precursor and CuBi 2 O 4 The proportion of the precursor can prepare a series of CuWO with different component proportions 4 /CuBi 2 O 4 A composite photocatalyst is provided.
The technical route takes water as a solvent, the preparation process is green, low in energy consumption and free of pollution, the preparation operation is simple, the reaction condition is mild, the cost is low, the operability is good, the repeatability is high, the generation of a byproduct bismuth tungstate in other conventional preparation methods can be avoided, and the method is suitable for large-scale preparation of the composite photocatalyst. Furthermore, by CuBi 2 O 4 Surface introduction of CuWO 4 The pn junction is constructed, so that the separation of a photon-generated carrier can be effectively promoted, the activity of the composite catalyst for degrading medical antibiotics is improved, and the composite catalyst has a wide application prospect in sewage treatment and environmental protection.
Drawings
FIG. 1 is a photograph of a film prepared in example 1CuWO 4 、CuBi 2 O 4 And CuWO 4 /CuBi 2 O 4 X-ray diffraction pattern of the composite photocatalyst.
FIG. 2 is a representation of CuBi prepared in example 2 2 O 4 And CuWO 4 /CuBi 2 O 4 Scanning electron microscopy of the composite photocatalyst.
FIG. 3 is CuWO prepared in example 3 4 、CuBi 2 O 4 And CuWO 4 /CuBi 2 O 4 The activity of the composite photocatalyst for photocatalytic degradation of tetracycline hydrochloride is shown in a comparison graph.
Detailed Description
For a better understanding of the present invention, the following examples and drawings are included to further illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
CuWO 4 /CuBi 2 O 4 The preparation method of the composite photocatalyst comprises the following specific steps:
dissolving 2.5mmol of copper nitrate, 5mmol of bismuth nitrate and 22.5mmol of sodium hydroxide in 80mL of deionized water, stirring for 30mins, centrifuging, and drying in air at room temperature to obtain CuBi 2 O 4 And (3) precursor.
Preparing copper nitrate and sodium tungstate solution, slowly dripping 40mL of 10mmol/L sodium tungstate solution into 40mL of 10mmol/L copper nitrate solution, stirring for 10mins, centrifuging, and drying in the air at room temperature to obtain CuWO 4 And (3) precursor.
The CuWO prepared in the above way 4 Precursor and CuBi 2 O 4 The precursor is fully ground in a mortar according to the mass fraction ratio of 0.6 4 /CuBi 2 O 4 A composite photocatalyst is provided.
FIG. 1 is CuWO 4 、CuBi 2 O 4 And CuWO 4 /CuBi 2 O 4 X-ray diffraction pattern of (a). Single component CuWO in the figure 4 、CuBi 2 O 4 Using and preparing CuWO 4 /CuBi 2 O 4 Preparing the composite photocatalyst with the same heat treatment parameters. From the figure, one-component CuWO can be seen 4 Is a triclinic system, and the corresponding PDF card is 72-0616; and single component of CuBi 2 O 4 Is monoclinic system, and the corresponding PDF card is 72-0493. The diffraction peak of the prepared composite photocatalyst simultaneously appears triclinic CuWO 4 And monoclinic system CuBi 2 O 4 Diffraction peaks, which indicate that CuWO is indeed the cause of the composite catalyst 4 And CuBi 2 O 4 And (4) forming. No diffraction peak of other impurities is detected, which indicates that the CuWO is prepared by the preparation method 4 /CuBi 2 O 4 The composite photocatalyst has the characteristic of high purity.
Example 2
CuWO 4 /CuBi 2 O 4 The preparation method of the composite photocatalyst comprises the following specific steps:
dissolving 2.5mmol of copper nitrate, 5mmol of bismuth nitrate and 22.5mmol of sodium hydroxide in 80mL of deionized water, stirring for 30mins, centrifuging, and drying in air at room temperature to obtain CuBi 2 O 4 And (3) precursor.
Preparing copper nitrate and sodium tungstate solution, slowly dropwise adding 40mL of 100mmol/L sodium tungstate solution into 40mL of 100mmol/L copper nitrate solution, stirring for 10mins, centrifuging, and drying in air at room temperature to obtain CuWO 4 And (3) precursor.
The CuWO prepared in the above way 4 Precursor and CuBi 2 O 4 The precursor is fully ground in a ball mill according to the mass fraction ratio of 0.7 to 1, and then calcined for 1h at 400 ℃ at the heating rate of 5 ℃/min, so that the 70wt% CuWO is obtained 4 /CuBi 2 O 4 A composite photocatalyst.
