CN109133145B - CuO-TiO2Composite micron tube, preparation method and application thereof - Google Patents
CuO-TiO2Composite micron tube, preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 57
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000005470 impregnation Methods 0.000 claims abstract description 25
- 239000000835 fiber Substances 0.000 claims description 58
- 240000004731 Acer pseudoplatanus Species 0.000 claims description 23
- 235000002754 Acer pseudoplatanus Nutrition 0.000 claims description 23
- 235000006485 Platanus occidentalis Nutrition 0.000 claims description 23
- 150000001879 copper Chemical class 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 210000004209 hair Anatomy 0.000 claims description 17
- 239000012266 salt solution Substances 0.000 claims description 16
- 238000007598 dipping method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 210000002268 wool Anatomy 0.000 claims description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 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 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 230000000593 degrading effect Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 4
- 229940012189 methyl orange Drugs 0.000 claims description 4
- 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 claims description 4
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 4
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229940063650 terramycin Drugs 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 35
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- 239000000243 solution Substances 0.000 description 14
- 239000013067 intermediate product Substances 0.000 description 13
- 239000004100 Oxytetracycline Substances 0.000 description 12
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 description 12
- 229960000625 oxytetracycline Drugs 0.000 description 12
- 235000019366 oxytetracycline Nutrition 0.000 description 12
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 12
- 239000000499 gel Substances 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
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- 238000005286 illumination Methods 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 4
- 235000013399 edible fruits Nutrition 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
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- 239000000047 product Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 244000045719 Syzygium Species 0.000 description 3
- 244000223014 Syzygium aromaticum Species 0.000 description 3
- 235000016639 Syzygium aromaticum Nutrition 0.000 description 3
- 235000012096 Syzygium samarangense Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910003471 inorganic composite material Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
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- 235000003261 Artemisia vulgaris Nutrition 0.000 description 2
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- 235000019441 ethanol Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 241000894006 Bacteria Species 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 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 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 230000001678 irradiating effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
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- 238000005215 recombination Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- 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
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
The invention discloses CuO-TiO2Composite micron tube, preparation method and application thereof, and CuO-TiO2CuO and TiO in composite micron tube2The molar ratio of the CuO to the TiO is 1: 1-52The diameter of the composite micron tube is 15-22 mu m, and the wall thickness is 1-3 mu m; the CuO-TiO is2The specific surface area of the composite micron tube is 120-140 m2(ii) in terms of/g. In material performance, as the sol-gel impregnation reaction is continuously carried out on the surface of the biological template, the high-efficiency combination and the uniform distribution of crystal grains in the compounding process of the two materials are promoted, and the stability and the performance of the composite material are fully improved. The hollow composite micro-nano material prepared by the method has a stable structure, can keep a better hollow structure, has the characteristics of low density, high specific surface area and the like, and has an excellent application effect.
Description
Technical Field
The invention belongs to the field of inorganic composite materials, and particularly relates to CuO-TiO2Composite micron tube, preparation method and application thereof.
Background
Among numerous micro-nano composite materials, the hollow composite material has the characteristics of low density, large specific surface area, capability of accommodating guest molecules and the like, and is widely applied to the fields of environmental protection, biomedicine, electronics and the like. The template method is the most important and widely applied method for preparing the hollow composite material, and takes monodisperse polymer particles, inorganic particles, emulsion droplets, vesicles, bubbles and the like as templates, coats one or more layers of substances on the surfaces of the monodisperse polymer particles, the inorganic particles, the emulsion droplets, the vesicles, the bubbles and the like by a chemical or physical method, and removes the templates by technologies such as calcination, solvent extraction and the like to obtain the hollow material. The template method has the characteristics of simple preparation process, high repetition rate, good predictability and the like, and is widely applied at present.
