CN108751168B - Preparation method of anatase type flower-like rhombic titanium dioxide/graphene composite material for photo-generated cathode corrosion prevention - Google Patents
Preparation method of anatase type flower-like rhombic titanium dioxide/graphene composite material for photo-generated cathode corrosion prevention Download PDFInfo
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- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
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Abstract
The invention discloses a preparation method of an anatase type flower-like rhombic titanium dioxide/graphene composite material for photo-generated cathode corrosion prevention, and belongs to the field of preparation of anticorrosive materials. According to the invention, firstly, graphene oxide dispersion liquid is added into a titanium tetrachloride solution, titanium tetrachloride is taken as a titanium source, anatase type titanium dioxide nanocrystals grow on graphene through processes of heating, calcining and the like, then a titanium dioxide seed crystal/graphene composite material is added into a titanium precursor solution, hydrothermal reaction is carried out, under the hydrothermal condition, the anatase type titanium dioxide rapidly grows due to the existence of the seed crystal, the flower-shaped shape of the titanium dioxide can be effectively promoted to be formed, and finally, the anatase type flower-shaped rhombic titanium dioxide/graphene photo-generated cathode protection material is obtained.
Description
Technical Field
The invention belongs to the field of preparation of anticorrosive materials, and particularly relates to a preparation method of an anatase type flower-like rhombic titanium dioxide/graphene composite material for photo-generated cathode corrosion prevention.
Background
The metal material, especially the steel structure, is often corroded in the using process, so that the environment pollution and the resource waste are caused, the work and the life of people are seriously harmed, and the huge loss is caused to the national economy. Therefore, metal protection is important. At present, the metal protection methods mainly include a sacrificial anode method, an impressed current method, a photocathode protection method and the like. The photoproduction cathodic protection is a novel anticorrosion technology developed in recent years, and has the advantages of no sacrifice of an anode, no consumption of electric energy, low price, environmental friendliness and the like.
Among a plurality of photo-generated cathode protection materials, titanium dioxide has the characteristics of no toxicity, good stability and the like, so that titanium dioxide is a hotspot of research in the photoelectric field all the time; in recent years, graphene occupies a seat in the field of photo-generated cathode protection due to its extremely high electrical conductivity. The titanium dioxide/graphene composite material combines the advantages of titanium dioxide and graphene, and has excellent photoproduction cathodic protection performance. The basic principle is as follows: under illumination, electrons on titanium dioxide in the composite material can be excited, the titanium dioxide is excited to generate photo-generated electrons to jump from a valence band to a conduction band, and the photo-generated electrons are used as a bridge for electron transmission due to the good conductivity of graphene, so that a large number of electrons are rapidly transferred from the conduction band of the titanium dioxide to a stainless steel electrode, the electron density on the stainless steel electrode is increased, the potential is reduced to be lower than the self-corrosion potential, the corrosion of metal is inhibited, and the stainless steel is effectively protected. Chinese patent (application No. 201510153765.3) provides a method for preparing rutile type flower-like titanium dioxide/graphene composite material, which shows superiority of flower-like titanium dioxide, i.e. larger specific surface area and electron transmission efficiency; however, rutile titanium dioxide is inferior in photoresponsive ability and photocathode protective properties to anatase titanium dioxide. However, the chinese patent (application No. 201410355247.5) provides a method for preparing an anatase titanium dioxide/graphene composite material, but it can only prepare a conventional anatase titanium dioxide crystal form, and the specific surface area of the crystal is not large enough. Therefore, the synthesis of the anatase flower-like diamond titanium dioxide/graphene composite material is particularly important.
Disclosure of Invention
Aiming at the problems in the background art, the invention provides an anatase type flower-shaped diamond titanium dioxide composite material for photoproduction cathodic protection, and the method has the advantages of simple preparation process and high photoproduction cathodic anticorrosion efficiency.
The invention provides a preparation method of the anatase type flower-like rhombic titanium dioxide/graphene composite material, which is characterized by comprising the following steps:
1. adding a titanium tetrachloride solution into the graphene oxide dispersion liquid, fully stirring, heating at 60-80 ℃ for 1-3 h, cooling to room temperature, washing to neutrality, drying the washed sample at 60-80 ℃, calcining at 400-600 ℃ in a nitrogen atmosphere for 1-3 h to obtain an anatase titanium dioxide seed crystal/graphene composite material,
wherein the mass concentration of graphene oxide in the graphene oxide dispersion liquid is 1-2 mg/mL, and the molar concentration of the titanium tetrachloride solution is 2.5-4.0 mol/L; the volume ratio of the graphene oxide dispersion liquid to the titanium tetrachloride solution is 45-70: 1-2.
