CN111905713A - Vanadium-doped TiO2Preparation method of/reduced graphene composite nano photocatalyst - Google Patents
Vanadium-doped TiO2Preparation method of/reduced graphene composite nano photocatalyst Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 24
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
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- 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
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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Abstract
The invention discloses vanadium-doped TiO2The preparation method of the/reduced graphene composite nano photocatalyst comprises the following steps: (1) preparing ethanol containing graphene oxide by an ultrasonic dissolution method; (2) preparing composite sol by using a sol-gel method by taking a vanadium compound and a titanium precursor as raw materials and ethanol containing graphene oxide as a solvent; (3) aging the composite sol, drying, and sintering at high temperature to obtain intermediate vanadium-doped TiO2Graphene oxide composite nanopowder; (4) doping the intermediate vanadium with TiO2Dissolving graphene oxide composite nano powder in water, and reducing by using hydrazine under stirring condition to prepare vanadium-doped TiO2Reduced graphene composite nano-photocatalyst. The method has the advantages of few steps, simplicity, convenience and feasibility, and is easy to realize large-scale production.
Description
Technical Field
The invention relates to the technical field of photocatalyst production, in particular to vanadium-doped TiO2A preparation method of a reduced graphene composite nano photocatalyst.
Background
With TiO2The typical photocatalyst has the characteristics of high chemical stability, safety and no toxicity, can effectively catalyze and decompose harmful organic and inorganic substances after photocatalysis, and can also eliminate germs, so the photocatalyst is widely applied to the fields of air and water purification, disinfection, food, daily necessities and the like. In the field of purification, researches show that the photocatalyst can degrade indoor harmful volatile organic matters such as formaldehyde, dichlorobenzene, toluene, xylene and TVOC into nontoxic and harmless micromolecule water and CO2And simultaneously, the toxin released by the bacterial fungi can be decomposed and harmlessly treated. In addition, the photocatalyst stock solution has the characteristic of quick drying, can be quickly dried after being coated on the surface of a base material and becomes a water-insoluble substance, and can reach the hardness equivalent to 4H of a pencil within 10 days. Under the condition of no serious environmental pollution, the photocatalyst itself will not change and lose as long as it is not worn and peeled off. Can continuously purify pollutants under the irradiation of light, and has the advantages of lasting time and continuous action. The surface processed by the photocatalyst is excited after being irradiated by ultraviolet rays, and can decompose the contacted organic matters, thereby not only playing a role in sterilization, but also decomposing harmful substances into harmless micromolecular substances. Meanwhile, due to the super-hydrophilic characteristic shown under the illumination condition, when dust falls on the photocatalyst coating, the purpose of cleaning the surface can be achieved only by cleaning with clean water.
However, in practice TiO is used2There are a number of use limitations. First, photoelectron hole pairs are easily recombined because they play a very important role in catalytic reactions, and contaminant degradation, photocatalytic disinfection, etc. all result from the generation of photoelectron hole pairs. However, the excited states of the photogenerated electrons and holes are unstable and can easily recombine. The high recombination rate of photogenerated carriers generated by photoexcitation is one of the main causes of the low quantum efficiency. Generally, the quantum yield of titanium dioxide is low, limiting its effectiveness for use. Second, conventional TiO2The solar energy utilization rate of (2) is low, it can only absorb ultraviolet ray in sunlight, and the ultraviolet ray in sunlight only accounts for 3-7%, so that in the course of practical use it can be matched with UV lamp, etc. to make hand light implement illuminationThe section is supplementary, and its energy consumption is high and the operation is inconvenient, and the restriction is great.
Research shows that TiO2Doping transition metal vanadium to improve TiO2The catalytic activity of (3). By simple use of transition metal on TiO2The visible light photocatalytic efficiency is improved by about 1.5 to 2 times before and after modification. In order to improve the efficiency to a greater extent, the vanadium-doped TiO is considered to be2Loaded on a graphene carrier and formed into a composite material with a nano-particle size scale. Graphene has a unique large pi-bond structure, is a material which is found at present and has the fastest electron transmission speed at room temperature, and the ultrahigh electron mobility of the graphene can play a role in promoting the transfer of electrons in catalytic reaction. Secondly, the doped graphene can be used as a photosensitizer of a semiconductor, so that the Fermi level of the composite material shifts towards a more positive direction, and the absorption performance of the material on visible light is further enhanced. Meanwhile, the formation of the graphene/semiconductor interface heterojunction can promote the separation of photo-generated electron hole pairs and improve the photocatalytic efficiency.
