CN113368854A - Nano TiO (titanium dioxide)2/Cu2Preparation method of O porous composite material - Google Patents
Nano TiO (titanium dioxide)2/Cu2Preparation method of O porous composite material Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000004408 titanium dioxide Substances 0.000 title claims description 19
- 238000000034 method Methods 0.000 title abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 41
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000002243 precursor Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 239000004065 semiconductor Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 239000004005 microsphere Substances 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 82
- 239000000243 solution Substances 0.000 description 36
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 14
- 229960000907 methylthioninium chloride Drugs 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 239000011941 photocatalyst Substances 0.000 description 12
- 229940112669 cuprous oxide Drugs 0.000 description 11
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 238000004626 scanning electron microscopy Methods 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 239000010881 fly ash Substances 0.000 description 4
- 239000002091 nanocage Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- -1 titanium dioxide compound Chemical class 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000012690 zeolite precursor Substances 0.000 description 2
- 241000282465 Canis Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910018292 Cu2In Inorganic materials 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
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- 239000008213 purified water Substances 0.000 description 1
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- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- 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
- B01J23/72—Copper
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/39—
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- B01J35/51—
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- 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
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- 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
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- 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
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- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention provides a nano TiO2/Cu2The preparation method of the O porous composite material adopts a low-temperature in-situ growth method to prepare Cu2O-doped TiO2Nano-hybrid TiO of porous microspheres2/Cu2The O composite semiconductor photocatalytic material can be prepared into anatase TiO with excellent catalytic performance and higher specific surface area under the temperature condition of 100-120 DEG C2/Cu2And (4) O porous balls. The method adopts in-situ growth method to obtain nano-dispersed TiO2/Cu2The O composite system has the advantages of tight heterojunction combination and large interface area, and can exert the advantages of energy band matching heterojunction system to the maximum extent.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to nano TiO2/Cu2A preparation method of an O porous composite material.
Background
With the increasing global environmental problems and the increasing environmental standards, the semiconductor heterogeneous catalysis technology has the advantages of mild reaction conditions, low price, high efficiency, high mineralization degree of organic matters, no secondary pollution and the like, and plays an increasingly important role in the aspects of treating refractory organic pollutants and deeply treating purified water at present when the coordinated development and the green development are advocated.
Titanium dioxide is an important semiconductor material, and becomes an important photocatalyst due to the advantages of stable physicochemical property, no toxicity, high photoelectric conversion rate (about 25%), high reaction thorough speed, low degradation selectivity and the like. But TiO22The solar energy collector has the defects of wide forbidden band width (Eg =3.2-3.5 eV), capability of only responding to ultraviolet light with the wavelength of less than 387nm and low utilization rate (2% -4%) of sunlight. In addition, the powder photocatalyst has high catalytic efficiency but has the problem of difficult separation and recovery, and the thin film photocatalyst has the defects of small specific surface area and low photocatalytic reaction efficiency, which greatly limits the wide application of the photocatalytic technology. Therefore, on the premise of fully exerting the excellent photocatalytic capability of the powder photocatalyst, improving the recycling rate and widening the wavelength range of the photocatalytic response become environmental pollution control and feasibleThe major problem of continuous energy development and utilization is solved. To TiO22The semiconductor composite and the fixed loading are effective means for solving the above problems.
The term semiconductor composite refers to a composite system in which two or more semiconductors form a certain microstructure. When a compound semiconductor is excited with light of sufficient energy, photogenerated carriers are injected from the energy level of one semiconductor to the energy level of the other semiconductor due to the difference in the conduction band and valence band energy levels, thereby promoting effective charge separation and improving photocatalytic efficiency. In recent years, much research has been conducted on TiO2The compound semiconductor mainly comprises CdS, CdSe and SiO2、Fe2O3、WO3、SnO2ZnO, etc.
Cu2O is a typical narrow band gap p-type semiconductor having a band gap of 2.0eV, has a photoresponsive property under visible light, and is considered to be a secondary TiO2One of the semiconductor photocatalysts with the most potential application in the fields of solar cells, wastewater treatment, photochromism and the like is increasingly paid attention to. Due to Cu2Forbidden band width of O to TiO2Narrow and thus have a specific TiO content2Higher light utilization (11% -13%), but the disadvantage is that the photoelectric conversion efficiency is higher than that of TiO2Low (a)<1%）。TiO2And Cu2The advantages and disadvantages of O are complemented by TiO2And Cu2The combination of the two compounds can better exert the photocatalytic performance.
