CN108686658B - C-QDs-Fe2O3/TiO2Composite photocatalyst and preparation method thereof - Google Patents
C-QDs-Fe2O3/TiO2Composite photocatalyst and preparation method thereof Download PDFInfo
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- CN108686658B CN108686658B CN201810494239.7A CN201810494239A CN108686658B CN 108686658 B CN108686658 B CN 108686658B CN 201810494239 A CN201810494239 A CN 201810494239A CN 108686658 B CN108686658 B CN 108686658B
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 48
- 239000002131 composite material Substances 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 229920002472 Starch Polymers 0.000 claims abstract description 16
- 235000019698 starch Nutrition 0.000 claims abstract description 16
- 239000008107 starch Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 12
- 239000008103 glucose Substances 0.000 claims abstract description 12
- 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 abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000011261 inert gas Substances 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 abstract description 2
- 230000004298 light response Effects 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
-
- B01J35/23—
-
- B01J35/39—
-
- B01J35/393—
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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 C-QDs-Fe2O3/TiO2A composite photocatalyst and a preparation method thereof relate to the technical field of photocatalysis. The preparation method comprises the following steps: dispersing starch in absolute ethyl alcohol, adding glucose, and violently stirring to obtain a first mixed solution. And dissolving the ferric salt in absolute ethyl alcohol to obtain a second mixed solution. And dropwise adding the second mixed solution into the first mixed solution, then adding acetone, stirring and mixing, then adding ethylene glycol, tetrabutyl titanate and absolute ethyl alcohol, and then dropwise adding water and absolute ethyl alcohol to obtain a mixture. The composite photocatalyst is subjected to heat treatment at 80-200 ℃ for 3-48 h, and a product obtained after separation, washing and drying is subjected to treatment at 300-800 ℃ for 1-10 h under the protection of inert gas to obtain the composite photocatalyst. The composite photocatalyst shows good catalytic activity and stability for degrading organic pollutants in the environment under the visible light response condition, can be repeatedly used, and is environment-friendly.
Description
Technical Field
The invention relates to the technical field of photocatalysis, and in particular relates to C-QDs-Fe2O3/TiO2A composite photocatalyst and a preparation method thereof.
Background
The photocatalysis technology can decompose water to produce hydrogen and oxidize and decompose environmental pollutants by a high-efficiency and environment-friendly method, and the principle is that electrons and holes generated by the excitation of a photocatalyst under illumination respectively play roles in reduction and oxidation. Therefore, the photocatalysis technology is considered to be an environment management technology with energy conservation, environmental protection and wide application prospect. Titanium dioxide (TiO) among commonly used photocatalysts2) The organic carbon catalyst is excellent in performance, is a common catalytic material, can be used for catalyzing and degrading organic matters under the illumination condition, receives much attention in the environmental field, and has great potential utilization value in the aspects of energy and the like. TiO 22There are two disadvantages in photocatalytic degradation of organic materials. Firstly, due to TiO2The forbidden band width of the solar cell is large, and only ultraviolet light can be utilized but sunlight cannot be effectively utilized; secondly, the photo-generated electron-hole pairs which participate in the oxidation-reduction reaction in the catalytic process are very easy to recombine, so that TiO is required to be subjected to2And (4) carrying out modification.
Recent studies have shown that in TiO2In the modification means, Fe2O3Doping of (b) is considered to be a simple and effective means, Fe2O3Can effectively reduce TiO2The forbidden band width of (A) is the visible light response characteristic obtained by the catalyst. Carbon quantum dots (C-QDs) are a novel carbon nano material with the size of less than 10nm, have the advantages of excellent fluorescence stability, water solubility, chemical inertness, low toxicity, easy functionalization and the like, and are widely applied to the fields of biological imaging, biomedicine, biomarkers and the like.The C-QDs have excellent electron donor and electron acceptor characteristics, so that the recombination of photogenerated electron-hole pairs can be effectively inhibited, and the photocatalytic efficiency is improved.
Disclosure of Invention
The invention aims to provide C-QDs-Fe2O3/TiO2The preparation method of the composite photocatalyst is simple, easy to operate and low in cost.