CN 110387737A discloses a preparation method of a graphene-titanium dioxide-bismuth vanadate photocatalytic functional fabric, which comprises the steps of dipping a fabric treated by plasma in a graphene oxide dispersion solution, dipping the fabric in a titanium dioxide hydrosol after microwave treatment, finally dipping the fabric in a bismuth vanadate sol, and carrying out microwave treatment, water washing and drying to obtain a target product. CN 105195131A discloses a preparation method of a graphene quantum dot/vanadium-doped mesoporous titanium dioxide composite photocatalyst, which is characterized in that vanadium-doped mesoporous titanium dioxide microspheres are firstly prepared and then mixed with a graphene quantum dot dispersion liquid to form a final target product. The method disclosed in the above patent has two disadvantages: firstly, the catalyst material is prepared by adopting a multi-step simple mixing method, self-stacking is easily formed between graphene layers, and TiO is easily formed2The particles are easy to form agglomeration, and the composite is low in mixing and dispersing uniformity, so that the contact area between the two materials is small, and the photocatalytic activity of the composite material is influenced to a great extent. Secondly, graphene oxide is adopted as TiO2The vector of (1). The graphene oxide is introduced into a carbon plane under the oxidation action of an acidic oxidantDue to the existence of a plurality of oxygen-containing groups on a carbon-carbon network, the graphene containing a large number of oxygen-containing functional groups has good dispersing performance in water or other organic solvents (such as PC, NMP, DMF and the like), and can be more easily used as a composite carrier. However, although the dispersibility of the material is improved by introducing the oxygen-containing functional group, the large pi conjugated structure of the graphene is greatly destroyed, so that the performances such as conductivity and the like of the graphene are remarkably reduced, and the effect of the graphene as an electron transmission lead cannot be well shown.
Disclosure of Invention
The invention aims to provide vanadium-doped TiO2The preparation method of the/reduced graphene composite nano photocatalyst has the advantages of few steps, simplicity, convenience and easiness in implementation and is easy to realize large-scale production.
The technical scheme adopted by the invention for solving the technical problems is as follows:
vanadium-doped TiO2The preparation method of the/reduced graphene composite nano photocatalyst comprises the following steps:
(1) preparing ethanol containing graphene oxide by an ultrasonic dissolution method;
(2) preparing composite sol by using a sol-gel method by taking a vanadium compound and a titanium precursor as raw materials and ethanol containing graphene oxide as a solvent;
(3) aging the composite sol, drying, and sintering at high temperature to obtain intermediate vanadium-doped TiO2Graphene oxide composite nanopowder;
(4) doping the intermediate vanadium with TiO2Dissolving graphene oxide composite nano powder in water, and reducing by using hydrazine under stirring condition to prepare vanadium-doped TiO2Reduced graphene composite nano-photocatalyst.
According to the method, vanadium, titanium and graphene are compounded in situ by adopting a sol-gel method, a titanium source and graphite oxide form a chemical bond during growth, the chemical bond is difficult to damage in a reduction process, and TiO in the compound prepared by the method2Is connected with the reduced graphene by chemical bonds, and the combination of the two is tight and the distribution is uniform, so that the titanium oxide particles are not easy to follow due to external forces such as stirring and the like in the photocatalysis processThe graphene falls off, so that the electron transfer between the titanium oxide and the graphene is more effective, and the photocatalytic activity of the titanium oxide and the graphene is improved. Meanwhile, in order to recover the electron transport performance of the graphene to the maximum extent, the reducing agent is used for reducing the graphene oxide, so that the number of oxygen-containing functional groups is greatly reduced, and the photocatalyst taking the reduced graphene as a carrier is obtained.
Preferably, the step (1) is specifically: dispersing graphene oxide powder in absolute ethyl alcohol by ultrasonic treatment to prepare the ethyl alcohol containing graphene oxide with the concentration of 0.01-0.1 mg/ml.
