CN110975860A - Chromium-doped titanium-oxygen cluster nano catalytic material, preparation method and application - Google Patents
Chromium-doped titanium-oxygen cluster nano catalytic material, preparation method and application Download PDFInfo
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- CN110975860A CN110975860A CN201911100122.7A CN201911100122A CN110975860A CN 110975860 A CN110975860 A CN 110975860A CN 201911100122 A CN201911100122 A CN 201911100122A CN 110975860 A CN110975860 A CN 110975860A
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000000463 material Substances 0.000 title claims abstract description 60
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- 230000015556 catabolic process Effects 0.000 claims abstract description 51
- 238000006731 degradation reaction Methods 0.000 claims abstract description 51
- 239000004098 Tetracycline Substances 0.000 claims abstract description 40
- 229960002180 tetracycline Drugs 0.000 claims abstract description 40
- 229930101283 tetracycline Natural products 0.000 claims abstract description 40
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 40
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 40
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims abstract description 35
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 32
- 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 30
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 238000004090 dissolution Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 27
- 238000007146 photocatalysis Methods 0.000 abstract description 19
- 230000007547 defect Effects 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000005286 illumination Methods 0.000 abstract description 2
- 238000002835 absorbance Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 10
- 150000001844 chromium Chemical class 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 229910003087 TiOx Inorganic materials 0.000 description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000007281 self degradation Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a chromium-doped titanium-oxygen cluster nano catalytic material, a preparation method and application thereof, comprising the steps of preparing titanium-oxygen cluster powder by taking pivalic acid as a precursor; and then adding titanium oxide cluster powder and chromium chloride into tetrabutyl titanate for ultrasonic dissolution, and reacting under the boiling condition to obtain the chromium-doped titanium oxide cluster nano catalytic material, wherein the mass ratio of the titanium oxide cluster powder to the chromium chloride is (6-8): 1. The chromium-doped composite titanium oxide cluster nano catalytic material prepared by the invention has the advantages of low technical cost, environmental protection, easy operation, high degradation efficiency and various degraded tetracycline varieties; the defects of poor dosage efficiency of single-molecule photocatalysis, poor visible light absorption efficiency, easy photoinduction charge combination and the like are overcome; the titanium-oxygen cluster compound has large specific surface area, is easy to form true vacancy under the condition of illumination, has more pores and has high catalytic performance.
Description
Technical Field
The invention belongs to the field of environmental protection, and relates to a chromium-doped titanium-oxygen cluster nano catalytic material, a preparation method and application thereof.
Background
The titanium-oxygen cage (or dissimilar metal titanium-oxygen cage, hereinafter referred to as titanium-oxygen cage) is also called titanium-oxygen cluster, and is a monodisperse nano molecular system, the basic framework of which is a cage-shaped molecular cluster constructed by a plurality of titanium atoms connected with each other through oxygen bridges, and the diameter of the cage-shaped molecular cluster is between 0.5 and 2.0 nm. The titanium-oxygen cage can be regarded as a type of nano titanium oxide with smaller size and organic functional groups on the surface, because a large amount of hole-loaded pollutant molecules can be generated to play a role in efficiently separating tetracycline pollutants from a water body, so far, research on nano cluster catalytic materials is relatively lacked, and methods for preparing nano porous titanium dioxide mainly comprise a sol-gel method and soft and hard template methods. Most of photocatalytic materials for degrading organic pollutants are single-component photocatalysts, and the single-component photocatalysts (TiO2, ZnO, SnO2 and the like) have some defects such as poor quantum efficiency, poor visible light absorption efficiency and easy photoinduced charge combination, so that the photocatalytic performance is low.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention aims to provide a chromium-doped titanium oxide cluster nano catalytic material, a preparation method and application thereof, solves the problem of ecological pollution of tetracycline, and has the defects of poor quantum efficiency, poor visible light absorption efficiency, easy photoinduced charge combination, low photocatalytic performance and the like of a single-component photocatalyst.
