CN118002126A - Titanium dioxide hollow sphere loaded nano copper photocatalyst and preparation method and application thereof - Google Patents
Titanium dioxide hollow sphere loaded nano copper photocatalyst and preparation method and application thereof Download PDFInfo
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- CN118002126A CN118002126A CN202410410456.9A CN202410410456A CN118002126A CN 118002126 A CN118002126 A CN 118002126A CN 202410410456 A CN202410410456 A CN 202410410456A CN 118002126 A CN118002126 A CN 118002126A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 184
- 239000010949 copper Substances 0.000 title claims abstract description 145
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 97
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 77
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 120
- 239000002105 nanoparticle Substances 0.000 claims abstract description 61
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 57
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 30
- 239000011257 shell material Substances 0.000 claims abstract description 21
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000005530 etching Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 104
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 45
- 239000008367 deionised water Substances 0.000 claims description 42
- 229910021641 deionized water Inorganic materials 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 30
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 28
- 238000004108 freeze drying Methods 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 229960003405 ciprofloxacin Drugs 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 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 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 39
- 235000019441 ethanol Nutrition 0.000 description 28
- 229910010413 TiO 2 Inorganic materials 0.000 description 25
- 239000005751 Copper oxide Substances 0.000 description 20
- 229910000431 copper oxide Inorganic materials 0.000 description 20
- 229960004643 cupric oxide Drugs 0.000 description 20
- 239000000463 material Substances 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000007769 metal material Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000295644 Staphylococcaceae Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 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
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000002784 hot electron Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000003306 quinoline derived antiinfective agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- -1 superoxide anions Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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 discloses a titanium dioxide hollow sphere supported nano copper photocatalyst, a preparation method and application thereof, and relates to the technical field of photocatalysis composite materials, wherein a hollow sphere shell material of the titanium dioxide hollow sphere supported nano copper photocatalyst is titanium dioxide, the particle size of the hollow sphere is 300-700 nm, and copper nano particles are supported in the shell; the preparation process comprises the following steps: firstly, loading copper nano particles on a silicon dioxide hard template, then coating titanium dioxide on the outside of the template loaded with the copper nano particles to form a shell, and finally etching the template serving as an inner core by utilizing ammonium bifluoride to obtain the titanium dioxide hollow sphere loaded nano copper photocatalyst.
Description
Technical Field
The invention relates to the technical field of photocatalysis composite materials, in particular to a titanium dioxide hollow sphere supported nano copper photocatalyst, a preparation method and application thereof.
Background
The widespread use of antibiotics has resulted in non-negligible pollution in water bodies. Ciprofloxacin (CIP) is widely used as a third-generation fluoroquinolone antibiotic because it has a strong antibacterial activity against gram-negative bacteria and a good antibacterial activity against staphylococci. The chemical stability of such antibiotics makes them difficult to break down by natural microorganisms. Residual CIP in the environment may lead to the production of resistant bacteria and enrichment of CIP in the food chain, posing a serious threat to the ecosystem and human health. Therefore, effective removal of antibiotic contaminants has become a research hotspot in the field of water treatment.
The photocatalytic oxidation technology has the advantages of strong oxidation capability, mild reaction conditions, no secondary pollution and the like, and is widely concerned in degradation of refractory organic matters. Titanium dioxide (TiO 2) is a highly degenerate semiconductor, has strong controllability, high stability and good ultraviolet spectral response, and is a relatively common photocatalyst for CIP degradation. The existing common synthetic method of nano titanium dioxide is to prepare the nano titanium dioxide by using a tetrabutyl titanate alcohol dissolution and hydrolysis method, and the nano titanium dioxide prepared by the preparation method has the advantages of wide particle size range and relatively uniform particles. However, the nano titanium dioxide particles have the common defects of mismatching among particle size, specific surface area and agglomeration phenomenon, when the particle size is smaller, such as common P25 particles (particle size 25 nm), the specific surface area of the material is large, the photocatalytic activity is higher, but the agglomeration phenomenon of the material is very serious, and the too small particle size also causes the problem that the nano particles in a dispersion system are difficult to recycle; when the particle size is larger, the specific surface area of the material is small, the photocatalytic activity is low, and most of the material in the center of the particle cannot participate in catalytic reaction.