Preferably, a hydrolysis inhibitor is added in the process of preparing the composite sol by adopting a sol-gel method, and the hydrolysis inhibitor is one or a mixture of two of nitric acid, hydrochloric acid, acetic acid and sulfuric acid. In the preparation process, the inhibitor for inhibiting the rapid hydrolysis of the titanium precursor is added, so that the phenomenon that the performance of the composite material is influenced by the fact that gel appears immediately after the two solutions are mixed is prevented.
Preferably, the hydrolysis inhibitor is concentrated nitric acid with a concentration of 60% -65%.
Preferably, the vanadium compound is ammonium metavanadate, and the titanium precursor is one of titanium tetrachloride, tetrabutyl titanate and titanium isopropoxide.
Preferably, the sol-gel method is specifically as follows:
adding 6-8ml of hydrolysis inhibitor and 8-12ml of deionized water into 100ml of absolute ethyl alcohol, adding 0.15-0.2g of vanadium compound, and dissolving by ultrasonic to obtain a solution A;
dissolving a titanium precursor with 200mL of ethanol containing graphene oxide mutually to obtain a solution B;
and (3) placing the solution B in a constant-temperature stirrer, slowly dripping the solution A into the solution B (the dripping speed is 1-5 mL/min) at the temperature of 30-35 ℃ under rapid stirring (1500-2000 rpm), continuing stirring for 30-60 minutes after finishing dripping, adding a pH regulator, regulating the pH of the system to 2.5-3.5, and continuing stirring for 5-8 minutes to obtain the gel.
The pH regulator is ammonium carbonate.
Preferably, the volume ratio of the titanium precursor to 200mL of the graphene oxide-containing ethanol is 1: 2.9-3.2.
Preferably, the aging time of the composite sol is 20 to 24 hours.
Preferably, the temperature of the high-temperature sintering is 400-500 ℃, and the sintering time is 2-3 h.
Preferably, hydrazine is hydrazine hydrate with the concentration of 80-85%, the reaction temperature of hydrazine reduction is 90-95 ℃, and the reaction time is 10-12 hours.
The invention has the beneficial effects that: the preparation method has the advantages of few preparation steps, simplicity, convenience and feasibility, and is easy to realize large-scale production. The prepared composite photocatalytic material has the advantages of nano-scale particle size, higher photocatalytic activity, better dispersion in a liquid phase and improved applicability in the fields of air purification and water purification. Meanwhile, vanadium doping modification and graphene loading can enable the Fermi level of the composite material to shift towards a more correct direction, so that the absorption performance of the material on visible light is enhanced, and the utilization rate of the light energy is improved. The formation of the graphene/semiconductor interface heterojunction can promote the separation of the photo-generated electron hole pairs, and the photocatalysis efficiency of the photo-generated electron hole pairs is ensured to a greater extent. The technical scheme of the invention has positive significance for solving the air and water pollution and realizing the sustainable development of natural resources.
Drawings
Fig. 1 is an SEM image of the composite nanophotocatalyst prepared according to the present invention, from which it is clearly seen that vanadium-doped titanium dioxide is uniformly attached to a graphene carrier and the particle size is in a nano-scale.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
putting 0.01g of graphene oxide powder into a beaker, adding 500ml of absolute ethyl alcohol, dispersing the graphene oxide powder into the ethyl alcohol by using ultrasound, fully mixing and preparing the ethyl alcohol solvent containing the graphene oxide with the concentration of 0.02 mg/ml.
② taking another beaker, adding 100ml of absolute ethyl alcohol, then adding 6ml of hydrolysis inhibitor and 8ml of deionized water, adding 0.05g of ammonium metavanadate, and carrying out ultrasonic dissolution on the mixture to obtain a solution A. Wherein the hydrolysis inhibitor is 60% concentrated nitric acid.
And thirdly, taking 200mL of ethanol containing graphene oxide prepared in the step I, adding 67mL of tetrabutyl titanate, and fully dissolving the tetrabutyl titanate with the ethanol to obtain a solution B.
Putting the solution B into a constant-temperature stirrer, slowly dripping the solution A into the solution B under the condition of rapid stirring at 30 ℃ (1800 rpm), wherein the dripping speed is about 4ml/min, continuously stirring for 0.5h after dripping is finished, adding ammonium carbonate, adjusting the pH value of the system to 3.0, and continuously stirring for 5min to obtain light yellow, uniform and transparent gel.