Another object of the present invention is to provide a C-QDs-Fe2O3/TiO2A composite photocatalyst, which is prepared by passing Fe2O3And modifying, and adding carbon quantum dots to obtain the visible light responsive composite photocatalyst with high photocatalytic efficiency.
The technical problem to be solved by the invention is realized by adopting the following technical scheme.
The invention provides C-QDs-Fe2O3/TiO2The preparation method of the composite photocatalyst is characterized by comprising the following steps:
s1, dispersing starch in absolute ethyl alcohol, adding glucose, and violently stirring to obtain a first mixed solution;
s2, dissolving ferric salt in absolute ethyl alcohol to obtain a second mixed solution, dropwise adding the second mixed solution into the first mixed solution, adding acetone after dropwise adding is finished, and stirring and mixing to obtain a third mixed solution;
s3, adding a titanium liquid into the third mixed solution, and then dropwise adding water and absolute ethyl alcohol to obtain a mixture, wherein the titanium liquid is a mixed solution of ethylene glycol, tetrabutyl titanate and absolute ethyl alcohol;
s4, transferring the mixture to a reaction kettle, carrying out heat treatment at 80-200 ℃ for 3-48 h, separating, washing and drying to obtain a dried product, and carrying out treatment on the dried product at 300-800 ℃ for 1-10 h under the protection of inert gas to obtain the composite photocatalyst.
The invention also provides C-QDs-Fe2O3/TiO2The composite photocatalyst is prepared by the preparation method.
The embodiment of the invention has the beneficial effects that:
to TiO 22Carrying out Fe2O3Doping to make TiO2The band gap is narrowed, and the visible light activity is higher. The material obtained from starch, glucose and the like at low cost is used as the source of the carbon quantum dot, the carbon quantum dot has excellent photostability, and good specificity of photoinduced electron transfer, Fe2O3And the carbon quantum dots are doped together, so that the recombination of electrons and holes is effectively prevented, and the photocatalytic activity of the product is greatly improved. Has excellent photocatalytic activity under visible light, no pollution, no toxicity and low cost.
The nano composite photocatalyst is obtained through hydrothermal reaction and low-temperature calcination, the preparation method is simple, various parameters are easy to control, the particle size of the obtained composite photocatalyst is about 5-20 nm, and the utilization rate of visible light can be further improved by utilizing the coupling effect among nano particles.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following examples of C-QDs-Fe of the present invention2O3/TiO2The composite photocatalyst and the preparation method thereof are concretely explained.
The embodiment of the invention provides C-QDs-Fe2O3/TiO2The preparation method of the composite photocatalyst comprises the following steps:
and S1, dispersing the starch in absolute ethyl alcohol, adding glucose, and stirring vigorously to obtain a first mixed solution.
Further, in the preferred embodiment of the invention, the mass ratio of the starch to the glucose is 1: 1-2, and more preferably, the mass ratio of the starch to the glucose is 1: 1. Starch and glucose are both carbohydrates, and are cheap and easily available.
Further, the feed-liquid ratio of the starch to the absolute ethyl alcohol is 1-3 g/ml.
Further, in the step, the speed of vigorous stirring is 5000-10000 r/min. And the starch and the glucose are stirred vigorously to form a first mixed solution with uniform quality.
S2, dissolving the ferric salt in the absolute ethyl alcohol to obtain a second mixed solution. And dropwise adding the second mixed solution into the first mixed solution, adding acetone after dropwise adding is finished, and stirring and mixing to obtain a third mixed solution.
Further, in a preferred embodiment of the present invention, the iron salt is selected from one or more of ferric nitrate, ferric sulfate and ferric chloride, and more preferably, the iron salt is selected from ferric nitrate.
Further, in the second mixed solution, the feed-liquid ratio of the ferric nitrate to the absolute ethyl alcohol is 0.01-0.05 g/ml.
Further, in the step, the second mixed solution is dripped into the first mixed solution at the speed of 1-3 drops/second. And stirring while dripping to ensure that the second mixed solution is stably and uniformly mixed into the first mixed solution to carry out Fe treatment3+Forming a carbohydrate coating structure.