CuO is widely used as a common p-type semiconductor material for electrode active materials, photoconductive materials, sensing materials, etc., while TiO2Is a typical n-type semiconductor, has excellent catalytic performance, stable chemical properties and is non-toxic and harmless. Preparation of CuO-TiO2The composite material can form an effective p-n heterojunction interface at the opposite position of the two energy band structures, is favorable for quickly separating photogenerated electrons from holes and inhibiting the recombination of the photogenerated electrons and the holes. Preparation of CuO-TiO by template method2In the research of the composite hollow material, the means for coating the composite material on the surface of the template and preparing the composite material mainly comprise sol-gelMethods, hydrothermal methods, self-assembly methods, and the like. Compared with other synthesis methods, the sol-gel method can prepare the materials in a low-temperature solution system under mild conditions, can achieve the level of molecular-level dispersion between the two materials, and has remarkable advantages. Based on the basic principle of the sol-gel method, the sol property changes with time and the hydrolysis speed is difficult to control in the hydrolysis reaction process of the titanium sol, so that the CuO-TiO is prepared by the traditional template method2When the hollow material is compounded, various technologies are used for assisting to control the slow hydrolysis process of the sol, such as adding a sol binder, precise low-temperature control, complex operation and the like. These additional conditions control make the experimental operation tedious and tedious, also result in low product yield and process not environmental friendly enough.
In recent years, reports of preparing micro-nano hollow structures by using biological structures as biological templates emerge. Bacteria, pollen, yeast, DNA, protein and the like are used as biological templates and are used for preparing micro-nano hollow materials such as metal oxides, bimetallic oxides and the like and researching the performance. Most of the work utilizes the natural appearance, surface activity, biological characteristics and the like of a biological structure, and the simple, convenient and quick preparation of the micro-nano hollow material with the novel appearance is realized. However, the preparation of CuO-TiO using a biological template2And the research on the hollow composite micro-nano material is less. How to fully exert the natural advantages of the biological template, a method for obtaining the hollow micro-nano composite material by a simple and green technical method needs to be deeply explored.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides CuO-TiO2A composite micron tube, its preparing process and its application are disclosed, which features that the biological structure is used as biological template (plant fibres containing natural water are used as example) and the sol-gel immersion method is used to prepare the composite hollow material.
In order to achieve the purpose, the invention is realized by adopting the following technologies:
CuO-TiO2Composite micron tube, said CuO-TiO2CuO and TiO in composite micron tube2The molar ratio of (A) to (B) is 1: 1-5;
the CuO-TiO is2The diameter of the composite micron tube is 15-22 mu m, and the wall thickness is 1-3 mu m;
the CuO-TiO is2The specific surface area of the composite micron tube is 120-140 m2/g。
Optionally, the micron tube is obtained by sequentially performing titanium source impregnation and copper salt solution impregnation and then calcining by using the sycamore hair fibers as the biological template, wherein the concentration of the copper salt solution is 2-5 mol/L.
Optionally, the impregnation time of the titanium source is 0.5-2h, and the impregnation time of the copper salt solution is 1-10 min.
Optionally, the calcining temperature is 400-600 ℃, and the calcining time is 1-4 h.
Optionally, the titanium source comprises one of n-butyl titanate, titanium tetrachloride and titanium tetrabromide, and the copper salt comprises one of copper sulfate, copper chloride and copper nitrate.
CuO-TiO2The preparation method of the composite micron tube comprises the steps of taking the sycamore wool fibers as a biological template, sequentially carrying out titanium source impregnation and copper salt solution impregnation, and then calcining to obtain the composite micron tube, wherein the concentration of copper salt is 2-5 mol/L.
Optionally, the impregnation time of the titanium source impregnation is 0.5-2h, and the impregnation time of the copper salt solution impregnation is 1-10 min;
the calcining temperature is 400-600 ℃, and the calcining time is 1-4 h;
the titanium source comprises one of n-butyl titanate, titanium tetrachloride and titanium tetrabromide, and the copper salt comprises one of copper sulfate, copper chloride and copper nitrate.