Titanium dioxide has many advantages as a wide band gap semiconductor photocatalyst, but has the disadvantage of requiring high energy ultraviolet light excitation and easy recombination of photo-generated electron-hole pairs, and the disadvantages can be effectively improved by loading a plasma metal material. The plasma metal nano structure can form local surface plasmon resonance, widens the light absorption range of the composite material, and can serve as a photon-generated electron conduction center to slow down the recombination of photon-generated electron hole pairs. The plasma metal materials which are widely used up to now mainly comprise noble metal materials such as gold, silver, platinum and the like, and have the defects of high price, low reserves, narrow light absorption range and the like. Copper is one of the most abundant elements on earth. Copper nanoparticles exhibit tunable localized surface plasmon resonance, covering the near infrared range. The real and imaginary components of the dielectric function of copper are similar to gold. Copper is therefore a promising alternative to noble metal plasma material. The nano copper is a non-noble metal plasma metal material with low cost and easy preparation, can increase light absorption in the photocatalysis reaction, provides the effects of hot electrons and the like, and can effectively increase the light absorption range of titanium dioxide. The existing copper nanoparticle loading method has several ways, namely a way of synthesizing the nano copper particles by a solvothermal method and then compositing the nano copper particles with a main photocatalyst, and the method has the problems of uneven distribution, weak binding force of the particles and easy falling of the copper nanoparticles. A method for impregnating organic copper material and then pyrolyzing at high temperature is adopted, and the copper nano particles loaded by the method have the problems of larger particle size, carbon coating and the like. One is an ion sputtering method which is only suitable for the loading of a film substrate and has poor suitability for powder photocatalytic materials. How to develop a loading method which can uniformly load copper nano particles on a powder substrate and has no carbon coating layer is of great significance for realizing the efficient utilization of the surface plasmon resonance property of the plasma metal nano particles to enhance the photocatalytic performance of the material.
Disclosure of Invention
The invention provides a titanium dioxide hollow sphere supported nano copper photocatalyst and a preparation method and application thereof, and aims to solve the problems that the prior noble metal plasma metal material is high in price, low in reserve and narrow in light absorption range, and the prior nano copper particle supporting method is uneven in load, has a coating layer and the like due to mismatching among the particle size, specific surface area and agglomeration phenomenon of the titanium dioxide.
The technical scheme adopted by the invention is as follows:
The titanium dioxide hollow sphere loaded nano copper photocatalyst is characterized in that a hollow sphere shell material of the titanium dioxide hollow sphere loaded nano copper photocatalyst is titanium dioxide, the particle size of the hollow sphere is 300-700 nm, and copper nano particles are loaded in the shell; the preparation process comprises the following steps: firstly, loading copper nano particles on a silicon dioxide hard template, then coating titanium dioxide on the outside of the template loaded with the copper nano particles to form a shell, and finally etching the template serving as an inner core by utilizing ammonium bifluoride to obtain the titanium dioxide hollow sphere loaded nano copper photocatalyst.
More preferably, the particle size of the silica hard template is 300-700 nm.
According to the preparation method of the titanium dioxide hollow sphere supported nano copper photocatalyst, copper nano particles are firstly supported on a silicon dioxide hard template, then titanium dioxide is coated outside the template supported with the copper nano particles to form a shell, and finally the template serving as a core is etched by using ammonium bifluoride to obtain the titanium dioxide hollow sphere supported nano copper photocatalyst.
Further, the preparation method comprises the following steps:
(1) Dropwise adding a copper nitrate solution into a silicon dioxide dispersion liquid with the pH value of 9-10, stirring, wherein the stirring temperature is 5-25 ℃, the stirring time is 0.5-2 h, aging, washing with deionized water and ethanol, filtering, freeze-drying, calcining and reducing in a mixed atmosphere of argon and hydrogen, and the calcining temperature is 300-700 ℃, thus obtaining copper nano particles/silicon dioxide precursors;
(2) Dispersing copper nano particles/silicon dioxide precursor in ethanol, adding tetrabutyl titanate and ammonia water (tetrabutyl titanate: ammonia water (V/V) =2:1) into the dispersion, stirring at 40-50 ℃ for 24 h ℃ and washing with deionized water and ethanol, centrifuging, freeze-drying, calcining and reducing in a mixed atmosphere of argon and hydrogen at 300-700 ℃ to obtain titanium dioxide/copper nano particles/silicon dioxide precursor;
(3) Dispersing titanium dioxide/copper nano particles/silicon dioxide precursor and ammonium bifluoride in deionized water, stirring at normal temperature for 0.5-2 h hours, washing with deionized water and ethanol, centrifuging, and freeze-drying to obtain the titanium dioxide hollow sphere supported nano copper photocatalyst.