Existing TiO2/Cu2The preparation method of the O composite material comprises the following steps:
(1) core-shell type
Chu et al prepared wet Cu by wet chemical precipitation2O particles, followed by Ti (OBu)4In Cu2Performing in-situ hydrolysis and recombination on the surface of O, calcining at the high temperature of 400 ℃ for 2h, and then adding Cu2O surface is coated with a layer of TiO with thickness of about 10-20nm2Layer of Cu2O@TiO2A core-shell heterojunction photocatalyst. The 4-nitrophenol (4-NP) shows excellent photocatalytic degradation performance under simulated sunlight irradiation. [ ChuS, ZHENGX, KongF, WuGLuoL, GuoYLiuH, WangYYuH, Zouz. ArchitectureofCu2O@TiO2core-shellheterojunctionandphotodegradationfor4-nitrophenolundersimulatedsunlightirradiation．Mater．Chem．Phys．2011，129(3)：1184-1188]In this study, TiO formation is desired2The crystalline phase of (2) needs to be calcined at a high temperature of 400 ℃ for 2 h. Secondly, the contact area of the formed core-shell structure heterojunction is Cu2O@TiO2The specific surface area of the core was 5.48m2/g。
Patent 201710474663.0 discloses a method for preparing a titanium dioxide/cuprous oxide composite photocatalyst. The method takes spherical titanium dioxide as an inner core, the surface of the spherical titanium dioxide is modified with cuprous oxide with nanometer scale, a method of combining spray drying and spray pyrolysis is adopted, amorphous titanium dioxide nanometer particles and copper salt solution which uniformly coats the surfaces of the amorphous titanium dioxide nanometer particles are subjected to evaporation and drying together in a low temperature region, and then the copper salt solution is subjected to thermal decomposition and sintering in a high temperature region, and the titanium dioxide/cuprous oxide composite photocatalyst with nanometer cuprous oxide is formed on the surface of the titanium dioxide through nucleation and growth, and has excellent photocatalytic performance. The preparation method also requires calcination, and the nucleation stage of the nano cuprous oxide needs high-temperature (300-600 ℃) treatment.
(2) Laminated type
Thangyi et al adopts an electrodeposition method to firstly deposit a layer of porous nano TiO with the thickness of 2-3um on transparent conductive glass TCO2Sintering the film at 450 deg.C for 30min, and performing electrolysis in a three-electrode electrolytic cell with TiO2TCO as working electrode on TiO2Cu with high purity is obtained on the film2O film (particle size 40-50 nm) to obtain p-Cu2O／n-TiO2Heterojunction electrode, and a lot of Cu 20 is filled into TiO2In pores of the layer, so that Cu2O and TiO2At the nanoscale, canine dental interdigitation, which greatly increases Cu 20 and TiO2The area of contact therebetween. [ Nano Cu ]2O／TiO2Preparation and characterization of heterojunction thin film electrode, inorganic materials science and report [ J]2006.21(2):453-458]. In this study, sintering at 450 ℃ was required for 30min to form a porous nano-TiO 2 film. Next, the heterojunction formed in this study was a stackIn the case of the structure, the substrate is transparent conductive glass having a relatively low surface area, and therefore, it is presumed that the heterojunction contact is not large.
(3) Load type
Patent 201410140436.0 describes a method for loading nano Cu on oyster shell2O-TiO2A preparation method of a photocatalytic composite material. The method takes pretreated oyster shell, copper acetate, ethanol, tetrabutyl titanate and the like as raw materials, and adopts the combination of a sol-gel method and a coprecipitation method to prepare the oyster shell loaded with nano Cu2O-TiO2A photocatalytic composite material. Under the irradiation of sunlight or ultraviolet light, the composite material shows excellent degradation performance to Congo red and methylene blue. However, high-temperature calcination is also an indispensable link, and the calcination conditions are as follows: the temperature is 600 ℃ and 800 ℃, and the time is 2-3 h. And the processing procedure of oyster shell is comparatively complicated: soaking with hydrochloric acid, soaking with sodium hydroxide, cleaning, oven drying, crushing, and sieving; then soaking the mixture in saturated NaCl, carrying out ultrasonic treatment, and drying for the second time. The oyster shell powder for experiments can be prepared through the steps.