Optionally, the method specifically includes:
(1) 1-2g of non-pretreated or pretreated sycamore fiber is put into 50-100mL of titanium source to be soaked for 0.5-2 h;
(2) dipping the sycamore fiber dipped by the titanium source in 100mL of copper salt solution for 1-10min to obtain a sycamore fiber compound;
(3) drying the sycamore fiber composite at 50-80 ℃, andcalcining the mixture for 1 to 4 hours at the temperature of between 400 and 600 ℃ in a muffle furnace to obtain CuO-TiO2A micron tube.
Optionally, the pretreatment comprises: and (3) soaking and cleaning the sycamore wool fibers by using deionized water and/or absolute ethyl alcohol.
The CuO-TiO of the invention2Composite micron tube or CuO-TiO described in the invention2CuO-TiO prepared by preparation method of composite micron tube2The composite micron tube is used for degrading methylene blue, methyl orange or terramycin.
The invention has the beneficial effects that:
the invention takes a biological structure as a template (taking plant fiber containing natural water as an example) and prepares the hollow composite micro-nano composite material by a sol-gel impregnation method. In the template selection, the biological template used in the method is from organisms, has wide material source and low cost, meets the requirement of green chemical production and has wide application prospect; in the preparation method, the method realizes the ingenious combination of two materials on a biological template platform by a sol-gel method while utilizing the natural characteristics of the biological template, thereby overcoming the defects of complicated operation and accurate control of various experimental parameters of the sol-gel method and omitting complicated experimental steps in the preparation process of the composite material; in material performance, as the sol-gel impregnation reaction is continuously carried out on the surface of the biological template, the high-efficiency combination and the uniform distribution of crystal grains in the compounding process of the two materials are promoted, and the stability and the performance of the composite material are fully improved. The hollow composite micro-nano material prepared by the method has a stable structure, can keep a better hollow structure, has the characteristics of low density, high specific surface area and the like, and has a better application effect.
Drawings
FIG. 1 is a CuO-TiO of the present invention2A micron tube synthesis mechanism diagram;
FIG. 2 is an electronic scanning photograph of the mugwort fiber used in example 1;
FIG. 3 is CuO-TiO 2 in example 12A super depth of field micrograph of the microtube;
FIG. 4 is CuO-TiO2Scanning electronic scanning photos of the microtubes;
FIG. 5 is CuO-TiO2Electronically scanning the picture of the pipe orifice of the micron pipe;
FIG. 6 is CuO-TiO2XRD pattern of the micron tube;
FIG. 7 shows CuO-TiO2EDX analysis of microtube samples;
FIG. 8 shows CuO-TiO2Raman spectra of microtube samples;
FIG. 9 shows CuO-TiO2Micron tube UV-vis diffuse reflectance spectroscopy.
Detailed Description
The research and development ideas and main innovation points of the invention are summarized as follows:
research and development ideas: the biological structure is used as a biological template, the high-efficiency synthesis of the hollow composite micro-nano material can be realized by utilizing the biological characteristics of a natural structure, and the method is a strategy different from the traditional inorganic composite material synthesis method. The specific synthetic mechanism is shown in figure 1. The method firstly immerses the syzygium indicum fruit hair into the sol, and utilizes the natural moisture in the biological structure to ensure that the sol can react on the surface of the fiber and be hydrolyzed to form a small amount of gel. Because the natural moisture content in the biological structure is not high and is distributed in the biological structure, the hydrolysis reaction on the surface of the biological template is mild, and a sol layer is loaded on the outer side of the biological structure while a gel layer is formed on the surface of the biological structure. The process does not need to accurately control the low-temperature condition, and the operation is simple and quick. Secondly, a sample after partial hydrolysis reaction is immersed in a copper salt solution, so that the hydrolysis reaction of a sol layer on the surface of the sample is realized, the aim of combining metal salt and a gel layer is fulfilled, the primary preparation of a precursor of the composite material is realized, and then the biological template is removed through calcination, so that the micro-nano inorganic composite material with a hollow structure is obtained. The dipping of the invention refers to that the biological template material is completely soaked in a liquid system (which can be gel, water or metal salt solution), so that the biological template material and the liquid system are fully contacted for a certain time, and the generation of the surface chemical reaction of the biological template material is realized.