In order to solve the problems, the invention adopts the technical scheme that:
a preparation method of chromium-doped titanium oxide cluster nano catalytic material comprises the steps of preparing titanium oxide cluster powder by taking pivalic acid as a precursor; and then adding titanium oxide cluster powder and chromium chloride into tetrabutyl titanate for ultrasonic dissolution, and reacting under the boiling condition to obtain the chromium-doped titanium oxide cluster nano catalytic material, wherein the mass ratio of the titanium oxide cluster powder to the chromium chloride is (6-8): 1.
Further, the method comprises the following steps:
the method comprises the following steps: mixing and heating pivalic acid, tetrabutyl titanate and ethylene glycol, and reacting to obtain titanium oxide cluster powder;
step two: adding titanium oxide cluster powder and chromium chloride into tetrabutyl titanate for ultrasonic dissolution, and reacting under the boiling condition to obtain the chromium-doped titanium oxide cluster nano catalytic material.
Further, the molar ratio of the pivalic acid to the tetrabutyl titanate in the first step is 1.8-2.2: 1.
Further, in the first step, the reaction temperature is 90-100 ℃, and the reaction time is 20-25 h.
Further, the method specifically comprises the following steps:
the method comprises the following steps: mixing and heating pivalic acid, tetrabutyl titanate and ethylene glycol, and reacting to obtain titanium oxide cluster powder, wherein the molar ratio of the pivalic acid to the tetrabutyl titanate is 2:1, the reaction temperature is 98 ℃, and the reaction time is 24 hours;
step two: adding titanium oxide cluster powder and chromium chloride into tetrabutyl titanate for ultrasonic dissolution, reacting for 60min under the boiling condition, and drying to obtain the chromium-doped titanium oxide cluster nano catalytic material, wherein the mass ratio of the titanium oxide cluster powder to the chromium chloride is 20: 3.
Further, the method specifically comprises the following steps:
the method comprises the following steps: mixing and heating 10.5mmol of pivalic acid, 5mmol of tetrabutyl titanate and 20mL of ethylene glycol, reacting at 98 ℃ for 24 hours, and drying to obtain titanium oxide cluster powder;
step two: adding 0.2g of titanium oxygen cluster powder and 0.03g of chromium chloride into tetrabutyl titanate for ultrasonic dissolution, reacting for 60min under the boiling condition, and drying at 70 ℃ to obtain the chromium-doped titanium oxygen cluster nano catalytic material.
The chromium-doped titanium-oxygen cluster nano catalytic material is prepared by the preparation method of the chromium-doped titanium-oxygen cluster nano catalytic material.
The chromium-doped titanium oxide cluster nano catalytic material prepared by the preparation method of the chromium-doped titanium oxide cluster nano catalytic material or the application of the chromium-doped titanium oxide cluster nano catalytic material in degrading tetracycline is provided, and the degradation rate of the chromium-doped titanium oxide cluster nano catalytic material to tetracycline is 90-95%.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) the method adopts a photocatalytic oxidation technology, has low cost, environmental protection, easy operation, high degradation efficiency and multiple types of degraded tetracycline, realizes the aim of green chemistry by utilizing solar light energy with inexhaustible natural sources, has simple preparation method and does not use large-scale complex instruments;
(2) the chromium chloride is doped to prepare the composite photocatalyst, so that the defects of poor dosage efficiency, poor visible light absorption efficiency, easy photoinduction charge combination and the like of a single-molecule photocatalyst are overcome;
(3) the titanium-oxygen cluster compound has large specific surface area, is easy to form a true vacancy under the condition of illumination, has more pore-loaded pollutant molecules, plays a role in efficiently separating tetracycline pollutants from a water body, and has high catalytic performance;
(4) the method has the advantages of wide linear range, low detection limit and small relative standard deviation, and can meet the national detection requirement on organic pollutants in the water body, and the degradation rate of the tetracycline in the water body can reach 93.2%.
The present invention will be further explained with reference to the following embodiments.
Detailed Description
The related reagents of the Pivalic Acid (PA), the ethylene glycol, the tetrabutyl titanate (Ti (OBu)4) and the like are purchased from pharmaceutical industry GmbH of the national medicine group. The instrument related information is as follows: scanning electron microscopy (JSM6700F, JEOL Ltd.); a photocatalytic reactor (BL-GHX-V type, Xianbi Biotech limited); a polytetrafluoroethylene lined reactor (heyday engineering machinery limited); vacuum drying oven (model DF-700, Shanghai-Heng scientific instruments, Inc.); ultraviolet-visible spectrophotometer (model BUV-765 shanghai precision instruments ltd).
