CN112619655A - SiO (silicon dioxide)2Loaded Cu2O-ZnO heterojunction photocatalytic degradation material and preparation method thereof - Google Patents
SiO (silicon dioxide)2Loaded Cu2O-ZnO heterojunction photocatalytic degradation material and preparation method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 113
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 75
- 239000000463 material Substances 0.000 title claims abstract description 64
- 235000012239 silicon dioxide Nutrition 0.000 title claims description 23
- 238000002360 preparation method Methods 0.000 title claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 114
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 71
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 71
- 239000010949 copper Substances 0.000 claims abstract description 53
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 25
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004246 zinc acetate Substances 0.000 claims abstract description 21
- GDGIVSREGUOIJZ-UHFFFAOYSA-N 5-amino-3h-1,3,4-thiadiazole-2-thione Chemical compound NC1=NN=C(S)S1 GDGIVSREGUOIJZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 20
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 19
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 19
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 19
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 19
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 12
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 37
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000002202 Polyethylene glycol Substances 0.000 claims description 19
- 229920001223 polyethylene glycol Polymers 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 18
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 18
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 13
- 238000007112 amidation reaction Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- -1 polyethylene Polymers 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 92
- 239000011787 zinc oxide Substances 0.000 abstract description 66
- 239000013078 crystal Substances 0.000 abstract description 4
- 239000002057 nanoflower Substances 0.000 abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 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 description 9
- 229960000907 methylthioninium chloride Drugs 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 4
- 239000005750 Copper hydroxide Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910001956 copper hydroxide Inorganic materials 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 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 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002086 nanomaterial 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
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/80—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 zinc, cadmium or mercury
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of photocatalyst and discloses SiO2Loaded Cu2O-ZnO heterojunction photocatalytic degradation material, mesoporous SiO prepared by taking tetraethoxysilane as silicon source2The surface hydroxyl can react with trimesoyl chloride to generate acyl chloride SiO2Which reacts with 2-amino-5-mercapto-1, 3, 4-thiadiazole to produce thiolated SiO2Copper sulfate reacts with sodium hydroxide and hydrazine hydrate to form cuprous oxide hollow spheres, cadmium is doped into cuprous oxide lattices in a positive divalent form to generate impurity energy levels, the forbidden bandwidth of cuprous oxide is reduced, zinc acetate and sodium hydroxide generate zinc oxide crystal nuclei,the zinc oxide nano-flower is assembled under the action of the surfactant, the cuprous oxide and the zinc oxide can form a p-n type heterojunction, when the zinc oxide nano-flower is irradiated by light, electrons of the cuprous oxide are transferred to a conduction band of the zinc oxide, and holes of the zinc oxide are transferred to a valence band of the cuprous oxide, so that the separation of the photoproduction electrons and the holes is realized.
Description
Technical Field
The invention relates to the technical field of photocatalyst, in particular to SiO2Loaded Cu2An O-ZnO heterojunction photocatalytic degradation material and a preparation method thereof.
Background
With the continuous acceleration of modern construction, the discharge amount of sewage is gradually increased, the safety of drinking water is greatly improved, organic dyes such as methylene blue, methyl orange and the like in the sewage are pollutants which are urgently needed to be treated in the sewage, the traditional adsorption degradation method is not sufficient in degradation and is easy to form secondary pollution, the photocatalytic degradation is a novel organic pollutant removing means, the nano zinc oxide is an electric n-type semiconductor metal oxide and has the advantages of high chemical stability, good thermal stability, rich sources and the like, the nano zinc oxide is widely applied in the fields of sensors, photoelectric devices, solar cells and the like, meanwhile, the nano zinc oxide has wider forbidden bandwidth and has certain application in the field of photocatalysis, however, the traditional nano zinc oxide has smaller specific surface area, fewer photocatalytic degradation active sites on the surface and can only absorb ultraviolet light, sunlight cannot be effectively utilized, and simultaneously, photoproduction electrons and holes of the nano zinc oxide are easy to be compounded, so that the nano zinc oxide cannot be independently used as a photocatalytic degradation material, and therefore the nano zinc oxide needs to be improved, and the photocatalytic degradation activity of the nano zinc oxide is improved.
The nano cuprous oxide is a metal oxide with narrow band gap, and has the characteristics of simple preparation method, wide source and excellent photoelectric property due to the existence of copper defect in the structure, so that the nano cuprous oxide becomes a common p-type semiconductor, has wide application in the fields of pesticides, analytical reagents, antifouling paints and the like, and has good photoelectric property, so that the nano cuprous oxide has wide research in the field of photocatalysis, however, when the traditional nano cuprous oxide is singly used as a photocatalytic degradation material, the further application of the nano cuprous oxide is limited by the small specific surface area and the electron-hole pair which is easy to compound, so that the nano cuprous oxide needs to be improved, on one hand, the surface area of the nano cuprous oxide can be improved by improving the shape of the nano cuprous oxide, on the other hand, the nano cuprous oxide can be compounded with inorganic nano materials such as titanium dioxide, zinc oxide and the like to form a heterojunction type photocatalytic degradation material, can effectively improve the photocatalytic degradation activity of the nano cuprous oxide.