The main innovation points are as follows:
(1) in the aspect of template selection, the biological template used by the method is from organisms, has wide material source and low price, meets the requirement of green chemical production and has wide application prospect; the method selects organisms as the template, can fully play the natural advantages of the biological structure and make up the defects of the traditional template method for preparing the micro-nano hollow composite material. Specifically, the natural water in the biological template can enable the reaction conditions of the sol-gel method to be milder and simpler, and the surface of the biological template is used as a reaction platform through two reactions, so that the composite material is synchronously and simply prepared.
(2) In the aspect of the preparation method, the method realizes the direct and ingenious combination of two materials on a biological template platform by a sol-gel impregnation method twice continuously while utilizing the natural characteristics of the biological template, not only overcomes the defects of complicated operation and need of accurately controlling various experimental parameters of the sol-gel method, but also omits the complicated experimental steps in the preparation process of the composite material.
(3) In the aspect of material performance, as the sol-gel impregnation reaction is continuously carried out on the surface of the biological template, the high-efficiency combination and the uniform distribution of crystal grains in the compounding process of the two materials are promoted, and the stability and the performance of the composite material are fully improved. The hollow composite micro-nano material prepared by the method has a stable structure, can keep a better hollow structure, has the characteristics of low density, high specific surface area and the like, and has a better application effect.
The specific scheme comprises the following steps:
(1) 1-2g of pretreated or non-pretreated fructus syzygii ambient ori hair fiber is put into 50-100mL of titanium source (comprising tetrabutyl titanate, titanium tetrachloride, titanium tetrabromide and the like) to be soaked for 0.5-2 h;
(2) taking out the intermediate product, transferring to a solution containing 100mL of copper salt (including copper sulfate, copper chloride, copper nitrate and the like) for second impregnation, wherein the concentration of the copper salt solution is 2-5mol/L, the soaking time is 1-10min, and a large amount of light blue precipitates are generated on the surface of the fiber;
(3) drying the reacted fiber at 50-80 ℃, and calcining the fiber in a muffle furnace at 400-600 ℃ for 1-4h to obtain CuO-TiO2A micron tube;
pretreatment of the sycamore hair: optionally, deionized water and anhydrous alcohol can be used for soaking and cleaning the sycamore hair independently or sequentially.
Obtained CuO-TiO2The micron tube maintains the morphological characteristics of the natural fructus syzygii comosi hair fiber, is in a micron tube shape with a rough surface, and has good dispersibility, the length of the micron tube is about 24 mu m, and the wall thickness is about 2 mu m. Preferably, CuO-TiO2The diameter of the composite micron tube is 15-22 mu m, and the wall thickness is 1-3 mu m; CuO-TiO2The specific surface area of the composite micron tube is 120-140 m2/g。
The specific embodiment is as follows:
the invention takes a biological structure as a template (taking plant fiber containing natural water as an example) and prepares the composite hollow micro-nano composite material by a sol-gel impregnation method. The specific implementation method is as follows.
Example 1:
weighing 1g of sycamore wool fiber by using an electronic balance, and soaking the 1g of sycamore wool fiber in 100mL of n-butyl titanate for 2 hours; taking out the intermediate product by using tweezers, transferring the intermediate product into 100mL of copper sulfate solution with the concentration of 3mol/L, keeping for 3min, carrying out second impregnation, drying the reacted fiber at 60 ℃, putting the fiber into a muffle furnace, calcining for 2h at 500 ℃, removing the biological template, and obtaining CuO-TiO2A micron tube.