The invention adopts a metal doping mode, and the prepared composite photocatalyst effectively overcomes the defects of poor dosage efficiency, poor visible light absorption efficiency, easy photoinduction charge combination and the like of a monomolecular catalyst. When the nano particles with catalytic performance are loaded on the metal framework to form the nano composite, the catalytic performance of the nano composite is greatly improved due to the synergistic effect, or the bifunctional catalyst is formed, so that the application range of the composite material in heterogeneous catalysis is greatly expanded. Among them, titanium dioxide nanomaterials have attracted extensive research attention in the past thirty years due to their application prospects in catalysis, photocatalysis, solar cells, and the like. Through a plurality of experimental researches, the titanium oxide cluster nano-material photocatalyst doped with 3% of chromium chloride and having good performance is prepared, the degradation rate of tetracycline pollutants in water can reach 93.2%, and the titanium oxide cluster nano-material photocatalyst has the advantages of wide linear range, low detection limit and small relative standard deviation.
Comprises preparing titanium oxide cluster powder by using pivalic acid as a precursor; and then adding titanium oxide cluster powder and chromium chloride into tetrabutyl titanate for ultrasonic dissolution, and reacting under the boiling condition to obtain the chromium-doped titanium oxide cluster nano catalytic material, wherein the mass ratio of the titanium oxide cluster powder to the chromium chloride is (6-8): 1.
The preparation method comprises the following steps:
the method comprises the following steps: mixing and heating pivalic acid, tetrabutyl titanate and ethylene glycol, and reacting to obtain titanium oxide cluster powder; the molar ratio of the pivalic acid to the tetrabutyl titanate is 1.8-2.2: 1; the reaction temperature is 90-100 ℃, and the reaction time is 20-25 h;
step two: adding titanium oxide cluster powder and chromium chloride into tetrabutyl titanate for ultrasonic dissolution, and reacting under the boiling condition to prepare the chromium-doped titanium oxide cluster nano catalytic material, wherein the mass ratio of the titanium oxide cluster powder to the chromium chloride is 20: 3.
In order to test the degradation effect of the chromium-doped titanium-oxygen cluster nano catalytic material prepared by the method on tetracycline organic pollutants in water, the photocatalytic degradation experimental method for the chromium-doped titanium-oxygen cluster nano catalytic material comprises the following steps: adding 0.010g of chromium-doped titanium oxide cluster nano catalytic material into 50ml of 30mg/L tetracycline solution, adsorbing for 30min under the dark condition, recording the absorbance at the moment, simulating sunlight irradiation for 90min under a photocatalytic reactor for photocatalysis, recording the absorbance of the solution every 10min, and judging the degradation effect.
The present invention will be described in further detail with reference to examples and comparative examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Therefore, within the scope of the claims and their equivalents, the invention may be practiced otherwise than as specifically described below.
Example 1:
according to the technical scheme, the embodiment provides the chromium-doped titanium-oxygen cluster nano catalytic material, the preparation method and the application thereof. The monocarboxylic acid used in this example was Pivalic Acid (PA), the metal salt was chromium salt, chromium chloride, and the following steps were specifically included:
the method comprises the following steps: 10.5mmol of PA and 5mmol of Ti (OBu)4Mixing, adding 20ml of ethylene glycol, stirring for 5min to obtain a mixed solution, and heating the mixed solution at the temperature of 98 ℃ for 24 h; then washing with anhydrous tetrahydrofuran for three times, centrifuging and drying at 65 ℃ to obtain powdery solid particles, namely the pure titanium oxide cluster nano catalytic material;
step two: and (3) weighing 0.2g of the titanium dioxide cluster powder obtained in the step one and 0.03g of chromium chloride, adding the titanium dioxide cluster powder and the chromium chloride into 10-20 mL of tetrabutyl titanate, performing ultrasonic dissolution for 30min, then boiling for 60min, then centrifuging by using deionized water, and drying at 70 ℃ to obtain the 3% chromium-doped titanium dioxide cluster nano catalytic material. Wherein the doping amount is equal to the mass of the chromium element/(the mass of the pure titanium-oxygen cluster + the mass of the chromium element).