The nano-silica is a nontoxic and tasteless inorganic material, and the porous nano-silica has an obvious net-shaped or porous structure, has the characteristics of small density, large specific surface area and certain adsorption performance, so that the porous nano-silica can be used as a carrier of a good photocatalytic degradation material, but the nano-silica has a very limited physical adsorption effect and cannot effectively adsorb organic pollutants such as methyl orange, methylene blue and the like in sewage, so that the porous nano-silica needs to be modified, small-molecule organic functional groups are covalently grafted on the surface of the porous nano-silica, and the adsorption performance of the nano-silica on the inorganic pollutants such as the methyl orange, the methylene blue and the like is further improved by combining the physical adsorption effect of the nano-silica with the chemical adsorption of the surface functional groups.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides SiO2Loaded Cu2The photocatalytic degradation material of O-ZnO heterojunction and the preparation method thereof solve the problem of single Cu2Poor photocatalytic degradation activity.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: SiO (silicon dioxide)2Loaded Cu2An O-ZnO heterojunction photocatalytic degradation material, the SiO2Loaded Cu2The preparation method of the O-ZnO heterojunction photocatalytic degradation material comprises the following steps:
(1) taking tetraethoxysilane as a silicon source, polyethylene oxide-polypropylene oxide-polyethylene oxide as a template and mesitylene as a pore-enlarging agent, and obtaining mesoporous silicon dioxide through hydrothermal reaction;
(2) adding a toluene solvent and mesoporous silica into a three-neck flask, performing uniform ultrasonic dispersion, filling nitrogen to remove oxygen, transferring to an oil bath pot, continuously adding trimesoyl chloride, raising the temperature to perform substitution reaction, centrifuging, washing and drying a product to obtain acyl chloride nano-silica;
(3) adding methanol solvent and acyl chloride nano-silica into a three-neck flask, ultrasonically mixing uniformly, transferring into an oil bath pot, continuously adding 2-amino-5-mercapto-1, 3, 4-thiadiazole, stirring uniformly, raising the temperature to perform amidation reaction, centrifuging, washing and drying after the reaction is finished to obtain thiolated silica;
(4) adding a deionized water solvent, copper sulfate and cadmium sulfate into a three-neck flask, after uniformly dispersing by ultrasonic, continuously adding sodium hydroxide and ethanolamine, mechanically stirring for 20-40min, adding hydrazine hydrate, transferring into a reaction kettle, placing into an oven for hydrothermal reaction, cooling a product, aging, centrifuging, washing and drying to obtain a cadmium-doped cuprous oxide hollow sphere;
(5) adding n-octanol solvent, cadmium-doped cuprous oxide hollow spheres, zinc acetate and sodium hydroxide into a three-necked bottle, ultrasonically dispersing uniformly, adding polyethylene glycol, transferring into a reaction kettle, placing into an oven for hydrothermal reaction, cooling the product, repeatedly washing with absolute ethyl alcohol and distilled water, and drying to obtain Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
(6) Adding deionized water solvent, sulfhydrylation silicon dioxide and Cu into a three-mouth bottle2The O-ZnO heterojunction photocatalytic degradation material is transferred to a reaction kettle after being dispersed uniformly by ultrasonic waves, is placed in an oven, is subjected to hydrothermal reaction for 2-6h at the temperature of 100-120 ℃, and is centrifuged, washed and dried after being cooled to obtain SiO2Loaded Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
Preferably, the mass ratio of the mesoporous silica to the trimesoyl chloride in the step (2) is 100: 220-260.
Preferably, the temperature of the substitution reaction in the step (2) is 80-100 ℃, and the reflux reaction is carried out for 5-10h under the nitrogen atmosphere.
Preferably, the mass ratio of the acylchlorinated nano-silica to the 2-amino-5-mercapto-1, 3, 4-thiadiazole in the step (3) is 100: 300-.
Preferably, the temperature of the amidation reaction in the step (3) is 40-60 ℃, and the reaction is carried out for 5-12h in a nitrogen atmosphere.
Preferably, the copper sulfate, the cadmium sulfate and the hydrogen and oxygen in the step (4)Sodium chloride, ethanolamine and N2H4The mass ratio of (1: 100:0.4-1:40-80: 140) and (340: 0.2-0.6).
Preferably, the temperature of the hydrothermal reaction in the step (4) is 110-.
Preferably, the mass ratio of the cadmium-doped cuprous oxide hollow spheres, the zinc acetate, the sodium hydroxide and the polyethylene glycol in the step (5) is 100:50-70:110-150: 220-330.
Preferably, the temperature of the hydrothermal reaction in the step (5) is 190-.