Further, the volume ratio of the acetone to the second mixed solution is 0.2-1: 1. After adding acetone, stirring and reacting for 30-60 min at the speed of 5000-10000 r/min.
Further, the mass ratio of the iron salt to the starch is 1: 6-50. More preferably, the ratio is 1: 10-30. Regulating C-QDs and Fe by regulating the mass ratio of carbohydrates2O3The doping amount of the photocatalyst is optimized, so that the synergistic effect of the two components is optimized, and the photocatalytic performance is better.
And S3, adding the titanium liquid into the third mixed solution, and then dropwise adding water and absolute ethyl alcohol to obtain a mixture, wherein the titanium liquid is a mixed solution of ethylene glycol, tetrabutyl titanate and absolute ethyl alcohol.
Further, in the step, the titanium liquid is ethylene glycol, tetrabutyl titanate and absolute ethyl alcohol in a volume ratio of 1-5: 3-10: 10-20.
Further, the volume ratio of the tetrabutyl titanate to the second mixed solution is 0.3-1: 1.
Further, in the step, the dropping speed of the water and the absolute ethyl alcohol is 1-3 drops/second, and stirring is carried out while dropping.
S4, transferring the mixture to a reaction kettle, carrying out heat treatment at 80-200 ℃ for 3-48 h, separating, washing and drying to obtain a dried product, and carrying out treatment on the dried product at 300-800 ℃ for 1-10 h under the protection of inert gas to obtain the composite photocatalyst.
Further, in the reaction kettle, the temperature is firstly increased to 80-100 ℃, heat treatment is carried out for 3-5 hours, then the temperature is increased to 160-180 ℃, and heat treatment is carried out for 9-16 hours. The hydrothermal reaction process is effectively controlled, the reaction is firstly carried out at a lower temperature and then carried out at a higher temperature, the reaction is promoted to be carried out, the substances are fully decomposed, the nano particles with uniform shapes can be formed, the crystallization degree of the composite photocatalyst is effectively controlled, and the composite photocatalyst with a better structure is obtained.
Further, in this step, the inert gas is nitrogen. Preferably, under the protection of nitrogen, the temperature is increased to 300-350 ℃ at the speed of 15-20 ℃/min, the temperature is maintained for 1-2 h, then the temperature is increased to 500-600 ℃ at the speed of 2-6 ℃/min, and the temperature is maintained for 3-6 h. The temperature is controlled by a program, the temperature is quickly raised to a lower temperature for processing, and then the temperature is slowly raised to a higher temperature, so that a more complete crystal structure is formed.
Further, the method also comprises the step of grinding the product after cooling to room temperature.
The embodiment of the invention provides C-QDs-Fe2O3/TiO2The composite photocatalyst is prepared by the preparation method.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
This example provides a C-QDs-Fe2O3/TiO2The preparation method of the composite photocatalyst comprises the following steps:
(1) dispersing 4g starch in 20ml absolute ethyl alcohol, adding 4g glucose, and vigorously stirring (8000 rpm) for 10min to obtain a mixed solution.
(2) 0.2g of ferric nitrate was dissolved in 10ml of anhydrous ethanol, and the solution was added to the mixture in (1) at a rate of 2 drops/sec. Then, 8ml of acetone was added to the above solution and stirred for 50min at 8000 rpm to obtain a mixed solution.
(3) Preparing a titanium solution containing 4mL of ethylene glycol, 8mL of tetrabutyl titanate and 18mL of absolute ethyl alcohol, adding the titanium solution into the mixed solution in the step (2), and then adding 6mL of deionized water and 12mL of absolute ethyl alcohol at the speed of 2 drops per second while stirring to obtain a mixed solution.
(4) And (3) transferring the mixture in the step (3) to a polytetrafluoroethylene reaction kettle with a stainless steel jacket, carrying out heat treatment for 16h at 180 ℃ to obtain a compound with dark-colored precipitates, washing the precipitates for 3 times respectively by using deionized water and absolute ethyl alcohol, and carrying out vacuum drying for 24h at 120 ℃. And then heating the dried product to 600 ℃ at the speed of 15 ℃/min in the nitrogen atmosphere, preserving the heat for 6 hours, cooling to room temperature, taking out and grinding to obtain the composite photocatalyst.