50mg of the prepared CuO-TiO is added into 50mL of oxytetracycline solution with the concentration of 20mg/L2The photocatalyst selects a 250W xenon lamp as a light source, and the degradation rate of the visible light for catalyzing and degrading the oxytetracycline is 91% when the illumination distance is 10 cm.
An electronic scanning photograph of the mugwort floss used in example 1 is shown in FIG. 2, CuO-TiO2The ultra-depth of field micrograph of the microtube is shown in FIG. 3, in which CuO-TiO can be seen2The micron tube maintains the morphological characteristics of the natural fructus syzygii comosi hair fiber, is in a tube shape with a rough surface, has good dispersibility and uniform length, and has the length of about 24 mu m and the wall thickness of about 2 mu m.
FIG. 4 is CuO-TiO2Scanning electronic scanning photos of the microtubes; as can be seen, CuO-TiO2The surface of the micron tube is rough and largeThe amount of nanoparticles, the sample having a hollow structure.
FIG. 5 is CuO-TiO2Electronically scanning the picture of the pipe orifice of the micron pipe; this figure illustrates the prepared CuO-TiO2The micron tube has a double-wall structure with different roughness degrees inside and outside, the outer wall is rough, but the inner wall is smooth, and the diameter of the tube opening is about 17 mu m.
FIG. 6 is CuO-TiO2XRD pattern of the micron tube; as shown in the figure, anatase type TiO is removed2(JCPDSNo. 21-1272) has diffraction peaks 2 theta of 25.2 DEG (101), 37.8 DEG (004), 48.0 DEG (200), 53.8 DEG (105), 55.1 DEG (211), 62.1 DEG (204) and 75.0 DEG (215), and the diffraction peaks 2 theta of other diffraction peaks are 32.5 DEG, 35.5 DEG, 38.7 DEG, 58.2 DEG, 53.5 DEG, 67.9 DEG, 65.7 DEG, 72.3 DEG and 75.3 DEG, which correspond to the (110), (-111), (111), (202), (020), (113), (022), (311), (22-2) crystal planes of monoclinic CuO (JCPDS No. 80-1916), respectively, and the sample is indicated to be composed of CuO and TiO crystal planes2Two kinds of crystals are obtained to obtain the composite material. CuO and TiO2In a molar ratio of 1: 2.
FIG. 7 shows CuO-TiO2EDX analysis of microtube samples the elemental composition of the samples was determined. CuO-TiO2The EDX spectrum of the micron tube proves that Ti, Cu, C and O elements exist in the sample.
FIG. 8 shows CuO-TiO2Raman spectrogram of a microtube sample, TiO2The micron tube is 145, 400, 510 and 630cm-1Has four peaks of anatase characteristic Raman spectrum. Irradiating CuO-TiO with light of wavelength lambda 485nm2When the pipe is a micron pipe, the composite material is electromagnetically enhanced and chemically enhanced, and SERS effect is generated, so that CuO and TiO are enabled to be combined2Produce strong Raman scattering, so at 145, 400, 510, 630cm-1The peak at (a) is clearly enhanced.
FIG. 9 shows CuO-TiO2The UV-vis diffuse reflection spectrum of the micron tube shows that CuO-TiO2The micron tube has good absorption in ultraviolet and visible light regions and has excellent optical performance.
Example 2:
and (3) cleaning the sycamore wool fibers with deionized water, and drying the fibers in an oven at 60 ℃.Weighing 1.5g of fructus Toosendan hair fiber by electronic balance, and adding 100ml of TiCl4Soaking for 1.5 h; taking out the intermediate product, transferring the intermediate product to 100mL of copper sulfate solution with the concentration of 4mol/L, keeping for 5min, and performing second impregnation; drying the reacted fiber at 70 ℃, putting the dried fiber into a muffle furnace, calcining the fiber for 3 hours at 500 ℃, and removing a biological template to obtain CuO-TiO2A micron tube.