Preferably, the silica hydrosulfide and Cu are sulfhydrylated in the step (6)2The mass ratio of the O-ZnO heterojunction photocatalytic degradation material is 100: 40-80.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the SiO2Loaded Cu2An O-ZnO heterojunction photocatalytic degradation material is prepared by taking tetraethoxysilane as a silicon source, polyethylene oxide-polypropylene oxide-polyethylene oxide as a template and mesitylene as a pore-enlarging agent, obtaining mesoporous silica through a hydrothermal reaction, wherein the surface of the hydrothermally synthesized nano silica contains a large amount of hydroxyl groups, and the mesoporous silica can be subjected to substitution reaction with acyl chloride groups of trimesoyl chloride to generate acyl chlorinated nano silica, the acyl chloride groups in the acyl chlorinated nano silica can be subjected to amidation reaction with amino groups in 2-amino-5-mercapto-1, 3, 4-thiadiazole to generate sulfhydrylated nano silica, and with the increase of the pH of a solution, sulfhydryls are volatilized to remove protons to form sulfur anions which can be electrostatically attracted with positively charged methylene blue, and the pore structure of the porous silica can also adsorb the methylene blue, cu is formed by hydrothermal recombination2The O-ZnO heterojunction photocatalytic degradation material is loaded on the surface of the nano-porous silicon dioxide, and the methylene blue concentration around the composite photocatalytic degradation material is improved through the adsorption effect of the sulfhydrylated nano-silicon dioxide, so that the degradation rate and the activity of the composite photocatalytic degradation material are further improved.
The SiO2Loaded Cu2An O-ZnO heterojunction photocatalytic degradation material, copper sulfate and sodium hydroxide react to generate a stable copper hydroxide precursor, free copper ions in a solution are reduced, the surface layer of the copper hydroxide is reduced under the action of hydrazine hydrate to generate a cuprous oxide coated copper hydroxide spherical shell, the internal copper hydroxide is gradually reduced by the hydrazine hydrate along with the continuous hydrothermal reaction, the generated cuprous oxide is gradually transferred to the shell layer to finally form a cuprous oxide hollow sphere, the hollow spherical cuprous oxide has a larger specific surface area, the photocatalytic degradation active sites on the surface are greatly increased, the photocatalytic activity of nano zinc oxide is improved, cadmium is doped into the crystal lattice of the nano cuprous oxide in a positive divalent form, the impurity level between a cuprous oxide valence band and a conduction band is generated, and the excitation energy required by the nano cuprous oxide is reduced, meanwhile, the forbidden bandwidth of the nano cuprous oxide is reduced, and the visible light absorption waveband of the nano cuprous oxide is widened, so that the photocatalytic degradation activity of the nano cuprous oxide is further improved.
The SiO2Loaded Cu2O-ZnO heterojunction photocatalytic degradation material, in the process of synthesizing zinc oxide nano-flower by hydrothermal method, zinc acetate reacts with sodium hydroxide to generate [ Zn (OH) ]4]2-Precursor, as the hydrothermal reaction proceeds, [ Zn (OH) ]4]2-The precursor is gradually decomposed into zinc oxide crystal nuclei, the zinc oxide crystal nuclei gradually grow under the action of a surfactant polyethylene glycol to form zinc oxide nano-sheets, and finally zinc oxide nano-flowers are assembled, the nano-zinc oxide with flower-shaped morphology has larger specific surface area and more photocatalytic degradation active sites on the surface, meanwhile, the larger specific surface area can have larger contact area with light energy, the photocatalytic degradation activity and the degradation rate of the nano-zinc oxide can be improved, in addition, cuprous oxide and zinc oxide can form p-n type heterojunction, because the position of a cuprous oxide conduction band is higher, when the composite photocatalytic degradation material is irradiated by light, electrons on the cuprous oxide conduction band are transferred to the zinc oxide conduction band, and meanwhile, the top position of the cuprous oxide valence band is lower than that of the zinc oxide, so that holes on the zinc oxide valence band can be transferred to the cuprous oxide valence band, thereby being effectiveThe separation of the photoproduction electrons and the holes is realized, the photocatalytic degradation activity of the composite photocatalytic degradation material is further improved, the photoproduction electrons gathered on the zinc oxide conduction band have extremely strong reduction effect, can react with water to generate superoxide radical and hydroxyl radical with strong oxidizing property, and can oxidize organic pollutants such as methyl orange, methylene blue and the like into carbon dioxide and water, thereby achieving the purpose of photocatalytic degradation of the organic pollutants.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: SiO (silicon dioxide)2Loaded Cu2The preparation method of the O-ZnO heterojunction photocatalytic degradation material comprises the following steps:
(1) taking tetraethoxysilane as a silicon source, polyethylene oxide-polypropylene oxide-polyethylene oxide as a template and mesitylene as a pore-enlarging agent, and obtaining mesoporous silicon dioxide through hydrothermal reaction;