Example 2
This example provides a C-QDs-Fe2O3/TiO2The preparation method of the composite photocatalyst comprises the following steps:
(1) dispersing 4g starch in 20ml absolute ethyl alcohol, adding 5g glucose, and vigorously stirring (8000 rpm) for 10min to obtain a mixed solution.
(2) 0.1g of ferric nitrate was dissolved in 10ml of anhydrous ethanol, and the solution was added to the mixture in (1) at a rate of 2 drops/sec. Then, 8ml of acetone was added to the above solution and stirred for 50min at 8000 rpm to obtain a mixed solution.
(3) Preparing a titanium solution containing 4mL of ethylene glycol, 8mL of tetrabutyl titanate and 18mL of absolute ethyl alcohol, adding the titanium solution into the mixed solution in the step (2), and then adding 6mL of deionized water and 12mL of absolute ethyl alcohol at the speed of 2 drops per second while stirring to obtain a mixed solution.
(4) And (3) transferring the mixture in the step (3) to a polytetrafluoroethylene reaction kettle with a stainless steel jacket, carrying out heat treatment for 16h at 180 ℃ to obtain a compound with dark-colored precipitates, washing the precipitates for 3 times respectively by using deionized water and absolute ethyl alcohol, and carrying out vacuum drying for 24h at 120 ℃. And then heating the dried product to 600 ℃ at the speed of 15 ℃/min in the nitrogen atmosphere, preserving the heat for 6 hours, cooling to room temperature, taking out and grinding to obtain the composite photocatalyst.
Example 3
This example provides a C-QDs-Fe2O3/TiO2The composite photocatalyst is different from the composite photocatalyst in example 1 in that:
the step (4) is as follows: and (3) transferring the mixture in the step (3) to a polytetrafluoroethylene reaction kettle with a stainless steel jacket, heating to 80 ℃, carrying out heat treatment for 4h, then heating to 180 ℃, carrying out heat treatment for 12h to obtain a compound with dark-colored precipitates, washing the precipitates for 3 times respectively by using deionized water and absolute ethyl alcohol, and then carrying out vacuum drying for 24h at 120 ℃. And then heating the dried product to 600 ℃ at the speed of 15 ℃/min in the nitrogen atmosphere, preserving the heat for 6 hours, cooling to room temperature, taking out and grinding to obtain the composite photocatalyst.
Example 4
This example provides a C-QDs-Fe2O3/TiO2The composite photocatalyst is different from the composite photocatalyst in example 1 in that:
the step (4) is as follows: and (3) transferring the mixture in the step (3) to a polytetrafluoroethylene reaction kettle with a stainless steel jacket, heating to 80 ℃, carrying out heat treatment for 4h, then heating to 180 ℃, carrying out heat treatment for 12h to obtain a compound with dark-colored precipitates, washing the precipitates for 3 times respectively by using deionized water and absolute ethyl alcohol, and then carrying out vacuum drying for 24h at 120 ℃. Then, the dried product is heated to 300 ℃ at the speed of 15 ℃/min and is kept for 1.5h under the nitrogen atmosphere, and then is heated to 600 ℃ at the speed of 5 ℃/min and is kept for 6 h. And cooling to room temperature, taking out and grinding to obtain the composite photocatalyst.
Comparative example 1
The comparative example provides Fe2O3/TiO2The preparation method of the composite photocatalyst comprises the following steps:
(1) 0.2g of ferric nitrate was dissolved in 10ml of absolute ethanol, and then 8ml of acetone was added to the above solution, and stirred for 50min to obtain a mixed solution at a stirring speed of 8000 rpm.
(2) Preparing a titanium solution containing 4mL of ethylene glycol, 8mL of tetrabutyl titanate and 18mL of absolute ethyl alcohol, adding the titanium solution into the mixed solution in the step (1), and then adding 6mL of deionized water and 12mL of absolute ethyl alcohol at the speed of 2 drops per second while stirring to obtain a mixed solution.