The chemical reaction equations involved in the above three steps are respectively:
Cu2++2OH-→Cu(OH)2
。
Further, the silica of step (1) is prepared by the following steps: adding tetraethyl silicate and ammonia water into alcohol respectively to prepare solution, then dripping tetraethyl silicate alcohol solution into ammonia water alcohol solution to mix, stirring for 6-8 h at 0-25 ℃, washing with deionized water and ethanol, centrifuging, and freeze-drying to obtain the silicon dioxide hard template. The chemical reaction equation is as follows:
Si(OC2H5)4+2H2O→4C2H5OH+SiO2。
preferably, in the preparation process of the silicon dioxide, the dosage of the tetraethyl silicate is 2-4 ml, the dosage of the ammonia water is 4-6 ml and the dosage of the alcohol is 20-200 ml calculated by a reaction system of 40-400 ml.
Further, the concentration of the copper nitrate solution in the step (1) is 0.01 to 0.04M.
Still further, the concentration of the ammonium bifluoride solution in step (3) is 15-25 g/L.
Further, the washing processes of the steps (1) - (3) with deionized water and ethanol are respectively carried out by washing with deionized water once, then washing with ethanol once, and circulating twice.
The titanium dioxide hollow sphere loaded nano copper photocatalyst is applied to degrading ciprofloxacin as a photocatalyst.
In summary, compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the invention, the copper serving as a non-noble metal plasma metal material is synthesized to replace a common noble metal plasma metal material, so that the synthesis cost of the plasma metal material is reduced, the response range of local surface plasmon resonance is enlarged, the copper is close to a metallographic phase, the copper reserves are rich, the cost is low, and the method is more suitable for mass production.
2. The invention realizes the successful preparation of the titanium dioxide hollow sphere layer, has uniform particle size, has larger specific surface area compared with solid powder titanium dioxide, and can better overcome the defect of easy agglomeration.
3. The invention realizes the uniform loading of copper nano particles on silicon dioxide particles, carries out in-situ loading of copper nano particles by an inorganic copper source, has uniform particle size of copper nano particles, stable adhesion on a silicon dioxide substrate, uniform distribution and no existence of a large number of carbon coating layers, and is more suitable for photocatalytic degradation of pollutants.
4. When the titanium dioxide hollow sphere supported nano copper photocatalyst is subjected to illumination, electrons on a titanium dioxide valence band can be transited to a conduction band after absorbing energy, and as the titanium dioxide can form a Schottky heterojunction with copper nanoparticles, photo-generated electrons can migrate from the titanium dioxide to the nano copper particles, so that the photo-generated electrons and holes are separated, the service life of photo-generated carriers is prolonged, the electrons on the nano copper particles react with oxygen to generate superoxide anions, holes left in the titanium dioxide react with water to generate hydroxyl radicals, and the rest holes directly react with pollutants to degrade ciprofloxacin.
Drawings
FIG. 1 is a flow chart of the preparation of a titanium dioxide hollow sphere supported nano-copper photocatalyst;
FIG. 2 is a scanning electron microscope image of the titanium dioxide hollow sphere supported nano copper photocatalyst prepared in example 3;
FIG. 3 is a transmission electron microscope image of the copper nanoparticle/silica precursor prepared in example 3;
FIG. 4 is a transmission electron microscope image of the titanium dioxide hollow sphere supported nano copper photocatalyst prepared in example 3;
FIG. 5 is an X-ray diffraction pattern of the titanium dioxide hollow sphere supported nano-copper photocatalyst prepared in examples 1-4;
FIG. 6 is a graph showing the degradation of ciprofloxacin by simulating sunlight photocatalysis by titanium dioxide and the titanium dioxide hollow sphere supported nano copper photocatalyst prepared in examples 1 to 4.