2. Adding 1-2 mL of titanium tetrachloride solution into hydrochloric acid solution with the molar concentration of 4.0-6.0 mol/L to prepare titanium precursor solution, adding the anatase titanium dioxide seed crystal/graphene composite material obtained in the step 1, performing ultrasonic dispersion, uniformly mixing, transferring the mixed dispersion liquid into a hydrothermal kettle, transferring the hydrothermal kettle into a drying oven, performing hydrothermal reaction for 10-16 h at the temperature of 150-180 ℃, cooling to room temperature, collecting filter cakes, washing to be neutral, drying at the temperature of 60-80 ℃ to obtain the anatase flower-shaped diamond titanium dioxide/graphene photo-generated cathode protective material,
wherein the molar concentration of the titanium tetrachloride solution is 2.5-4.0 mol/L.
The invention has the following beneficial effects:
(1) according to the invention, titanium tetrachloride is taken as a titanium source to grow anatase titanium dioxide nanocrystals on graphite oxide to obtain an anatase titanium dioxide seed crystal/graphene composite material, and then a titanium precursor solution is supplemented again, so that the anatase titanium dioxide with a regular shape can be rapidly grown on the basis of the seed crystal as the titanium source under a hydrothermal condition;
(2) compared with the traditional hydrothermal method, the method has the advantages of simple process, less required operation steps, high efficiency, less variables to be controlled in the preparation process and capability of improving the product accuracy;
(3) due to the lamellar structure of the graphene in the composite material, the graphene can play a lamellar barrier role on metal, the protected metal is prevented from being directly contacted with a corrosive medium, and the high conductivity of the graphene can promote the separation of photo-generated electrons and holes.
Drawings
FIG. 1 is an X-ray diffraction pattern of the anatase flower-like rhombohedral titanium dioxide/graphene composite prepared in example 1;
FIG. 2 is a scanning electron microscope image of the anatase flower-like diamond titanium dioxide/graphene composite prepared in example 1;
FIG. 3 is a graph comparing photocurrent-time curves of anatase flower-like rhombic titania/graphene composite materials prepared in example 1 and comparative examples 1, 2 and 3.
Detailed Description
Example 1
1. Taking 60mL of 1mg/mL graphene oxide dispersion liquid, transferring the graphene oxide dispersion liquid into a three-neck flask, dropwise adding 1mL titanium tetrachloride solution, stirring for 2h at normal temperature, then transferring the graphene oxide dispersion liquid into an oven for heat preservation at 60 ℃ for 2h, cooling to room temperature, washing, drying the washed sample at 60 ℃, and calcining the dried sample at 500 ℃ in a nitrogen atmosphere for 2h to obtain an anatase type titanium dioxide seed crystal/graphene composite material;
2. mixing 1mL of titanium tetrachloride solution and 30mL of hydrochloric acid solution with the molar concentration of 5.0mol/L to prepare a titanium precursor aqueous solution, adding 100mg of anatase titanium dioxide nano seed crystal/graphene composite material, fully stirring, moving a hydrothermal kettle into an oven, carrying out hydrothermal reaction at 160 ℃ for 12h, cooling to room temperature, washing, and drying the washed sample at 60 ℃ to obtain the anatase flower-like rhombic titanium dioxide/graphene composite material.
Example 2
1. Taking 45mL of 1.5mg/mL graphene oxide dispersion liquid, transferring the dispersion liquid into a three-neck flask, dropwise adding 1mL titanium tetrachloride solution, stirring for 1h at normal temperature, then transferring the dispersion liquid into an oven at 60 ℃, preserving the heat for 1h, cooling to room temperature, washing, drying a washed sample at 60 ℃, and calcining the dried sample for 1h at 400 ℃ in a nitrogen atmosphere to obtain a titanium dioxide seed crystal/graphene composite material;
2. mixing 1mL of titanium tetrachloride solution and 30mL of hydrochloric acid solution with the molar concentration of 4.0mol/L to prepare a titanium precursor aqueous solution, adding 100mg of anatase titanium dioxide nano seed crystal/graphene composite material, fully stirring, moving a hydrothermal kettle into an oven, carrying out hydrothermal reaction at 150 ℃ for 10h, cooling to room temperature, washing, and drying the washed sample at 60 ℃ to obtain the anatase flower-like rhombic titanium dioxide/graphene composite material.