50mg of the prepared CuO-TiO is added into 50mL of oxytetracycline solution with the concentration of 20mg/L2The photocatalyst selects a 250W xenon lamp as a light source, and the degradation rate of the visible light for catalyzing and degrading the oxytetracycline is 88% when the illumination distance is 10 cm.
Example 3:
and (3) cleaning the sycamore wool fibers with deionized water, and drying the fibers in a 50 ℃ oven. 1g of the fiber was weighed by an electronic balance and placed in a beaker containing absolute ethanol, and soaked for 1 hour. Putting the syzygium aromaticum fruit hair fibers into 80mL of n-butyl titanate to be soaked for 1 h; taking out the intermediate product, transferring the intermediate product to a copper chloride solution with the concentration of 3.5mol/L and keeping for 7min, and carrying out second impregnation; drying the reacted fiber at 65 ℃ and calcining the fiber in a muffle furnace at 550 ℃ for 2h, and removing the biological template to obtain CuO-TiO2A micron tube.
50mg of the prepared CuO-TiO is added into 50mL of oxytetracycline solution with the concentration of 20mg/L2The photocatalyst selects a 250W xenon lamp as a light source, and the degradation rate of the visible light for catalyzing and degrading the oxytetracycline is 85% when the illumination distance is 10 cm.
Example 4:
the sycamore wool fibers are cleaned by deionized water and ethanol and then are dried in an oven at the temperature of 60 ℃. Weighing 2g of syzygium barometz hair fibers by using an electronic balance, and putting 80mL of TiBr4Soaking for 2 h; taking out the intermediate product, transferring the intermediate product to a copper chloride solution with the concentration of 4mol/L and keeping for 4min, and carrying out second impregnation; drying the reacted fiber at 60 ℃, putting the fiber into a muffle furnace, calcining the fiber for 2 hours at 550 ℃, and removing a biological template to obtain CuO-TiO2A micron tube.
50mg of the prepared CuO-TiO is added into 50mL of oxytetracycline solution with the concentration of 20mg/L2The photocatalyst selects a 250W xenon lamp as a light sourceAnd the degradation rate of the visible light catalytic degradation oxytetracycline is 84% when the illumination distance is 10 cm.
Example 5:
cleaning the sycamore hair fiber with ethanol, putting the fiber into a 60 ℃ oven, and drying. 1.5g of the syzygium indicum linn hair fibers were weighed by an electronic balance and placed in a beaker containing deionized water, and soaked for 1 hour. Putting the syzygium aromaticum fruit hair fibers into 90mL of n-butyl titanate to be soaked for 1.7 h; taking out the intermediate product, transferring the intermediate product to 100mL of 3.5mol/L copper nitrate solution, keeping for 7min, and carrying out second impregnation; drying the reacted fiber at 70 ℃, putting the dried fiber into a muffle furnace, calcining the fiber for 4 hours at 500 ℃, and removing a biological template to obtain CuO-TiO2A micron tube.
50mg of the prepared CuO-TiO is added into 50mL of oxytetracycline solution with the concentration of 20mg/L2The photocatalyst selects a 250W xenon lamp as a light source, and the degradation rate of the visible light for catalyzing and degrading the oxytetracycline is 83% when the illumination distance is 10 cm.
Example 6:
2g of the fiber was weighed by an electronic balance and placed in a beaker containing absolute ethanol, and soaked for 1 hour. Putting the syzygium aromaticum fruit hair fibers into 90mL of n-butyl titanate to be soaked for 1.7 h; taking out the intermediate product, transferring the intermediate product to 100mL of 3mol/L copper nitrate solution, keeping for 4min, and carrying out second impregnation; drying the reacted fiber at 50 ℃, putting the dried fiber into a muffle furnace to calcine the fiber for 2.5 hours at 550 ℃, and removing a biological template to obtain CuO-TiO2A micron tube.
50mg of the prepared CuO-TiO is added into 50mL of oxytetracycline solution with the concentration of 20mg/L2The photocatalyst selects a 250W xenon lamp as a light source, and the degradation rate of the visible light for catalyzing and degrading the oxytetracycline is 86% when the illumination distance is 10 cm.