(2) adding a toluene solvent and mesoporous silica into a three-neck flask, ultrasonically dispersing uniformly, filling nitrogen to remove oxygen, transferring to an oil bath pot, continuously adding trimesoyl chloride, wherein the mass ratio of the mesoporous silica to the trimesoyl chloride is 100: 220-;
(3) adding a methanol solvent and acylchloridized nano-silica into a three-neck flask, ultrasonically mixing uniformly, transferring the mixture into an oil bath pot, continuously adding 2-amino-5-mercapto-1, 3, 4-thiadiazole, wherein the mass ratio of the acylchloridized nano-silica to the 2-amino-5-mercapto-1, 3, 4-thiadiazole is 100:300-350, stirring uniformly, carrying out amidation reaction for 5-12h at 40-60 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished to obtain thiolated silica;
(4) adding deionized water solvent, copper sulfate and cadmium sulfate into a three-neck flask, ultrasonically dispersing uniformly, continuously adding sodium hydroxide and ethanolamine, mechanically stirring for 20-40min, and adding hydrazine hydrate, wherein the copper sulfate, the cadmium sulfate, the sodium hydroxide, the ethanolamine and N are2H4The mass ratio of (A) to (B) is 100:0.4-1:40-80:140-340:0.2-0.6, transferring the product into a reaction kettle, placing the reaction kettle in an oven, reacting for 10-20h at the temperature of 110-;
(5) adding n-octanol solvent, cadmium-doped cuprous oxide hollow spheres, zinc acetate and sodium hydroxide into a three-neck flask, ultrasonically dispersing uniformly, adding polyethylene glycol, transferring the mixture into a reaction kettle, placing the reaction kettle into an oven, carrying out hydrothermal reaction for 2-6h at the temperature of 190-70 ℃ by using 150-220-containing zinc acetate, zinc acetate and polyethylene glycol in a mass ratio of 100:50-70:110, repeatedly washing and drying the product after cooling the product to obtain Cu-containing organic compound2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
(6) Adding a deionized water solvent, sulfhydrylation silicon dioxide and Cu with the mass ratio of 100:40-80 into a three-mouth bottle2The O-ZnO heterojunction photocatalytic degradation material is transferred to a reaction kettle after being dispersed uniformly by ultrasonic waves, is placed in an oven, is subjected to hydrothermal reaction for 2-6h at the temperature of 100-120 ℃, and is centrifuged, washed and dried after being cooled to obtain SiO2Loaded Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
Example 1
(1) Taking tetraethoxysilane as a silicon source, polyethylene oxide-polypropylene oxide-polyethylene oxide as a template and mesitylene as a pore-enlarging agent, and obtaining mesoporous silicon dioxide through hydrothermal reaction;
(2) adding a toluene solvent and mesoporous silica into a three-neck flask, ultrasonically dispersing uniformly, then filling nitrogen to remove oxygen, transferring to an oil bath pot, continuously adding trimesoyl chloride, wherein the mass ratio of the mesoporous silica to the trimesoyl chloride is 100:220, carrying out reflux reaction for 5 hours at 80 ℃ in a nitrogen atmosphere, centrifuging, washing and drying a product to obtain the acyl chloride nano-silica;
(3) adding methanol solvent and acyl chloride nano-silica into a three-neck bottle, ultrasonically mixing uniformly, transferring the mixture into an oil bath pot, continuously adding 2-amino-5-mercapto-1, 3, 4-thiadiazole, wherein the mass ratio of the acyl chloride nano-silica to the 2-amino-5-mercapto-1, 3, 4-thiadiazole is 100:300, stirring uniformly, carrying out amidation reaction for 5 hours at 40 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, thus obtaining thiolated silica;
(4) adding deionized water solvent, copper sulfate and cadmium sulfate into a three-neck flask, ultrasonically dispersing uniformly, continuously adding sodium hydroxide and ethanolamine, mechanically stirring for 20min, and adding hydrazine hydrate, wherein the copper sulfate, the cadmium sulfate, the sodium hydroxide, the ethanolamine and N are2H4The mass ratio of the cadmium-doped cuprous oxide hollow spheres to the cadmium-doped cuprous oxide hollow spheres is 100:0.4:40:140:0.2, the cadmium-doped cuprous oxide hollow spheres are transferred to a reaction kettle, placed in an oven and reacted for 10 hours at 110 ℃, and the product is aged, centrifuged, washed and dried after being cooled to obtain the cadmium-doped cuprous oxide hollow spheres;
(5) adding n-octanol solvent, cadmium-doped cuprous oxide hollow spheres, zinc acetate and sodium hydroxide into a three-necked bottle, adding polyethylene glycol after ultrasonic dispersion is uniform, wherein the mass ratio of the cadmium-doped cuprous oxide hollow spheres to the zinc acetate to the sodium hydroxide to the polyethylene glycol is 100:50:110:220, transferring the mixture into a reaction kettle, placing the reaction kettle into an oven, carrying out hydrothermal reaction for 2 hours at 190 ℃, cooling the product, repeatedly washing and drying the product by using absolute ethyl alcohol and distilled water to obtain Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
(6) Adding a deionized water solvent, sulfhydrylation silicon dioxide and Cu with the mass ratio of 100:40 into a three-mouth bottle2The O-ZnO heterojunction photocatalytic degradation material is transferred to a reaction kettle after being dispersed uniformly by ultrasonic waves, is placed in an oven, is subjected to hydrothermal reaction for 2 hours at the temperature of 100 ℃, and is centrifuged, washed and dried after being cooled to obtain SiO2Loaded Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