In order to test the degradation effect of the photocatalytic material prepared in the embodiment on tetracycline in water, the photocatalytic degradation experiment method is used for testing. The absorbance of the tetracycline solution before and after photocatalysis was recorded and the degradation rate was calculated as shown in table one. The photocatalytic degradation experimental method comprises the following steps: adding 0.010g of chromium-doped titanium oxygen cluster nano catalytic material into 50ml of 30mg/L tetracycline solution, adsorbing for 30min under the dark condition, and recording the absorbance at the moment as A0And then simulating sunlight irradiation for 90min under a photocatalytic reactor for photocatalysis, recording the absorbance of the solution before and after irradiation, and judging the degradation effect. The degradation rate was 93.2%.
Comparative example 2:
the preparation method of this example is the same as that of example 1, except that the kind of monocarboxylic acid used in the preparation process is different, and Pivalic Acid (PA) is changed to propionic acid in this example, and the other conditions are not changed. The absorbance of the tetracycline solution before and after photocatalysis was recorded and the degradation rate was calculated as shown in table one. The degradation rate is 54.3 percent
Comparative example 3:
the preparation method of this example is the same as that of example 1, except that the kind of monocarboxylic acid used in the preparation process is different, and Pivalic Acid (PA) is changed to methacrylic acid in this example, and the other conditions are not changed. The absorbance of the tetracycline solution before and after photocatalysis was recorded and the degradation rate was calculated as shown in table one. The degradation rate was 66.8%.
It can be seen from the above examples and table one that the degradation rates of tetracycline in water are 93.2%, 54.3% and 66.8% respectively under the same conditions by changing the types of monocarboxylic acids in the catalytic material, so that the absorbance of the tetracycline solution is most reduced when pivalic acid is used as a precursor, and the degradation effect is the best. The reason is that the catalytic material is prepared by taking pivalic acid as a precursor, the surface of the catalytic material is rich in a large amount of active carboxyl, the catalytic material has strong affinity to metal ions and strong binding force with chromium ions, and the degradation effect on tetracycline is better than that of the catalytic material taking other acids as the precursor.
Comparative example 4:
the preparation method of this example is the same as that of example 1, except that the kind of the metal salt in the preparation process is different,the metal salt in this embodiment is changed to FeCl32H2O, the remaining conditions being unchanged. The absorbance of the tetracycline solution before and after photocatalysis was recorded and the degradation rate was calculated as shown in table one. The degradation rate was 50.1%.
Comparative example 5
The preparation method of this example is the same as that of example 1, except that the kind of the metal salt in the preparation process is different, and the salt in this example is CuCl2·6H2O, and the rest conditions are unchanged. The absorbance of the tetracycline solution before and after photocatalysis was recorded and the degradation rate was calculated as shown in table one. The degradation rate was 62.4%.
Comparative example 6
The preparation method of this example is the same as that of example 1, except that the kind of metal salt in the preparation process is different, and the salt in this example is changed to CoCl2·6H2O, and the rest conditions are unchanged. The absorbance of the tetracycline solution before and after photocatalysis was recorded and the degradation rate was calculated as shown in table one. The degradation rate was 65.4%.
Comparative example 7
The preparation method of this example is the same as that of example 1, except that no metal salt is doped during the preparation process, and the remaining conditions are unchanged. The absorbance of the tetracycline solution before and after photocatalysis was recorded and the degradation rate was calculated as shown in table one. The degradation rate was 44.6%.