Fig. 7 is a graph showing the first order kinetic profile of the simulation of the photocatalytic degradation of ciprofloxacin by sunlight using the titanium dioxide and the titanium dioxide hollow sphere supported nano copper photocatalyst prepared in examples 1 to 4.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the particular embodiments described herein are illustrative only and are not intended to limit the invention, i.e., the embodiments described are merely some, but not all, of the embodiments of the invention.
The word "embodiment" as used herein does not necessarily mean that any embodiment described as "exemplary" is preferred or advantageous over other embodiments. Performance index testing in this method example unless otherwise specified, conventional testing methods in the art were employed. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; other raw materials, reagents, test methods and technical means not specifically mentioned in the present invention refer to raw materials and reagents commonly used by those skilled in the art, and experimental methods and technical means commonly employed.
As shown in fig. 1, a flowchart of the preparation of the titanium dioxide hollow sphere supported nano copper photocatalyst provided by the invention is shown, and the following examples are used for preparing the titanium dioxide hollow sphere supported nano copper photocatalyst according to the flowchart.
Example 1
The preparation process of the titanium dioxide hollow sphere supported nano copper photocatalyst provided by the embodiment comprises the following steps:
(1) Measuring 3 ml tetraethyl silicate by a pipette, dispersing in 20ml absolute ethyl alcohol to prepare solution A, measuring 5 ml ammonia water, dispersing in 20ml absolute ethyl alcohol to prepare solution B, respectively stirring for 20 minutes at normal temperature, dripping the solution A into the solution B, stirring for 8 hours in an ice bath, washing for a plurality of times by ethanol and deionized water, centrifuging, freeze-drying for 24h, and obtaining the silicon dioxide nanospheres about 500 nm.
(2) Dispersing the obtained silicon dioxide with 0.5 g in 200ml deionized water by an analytical balance, carrying out ultrasonic dispersion for 20 minutes, stirring, adding sodium carbonate aqueous solution, regulating the pH of the dispersion to 10, preparing solution A, weighing 0.4832 g copper nitrate trihydrate Cu (NO 3)2·3H2 O is added into 200ml deionized water to prepare 0.01M copper nitrate aqueous solution B), dropwise adding the solution B into the solution A under the stirring condition, stirring 1h, washing with ethanol and deionized water for several times, carrying out suction filtration, and freeze-drying 24 h to obtain a copper/silicon dioxide precursor, carrying out argon-hydrogen=1:1 on the obtained copper/silicon dioxide precursor, carrying out heat preservation at 400 ℃ for 3 h reduction on copper at a flow rate of 50 sccm and a heating rate of 10 ℃/min, and obtaining copper/silicon dioxide nano particles.
(3) 0.25 G copper/silicon dioxide nano particles are weighed by an analytical balance and dispersed in 450 ml absolute ethanol, the ultrasonic treatment is carried out for 20 s, the stirring is carried out for 1 h, 1.75 ml ammonia water and 3.5 ml tetrabutyl titanate are added, the stirring is carried out for 24h at 45 ℃, the centrifugation is carried out, the ethanol and deionized water are used for washing for a plurality of times, and the freeze drying is carried out for 24h, thus obtaining the titanium dioxide/copper/silicon dioxide precursor.
(4) The titania/copper/silica precursor obtained was subjected to argon: hydrogen=1:1, the flow rates were 50sccm, the heating rate of 10 ℃/min, and the calcination temperature was 2h at 700 ℃, to obtain titania/copper/silica nanoparticles.
(5) Weighing 0.1 g titanium dioxide/copper/silicon dioxide nano-particles and 1 g ammonium bifluoride by using an analytical balance, adding 50ml deionized water, stirring for 30 minutes, centrifuging, washing with ethanol and deionized water for several times, and freeze-drying for 24 h to obtain the copper nano-particles/titanium dioxide hollow spherical shell. The resulting sample was recorded as TiO 2/Cu 0.01M.