FIG. 2 shows CuBi 2 O 4 And CuWO 4 /CuBi 2 O 4 The scanning electron microscope image of the composite photocatalyst shows that the method for preparing CuWO by pyrolyzing the mixed precursors 4 /CuBi 2 O 4 The composite photocatalyst is prepared in CuWO 4 And CuBi 2 O 4 The interface of the semiconductor substrate has close pn junction contact, and the composite structure can effectively increase the photo-generated carriers in CuWO 4 And CuBi 2 O 4 The separation between the two is beneficial to improving the photocatalytic activity.
Example 3
CuWO 4 /CuBi 2 O 4 The preparation method of the composite photocatalyst comprises the following specific steps:
dissolving 2.5mmol of copper nitrate, 5mmol of bismuth nitrate and 22.5mmol of sodium hydroxide in 80mL of deionized water, stirring for 30mins, centrifuging, and drying in air at room temperature to obtain CuBi 2 O 4 And (3) precursor.
Preparing copper nitrate and sodium tungstate solution, slowly dripping 40mL of sodium tungstate solution with the concentration of 500mmol/L into 40mL of copper nitrate solution with the concentration of 500mmol/L, stirring for 10mins, centrifuging, drying in the air at room temperature, and preparing to obtain CuWO 4 And (3) precursor.
The CuWO prepared above is added 4 Precursor and CuBi 2 O 4 The precursor was sufficiently ground in a mortar in a mass fraction ratio of 0.1:1, and then calcined at 450 ℃ for 10 hours at a temperature-rise rate of 10 ℃/min, to obtain a CuWO having a nominal 10wt% of the total weight of CuWO 4 /CuBi 2 O 4 A composite photocatalyst is provided.
FIG. 3 is a graph comparing the photodegradation activities of tetracycline hydrochloride by different photocatalysts. The test condition adopts visible light as a light source, and the initial concentration of 30mg of catalyst for photocatalytic degradation is 50mg L -1 Tetracycline hydrochloride. As can be seen from the figure, the comparative monocomponent CuBi 2 O 4 Or CuWO 4 The prepared 10wt% composite catalyst has high-efficiency photocatalytic tetracycline hydrochloride degradation activity, and the prepared composite catalyst constructs a pn junction, so that the separation of photon-generated carriers is remarkably accelerated, and the photocatalytic activity is improved.
Claims (7)
1. CuWO 4 /CuBi 2 O 4 The preparation method of the composite photocatalyst is characterized by comprising the following steps:
(1) Dissolving copper nitrate, bismuth nitrate and sodium hydroxide in deionized water, mixing and stirring, centrifuging, washing with water, and drying in air at room temperature to obtain CuBi 2 O 4 A precursor;
(2) Preparing an inorganic copper salt aqueous solution and a tungsten source aqueous solution, mixing and stirring the two aqueous solutions, centrifuging, and drying in the air at room temperature to obtain CuWO 4 A precursor;
(3) Uniformly mixing the two prepared precursors in a certain mode to obtain a mixed precursor, and pyrolyzing the mixed precursor in air atmosphere to obtain CuWO 4 /CuBi 2 O 4 A composite photocatalyst.
2. CuWO according to claim 1 4 /CuBi 2 O 4 The preparation method of the composite photocatalyst is characterized in that the molar ratio of copper nitrate, bismuth nitrate and sodium hydroxide in the step (1) is 1.
3. CuWO according to claim 1 4 /CuBi 2 O 4 The preparation method of the composite photocatalyst is characterized in that the molar ratio of copper to tungsten is 1.
4. CuWO according to claim 1 4 /CuBi 2 O 4 The preparation method of the composite photocatalyst is characterized in that when the inorganic copper salt aqueous solution and the tungsten source aqueous solution are mixed in the step (2), the tungsten source aqueous solution is required to be dropwise added into the inorganic copper salt aqueous solution.
5. CuWO according to claim 1 4 /CuBi 2 O 4 The preparation method of the composite photocatalyst is characterized in that the mixing in the certain mode in the step (3) is grinding and mixing in a mortar or ball milling and mixing.
6. CuWO according to claim 1 4 /CuBi 2 O 4 The preparation method of the composite photocatalyst is characterized in that,and (4) pyrolyzing in the step (3), wherein the temperature is 400-500 ℃, the heating rate is 1-10 ℃/min, and the calcining time is 0.5-10h.
7. CuWO 4 /CuBi 2 O 4 A composite photocatalyst obtainable by a process as claimed in any one of claims 1 to 6.
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