As can be seen from example 1, comparative examples 4 to 7 and Table I, the degradation rates of tetracycline in the water body are respectively 93.2%, 50.1%, 62.4%, 65.4% and 44.6% by changing the types of the metal salts and whether the metal salts are doped, so that the absorbance of the tetracycline solution is reduced most when the chromium chloride is doped, and the degradation effect is the best. The self degradation rate of the titanium oxide cluster powder is 44.6%, the degradation rate of the chromium salt is 20.38%, and the degradation rate of the doped chromium chloride is 93.2%, and the result of example 1 shows that when the nano-particle chromium with catalytic performance is loaded on the titanium oxide cluster with the metal framework to form a nano-composite, the catalytic performance is greatly improved due to the synergistic effect, a dual-function catalyst is formed, and the application range of the composite material in heterogeneous catalysis is greatly expanded.
Comparative example 8
The preparation method of this example is the same as that of example 1, except that the doping ratio of chromium chloride in the preparation process is different, and the molar ratio of chromium chloride to tetrabutyl titanate in this example is 5:100, that is, the percentage content of chromium in the chromium salt is 0.5%, and the rest conditions are unchanged. The absorbance of the tetracycline solution before and after photocatalysis was recorded and the degradation rate was calculated as shown in table one. The degradation rate was 53.2%.
Comparative example 9
The preparation method of this example is the same as that of example 1, except that the doping ratio of chromium chloride in the preparation process is different, and the molar ratio of chromium chloride to tetrabutyl titanate in this example is 1:100, that is, the percentage content of chromium in the chromium salt is 1%, and the rest conditions are unchanged. The absorbance of the tetracycline solution before and after photocatalysis was recorded and the degradation rate was calculated as shown in table one. The degradation rate is 48.3%.
Comparative example 10
The preparation method of this example is the same as that of example 1, except that the doping ratio of chromium chloride in the preparation process is different, and the molar ratio of chromium chloride to tetrabutyl titanate in this example is 5:100, that is, the percentage content of chromium in the chromium salt is 5%, and the rest conditions are unchanged. The absorbance of the tetracycline solution before and after photocatalysis was recorded and the degradation rate was calculated as shown in table one. The degradation rate was 39.5%.
Comparative example 11
The preparation method of this example is the same as that of example 1, except that the doping ratio of chromium chloride in the preparation process is different, and the molar ratio of chromium chloride to tetrabutyl titanate in this example is 10:100, that is, the percentage content of chromium in the chromium salt is 10%, and the rest conditions are unchanged. The absorbance of the tetracycline solution before and after photocatalysis was recorded and the degradation rate was calculated as shown in table one. The degradation rate was 43.8%.
It can be seen from the above examples and table one that, by changing the addition ratio of chromium chloride to tetrabutyl titanate, the degradation rates of the finally prepared chromium-doped titanium oxide cluster nano catalytic material to tetracycline in water are 93.2%, 53.2%, 48.3%, 39.5% and 43.8%, respectively, so that the absorbance of the tetracycline solution is reduced the most when the doping ratio of chromium chloride is 3%, and the degradation effect is the best.
Comparative example 12
The preparation method of this example is the same as that of example 1, except that the amount of pure TiOx cluster material used in the preparation process is different, the amount of pure TiOx cluster in this example is changed to 0.1g, and the rest conditions are unchanged. The absorbance of the tetracycline solution before and after photocatalysis was recorded and the degradation rate was calculated as shown in table one. The degradation rate was 45.3%.
Comparative example 13
The preparation method of this example is the same as that of example 1, except that the amount of pure TiOx cluster material used in the preparation process is different, the amount of pure TiOx cluster in this example is changed to 0.3g, and the rest conditions are unchanged. The absorbance of the tetracycline solution before and after photocatalysis was recorded and the degradation rate was calculated as shown in table one. The degradation rate was 46.2%.
It can be seen from the above examples and table one that, by changing the amount of the pure titanium oxygen cluster material, the degradation rates of the finally prepared chromium-doped titanium oxygen cluster nano catalytic material to tetracycline in water are 93.2%, 45.3% and 46.2% respectively, so that the absorbance of the tetracycline solution is reduced the most when the amount of the pure titanium oxygen cluster material is 0.2g, and the degradation effect is the best. The dosage of the pure titanium oxygen cluster material is 0.2g, when the doping amount of the chromium salt is 3%, the specific surface area is larger than that of other materials with doping amounts, the pore distribution is uniform, the porosity is high, and the photocatalysis effect is best.