Example 2
The preparation process of the titanium dioxide hollow sphere supported nano copper photocatalyst provided by the embodiment comprises the following steps:
(1) Measuring 3ml tetraethyl silicate by a pipette, dispersing in 20ml absolute ethyl alcohol to prepare a solution A, measuring 5 ml ammonia water, dispersing in 20ml absolute ethyl alcohol to prepare a solution B, respectively stirring for 20 minutes at normal temperature, dripping the solution A into the solution B, stirring for 8 hours in an ice bath, washing for a plurality of times by ethanol and deionized water, centrifuging, and freeze-drying for 24h to obtain the silicon dioxide nanospheres with the particle size of about 500 nm.
(2) Dispersing the obtained silicon dioxide with 0.5 g in 200ml deionized water by an analytical balance, carrying out ultrasonic dispersion for 20 minutes, stirring, adding sodium carbonate aqueous solution, regulating the pH of the dispersion to 10, preparing solution A, weighing 0.9664 g copper nitrate trihydrate Cu (NO 3)2·3H2 O is added into 200ml deionized water to prepare 0.02M copper nitrate aqueous solution B), dropwise adding the solution B into the solution A under the stirring condition, stirring 1h, washing with ethanol and deionized water for several times, carrying out suction filtration, and freeze-drying 24 h to obtain a copper/silicon dioxide precursor.
(3) 0.25 G copper/silicon dioxide nano particles are weighed by an analytical balance and dispersed in 450 ml absolute ethanol, the ultrasonic treatment is carried out for 20 s, the stirring is carried out for 1 h, 1.75 ml ammonia water and 3.5 ml tetrabutyl titanate are added, the stirring is carried out for 24h at 45 ℃, the centrifugation is carried out, the ethanol and deionized water are used for washing for a plurality of times, and the freeze drying is carried out for 24h, thus obtaining the titanium dioxide/copper/silicon dioxide precursor.
(4) The titania/copper/silica precursor obtained was subjected to argon: hydrogen=1:1, the flow rates were 50sccm, the heating rate of 10 ℃/min, and the calcination temperature was 2h at 700 ℃, to obtain titania/copper/silica nanoparticles.
(5) Weighing 0.1 g titanium dioxide/copper/silicon dioxide nano-particles and 1 g ammonium bifluoride by using an analytical balance, adding 50ml deionized water, stirring for 30 minutes, centrifuging, washing with ethanol and deionized water for several times, and freeze-drying for 24 h to obtain the copper nano-particles/titanium dioxide hollow spherical shell. The resulting sample was recorded as TiO 2/Cu 0.02M.
Example 3
The preparation process of the titanium dioxide hollow sphere supported nano copper photocatalyst provided by the embodiment comprises the following steps:
(1) Measuring 3ml tetraethyl silicate by a pipette, dispersing in 20ml absolute ethyl alcohol to prepare a solution A, measuring 5 ml ammonia water, dispersing in 20ml absolute ethyl alcohol to prepare a solution B, respectively stirring for 20 minutes at normal temperature, dripping the solution A into the solution B, stirring for 8 hours in an ice bath, washing for a plurality of times by ethanol and deionized water, centrifuging, and freeze-drying for 24h to obtain the silicon dioxide nanospheres with the particle size of about 500 nm.
(2) Dispersing the obtained silicon dioxide with 0.5 g in 200ml deionized water by an analytical balance, carrying out ultrasonic dispersion for 20 minutes, stirring, adding sodium carbonate aqueous solution, regulating the pH of the dispersion to 10, preparing solution A, weighing 1.4496 g copper nitrate trihydrate Cu (NO 3)2·3H2 O is added into 200ml deionized water to prepare 0.03M copper nitrate aqueous solution B), dropwise adding the solution B into the solution A under the stirring condition, stirring 1h, washing with ethanol and deionized water for several times, carrying out suction filtration, and freeze-drying 24 h to obtain a copper/silicon dioxide precursor, carrying out argon-hydrogen=1:1 on the obtained copper/silicon dioxide precursor, carrying out heat preservation at 400 ℃ for 3 h reduction on copper at a flow rate of 50 sccm and a heating rate of 10 ℃/min, and obtaining copper/silicon dioxide nano particles.