Example 2
(1) Taking tetraethoxysilane as a silicon source, polyethylene oxide-polypropylene oxide-polyethylene oxide as a template and mesitylene as a pore-enlarging agent, and obtaining mesoporous silicon dioxide through hydrothermal reaction;
(2) adding a toluene solvent and mesoporous silica into a three-neck flask, ultrasonically dispersing uniformly, then filling nitrogen to remove oxygen, transferring to an oil bath pot, continuously adding trimesoyl chloride, wherein the mass ratio of the mesoporous silica to the trimesoyl chloride is 100:234, carrying out reflux reaction for 6 hours at 85 ℃ in a nitrogen atmosphere, centrifuging, washing and drying a product to obtain the acyl chloride nano-silica;
(3) adding methanol solvent and acyl chloride nano-silica into a three-neck bottle, ultrasonically mixing uniformly, transferring the mixture into an oil bath pot, continuously adding 2-amino-5-mercapto-1, 3, 4-thiadiazole, wherein the mass ratio of the acyl chloride nano-silica to the 2-amino-5-mercapto-1, 3, 4-thiadiazole is 100:315, stirring uniformly, carrying out amidation reaction for 6 hours at 45 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, thus obtaining thiolated silica;
(4) adding deionized water solvent, copper sulfate and cadmium sulfate into a three-neck flask, ultrasonically dispersing uniformly, continuously adding sodium hydroxide and ethanolamine, mechanically stirring for 25min, and adding hydrazine hydrate, wherein the copper sulfate, the cadmium sulfate, the sodium hydroxide, the ethanolamine and N are2H4The mass ratio of the cadmium-doped cuprous oxide hollow spheres to the cadmium-doped cuprous oxide hollow spheres is 100:0.6:54:200:0.32, the cadmium-doped cuprous oxide hollow spheres are transferred to a reaction kettle, placed in an oven and reacted for 12 hours at 115 ℃, and the product is aged, centrifuged, washed and dried after being cooled to obtain the cadmium-doped cuprous oxide hollow spheres;
(5) adding n-octanol solvent, cadmium-doped cuprous oxide hollow spheres, zinc acetate and sodium hydroxide into a three-neck bottle, adding polyethylene glycol after ultrasonic dispersion is uniform, wherein the mass ratio of the cadmium-doped cuprous oxide hollow spheres to the zinc acetate to the sodium hydroxide to the polyethylene glycol is 100:56:122:250, transferring the mixture into a reaction kettle, placing the reaction kettle into an oven, carrying out hydrothermal reaction for 3 hours at 195 ℃, cooling the product, repeatedly washing the product with absolute ethyl alcohol and distilled water, and drying the product to obtain Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
(6) Adding a deionized water solvent, sulfhydrylation silicon dioxide and Cu with the mass ratio of 100:54 into a three-mouth bottle2The O-ZnO heterojunction photocatalytic degradation material is transferred to a reaction kettle after being dispersed uniformly by ultrasonic waves, is placed in an oven, is subjected to hydrothermal reaction for 3 hours at 105 ℃, and is centrifuged, washed and dried after being cooled to obtain SiO2Loaded Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
Example 3
(1) Taking tetraethoxysilane as a silicon source, polyethylene oxide-polypropylene oxide-polyethylene oxide as a template and mesitylene as a pore-enlarging agent, and obtaining mesoporous silicon dioxide through hydrothermal reaction;
(2) adding a toluene solvent and mesoporous silica into a three-neck flask, ultrasonically dispersing uniformly, then filling nitrogen to remove oxygen, transferring to an oil bath pot, continuously adding trimesoyl chloride, wherein the mass ratio of the mesoporous silica to the trimesoyl chloride is 100:250, carrying out reflux reaction for 8 hours at 90 ℃ in a nitrogen atmosphere, centrifuging, washing and drying a product to obtain the acyl chloride nano-silica;
(3) adding methanol solvent and acyl chloride nano-silica into a three-neck bottle, ultrasonically mixing uniformly, transferring the mixture into an oil bath pot, continuously adding 2-amino-5-mercapto-1, 3, 4-thiadiazole, wherein the mass ratio of the acyl chloride nano-silica to the 2-amino-5-mercapto-1, 3, 4-thiadiazole is 100:330, stirring uniformly, carrying out amidation reaction at 50 ℃ in a nitrogen atmosphere for 10 hours, centrifuging, washing and drying after the reaction is finished, thus obtaining thiolated silica;
(4) adding deionized water solvent, copper sulfate and cadmium sulfate into a three-neck bottle, ultrasonically dispersing uniformly, continuously adding sodium hydroxide and ethanolamine, mechanically stirring for 30min, and adding hydrazine hydrate, wherein the copper sulfate, the cadmium sulfate, the sodium hydroxide, the ethanolamine and N are2H4The mass ratio of the cadmium-doped cuprous oxide hollow spheres to the cadmium-doped cuprous oxide hollow spheres is 100:0.8:66:280:0.46, the cadmium-doped cuprous oxide hollow spheres are transferred to a reaction kettle, placed in an oven and reacted for 18 hours at 120 ℃, and the product is aged, centrifuged, washed and dried after being cooled to obtain the cadmium-doped cuprous oxide hollow spheres;