Example 3
1. Taking 50mL of 1.8mg/mL graphene oxide dispersion liquid, transferring the graphene oxide dispersion liquid into a three-neck flask, dropwise adding 1.5mL titanium tetrachloride solution, stirring for 1.5h at normal temperature, then transferring the graphene oxide dispersion liquid into an oven at 70 ℃, preserving heat for 1.5h, cooling to room temperature, washing, drying a washed sample at 70 ℃, calcining the dried sample for 2h at 500 ℃ in a nitrogen atmosphere, and thus obtaining a titanium dioxide seed crystal/graphene composite material;
2. mixing 1.5mL of titanium tetrachloride solution and 30mL of hydrochloric acid solution with the molar concentration of 5.0mol/L to prepare a titanium precursor aqueous solution, adding 100mg of anatase titanium dioxide nano crystal seed/graphene composite material, fully stirring, moving a hydrothermal kettle into an oven, carrying out hydrothermal reaction at 165 ℃ for 13h, cooling to room temperature, carrying out centrifugal washing, and drying the washed sample at 70 ℃ to obtain the anatase flower-like rhombic titanium dioxide/graphene composite material.
Example 4
1. Taking 60mL of 2mg/mL graphene oxide dispersion liquid, transferring the graphene oxide dispersion liquid into a three-neck flask, dropwise adding 2mL titanium tetrachloride solution, stirring for 2h at normal temperature, then transferring the graphene oxide dispersion liquid into an oven at 80 ℃, preserving the heat for 2h, cooling to room temperature, centrifuging, washing, drying a washed sample at 80 ℃, calcining the dried sample for 3h at 600 ℃ in a nitrogen atmosphere, and obtaining a titanium dioxide seed crystal/graphene composite material;
2. mixing 2mL of titanium tetrachloride solution and 30mL of hydrochloric acid solution with the molar concentration of 6.0mol/L to prepare a titanium precursor aqueous solution, adding 100mg of anatase titanium dioxide nano seed crystal/graphene composite material, fully stirring, moving a hydrothermal kettle into an oven, carrying out hydrothermal reaction at 180 ℃ for 16h, cooling to room temperature, washing, and drying the washed sample at 80 ℃ to obtain the anatase flower-like rhombic titanium dioxide/graphene composite material.
Comparative example 1
The method for preparing the anatase titanium dioxide/graphene composite material by the conventional method comprises the following steps:
preparing graphene oxide by using a Hummers method, dissolving the graphene oxide in ethanol, and performing ultrasonic treatment for 2 hours to obtain a graphene oxide solution with the concentration of 3 mg/mL; adding 3.74g of hexadecylamine into 240mL of absolute ethyl alcohol and 1.3mL of potassium chloride (0.1M) aqueous solution, performing ultrasonic treatment for 10min, placing the solution on a magnetic stirrer, stirring the solution at room temperature, slowly and dropwise adding 5.4mL of isopropyl titanate into the mixed solution, reacting for 18h, filtering the reaction solution, repeatedly washing the solution for 3 times by using ethyl alcohol, and drying the solution to obtain a titanium dioxide precursor; dissolving 1.6g of titanium dioxide precursor in 20mL of anhydrous ethanol and 10mL of water, dropwise adding 255 mu L of ammonia water solution, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 16h at 180 ℃, cooling, filtering and drying the sample to obtain titanium dioxide nanoparticles; mixing 0.3g of titanium dioxide nanoparticles into 20mL of graphene oxide solution (3mg/mL), performing ultrasonic treatment for 30min, adding ammonia water, placing the mixture into a hydrothermal reaction kettle, and reacting for 16h at 180 ℃; then cooling the reaction product to room temperature, filtering, absorbing the water on the surface of the sample by using filter paper, and carrying out freeze drying treatment; and finally, carrying out heat treatment on the dried sample in a tube furnace protected by argon atmosphere at 500 ℃ for 2h to obtain the anatase type titanium dioxide/graphene composite material.
Comparative example 2
In example 1, the step of growing the seed crystal on the surface of the graphene in example 1 was omitted, and the other operations were the same as in example 1:
1. adding 100mg of graphite oxide, 15mL of concentrated hydrochloric acid and 15mL of deionized water into a hydrothermal kettle, then dropwise adding 1mL of titanium tetrachloride solution, fully stirring, moving the hydrothermal kettle into an oven, carrying out hydrothermal reaction at 160 ℃ for 12h, cooling to room temperature, carrying out centrifugal washing, and drying the washed sample at 60 ℃ to obtain the titanium dioxide/graphite oxide composite material;
2. and calcining the titanium dioxide/graphite oxide composite material for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain the titanium dioxide/graphene composite material.