Fifthly, placing the obtained gel in a beaker for aging for 20 hours until the gel loses fluidity, drying the gel in a drying oven at 150 ℃, grinding the dried solid powder, sintering the powder in a muffle furnace at the high temperature of 400 ℃ for 3 hours, and grinding the powder to obtain the in-situ composite vanadium-doped TiO2Graphene oxide composite nanopowder.
Sixthly, doping vanadium with TiO2The graphene oxide composite nano powder is dissolved in 300ml of deionized water, is assisted by ultrasonic waves and is fully dispersed, 10ml of reducing agent, namely 80% hydrazine hydrate is added, and the mixture is stirred and reacts for 10 hours at the temperature of 90 ℃. Filtering and drying the mixed solution after reaction to obtain the in-situ composite vanadium-doped TiO2Reduced graphene composite nanopowder.
Evaluation of photocatalytic activity:
simple mixed vanadium doped TiO preparation with reference to the same process conditions as in example 12A graphene catalyst.
Adding 100ml of absolute ethyl alcohol into a beaker, then adding 6ml of hydrolysis inhibitor and 8ml of deionized water, adding 0.01mol/L of ammonium metavanadate, and carrying out ultrasonic dissolution on the mixture to obtain a solution A. Wherein the hydrolysis inhibitor is 60% concentrated nitric acid.
② taking 200mL of absolute ethyl alcohol, adding 67mL of tetrabutyl titanate to be fully dissolved with the absolute ethyl alcohol to obtain solution B.
Thirdly, placing the solution B in a constant temperature stirrer, slowly dripping the solution A into the solution B under the condition of rapid stirring at 30 ℃ (1800 rpm), wherein the dripping speed is about 4ml/min, continuously stirring for 0.5h after dripping is finished, adjusting the pH value of the system to 3.0, and continuously stirring for 5min to obtain the gel.
Putting the obtained gel in a beaker for aging for 20 hours until the gel loses fluidity, drying the gel in a drying oven at 150 ℃, grinding the dried solid powder, sintering the powder in a muffle furnace at the high temperature of 400 ℃ for 2 hours, and grinding the powder to obtain vanadium-doped TiO2And (4) nano powder.
Doping TiO with vanadium2Dissolving the nano powder into 200ml of graphene oxide aqueous solution with the concentration of 0.02mg/ml, using ultrasonic to assist dissolution and fully disperse, taking 100ml of mixed solution, carrying out suction filtration and drying to obtain simply mixed vanadium-doped TiO2Graphene oxide catalyst powder.
A further 100ml of the mixture was added with hydrazine reducing agent and reacted at 90 ℃ for 10 hours with stirring. Filtering and drying the mixed solution after reaction to obtain the simply mixed vanadium-doped TiO2Reduced graphene composite nanopowder.
Four groups of 250ml of freshly prepared methylene blue solutions with the concentration of 10mg/L are respectively placed in a suspension type photocatalytic reactor, 100mg of the photocatalyst prepared by the method is respectively added into the reaction solution under magnetic stirring, and a comparative experiment is carried out. After being stirred and dispersed, the ultraviolet lamp is turned on (the illumination intensity at the surface of the sample is 1.5 mW/cm)2) And reacting for 120 min. Centrifuging 2ml of solution at 3000rpm for 5min, respectively measuring the absorbance value of the supernatant at 664nm on an ultraviolet visible spectrophotometer by using a 1cm cuvette and adjusting to zero with water, and obtaining the concentration of the photocatalytic degradation methylene blue according to a standard working curve of the methylene blue. Repeating the above experiment, replacing two groups of ultraviolet lamps with two groups of visible light lamps (300W xenon lamp, dominant wavelength 400-760 nm, and using cutoff filter with wavelength above 420nm to filter out ultraviolet ray below 420 nm), measuring the degradation concentration of methylene blue, and comparing the degradation concentration before and after reactionThe photocatalytic degradation rate was obtained from the concentration of (A) and the results are shown in the table:
| catalyst and process for preparing same | Degradation rate of methylene blue under ultraviolet light | Degradation rate of methylene blue under visible light |
| In-situ composite vanadium doped TiO2Graphene oxide | 91.8% | 49.6% |
| In-situ composite vanadium doped TiO2Reduced graphene | 97.9% | 63.3% |
| Simple mixed vanadium doped TiO2Graphene oxide | 85.2% | 34.9% |
| Simple mixed vanadium doped TiO2Reduced graphene | 81.5% | 21.7% |
Experimental data show that the photocatalytic activity of the catalyst prepared by the in-situ composite method is higher than that of the catalyst prepared by the simple mixing method, and the performance of the reduced graphene serving as a carrier doped with titanium oxide is better than that of the graphene oxide. But for simple mixed catalysts, reduced graphene doesThe performance of the support is rather inferior to that of graphene oxide, because of the simple mixing of TiO in the process2The graphene oxide is not grown on active sites of the graphene oxide, no bonding effect exists, and the tightness degree between the graphene oxide and the graphene oxide is low. After the graphene oxide is reduced, the number of oxygen-containing functional groups of the graphene oxide is greatly reduced, the dispersion performance of the graphene oxide is sharply reduced compared with that of the graphene oxide, and the graphene oxide is locally and rapidly agglomerated and precipitated, so that the catalytic performance of the graphene oxide is greatly reduced.