(5) adding n-octanol solvent, cadmium-doped cuprous oxide hollow spheres, zinc acetate and sodium hydroxide into a three-necked bottle, adding polyethylene glycol after ultrasonic dispersion is uniform, transferring the cadmium-doped cuprous oxide hollow spheres, the zinc acetate, the sodium hydroxide and the polyethylene glycol in a mass ratio of 100:64:138:280 into a reaction kettle, placing the reaction kettle into an oven, carrying out hydrothermal reaction for 5 hours at 200 ℃, cooling the product, repeatedly washing the product with absolute ethyl alcohol and distilled water, and drying the product to obtain Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
(6) Adding a deionized water solvent, sulfhydrylation silicon dioxide and Cu with the mass ratio of 100:70 into a three-mouth bottle2The O-ZnO heterojunction photocatalytic degradation material is transferred to the material after being dispersed uniformly by ultrasonic wavePlacing the reaction kettle in an oven, carrying out hydrothermal reaction for 5 hours at 115 ℃, cooling the product, centrifuging, washing and drying to obtain SiO2Loaded Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
Example 4
(1) Taking tetraethoxysilane as a silicon source, polyethylene oxide-polypropylene oxide-polyethylene oxide as a template and mesitylene as a pore-enlarging agent, and obtaining mesoporous silicon dioxide through hydrothermal reaction;
(2) adding a toluene solvent and mesoporous silica into a three-neck flask, ultrasonically dispersing uniformly, then filling nitrogen to remove oxygen, transferring to an oil bath pot, continuously adding trimesoyl chloride, wherein the mass ratio of the mesoporous silica to the trimesoyl chloride is 100:260, carrying out reflux reaction for 10 hours at 100 ℃ in a nitrogen atmosphere, centrifuging, washing and drying a product to obtain the acyl chloride nano-silica;
(3) adding methanol solvent and acyl chloride nano-silica into a three-neck bottle, ultrasonically mixing uniformly, transferring the mixture into an oil bath pot, continuously adding 2-amino-5-mercapto-1, 3, 4-thiadiazole, wherein the mass ratio of the acyl chloride nano-silica to the 2-amino-5-mercapto-1, 3, 4-thiadiazole is 100:350, stirring uniformly, carrying out amidation reaction for 12h at 60 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, thus obtaining thiolated silica;
(4) adding deionized water solvent, copper sulfate and cadmium sulfate into a three-neck bottle, ultrasonically dispersing uniformly, continuously adding sodium hydroxide and ethanolamine, mechanically stirring for 40min, and adding hydrazine hydrate, wherein the copper sulfate, the cadmium sulfate, the sodium hydroxide, the ethanolamine and N are2H4The mass ratio of the cadmium-doped cuprous oxide hollow spheres to the cadmium-doped cuprous oxide hollow spheres is 100:1:80:340:0.6, the cadmium-doped cuprous oxide hollow spheres are transferred to a reaction kettle, placed in an oven and reacted for 20 hours at 130 ℃, and the product is aged, centrifuged, washed and dried after being cooled to obtain the cadmium-doped cuprous oxide hollow spheres;
(5) adding n-octanol solvent, cadmium-doped cuprous oxide hollow spheres, zinc acetate and sodium hydroxide into a three-neck bottle, adding polyethylene glycol after ultrasonic dispersion is uniform, wherein the mass ratio of the cadmium-doped cuprous oxide hollow spheres to the zinc acetate to the sodium hydroxide to the polyethylene glycol is 100:70:150:330, transferring into a reaction kettle,placing in a drying oven, carrying out hydrothermal reaction for 6h at 210 ℃, cooling the product, repeatedly washing with absolute ethyl alcohol and distilled water, and drying to obtain Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
(6) Adding a deionized water solvent, sulfhydrylation silicon dioxide and Cu with the mass ratio of 100:80 into a three-mouth bottle2The O-ZnO heterojunction photocatalytic degradation material is transferred to a reaction kettle after being dispersed uniformly by ultrasonic waves, is placed in an oven, is subjected to hydrothermal reaction for 6 hours at 120 ℃, and is centrifuged, washed and dried after being cooled to obtain SiO2Loaded Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
Comparative example 1
(1) Taking tetraethoxysilane as a silicon source, polyethylene oxide-polypropylene oxide-polyethylene oxide as a template and mesitylene as a pore-enlarging agent, and obtaining mesoporous silicon dioxide through hydrothermal reaction;
(2) adding a toluene solvent and mesoporous silica into a three-neck flask, ultrasonically dispersing uniformly, then filling nitrogen to remove oxygen, transferring to an oil bath pot, continuously adding trimesoyl chloride, wherein the mass ratio of the mesoporous silica to the trimesoyl chloride is 100:205, carrying out reflux reaction for 2 hours at 80 ℃ in a nitrogen atmosphere, centrifuging, washing and drying a product to obtain the acyl chloride nano-silica;
(3) adding methanol solvent and acyl chloride nano-silica into a three-neck bottle, ultrasonically mixing uniformly, transferring the mixture into an oil bath pot, continuously adding 2-amino-5-mercapto-1, 3, 4-thiadiazole, wherein the mass ratio of the acyl chloride nano-silica to the 2-amino-5-mercapto-1, 3, 4-thiadiazole is 100:285, stirring uniformly, carrying out amidation reaction for 4 hours at 40 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, thus obtaining thiolated silica;
(4) adding deionized water solvent, copper sulfate and cadmium sulfate into a three-neck flask, ultrasonically dispersing uniformly, continuously adding sodium hydroxide and ethanolamine, mechanically stirring for 10min, and adding hydrazine hydrate, wherein the copper sulfate, the cadmium sulfate, the sodium hydroxide, the ethanolamine and N are2H4The mass ratio of 100:0.2:26:80:0.1, transferring the mixture into a reaction kettle, placing the reaction kettle into an oven, reacting for 5 hours at 110 ℃, cooling the product, aging and separatingThe core is washed and dried to obtain the cadmium-doped cuprous oxide hollow sphere;