(3) And (3) transferring the mixture in the step (2) to a polytetrafluoroethylene reaction kettle with a stainless steel jacket, carrying out heat treatment for 16h at 180 ℃ to obtain a compound with dark-colored precipitates, washing the precipitates for 3 times respectively by using deionized water and absolute ethyl alcohol, and carrying out vacuum drying for 24h at 120 ℃. And then heating the dried product to 600 ℃ at the speed of 15 ℃/min in the nitrogen atmosphere, preserving the heat for 6 hours, cooling to room temperature, taking out and grinding to obtain the composite photocatalyst.
Test example 1
The photocatalytic activities of the composite photocatalysts provided in examples 1 to 4 and comparative example 1 were measured, respectively.
Measuring 50ml of methyl orange solution with the concentration of 10mg/l as reaction liquid, simulating a water purification process, adding 20mg of composite photocatalyst into a 300W xenon lamp as a light source, starting magnetic stirring after the light source is 15cm away from the liquid surface, fully stirring the suspension in a dark room for 30min, starting the light source, sampling at regular intervals, and measuring the absorbance value of the supernatant.
The measurement results are shown in table 1.
TABLE 1 photocatalytic activity measurement results Table
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (8)
1. C-QDs-Fe2O3/TiO2The preparation method of the composite photocatalyst is characterized by comprising the following steps:
s1, dispersing starch in absolute ethyl alcohol, adding glucose, and violently stirring to obtain a first mixed solution;
s2, dissolving ferric salt in absolute ethyl alcohol to obtain a second mixed solution, dropwise adding the second mixed solution into the first mixed solution, adding acetone after dropwise adding is finished, and stirring and mixing to obtain a third mixed solution; wherein the mass ratio of the ferric salt to the starch is 1: 6-50;
s3, adding a titanium liquid into the third mixed solution, and then dropwise adding water and absolute ethyl alcohol to obtain a mixture, wherein the titanium liquid is a mixed solution of ethylene glycol, tetrabutyl titanate and absolute ethyl alcohol;
s4, transferring the mixture into a reaction kettle, heating to 80-100 ℃, carrying out heat treatment for 3-5 hours, heating to 160-180 ℃, carrying out heat treatment for 9-16 hours, separating, washing and drying to obtain a dried product, heating the dried product to 300-350 ℃ at a speed of 15-20 ℃/min under the protection of nitrogen, keeping for 1-2 hours, heating to 500-600 ℃ at a speed of 2-6 ℃/min, and keeping for 3-6 hours to obtain the composite photocatalyst.
2. C-QDs-Fe according to claim 12O3/TiO2The preparation method of the composite photocatalyst is characterized in that in the step S1, the mass ratio of the starch to the glucose is 1: 1-2, and the feed-liquid ratio of the starch to the absolute ethyl alcohol is 1-3 g/ml.
3. C-QDs-Fe according to claim 12O3/TiO2The preparation method of the composite photocatalyst is characterized in that in the step S1, the violent stirring speed is 5000-10000 r/min.
4. C-QDs-Fe according to claim 12O3/TiO2The preparation method of the composite photocatalyst is characterized in that in step S2, the second mixed solution is dripped into the first mixed solution at a speed of 1-3 drops/second.
5. C-QDs-Fe according to claim 12O3/TiO2The preparation method of the composite photocatalyst is characterized in that in step S2, the ferric salt is selected from one or more of ferric nitrate, ferric sulfate and ferric chloride, and the feed-liquid ratio of the ferric salt to the absolute ethyl alcohol in the second mixed solution is 0.01-0.05 g/ml.
6. C-QDs-Fe according to claim 12O3/TiO2The preparation method of the composite photocatalyst is characterized in that in the step S3, the volume usage ratio of the ethylene glycol, the tetrabutyl titanate and the absolute ethyl alcohol is 1-5: 3-10: 10-20.
7. C-QDs-Fe according to claim 12O3/TiO2The preparation method of the composite photocatalyst is characterized in that in the step S2, the volume ratio of the acetone to the second mixed solution is 0.2-1: 1.
8. C-QDs-Fe2O3/TiO2The composite photocatalyst is characterized by being prepared by the preparation method of any one of claims 1 to 7.
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