(3) 0.25 G copper/silicon dioxide nano particles are weighed by an analytical balance and dispersed in 450 ml absolute ethanol, the ultrasonic treatment is carried out for 20 s, the stirring is carried out for 1 h, 1.75 ml ammonia water and 3.5 ml tetrabutyl titanate are added, the stirring is carried out for 24h at 45 ℃, the centrifugation is carried out, the ethanol and deionized water are used for washing for a plurality of times, and the freeze drying is carried out for 24h, thus obtaining the titanium dioxide/copper/silicon dioxide precursor.
(4) The titania/copper/silica precursor obtained was subjected to argon: hydrogen=1:1, the flow rates were 50sccm, the heating rate of 10 ℃/min, and the calcination temperature was 2h at 700 ℃, to obtain titania/copper/silica nanoparticles.
(5) Weighing 0.1 g titanium dioxide/copper/silicon dioxide nano-particles and 1 g ammonium bifluoride by using an analytical balance, adding 50ml deionized water, stirring for 30 minutes, centrifuging, washing with ethanol and deionized water for several times, and freeze-drying for 24 h to obtain the copper nano-particles/titanium dioxide hollow spherical shell. The resulting sample was recorded as TiO 2/Cu 0.03M.
Example 4
The preparation process of the titanium dioxide hollow sphere supported nano copper photocatalyst provided by the embodiment comprises the following steps:
(1) Measuring 3ml tetraethyl silicate by a pipette, dispersing in 20ml absolute ethyl alcohol to prepare a solution A, measuring 5 ml ammonia water, dispersing in 20ml absolute ethyl alcohol to prepare a solution B, respectively stirring for 20 minutes at normal temperature, dripping the solution A into the solution B, stirring for 8 hours in an ice bath, washing for a plurality of times by ethanol and deionized water, centrifuging, and freeze-drying for 24h to obtain the silicon dioxide nanospheres with the particle size of about 500 nm.
(2) Dispersing the obtained silicon dioxide with 0.5 g in 200 ml deionized water by an analytical balance, carrying out ultrasonic dispersion for 20 minutes, stirring, adding sodium carbonate aqueous solution, regulating the pH of the dispersion to 10, preparing solution A, weighing 1.9328 g copper nitrate trihydrate Cu (NO 3)2·3H2 O is added into 200 ml deionized water to prepare 0.04M copper nitrate aqueous solution B), dropwise adding the solution B into the solution A under the stirring condition, stirring 1 h, washing with ethanol and deionized water for several times, carrying out suction filtration, and freeze-drying 24 h to obtain a copper/silicon dioxide precursor.
(3) 0.25 G copper/silicon dioxide nano particles are weighed by an analytical balance and dispersed in 450 ml absolute ethanol, the ultrasonic treatment is carried out for 20 s, the stirring is carried out for 1 h, 1.75 ml ammonia water and 3.5 ml tetrabutyl titanate are added, the stirring is carried out for 24h at 45 ℃, the centrifugation is carried out, the ethanol and deionized water are used for washing for a plurality of times, and the freeze drying is carried out for 24h, thus obtaining the titanium dioxide/copper/silicon dioxide precursor.
(4) The titania/copper/silica precursor obtained was subjected to argon: hydrogen=1:1, the flow rates were 50 sccm, the heating rate of 10 ℃/min, and the calcination temperature was 2h at 700 ℃, to obtain titania/copper/silica nanoparticles.
(5) Weighing 0.1 g titanium dioxide/copper/silicon dioxide nano-particles and 1 g ammonium bifluoride by using an analytical balance, adding 50ml deionized water, stirring for 30 minutes, centrifuging, washing with ethanol and deionized water for several times, and freeze-drying for 24 h to obtain the copper nano-particles/titanium dioxide hollow spherical shell. The resulting sample was recorded as TiO 2/Cu 0.04M.