Patent 201810461301.2 discloses a method for preparing a high-water-permeability durable water-permeable brick with photocatalytic effect, wherein cuprous oxide and titanium dioxide are modified by compounding, cuprous oxide particles are deposited on the surface of titanium dioxide, and copper ions can be transferred into TiO by high-temperature roasting2Among the lattice structures.
The doping of metal ions can narrow the forbidden band width of titanium dioxide and generate new energy level, thereby enhancing the TiO2The photocatalysis capability in the visible light field. But in the preparation process of the cuprous oxide/titanium dioxide compound, the cuprous oxide/titanium dioxide compound needs to be placed into a muffle furnace to be roasted for 3-5h in the air atmosphere at the temperature of 400-; and the pretreatment process of the load (fly ash) is complicated. Specifically, the acidification treatment of the fly ash: treating for 22-25h at 40-60 ℃ by using 0.5-2mol/L hydrochloric acid solution, washing for multiple times by using deionized water, filtering, drying the filtered fly ash for 20-22 h at 100-110 ℃, and then sieving by using a 400-800-mesh separation sieve to finally obtain the acidified fly ash.
(4) Hybrid type
Patent 201611205870.8 discloses a nano Cu2O/Ag/TiO2A preparation method of a zeolite hybrid mesoporous molecular sieve composite material. Synthesizing a zeolite precursor by using a silicon source and an aluminum source, adding the zeolite precursor into an alkali solution of a mesoporous molecular sieve, fully mixing, and reacting at 90-150 ℃ for 1-5h to obtain hydrogel; and adding nano Ag and nano Cu into hydrogel2O and TiO2Preparing mixed gel; obtaining an intermediate after crystallization treatment, and calcining the intermediate at high temperature to obtain the nano Cu2O/Ag/TiO2-zeolite hybrid mesoporous molecular sieve composite. Tests show that the composite material has obviously improved separation and degradation efficiency of organic pollutants. However, the crystallization of titanium dioxide still requires high-temperature calcination treatment. Wherein the calcining conditions are as follows: calcining at 300-700 deg.C under atmospheric pressure for 3-10 h.
(5) Nano cage type
Patent 201710043129.4 describes a Cu with hollow nanocage structure2O-CuO-TiO2A method for preparing a composite material. The method uses a film reagent method to synthesize Cu2Adding TiF into the mixture by adopting a one-step hydrothermal method4Uniformly stirring the solution, and then carrying out 160-180 ℃ hydrothermal treatment for 15-60min to prepare the Cu with the hollow nano cage structure2O-CuO-TiO2A composite material. But TiO22The particles being only in part Cu2The O hollow nano cage is attached, so that the defect of small contact area of a heterojunction exists.
(6) Other types of
Yang et al used an electrochemical deposition method with TiO2The nanotube array is a network framework, and forms unique Cu2O／TiO2Nano-heterojunctions (SEM pictures clearly showing flocculent TiO)2Network structure and Cu embedded therein2O nanoparticles). Under visible light, the composite material shows high-efficiency photocatalytic performance. But in CuOAnodised TiO before deposition2NTs required 550 ℃ sintering for 5h (in an oxygen atmosphere). And TiO22Nanotube and Cu formed therein2The O films have a defect of small contact area. The process of [ YangL,LuoS,LiY,XiaoY,KangQ,CaiQ.Highefficientphotocatalyticdegradationofp-nitrophenolonauniqueCu2O/TiO2p-nheterojunctionnetworkcatalyst.Environ.Sci.Technol.2011.44(19):7641-7646.]
but existing TiO2/Cu2The preparation method of the O composite material has the following problems:
firstly, the anatase TiO with better catalytic performance can be obtained only by the subsequent high-temperature heat treatment at 500 ℃ in the prior art2Greatly limit TiO2/Cu2And O is applied to substrates with poor heat resistance such as wood, plastics and the like. Second, TiO prepared by the prior art2/Cu2Most of the structures of the O composite system have the defect of small contact area of heterojunction, and the photocatalytic degradation efficiency is influenced. Thirdly, the pretreatment process of the carrier by the supported photocatalytic composite material is complicated.