Example 2:
putting 0.08g of graphene oxide powder into a beaker, adding 500ml of absolute ethyl alcohol, dispersing the graphene oxide powder into the ethyl alcohol by using ultrasound, fully mixing and preparing the ethyl alcohol containing the graphene oxide with the concentration of 0.16 mg/ml.
② taking another beaker, adding 100ml of absolute ethyl alcohol, then adding 8ml of hydrolysis inhibitor and 8ml of deionized water, adding 0.2g of ammonium metavanadate, and carrying out ultrasonic dissolution on the mixture to obtain a solution A. Wherein the hydrolysis inhibitor is 65% concentrated nitric acid.
And thirdly, taking 200mL of ethanol containing graphene oxide prepared in the step I, adding 67mL of tetrabutyl titanate, and fully dissolving the tetrabutyl titanate with the ethanol to obtain a solution B.
Putting the solution B into a constant-temperature stirrer, slowly dripping the solution A into the solution B under the condition of rapid stirring at the temperature of 30 ℃ (2000 rpm), wherein the dripping speed is about 2ml/min, continuously stirring for 1h after dripping is finished, adding ammonium carbonate, adjusting the pH value of the system to 3.2, and continuously stirring for 8min to obtain light yellow, uniform and transparent gel.
Fifthly, placing the obtained gel in a beaker for aging for 24 hours until the gel loses fluidity, drying the gel in a drying oven at 150 ℃, grinding the dried solid powder, sintering the powder in a muffle furnace at a high temperature of 500 ℃ for 2 hours, and grinding the powder to obtain an intermediate vanadium-doped TiO2Graphene oxide composite nanopowder.
Sixthly, dissolving the intermediate powder into 300ml of deionized water, using ultrasonic to assist dissolution and fully dispersing, then adding 10ml of hydrazine (80% hydrazine hydrate), and stirring and reacting for 10 hours at 90 ℃. Filtering and drying the mixed solution after reaction to obtain vanadium-doped TiO2Reduced graphene composite nano photocatalystAnd (3) powder.
The catalytic activity of the catalyst was characterized by referring to the method in example 1, which showed that the degradation rate of methylene blue under ultraviolet light was 96.9% and the degradation rate of methylene blue under visible light was 57.8%.