Sample TiO 2/Cu 0.03M prepared in example 3 was selected for SEM characterization analysis. As shown in fig. 2, the synthesized TiO 2/Cu is a complete spherical structure, and can observe the partially broken spherical shell material, and can be approximately considered to be successful preparation of the hollow spherical shell material. Meanwhile, in order to observe the loading condition of Cu nano particles on the surface of SiO 2, TEM characterization analysis is performed on the intermediate Cu/SiO 2 prepared in example 3. As shown in fig. 3, the Cu nanoparticles with uniform size are uniformly distributed on the SiO 2 nanoparticles, and the particle size is mainly 5-10 nm. From this, it was observed that the lattice fringes of the Cu element were observed, and the lattice spacing of 0.21 nm corresponded to the (111) crystal plane of the Cu element. The element distribution condition of Cu/SiO 2 is observed through EDS, and Cu elements are uniformly distributed on the surface of SiO 2 nano particles. This demonstrates that the Cu element was successfully and uniformly supported on the SiO 2 nanoparticle surface in the form of nanoparticles.
In order to further explore the microstructure of the hollow shell layer of the TiO 2/Cu material and the distribution condition of Cu nano particles in the composite material, TEM characterization analysis was performed on the sample TiO 2/Cu 0.03M prepared in example 3. As shown in fig. 4, the synthesized TiO 2/Cu is a distinct hollow spherical shell structure, from which lattice fringes of Cu nanoparticles and TiO 2 can be observed, the lattice spacing of 0.21 nm corresponds to the (111) crystal plane of the Cu simple substance, and the lattice spacing of 0.35 nm corresponds to the (101) crystal plane of TiO 2, which proves that the Cu nanoparticles are successfully loaded on the TiO 2 shell layer. The element distribution condition of the TiO 2/Cu material is observed through EDS, and Cu elements are uniformly distributed in the TiO 2/Cu material. This demonstrates the successful preparation of TiO 2/Cu spherical shell material.
XRD characterization analysis is carried out on the samples TiO 2/Cu 0.01 M、TiO2/Cu 0.02 M、TiO2/Cu 0.03 M、TiO2/Cu 0.04 and M prepared in examples 1-4, and as shown in FIG. 5, successful preparation of anatase TiO 2 and Cu simple substances is proved. The Cu content of the TiO 2/Cu material exhibits a rule of increasing and decreasing with increasing concentration of Cu (NO 3)2, wherein the Cu content of TiO 2/Cu 0.03M is highest. It is generally considered by analysis that excessive Cu (NO 3)2 causes formation of excessive larger Cu nanoparticles, which become nucleation centers of TiO 2, causing large numbers of scattered TiO 2 without forming shells to form larger nanoparticles, which leads to a large increase in the TiO 2 content of the material and a relative decrease in Cu concentration).
Titanium dioxide is used as a control group, and the catalytic performance of the sample TiO 2/Cu 0.01 M、TiO2/Cu 0.02 M、TiO2/Cu 0.03 M、TiO2/Cu 0.04M prepared in the examples 1-4 in ciprofloxacin sunlight photocatalytic degradation is verified, wherein the verification process is as follows:
(1) 5 parts of 50ml CIP solution (10 mg/L) were taken, respectively, 20 mg titanium dioxide powder, 20 mg of 0.01, 0.02, 0.03 and 0.04 of M TiO 2/Cu were added to disperse in the CIP solution, and stirred well. Stirring under dark room condition for 30min to reach adsorption equilibrium.
(2) The simulated sunlight source is started to start degradation reaction, 3ml is sampled at 20, 40, 60, 80, 100 and 120 min respectively, the sampled sample is centrifuged at 4000 r/min for 5min, the supernatant is tested for absorbance at 271 nm by using an ultraviolet-visible spectrophotometer, and the absorbance of the solution is proportional to the concentration, so that the concentration of CIP solution at different times can be calculated.
The degradation curve graph and the first-order dynamics fitting curve graph are respectively shown in fig. 6 and 7, the photocatalytic degradation rates of titanium dioxide and 0.01-0.04M titanium dioxide hollow sphere supported nano copper photocatalyst are 17%, 23%, 30%, 37% and 27% respectively after being irradiated under a simulated sunlight light source, the catalytic effect of the titanium dioxide hollow sphere supported nano copper photocatalyst is obviously superior to that of titanium dioxide powder, and the catalytic rate of the titanium dioxide hollow sphere supported nano copper photocatalyst has obvious advantages as seen from the first-order dynamics fitting curve, and the TiO 2/Cu 0.03M has obvious advantages regardless of the catalytic rate or the degradation rate in the same time.