Disclosure of Invention
Aiming at the technical problem, the invention provides nano TiO2/Cu2The preparation method of the O porous composite material adopts the technical scheme that:
nano TiO (titanium dioxide)2/Cu2The preparation method of the O porous composite material comprises the following steps:
step 1: taking 0.024-0.178g of nano Cu2Putting the O powder into a conical flask, slowly adding 55-120g of ethylene glycol into the conical flask, and ultrasonically oscillating for 1-1.5 h to obtain a solution A;
step 2: taking 2g-3g of tetrabutyl titanate and TBT, adding 98% of the solution A quickly, placing the solution A in a reaction kettle at room temperature, and stirring for 9h-12h under a closed condition to obtain a glycolate precursor solution B;
and step 3: quickly pouring the solution B into 100-375mL of acetone containing a small amount of water to ensure that the concentration of the precursor B in the acetone is 24mM-60mM, violently stirring by magnetic force for 20-40min, and then aging at room temperature for 30-60 min; centrifuging the formed precipitate at the rotating speed of 3000-5000r/min for 4-6min, and then separating; washing with anhydrous ethanol and deionized water for 4-6 times, vacuum drying in a vacuum drying oven at 50-60 deg.C for 4-6 hr to obtain a precursor C;
and 4, step 4: getAdding 0.4-0.8g of the composite precursor C into a conical flask containing 100mL-200mL of deionized water, magnetically stirring for 30min, placing the conical flask in an oil bath at the temperature of 100-120 ℃, and stirring and reacting for 90-120min under the reflux condition; after the reaction is finished, centrifuging the precipitate in the system for 4-6min at the speed of 3000-5000r/min, and then separating; washing with ethanol and deionized water for 4-6 times, and drying in vacuum drying oven at 50-60 deg.C for 4-6 hr to obtain TiO2/Cu2O porous ball composite material.
Preferably, in the step 3, the content of water is 0.3-2 wt%.
Preferably, Cu is not added2In the case of O, single-phase anatase TiO can be obtained according to the operation of the steps 1-42A porous ball.
TiO prepared by the invention2/Cu2The diameter of the O porous ball is 100-380 nm. Cu2Passage of O nanoparticles through TiO2In situ growth doping to TiO2In the porous structure of (A), a tightly bound nano-dispersed TiO is formed2/Cu2The O heterojunction structure effectively improves the separation efficiency of photo-generated electrons and holes of the composite photocatalyst and improves the efficiency of light quanta. The preparation method can regulate and control the concentration of the glycolate precursor B in an acetone/water system2/Cu2The diameter of the O porous ball is easy to control, and the repeatability is good. TiO prepared by the invention2/Cu2The photocatalysis of the O porous ball composite material is applied to a photocatalytic degradation experiment, ultraviolet light is used as a light source, methylene blue is used as a target degradation pollutant for photocatalytic degradation treatment, and compared with a commercial photocatalyst, the O porous ball composite material has a good degradation effect.
The advantages of the invention include:
(1) the invention adopts a low-temperature in-situ growth method to prepare Cu2O-doped TiO2Nano-hybrid TiO of porous microspheres2/Cu2O composite semiconductor photocatalytic material. The preparation method has the advantages of simple and clear process, simple and convenient operation, and low price and easy obtainment of raw materials.
(2) Compared with the prior art, the method mostly needs high temperature treatment at 500 DEG CIn contrast, the anatase TiO with excellent catalytic performance and larger specific surface area can be prepared under the temperature condition of 100-120 DEG C2/Cu2O porous ball; increase TiO2/Cu2The possibility of applying O to substrates with poor heat resistance (such as plastics and wood).
(3) Anatase TiO prepared by the method2/Cu2The O porous ball composite system has the characteristics of tight heterojunction combination and large interface area, and greatly improves the photocatalytic degradation efficiency.