(5) adding n-octanol solvent, cadmium-doped cuprous oxide hollow spheres, zinc acetate and sodium hydroxide into a three-necked bottle, adding polyethylene glycol after ultrasonic dispersion is uniform, wherein the mass ratio of the cadmium-doped cuprous oxide hollow spheres to the zinc acetate to the sodium hydroxide to the polyethylene glycol is 100:44:95:190, transferring the mixture into a reaction kettle, placing the reaction kettle into an oven, carrying out hydrothermal reaction for 1h at 190 ℃, cooling the product, repeatedly washing with absolute ethyl alcohol and distilled water, and drying to obtain Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
(6) Adding a deionized water solvent, sulfhydrylation silicon dioxide and Cu with the mass ratio of 100:28 into a three-mouth bottle2The O-ZnO heterojunction photocatalytic degradation material is transferred to a reaction kettle after being dispersed uniformly by ultrasonic waves, is placed in an oven, is subjected to hydrothermal reaction for 1h at the temperature of 100 ℃, and is centrifuged, washed and dried after being cooled to obtain SiO2Loaded Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
Comparative example 2
(1) Taking tetraethoxysilane as a silicon source, polyethylene oxide-polypropylene oxide-polyethylene oxide as a template and mesitylene as a pore-enlarging agent, and obtaining mesoporous silicon dioxide through hydrothermal reaction;
(2) adding a toluene solvent and mesoporous silica into a three-neck flask, ultrasonically dispersing uniformly, then filling nitrogen to remove oxygen, transferring to an oil bath pot, continuously adding trimesoyl chloride, wherein the mass ratio of the mesoporous silica to the trimesoyl chloride is 100:274, carrying out reflux reaction for 12 hours at 100 ℃ in a nitrogen atmosphere, centrifuging, washing and drying a product to obtain the acyl chloride nano-silica;
(3) adding a methanol solvent and acyl chloride nano-silica into a three-neck bottle, ultrasonically mixing uniformly, transferring the mixture into an oil bath pot, continuously adding 2-amino-5-mercapto-1, 3, 4-thiadiazole, wherein the mass ratio of the acyl chloride nano-silica to the 2-amino-5-mercapto-1, 3, 4-thiadiazole is 100:365, stirring uniformly, carrying out amidation reaction at 60 ℃ in a nitrogen atmosphere for 15h, centrifuging, washing and drying after the reaction is finished, so as to obtain thiolated silica;
(4) adding deionized water solvent, copper sulfate and cadmium sulfate into a three-neck flask, ultrasonically dispersing uniformly, continuously adding sodium hydroxide and ethanolamine, mechanically stirring for 60min, and adding hydrazine hydrate, wherein the copper sulfate, the cadmium sulfate, the sodium hydroxide, the ethanolamine and N are2H4The mass ratio of the cadmium-doped cuprous oxide hollow spheres to the cadmium-doped cuprous oxide hollow spheres is 100:1.2:94:400:0.7, the cadmium-doped cuprous oxide hollow spheres are transferred to a reaction kettle, placed in an oven and reacted for 25 hours at 130 ℃, and the product is aged, centrifuged, washed and dried after being cooled to obtain the cadmium-doped cuprous oxide hollow spheres;
(5) adding n-octanol solvent, cadmium-doped cuprous oxide hollow spheres, zinc acetate and sodium hydroxide into a three-necked bottle, adding polyethylene glycol after ultrasonic dispersion is uniform, transferring the cadmium-doped cuprous oxide hollow spheres, the zinc acetate, the sodium hydroxide and the polyethylene glycol in a mass ratio of 100:76:164:360 into a reaction kettle, placing the reaction kettle into an oven, carrying out hydrothermal reaction for 8 hours at 210 ℃, cooling the product, repeatedly washing the product with absolute ethyl alcohol and distilled water, and drying the product to obtain Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
(6) Adding a deionized water solvent, sulfhydrylation silicon dioxide and Cu with the mass ratio of 100:40-80 into a three-mouth bottle2The O-ZnO heterojunction photocatalytic degradation material is transferred to a reaction kettle after being dispersed uniformly by ultrasonic waves, is placed in an oven, is subjected to hydrothermal reaction for 2-6h at the temperature of 100-120 ℃, and is centrifuged, washed and dried after being cooled to obtain SiO2Loaded Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
Preparing SiO with the concentration of 5%2Loaded Cu2The method comprises the steps of mixing an O-ZnO heterojunction photocatalytic degradation material and a methylene blue mixed solution with the concentration of 1.5%, adjusting the pH of the solution to 9, using a 300W xenon lamp as a light source to carry out photocatalytic degradation for 5h, using a UV754N ultraviolet visible spectrophotometer to test the absorbance of the methylene blue solution, and calculating the degradation rate.
Preparing SiO with the concentration of 10%2Loaded Cu2O-ZnO heterojunction photocatalytic degradation material and concentration of the material is 4 percentAnd (3) mixing the rhodamine B solution, adjusting the pH of the solution to 9, carrying out photocatalytic degradation for 5h by using a 300W xenon lamp as a light source, testing the absorbance of the rhodamine B solution by using a UV754N ultraviolet-visible spectrophotometer, and calculating the degradation rate.