The above examples merely illustrate specific embodiments of the application, which are described in more detail and are not to be construed as limiting the scope of the application. It should be noted that it is possible for a person skilled in the art to make several variants and modifications without departing from the technical idea of the application, which fall within the scope of protection of the application.
Claims (10)
1. The titanium dioxide hollow sphere supported nano copper photocatalyst is characterized in that a hollow sphere shell material of the titanium dioxide hollow sphere supported nano copper photocatalyst is titanium dioxide, the particle size of the hollow sphere is 300-700 nm, and copper nano particles are supported in the shell; the preparation process comprises the following steps: firstly, loading copper nano particles on a silicon dioxide hard template, then coating titanium dioxide on the outside of the template loaded with the copper nano particles to form a shell, and finally etching the template serving as an inner core by utilizing ammonium bifluoride to obtain the titanium dioxide hollow sphere loaded nano copper photocatalyst.
2. The titanium dioxide hollow sphere supported nano copper photocatalyst according to claim 1, wherein the particle size of the silicon dioxide hard template is 300-700 nm.
3. The method for preparing the titanium dioxide hollow sphere supported nano copper photocatalyst according to claim 1 or 2, which is characterized in that copper nano particles are firstly supported on a silicon dioxide hard template, then titanium dioxide is coated outside the template supported with the copper nano particles to form a shell, and finally the template serving as an inner core is etched by ammonium bifluoride to obtain the titanium dioxide hollow sphere supported nano copper photocatalyst.
4. A method of preparation as claimed in claim 3, comprising the steps of:
(1) Dropwise adding a copper nitrate solution into a silicon dioxide dispersion liquid with the pH value of 9-10, stirring, wherein the stirring temperature is 5-25 ℃, the stirring time is 0.5-2 h, aging, washing with deionized water and ethanol, filtering, freeze-drying, calcining and reducing in a mixed atmosphere of argon and hydrogen, and the calcining temperature is 300-700 ℃, thus obtaining copper nano particles/silicon dioxide precursors;
(2) Dispersing copper nano particles/silicon dioxide precursor in ethanol, adding tetrabutyl titanate and ammonia water into the dispersion liquid, stirring at 40-50 ℃ for 24h ℃ and washing with deionized water and ethanol, centrifuging, freeze-drying, calcining and reducing in a mixed atmosphere of argon and hydrogen at 300-700 ℃ to obtain titanium dioxide/copper nano particles/silicon dioxide precursor;
(3) Dispersing titanium dioxide/copper nano particles/silicon dioxide precursor and ammonium bifluoride in deionized water, stirring at normal temperature for 0.5-2 h hours, washing with deionized water and ethanol, centrifuging, and freeze-drying to obtain the titanium dioxide hollow sphere supported nano copper photocatalyst.
5. The method of claim 4, wherein the silica of step (1) is prepared by: adding tetraethyl silicate and ammonia water into alcohol respectively to prepare solution, then dripping tetraethyl silicate alcohol solution into ammonia water alcohol solution to mix, stirring for 6-8 h at 0-25 ℃, washing with deionized water and ethanol, centrifuging, and freeze-drying to obtain the silicon dioxide hard template.
6. The method according to claim 5, wherein the silica is prepared by using a reaction system of 40 to 400 ml, wherein the amount of tetraethyl silicate is 2 to 4ml, the amount of ammonia water is 4 to 6 ml, and the amount of alcohol is 20 to 200 ml.
7. The method according to claim 4, wherein the concentration of the copper nitrate solution in the step (1) is 0.01 to 0.04M.
8. The process according to claim 4, wherein the concentration of the ammonium bifluoride solution in step (3) is 15-25 g/L.
9. The method according to claim 4, wherein the washing with deionized water and ethanol in steps (1) - (3) is performed by washing with deionized water once, washing with ethanol once, and circulating twice.
10. The use of a titanium dioxide hollow sphere supported nano copper photocatalyst according to claim 1 or 2 as a photocatalyst in degrading ciprofloxacin.
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