(4) Compared with the preparation of the load type composite material, the method only needs simple pretreatment (ethanol, ultrasonic after acetone cleaning) on the carrier, and simplifies the process steps.
(5) In the absence of Cu2In the case of O, single-phase anatase TiO can be obtained by the same procedure2A porous ball.
Drawings
FIG. 1 example 1 Nano TiO2TEM (left) and nano TiO of porous ball precursor2/Cu2SEM of O porous spheres (right);
FIG. 2 example 2 Nano TiO2TEM (left) and nano TiO of porous ball precursor2/Cu2SEM of O porous spheres (right);
FIG. 3 example 3 Nano TiO2TEM (left) and nano TiO of porous ball precursor2/Cu2SEM of O porous spheres (right);
FIG. 4 example 4 Nano TiO2TEM (left) and nano TiO of porous ball precursor2/Cu2SEM of O porous spheres (right);
FIG. 5 SEM Picture (a) Cu2O (b) TiO2(the inset is a photograph at low resolution) (c, d) 10% Cu2O/TiO2；
FIG. 6 TEM Pattern (a) 15% Cu2O/TiO2；（b）15%Cu2O/TiO2The HRTEM image of (1);
FIG. 7 XRD spectra (a) of pure Cu2O; (b) pure TiO2Porous spheres (c) 20wt% Cu2O/TiO2；
FIG. 8N2Adsorption-desorption curve and BJH pore size distribution (a) 10wt% Cu2O/TiO2Pure Cu2O；
FIG. 9 photo-catalytic degradation curves (a) and ln (C/C) of different materials under UV light for MB0) Graph (b) over time.
Detailed Description
Example 1:
taking 0.024g of nano Cu2Putting the O powder into a 100ml conical flask, then slowly adding 55g of ethylene glycol into the conical flask, and performing ultrasonic oscillation for 1 hour to obtain a solution A; and (3) quickly adding 2g of tetrabutyl titanate into the solution A, placing the solution A in a YTMA-250ML reaction kettle, and stirring the solution A for 9 hours at room temperature under a closed condition to obtain a solution B. And quickly pouring the solution B into 100mL of acetone solution containing 1wt% of water, stirring vigorously by magnetic force for 30min, then aging at room temperature for 30min, then performing centrifugal filtration in a centrifugal machine at 4000r/min for 4min, washing with absolute ethyl alcohol and deionized water for multiple times, and finally placing in a vacuum drying oven to dry for 6h at 50 ℃ to obtain a complex precursor. 0.5g of the composite precursor is added into a conical flask containing 120mL of deionized water and stirred for 30min by magnetic force. Then, the flask was put in an oil bath at 100 ℃ and the reaction was stirred under reflux for 90 minutes. After the reaction is finished, centrifuging the precipitate for 4min at 5000r/min by using a centrifuge, washing the precipitate for 5 times by using ethanol and deionized water respectively, and drying the precipitate for 6h in a vacuum drying oven at the temperature of 50 ℃ to obtain Cu2TiO with O content of 5wt%2/Cu2And (3) an O porous ball composite system.
In this example, the concentration of precursor B in acetone was 60 mM.
TEM photograph and TiO of precursor C obtained in this example2/Cu2SEM analysis of the porous O spheres showed (FIG. 1) that TiO was prepared under this condition2/Cu2The diameter of the O porous ball is about 380nm, the particle size distribution is uniform, and the shape is completely regular. TiO22/Cu2The surface of the O porous ball is rough, and a large number of pore structures are distributed.
0.02g of the prepared composite system is weighed and subjected to an experiment of catalytic degradation of methylene blue under ultraviolet light, the concentration of the methylene blue is 10mg/L, and the degradation rate of the methylene blue is 63.8% after the composite system is irradiated by the ultraviolet light for 60 min.
Nano Cu used in examples2The O powder can be prepared into the Cu powder with the grain diameter of nanometer by adopting a microwave liquid phase deposition method2O, as disclosed in patent 202010247355.6 or obtained in other ways.