Preparation of CuO-TiO in accordance with the prior art by reference to the literature2The means, the product characteristics and the photocatalytic performance are compared, and the characteristics of simple operation, environment-friendly and energy-saving process, wide template source, excellent product performance and the like are highlighted. Specific comparison results are shown in table 1:
TABLE 1
The CuO-TiO used in the two prior art processes (hydrothermal and coprecipitation) listed in Table 1 was selected by consulting the literature2The photocatalytic system and conditions are used for carrying out photocatalytic degradation experiments aiming at methylene blue and methyl orange, and the excellent photocatalytic performance of the product disclosed by the invention is highlighted. The CuO-TiO prepared in examples 1 to 62The photocatalytic conditions and degradation results of the micron tube for methylene blue and methyl orange are shown in table 2:
TABLE 2
Claims (7)
1. CuO-TiO2The composite micron tube is characterized in that the CuO-TiO is2CuO and TiO in composite micron tube2The molar ratio of (A) to (B) is 1: 1-5;
the CuO-TiO is2The diameter of the composite micron tube is 15-22 mu m, and the wall thickness is 1-3 mu m;
the CuO-TiO is2The specific surface area of the composite micron tube is 120-140 m2/g；
The micron tube is prepared by sequentially dipping a titanium source and a copper salt solution in a titanium source dipping mode and calcining the dipped copper salt solution by taking the sycamore hair fiber as a biological template, wherein the concentration of the copper salt solution is 2-5 mol/L;
the dipping time of the titanium source dipping is 0.5-2h, and the dipping time of the copper salt solution dipping is 1-10 min.
2. The CuO-TiO of claim 12Composite micro-meterThe rice tube is characterized in that the calcining temperature is 400-600 ℃, and the calcining time is 1-4 h.
3. The CuO-TiO of claim 12The composite micron tube is characterized in that the titanium source comprises one of n-butyl titanate, titanium tetrachloride and titanium tetrabromide, and the copper salt comprises one of copper sulfate, copper chloride and copper nitrate.
4. CuO-TiO2The preparation method of the composite micron tube is characterized in that the composite micron tube is obtained by using the sycamore hair fiber as a biological template and sequentially carrying out titanium source impregnation and copper salt solution impregnation and then calcining, wherein the concentration of copper salt is 2-5 mol/L;
the dipping time of the titanium source dipping is 0.5-2h, and the dipping time of the copper salt solution dipping is 1-10 min;
the calcining temperature is 400-600 ℃, and the calcining time is 1-4 h;
the titanium source comprises one of n-butyl titanate, titanium tetrachloride and titanium tetrabromide, and the copper salt comprises one of copper sulfate, copper chloride and copper nitrate.
5. The CuO-TiO of claim 42The preparation method of the composite micron tube is characterized by specifically comprising the following steps:
(1) 1-2g of non-pretreated or pretreated sycamore fiber is put into 50-100mL of titanium source to be soaked for 0.5-2 h;
(2) dipping the sycamore fiber dipped by the titanium source in 100mL of copper salt solution for 1-10min to obtain a sycamore fiber compound;
(3) drying the sycamore wool fiber composite at 50-80 ℃, and calcining the sycamore wool fiber composite in a muffle furnace at 400-600 ℃ for 1-4h to obtain CuO-TiO2A micron tube.
6. The CuO-TiO of claim 52The preparation method of the composite micron tube is characterized in that the pretreatment comprises the following steps: by usingAnd (3) soaking and cleaning the sycamore hair fibers by using deionized water and/or absolute ethyl alcohol.
7. The CuO-TiO according to any one of claims 1 to 32Composite microtubes or CuO-TiO as claimed in any of claims 4 to 62CuO-TiO prepared by preparation method of composite micron tube2The composite micron tube is used for degrading methylene blue, methyl orange or terramycin.
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