Comparative example 14
In the embodiment, the chromium salt is only used for degrading tetracycline organic pollutants in the water body, the absorbance of the tetracycline solution before and after photocatalysis is recorded, and the degradation rate is calculated and shown in table one. The degradation rate of the nickel salt was 20.38%.
TABLE 1 Effect of different conditions on the degradation Rate of Tetracycline in Water
While embodiments of the present invention have been described, the present invention is not limited to the above-described embodiments, which are intended to be illustrative rather than limiting, and it will be within the purview of one skilled in the art to make and use the teachings of the present invention without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. The preparation method of the chromium-doped titanium-oxygen cluster nano catalytic material is characterized by comprising the steps of preparing titanium-oxygen cluster powder by taking pivalic acid as a precursor; and then adding titanium oxide cluster powder and chromium chloride into tetrabutyl titanate for ultrasonic dissolution, and reacting under the boiling condition to obtain the chromium-doped titanium oxide cluster nano catalytic material, wherein the mass ratio of the titanium oxide cluster powder to the chromium chloride is (6-8): 1.
2. The method for preparing chromium-doped titanium-oxygen cluster nano-catalytic material according to claim 1, characterized by comprising the following steps:
the method comprises the following steps: mixing and heating pivalic acid, tetrabutyl titanate and ethylene glycol, and reacting to obtain titanium oxide cluster powder;
step two: adding titanium oxide cluster powder and chromium chloride into tetrabutyl titanate for ultrasonic dissolution, and reacting under the boiling condition to obtain the chromium-doped titanium oxide cluster nano catalytic material.
3. The method for preparing chromium-doped titanium-oxygen cluster nano-catalytic material according to claim 2, wherein the molar ratio of the pivalic acid to the tetrabutyl titanate in the step one is 1.8-2.2: 1.
4. The preparation method of the chromium-doped titanium-oxygen cluster nano-catalytic material as claimed in claim 2, wherein the reaction temperature in the first step is 90-100 ℃ and the reaction time is 20-25 h.
5. The preparation method of chromium-doped titanium-oxygen cluster nano-catalytic material as claimed in claim 2, which comprises:
the method comprises the following steps: mixing and heating pivalic acid, tetrabutyl titanate and ethylene glycol, and reacting to obtain titanium oxide cluster powder, wherein the molar ratio of the pivalic acid to the tetrabutyl titanate is 2.1:1, the reaction temperature is 98 ℃, and the reaction time is 24 hours;
step two: adding titanium oxide cluster powder and chromium chloride into tetrabutyl titanate for ultrasonic dissolution, reacting for 60min under the boiling condition, and drying to obtain the chromium-doped titanium oxide cluster nano catalytic material, wherein the mass ratio of the titanium oxide cluster powder to the chromium chloride is 20: 3.
6. The preparation method of chromium-doped titanium-oxygen cluster nano-catalytic material as claimed in claim 2, which comprises:
the method comprises the following steps: mixing and heating 10.5mmol of pivalic acid, 5mmol of tetrabutyl titanate and 20mL of ethylene glycol, reacting at 98 ℃ for 24 hours, and drying to obtain titanium oxide cluster powder;
step two: adding 0.2g of titanium oxygen cluster powder and 0.03g of chromium chloride into tetrabutyl titanate for ultrasonic dissolution, reacting for 60min under the boiling condition, and drying at 70 ℃ to obtain the chromium-doped titanium oxygen cluster nano catalytic material.
7. The chromium-doped titanium-oxygen cluster nano catalytic material is characterized in that the chromium-doped titanium-oxygen cluster nano catalytic material is prepared by the preparation method of the chromium-doped titanium-oxygen cluster nano catalytic material as claimed in any one of claims 1 to 6.
8. The chromium-doped titanium-oxygen cluster nano-catalysis material prepared by the preparation method of the chromium-doped titanium-oxygen cluster nano-catalysis material according to any one of claims 1 to 6 or the application of the chromium-doped titanium-oxygen cluster nano-catalysis material according to claim 7 in tetracycline degradation, wherein the degradation rate of the chromium-doped titanium-oxygen cluster nano-catalysis material to tetracycline is 90-95%.
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