Example 2:
taking 0.047g of nano Cu2Putting the O powder into a 100mL conical flask, then slowly adding 80g of ethylene glycol into the conical flask, and performing ultrasonic oscillation for 1h to obtain a solution A; and (3) quickly adding 2g of tetrabutyl titanate into the solution A, placing the solution A in a YTMA-250ML reaction kettle, and stirring the solution A for 10 hours at room temperature under a closed condition to obtain a solution B. And quickly pouring the solution B into 120mL of acetone solution containing 1.5wt% of water, stirring vigorously by magnetic force for 25min, then aging at room temperature for 40min, then performing centrifugal filtration in a centrifugal machine at 4000r/min for 3min, washing with absolute ethyl alcohol and deionized water for multiple times, and finally placing in a vacuum drying oven to dry for 5h at 50 ℃ to obtain a complex precursor. 0.5g of the composite precursor is added into a conical flask containing 150mL of deionized water and stirred for 30min by magnetic force. Then, the flask was put in an oil bath at 100 ℃ and the reaction was stirred under reflux for 100 minutes. After the reaction is finished, the precipitate is centrifugally separated for 4min at 5000r/min by a centrifugal machine, then is respectively washed for 5 times by ethanol and deionized water, and is dried for 5h in a vacuum drying oven at the temperature of 50 ℃ to obtain Cu2TiO with O content of 10wt%2/Cu2And (3) an O porous ball composite system.
In this example, the concentration of precursor B in acetone was 50 mM.
TEM photograph and TiO of precursor C obtained in this example2/Cu2SEM analysis of the porous O spheres showed (FIG. 1) that TiO was prepared under this condition2/Cu2The diameter of the O porous ball is about 300nm, the particle size distribution is uniform, and the shape is completely regular. TiO22/Cu2The surface of the O porous ball is rough, and a large number of pore structures are distributed.
SEM analysis (FIG. 5) of the different photocatalysts in this example shows that the resulting Cu is2O has a particle diameter of about 6 to 13nmThe present invention is spherical. Preparation of the resulting TiO2SEM analysis of the porous spheres showed that TiO2The diameter of the porous ball is about 380nm, and the shape is completely regular. TiO22/Cu2SEM analysis of O showed TiO2/Cu2The O composite porous ball has good dispersibility, uniform particle size and rough particle surface.
N of the sample obtained in this example2The adsorption-desorption curves and BJH pore size distributions are shown in fig. 8 and table 1;
TABLE 1N2Adsorption-desorption curve and BJH pore size distribution
Analysis revealed 10wt% Cu2O/TiO2And pure Cu2O has larger specific surface area of 418.36 and 253.26 m/g respectively. Due to TiO2Is in Cu2O is synthesized in situ in the system, so that on one hand, the two have a heterojunction structure in close contact. On the other hand, it is considered that TiO is calculated by theory2/Cu2The contact area of the formed heterojunction of O should be Cu2Specific surface area component value of O incorporation amount. I.e. at 10wt% Cu2O/TiO2In the system, the contact area of the heterojunction formed should be 25.326 m/g. This value is much greater than the Cu prepared by wet chemical precipitation method of Chu et al, supra2O@TiO2Core-shell heterojunction contact area of 5.48m2Per gram, titanium dioxide/cuprous oxide composite photocatalyst introduced in patent 201710474663.0 and laminated nano Cu prepared in Tangyi province2O／TiO2Contact area of the heterojunction film.
0.02g of the prepared composite system is weighed and subjected to an experiment of catalytic degradation of methylene blue under ultraviolet light, the concentration of the methylene blue is 10mg/L, and the photocatalytic degradation curve (a) and ln (C/C) of the methylene blue are shown0) The graph (b) shows (FIG. 9) that TiO2/Cu2The efficiency of the O photocatalytic degradation of MB is obviously superior to that of single-phase TiO2And Cu2And O. After 60min of ultraviolet irradiation, TiO2/Cu2The efficiency of O photodegradation of MB is 79.1%, and the efficiency is single-phase Cu2O and TiO28.01 and 3.62 times. TiO22/Cu2The first-order degradation rate constants of O photodegradation MB are respectively single-phase Cu2O and TiO216.36 times and 4.41 times.