In addition to the above examples, the invention can be adapted within the scope of the following claims with reference to the methods of the above examples:
vanadium-doped TiO2The preparation method of the/reduced graphene composite nano photocatalyst comprises the following steps:
(1) dispersing graphene oxide powder in absolute ethyl alcohol by ultrasonic treatment to prepare 0.01-0.1mg/ml graphene oxide-containing ethyl alcohol;
(2) preparing composite sol by adopting a sol-gel method:
adding 6-8ml of hydrolysis inhibitor and 8-12ml of deionized water into 100ml of absolute ethyl alcohol, adding 0.15-0.2g of vanadium compound, and dissolving by ultrasonic to obtain a solution A;
dissolving a titanium precursor with 200mL of ethanol containing graphene oxide mutually to obtain a solution B;
placing the solution B in a constant-temperature stirrer, slowly dropwise adding the solution A into the solution B under rapid stirring at the temperature of 30-35 ℃, continuously stirring for 30-60 minutes after dropwise adding is finished, adding a pH regulator, regulating the pH of the system to 2.5-3.5, and continuously stirring for 5-8 minutes to obtain gel; adding a hydrolysis inhibitor in the process of preparing the composite sol by adopting a sol-gel method, wherein the hydrolysis inhibitor is one or a mixture of two of nitric acid, hydrochloric acid, acetic acid and sulfuric acid; the hydrolysis inhibitor is preferably concentrated nitric acid with the concentration of 60-65%; the vanadium compound is ammonium metavanadate, and the titanium precursor is one of titanium tetrachloride, tetrabutyl titanate and titanium isopropoxide;
(3) after the composite sol is aged (the aging time is 20-24 hours), drying and high-temperature sintering are carried out, the temperature of the high-temperature sintering is 400-500 ℃, and the sintering time is 2-3 hours, thus obtaining the intermediate vanadium-doped TiO2Graphene oxide composite nanopowder;
(4) doping the intermediate vanadium with TiO2The graphene oxide composite nano powder is dissolved in waterAnd preparing vanadium doped TiO by hydrazine reduction under stirring condition2Reducing graphene composite nano photocatalyst, wherein hydrazine reduced by hydrazine is hydrazine hydrate with the concentration of 80-85%, the reaction temperature of hydrazine reduction is 90-95 ℃, and the reaction time is 10-12 hours.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. Vanadium-doped TiO2The preparation method of the/reduced graphene composite nano photocatalyst is characterized by comprising the following steps:
(1) preparing ethanol containing graphene oxide by an ultrasonic dissolution method;
(2) preparing composite sol by using a sol-gel method by taking a vanadium compound and a titanium precursor as raw materials and ethanol containing graphene oxide as a solvent;
(3) aging the composite sol, drying, and sintering at high temperature to obtain intermediate vanadium-doped TiO2Graphene oxide composite nanopowder;
(4) doping the intermediate vanadium with TiO2Dissolving graphene oxide composite nano powder in water, and reducing by using hydrazine under stirring condition to prepare vanadium-doped TiO2Reduced graphene composite nano-photocatalyst.
2. The preparation method according to claim 1, wherein the step (1) is specifically: dispersing graphene oxide powder in absolute ethyl alcohol by ultrasonic treatment to prepare the ethyl alcohol containing graphene oxide with the concentration of 0.01-0.1 mg/ml.
3. The preparation method according to claim 1, wherein a hydrolysis inhibitor is added in the process of preparing the composite sol by adopting a sol-gel method, and the hydrolysis inhibitor is one or a mixture of two of nitric acid, hydrochloric acid, acetic acid and sulfuric acid.
4. The method of claim 3, wherein the hydrolysis inhibitor is concentrated nitric acid having a concentration of 60% to 65%.
5. The method according to claim 1, wherein the vanadium compound is ammonium metavanadate, and the titanium precursor is one of titanium tetrachloride, tetrabutyl titanate, and titanium isopropoxide.
6. The preparation method according to claim 1, wherein the sol-gel method specifically comprises:
adding 6-8ml of hydrolysis inhibitor and 8-12ml of deionized water into 100ml of absolute ethyl alcohol, adding 0.15-0.2g of vanadium compound, and dissolving by ultrasonic to obtain a solution A;
dissolving a titanium precursor with 200mL of ethanol containing graphene oxide mutually to obtain a solution B;
and (3) placing the solution B in a constant-temperature stirrer, slowly dripping the solution A into the solution B under the condition of rapid stirring at the temperature of 30-35 ℃, continuously stirring for 30-60 minutes after dripping is finished, adding a pH regulator, regulating the pH of the system to 2.5-3.5, and continuously stirring for 5-8 minutes to obtain the gel.
7. The method according to claim 1, wherein the volume ratio of the titanium precursor to 200mL of the graphene oxide-containing ethanol is 1: 2.9-3.2.
8. The method according to claim 1, wherein the aging time of the composite sol is 20 to 24 hours.
9. The method as claimed in claim 1, wherein the temperature of the high temperature sintering is 400-500 ℃ and the sintering time is 2-3 h.