Claims (10)
1. SiO (silicon dioxide)2Loaded Cu2The O-ZnO heterojunction photocatalytic degradation material is characterized in that: the SiO2Loaded Cu2The preparation method of the O-ZnO heterojunction photocatalytic degradation material comprises the following steps:
(1) taking tetraethoxysilane as a silicon source, polyethylene oxide-polypropylene oxide-polyethylene oxide as a template and mesitylene as a pore-enlarging agent, and obtaining mesoporous silicon dioxide through hydrothermal reaction;
(2) adding mesoporous silica into a toluene solvent, performing ultrasonic dispersion uniformly, filling nitrogen to remove oxygen, transferring to an oil bath pot, continuously adding trimesoyl chloride, raising the temperature for substitution reaction, centrifuging, washing and drying a product to obtain acyl chloride nano-silica;
(3) adding acylchlorination nano-silica into a methanol solvent, ultrasonically mixing uniformly, transferring into an oil bath pot, continuously adding 2-amino-5-mercapto-1, 3, 4-thiadiazole, stirring uniformly, raising the temperature to perform amidation reaction, centrifuging, washing and drying after the reaction is finished to obtain sulfhydrylation silica;
(4) adding copper sulfate and cadmium sulfate into a deionized water solvent, continuously adding sodium hydroxide and ethanolamine after uniform ultrasonic dispersion, mechanically stirring for 20-40min, adding hydrazine hydrate, transferring into a reaction kettle, placing into an oven for hydrothermal reaction, cooling a product, and then aging, centrifuging, washing and drying to obtain a cadmium-doped cuprous oxide hollow sphere;
(5) adding cadmium-doped cuprous oxide hollow spheres, zinc acetate and sodium hydroxide into n-octanol solvent, ultrasonically dispersing uniformly, adding polyethylene glycol, transferring into a reaction kettle, placing into an oven for hydrothermal reaction, cooling the product, repeatedly washing with absolute ethyl alcohol and distilled water, and drying to obtain Cu2An O-ZnO heterojunction photocatalytic degradation material;
(6) adding thiolated silica and Cu to deionized water solvent2The O-ZnO heterojunction photocatalytic degradation material is transferred to a reaction kettle after being dispersed uniformly by ultrasonic waves, is placed in an oven, is subjected to hydrothermal reaction for 2-6h at the temperature of 100-120 ℃, and is centrifuged, washed and dried after being cooled to obtain SiO2Loaded Cu2And (3) carrying out photocatalytic degradation on the material by using an O-ZnO heterojunction.
2. An SiO as claimed in claim 12Loaded Cu2The O-ZnO heterojunction photocatalytic degradation material is characterized in that: the mass ratio of the mesoporous silica to the trimesoyl chloride in the step (2) is 100: 220-260.
3. An SiO as claimed in claim 12Loaded Cu2The O-ZnO heterojunction photocatalytic degradation material is characterized in that: the temperature of the substitution reaction in the step (2) is 80-100 ℃, and the reflux reaction is carried out for 5-10h under the nitrogen atmosphere.
4. An SiO as claimed in claim 12Loaded Cu2The O-ZnO heterojunction photocatalytic degradation material is characterized in that: in the step (3), the mass ratio of the acyl chloride nano-silica to the 2-amino-5-mercapto-1, 3, 4-thiadiazole is 100: 300-350.
5. An SiO as claimed in claim 12Loaded Cu2The O-ZnO heterojunction photocatalytic degradation material is characterized in that: the temperature of the amidation reaction in the step (3) is 40-60 ℃, and the reaction is carried out for 5-12h in a nitrogen atmosphere.
6. According to claim 1SiO as described2Loaded Cu2The O-ZnO heterojunction photocatalytic degradation material is characterized in that: copper sulfate, cadmium sulfate, sodium hydroxide, ethanolamine and N in the step (4)2H4The mass ratio of (1: 100:0.4-1:40-80: 140) and (340: 0.2-0.6).
7. An SiO as claimed in claim 12Loaded Cu2The O-ZnO heterojunction photocatalytic degradation material is characterized in that: the temperature of the hydrothermal reaction in the step (4) is 110-130 ℃, and the reaction time is 10-20 h.
8. An SiO as claimed in claim 12Loaded Cu2The O-ZnO heterojunction photocatalytic degradation material is characterized in that: the mass ratio of the cadmium-doped cuprous oxide hollow spheres, the zinc acetate, the sodium hydroxide and the polyethylene glycol in the step (5) is 100:50-70:110-150: 220-330.
9. An SiO as claimed in claim 12Loaded Cu2The O-ZnO heterojunction photocatalytic degradation material is characterized in that: the temperature of the hydrothermal reaction in the step (5) is 190-210 ℃, and the reaction time is 2-6 h.
10. An SiO as claimed in claim 12Loaded Cu2The O-ZnO heterojunction photocatalytic degradation material is characterized in that: sulfhydrylated silica and Cu in the step (6)2The mass ratio of the O-ZnO heterojunction photocatalytic degradation material is 100: 40-80.
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