Example 3:
0.106g of nano Cu is taken2Putting the O powder into a 150ml conical flask, then slowly adding 110g of ethylene glycol into the conical flask, and ultrasonically oscillating for 1.5h to obtain a solution A; and (3) quickly adding 3g of tetrabutyl titanate into the solution A, placing the solution A in a YTMA-250ML reaction kettle, and stirring the solution A for 12 hours at room temperature under a closed condition to obtain a solution B. And quickly pouring the solution B into 225mL of acetone solution containing 2wt% of water, stirring vigorously by magnetic force for 30min, aging at room temperature for 40min, centrifuging and filtering in a centrifuge at 4000r/min for 5min, washing with anhydrous ethanol and deionized water for multiple times, and finally drying in a vacuum drying oven at 50 ℃ for 6h to obtain the complex precursor. 0.5g of the composite precursor is added into a conical flask containing 150mL of deionized water and stirred for 30min by magnetic force. Then, the flask was put in an oil bath at 100 ℃ and the reaction was stirred under reflux for 120 minutes. After the reaction is finished, centrifuging the precipitate for 4min at 5000r/min by using a centrifuge, washing the precipitate for 5 times by using ethanol and deionized water respectively, and drying the precipitate for 6h in a vacuum drying oven at the temperature of 50 ℃ to obtain Cu2TiO with O content of 15 wt%2/Cu2And (3) an O porous ball composite system.
In this example, the concentration of precursor B in acetone was 40 mM.
TEM photograph and TiO of precursor C obtained in this example2/Cu2SEM analysis of the porous O spheres showed (FIG. 3) that TiO prepared under this condition2/Cu2The diameter of the O porous ball is about 250nm, the particle size distribution is uniform, and the shape is completely regular. TiO22/Cu2The surface of the O porous ball is rough, and a large number of pore structures are distributed.
TiO obtained in this example2/Cu2TEM (a) analysis of O showed (FIG. 6), TiO2/Cu2The O composite porous ball has good dispersibility and uniform particle size. TiO22/Cu2HRTEM (b) analysis of O showed TiO2/Cu2Clear O lattice fringes, TiO2And Cu2O exhibits nano-scale dispersion, TiO2And Cu2The O is tightly contacted to form a nano-scale dispersed heterojunction structure. The interface structure in close contact is beneficial to forming a II-type heterojunction, and further effectively improves the separation efficiency of photon-generated carriers.
0.02g of the prepared composite system is weighed and subjected to an experiment of catalytic degradation of methylene blue under ultraviolet light, the concentration of the methylene blue is 10mg/L, and the degradation rate of the methylene blue is 73.1% after the composite system is irradiated by the ultraviolet light for 60 min.
Example 4:
taking 0.141g of nano Cu2Putting the O powder into a 200ml conical flask, then slowly adding 120g of ethylene glycol into the conical flask, and ultrasonically oscillating for 1.5h to obtain a solution A; and (3) quickly adding 3g of tetrabutyl titanate into the solution A, placing the solution A in a YTMA-250ML reaction kettle, and stirring the solution A for 12 hours at room temperature under a closed condition to obtain a solution B. And quickly pouring the solution B into 375mL of acetone solution containing 2wt%, vigorously stirring for 40min by magnetic force, aging for 50min at room temperature, centrifuging and filtering for 6min in a centrifuge at 5000r/min, washing with anhydrous ethanol and deionized water for multiple times, and finally drying in a vacuum drying oven at 50 ℃ for 6h to obtain the complex precursor. 0.5g of the composite precursor is added into a conical flask containing 150mL of deionized water and stirred for 30min by magnetic force. Then, the flask was put in an oil bath at 120 ℃ and the reaction was stirred under reflux for 120 minutes. After the reaction is finished, centrifuging the precipitate for 4min at 5000r/min by using a centrifuge, washing the precipitate for 5 times by using ethanol and deionized water respectively, and drying the precipitate for 6h in a vacuum drying oven at the temperature of 50 ℃ to obtain Cu2TiO with the mass percent of O being 20 percent2/Cu2And (3) an O porous ball composite system.
In this example, the concentration of precursor B in acetone was 24 mM.