10. The method according to claim 1, wherein the hydrazine is hydrazine hydrate at a concentration of 80 to 85%, and the reaction temperature of the hydrazine reduction is 90 to 95 ℃ and the reaction time is 10 to 12 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113106470A (en) * | 2021-04-06 | 2021-07-13 | 湖州宏兆化工贸易有限公司 | Vanadium-doped titanium dioxide/graphene electrocatalyst suitable for electrochemical nitrogen reduction and preparation method thereof |
| CN113262772A (en) * | 2021-05-13 | 2021-08-17 | 岭南师范学院 | Preparation method of high photocatalytic efficiency nano composite material |
| CN113385164A (en) * | 2021-07-02 | 2021-09-14 | 青岛瑞利特新材料科技有限公司 | Formaldehyde-removing graphene nano composite gel and preparation process thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357329A (en) * | 2008-08-14 | 2009-02-04 | 上海交通大学 | Preparation method of vanadium-doped nano titanic oxide catalyst |
| CN105195131A (en) * | 2015-10-15 | 2015-12-30 | 南昌航空大学 | Preparation method of graphene quantum dot/vanadium-doped mesoporous titanium dioxide composite photocatalyst |
| CN106492776A (en) * | 2016-11-02 | 2017-03-15 | 吉林大学 | One kind prepares TiO2The method of graphene composite material |
| CN107159181A (en) * | 2017-06-23 | 2017-09-15 | 攀枝花学院 | Zinc doping TiO2/ graphene composite material and preparation method thereof |
| CN109290064A (en) * | 2018-09-20 | 2019-02-01 | 东北大学秦皇岛分校 | A kind of preparation method of the compound self-degradation flocculant of graphene/titanium dioxide/polyacrylamide |
| CN109621987A (en) * | 2018-12-18 | 2019-04-16 | 广西金茂钛业有限公司 | A kind of preparation method of the composite material containing titanium dioxide |
-
2020
- 2020-09-09 CN CN202010939572.1A patent/CN111905713A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357329A (en) * | 2008-08-14 | 2009-02-04 | 上海交通大学 | Preparation method of vanadium-doped nano titanic oxide catalyst |
| CN105195131A (en) * | 2015-10-15 | 2015-12-30 | 南昌航空大学 | Preparation method of graphene quantum dot/vanadium-doped mesoporous titanium dioxide composite photocatalyst |
| CN106492776A (en) * | 2016-11-02 | 2017-03-15 | 吉林大学 | One kind prepares TiO2The method of graphene composite material |
| CN107159181A (en) * | 2017-06-23 | 2017-09-15 | 攀枝花学院 | Zinc doping TiO2/ graphene composite material and preparation method thereof |
| CN109290064A (en) * | 2018-09-20 | 2019-02-01 | 东北大学秦皇岛分校 | A kind of preparation method of the compound self-degradation flocculant of graphene/titanium dioxide/polyacrylamide |
| CN109621987A (en) * | 2018-12-18 | 2019-04-16 | 广西金茂钛业有限公司 | A kind of preparation method of the composite material containing titanium dioxide |
Non-Patent Citations (5)
| Title |
|---|
| ABIYE KEBEDE AGEGNEHU ET AL.: "Visible light responsive noble metal-free nanocomposite of V-doped TiO2 nanorod with highly reduced graphene oxide for enhanced solar H2 production", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| 孙晓君等: "掺V的TiO2纳米粒子的制备和表征及其光催化性能" * |
| 孙晓君等: "掺V的TiO2纳米粒子的制备和表征及其光催化性能", 《硅酸盐学报》 * |
| 耿静漪等: "TiO2-石墨烯光催化剂：制备及引入石墨烯的方法对光催化性能的影响" * |
| 耿静漪等: "TiO2-石墨烯光催化剂：制备及引入石墨烯的方法对光催化性能的影响", 《无机化学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113106470A (en) * | 2021-04-06 | 2021-07-13 | 湖州宏兆化工贸易有限公司 | Vanadium-doped titanium dioxide/graphene electrocatalyst suitable for electrochemical nitrogen reduction and preparation method thereof |
| CN113106470B (en) * | 2021-04-06 | 2024-05-03 | 宁波烯固数造电池科技有限公司 | Vanadium-doped titanium dioxide/graphene electrocatalyst suitable for electrochemical nitrogen reduction and preparation method thereof |
| CN113262772A (en) * | 2021-05-13 | 2021-08-17 | 岭南师范学院 | Preparation method of high photocatalytic efficiency nano composite material |
| CN113385164A (en) * | 2021-07-02 | 2021-09-14 | 青岛瑞利特新材料科技有限公司 | Formaldehyde-removing graphene nano composite gel and preparation process thereof |
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