Comparative example 3
Anatase type nano titanium dioxide:
taking 20mL of 2.5mol/L titanium tetrachloride solution into a three-neck flask, taking 60mL of 2.5mol/L sodium hydroxide solution into a dropping funnel, dropwise adding the sodium hydroxide solution into the titanium tetrachloride solution while stirring at room temperature, wherein the dropwise adding speed is 3mL/min, continuously stirring for 30min after dropwise adding, heating the system to 85 ℃, maintaining for 2h, adjusting the pH value to 5-6 by using hydrochloric acid after the reaction is finished, then carrying out suction filtration and washing, and drying a filter cake at 80 ℃ to obtain the anatase type nano titanium dioxide.
As can be seen in the X-ray diffraction pattern of FIG. 1, the titanium dioxide in the composite material produced by the present invention is anatase titanium dioxide.
As can be seen from a scanning electron microscope image in FIG. 2, the titanium dioxide in the composite material prepared by the invention has a unique flower-like diamond structure. This structure greatly increases the specific surface area of the composite material, which is not possessed by the titanium dioxide in comparative example 1, comparative example 2 and comparative example 3.
And (3) testing the corrosion resistance: 50mg of the materials prepared in example 1, comparative example 2 and comparative example 3 were sufficiently dispersed in 1mL of water by sonication, and 50. mu.L of the dispersion was uniformly applied to an area of 1cm2After the round 304 stainless steel electrode is naturally dried, the electrode is immersed in a sodium chloride solution with solute mass fraction of 3.5%, a saturated calomel electrode is used as a reference electrode, a platinum wire electrode is used as an auxiliary electrode, a 350W xenon lamp is used as a light source, and a photocurrent-time curve of the electrode is tested on a CHI 660D type electrochemical workstation.
As can be seen from fig. 3, during illumination, the photocurrent density in the material rapidly increases, a large number of electrons and holes are generated at this time, and the current returns to the vicinity of the initial value after the illumination is stopped, and compared with comparative example 1, comparative example 2, and comparative example 3, the photocurrent density of the anatase flower-like diamond titanium dioxide/graphene composite material prepared in example 1 under the illumination condition is significantly increased, which indicates that the unique structure thereof can achieve higher photoelectric conversion efficiency.
Claims (5)
1. The application of the anatase type flower-like diamond titanium dioxide/graphene composite material in photo-induced cathode corrosion prevention is characterized in that the anatase type flower-like diamond titanium dioxide/graphene composite material is prepared by the following specific steps:
(1) adding a titanium tetrachloride solution into the graphene oxide dispersion liquid, fully stirring, heating, cooling to room temperature after heating, washing to be neutral, drying a sample, and calcining at 400-600 ℃ in a nitrogen atmosphere to obtain an anatase titanium dioxide seed crystal/graphene composite material; the heating temperature is 60-80 ℃, and the heating time is 1-3 h;
(2) adding a titanium tetrachloride solution into a hydrochloric acid solution to prepare a titanium precursor solution, adding the anatase titanium dioxide seed crystal/graphene composite material obtained in the step (1) into the titanium precursor solution, performing ultrasonic dispersion uniformly to obtain a mixed dispersion liquid, transferring the mixed dispersion liquid into a hydrothermal kettle, and transferring the hydrothermal kettle into an oven for hydrothermal reaction; the hydrothermal reaction temperature is 150-180 ℃, and the hydrothermal reaction time is 10-16 h; and cooling to room temperature after reaction, filtering, collecting a filter cake, washing to be neutral, and drying to obtain the anatase type flower-like diamond titanium dioxide/graphene photo-generated cathode protective material.
2. The application of the anatase flower-like diamond titanium dioxide/graphene composite material in photo-generated cathode corrosion prevention according to claim 1 is characterized in that: the mass concentration of graphene oxide in the graphene oxide dispersion liquid in the step (1) is 1-2 mg/mL; the molar concentration of the titanium tetrachloride solution is 2.5-4.0 mol/L; the volume ratio of the graphene oxide dispersion liquid to the titanium tetrachloride solution is 45-70: 1-2.
3. The application of the anatase flower-like diamond titanium dioxide/graphene composite material in photo-generated cathode corrosion prevention according to claim 1 is characterized in that: the drying temperature in the step (1) is 60-80 ℃; the calcination time is 1-3 h.
4. The application of the anatase flower-like diamond titanium dioxide/graphene composite material in photo-generated cathode corrosion prevention according to claim 1 is characterized in that: the molar concentration of the titanium tetrachloride solution in the step (2) is 2.5-4.0 mol/L; the molar concentration of the hydrochloric acid solution is 4.0-6.0 mol/L.
5. The application of the anatase flower-like diamond titanium dioxide/graphene composite material in photo-generated cathode corrosion prevention according to claim 1 is characterized in that: the drying temperature in the step (2) is 60-80 ℃.
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