TEM photograph and TiO of precursor C obtained in this example2/Cu2SEM analysis of the porous O spheres showed (FIG. 4) that TiO prepared under this condition2/Cu2The diameter of the O porous ball is about 100nm, the particle size distribution is uniform, and the shape is completely regular.TiO2/Cu2The surface of the O porous ball is rough, and a large number of pore structures are distributed.
XRD (figure 7) analysis of the obtained product shows that the Cu prepared by the method2TiO with O mass percent of 5%2/Cu2The characteristic peaks of the O porous ball complex system at the 2 theta of 25.5 degrees, 37.85 degrees, 48.11 degrees, 54.04 degrees and 62.75 degrees correspond to anatase TiO2Characteristic absorption peak of (a); the characteristic peaks at 29.7 °, 36.6 °, 42.4 °, 61.5 ° and 74.40 ° of 2 θ correspond to Cu2Characteristic peak of O. Rutile type TiO and brookite type TiO do not appear in XRD pattern2The characteristic absorption peaks of CuO and Cu are not present. The samples obtained are illustrated as cuprous oxide and anatase TiO2The composite system of (3) has no other impurities generated in the system.
0.02g of the prepared composite system is weighed and subjected to an experiment of catalytic degradation of methylene blue under ultraviolet light, the concentration of the methylene blue is 10mg/L, and the degradation rate of the methylene blue is 70.9% after the composite system is irradiated by the ultraviolet light for 60 min.
Nano Cu used in examples 1 to 42The O powder can be prepared into the Cu powder with the grain diameter of nanometer by adopting a microwave liquid phase deposition method2O, as disclosed in patent 202010247355.6 or obtained in other ways. The ultrasonic vibration adopts YM-030S type ultrasonic oscillator, the magnetic stirring adopts MS5S magnetic stirrer, the centrifugation adopts H1650 type centrifuge, the vacuum drying adopts DZF-6050B vacuum drying box, and the oil bath adopts DF-101S type oil bath.
The ethylene glycol used was: analytically pure, 98%, acetone was: analytically pure, 99.5%.
Claims (3)
1. Nano TiO (titanium dioxide)2/Cu2The preparation method of the O porous composite material is characterized by comprising the following steps:
step 1: taking 0.024-0.178g of nano Cu2Putting the O powder into a conical flask, slowly adding 55-120g of ethylene glycol into the conical flask, and ultrasonically oscillating for 1-1.5 h to obtain a solution A;
step 2: taking 98% of 2g-3g tetrabutyl titanate, quickly adding the solution A, placing the solution A in a reaction kettle at room temperature, and stirring for 9h-12h under a closed condition to obtain a glycolate precursor solution B;
and step 3: quickly pouring the solution B into 100-375mL of acetone containing a small amount of water to ensure that the concentration of the precursor B in the acetone is 24mM-60mM, violently stirring by magnetic force for 20-40min, and then aging at room temperature for 30-60 min; centrifuging the formed precipitate at the rotating speed of 3000-5000r/min for 4-6min, and then separating; washing with anhydrous ethanol and deionized water for 4-6 times, vacuum drying in a vacuum drying oven at 50-60 deg.C for 4-6 hr to obtain a precursor C;
and 4, step 4: adding 0.4-0.8g of the composite precursor C into a conical flask containing 100mL-200mL of deionized water, magnetically stirring for 30min, placing the conical flask in an oil bath at the temperature of 100-120 ℃, and stirring and reacting for 90-120min under the reflux condition; after the reaction is finished, centrifuging the precipitate in the system for 4-6min at the speed of 3000-5000r/min, and then separating; washing with ethanol and deionized water for 4-6 times, and drying in vacuum drying oven at 50-60 deg.C for 4-6 hr to obtain TiO2/Cu2O porous ball composite material.
2. The nano TiO of claim 12/Cu2The preparation method of the O porous composite material is characterized in that in the step 3, the content of water is 0.3-2 wt%.
3. The nano TiO of claim 12/Cu2The preparation method of the O porous composite material is characterized in that Cu is not added2In the case of O, single-phase anatase TiO can be obtained according to the operation of the steps 1-42A porous ball.
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