CN108359994B - Preparation method of one-dimensional nano titanium dioxide photocathode protection composite material with conductive mica as carrier - Google Patents
Preparation method of one-dimensional nano titanium dioxide photocathode protection composite material with conductive mica as carrier Download PDFInfo
- Publication number
- CN108359994B CN108359994B CN201810190036.9A CN201810190036A CN108359994B CN 108359994 B CN108359994 B CN 108359994B CN 201810190036 A CN201810190036 A CN 201810190036A CN 108359994 B CN108359994 B CN 108359994B
- Authority
- CN
- China
- Prior art keywords
- solution
- stirring
- powder
- deionized water
- conductive mica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
- C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
- C23F13/12—Electrodes characterised by the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1245—Inorganic substrates other than metallic
Abstract
The invention discloses a preparation method of a one-dimensional nano titanium dioxide photocathode protection composite material taking conductive mica as a carrier, which comprises the steps of adding a titanium salt solution into deionized water under an ice bath condition, stirring to obtain a transparent solution, dispersing conductive mica powder into the solution under the ice bath condition, reacting, drying and calcining to obtain composite powder; dispersing the composite powder in deionized water, adding an anionic surfactant under the condition of heating and stirring, stirring and cooling to room temperature, and carrying out suction filtration, washing and drying to obtain modified powder; and adding the obtained modified powder into a mixed solution of titanium salt and hydrochloric acid, carrying out hydrothermal reaction, cooling to room temperature, carrying out suction filtration, washing and drying to obtain the one-dimensional nano titanium dioxide photocathode protection composite material taking the conductive mica as a carrier.
Description
Technical Field
The invention relates to a photocathode protection material and a preparation method thereof, in particular to a preparation method of a one-dimensional nano titanium dioxide photocathode protection composite material taking conductive mica as a carrier.
Background
TiO2The material is a common photoelectric material, has good effects of photocatalysis, photosensitization and the like, has great development prospect, and is widely applied to the fields of wastewater treatment, air purification, solar cells and the like. More importantly, the use of TiO2The green and environment-friendly metal corrosion protection method of metal cathodic protection by photo-generated electrons of semiconductors has attracted great interest. TiO 22The principle for photocathode protection is: under illumination conditions, TiO2Photons of appropriate energy are absorbed to generate photo-generated electron-hole pairs, and then the photo-generated electrons are transferred to the protected metal surface, so that the potential of the photo-generated electrons is far lower than the self-corrosion potential, thereby inhibiting the corrosion reaction of the photo-generated electrons, and simultaneously, the holes are captured by a hole capture agent in a medium. In the study of photo-generated cathodic protectionTiO of different morphologies2The nano-materials are as follows: nanoparticle films, nanotube films, nanowire films, and the like have been used. In TiO2In nanoparticle films, electron transport is mainly by a transition mechanism due to energy barriers between the particles.
Mica is a non-metallic mineral with a special layered structure, and has the advantages of wide source, low price and good corrosion resistance. In recent years, many studies have been made on the preparation of functional composite powder by surface coating and modification of mica, for example, mica pearlescent pigments of various colors can be prepared by coating high refractive index oxide on the surface of mica, and mica powder coated with metal on the surface can be used for the preparation of conductive composite materials, electromagnetic shielding materials, antistatic materials and wave-absorbing materials. The mica is coated and modified, so that the sheet structure of the powder can be kept, and a new function can be given to the mica powder.
Titanium oxide in the existing mica/titanium oxide composite material is generally in a particle shape and cannot rapidly and effectively conduct electrons; and the mica in the existing mica/titanium oxide composite material is not a good conductor of electrons, and the electrons are not easy to be conducted to the protected metal.
Disclosure of Invention
The invention aims to provide a preparation method of a one-dimensional nano titanium dioxide photocathode protection composite material taking conductive mica as a carrier.
The preparation method specifically comprises the following steps:
(1) under the ice bath condition of-5-0 ℃, adding a titanium salt solution into deionized water, and stirring for 0.5-1 h to obtain a transparent solution, wherein the volume ratio of the titanium salt solution to the deionized water is 0.06-0.1: 1; dispersing conductive mica powder into the solution while stirring in ice bath, wherein the conductive mica powder and TiO are2The mass (calculated by theoretical mass) ratio is 0.05-2: 1, and the mixture is stirred and reacted for 0.5-2 hours at the temperature of 50-70 ℃; filtering and washing with deionized water until the pH value of the filtrate is 5-6, drying the filter cake at 40-60 ℃ for 4-8 h, and calcining in a muffle furnace at 400-550 ℃ for 1-2 h to obtain composite powder;
(2) dispersing the composite powder obtained in the step (1) in deionized water, wherein the mass ratio of the composite powder to the deionized water is 0.05-0.2: 1, and raising the temperature of the system to 85-90 ℃; adding an anionic surfactant while stirring, stirring for 0.5-1 h, naturally cooling to room temperature, performing suction filtration, washing, and drying at 40-60 ℃ for 4-8 h to obtain modified powder;
(3) adding the modified powder obtained in the step (2) into a mixed solution of titanium salt and hydrochloric acid, wherein the mass ratio of the modified powder to the titanium salt solution is 0.1-0.2: 1, the volume ratio of the titanium salt solution to the hydrochloric acid solution is 1:30, carrying out hydrothermal treatment for 4-12 h at the temperature of 180-210 ℃, cooling to room temperature, carrying out suction filtration and washing, and drying for 4-8 h at the temperature of 40-60 ℃ to obtain the one-dimensional nano titanium dioxide photocathode protective composite material taking conductive mica as a carrier.
The titanium salt solution in the steps (1) and (3) can be a titanium tetrachloride solution, and the molar concentration is 3-5 mol/L;
the preparation method of the conductive mica in the step (1) is disclosed in Chinese patent CN 105513716A;
in the step (2), the anionic surfactant is one of sodium stearate or sodium laurate;
in the step (2), the surfactant accounts for 5-15% of the total mass of the composite powder;
the mass concentration of the hydrochloric acid solution in the step (3) is 36-38%;
according to the invention, the anionic surfactant is adopted to modify the composite powder in the second step, so that the mica composite powder with the titanium oxide seed crystal obtained in the first step is hydrophobic, and the mica composite powder with the titanium oxide seed crystal is enabled to float on the mica composite powder without sinking when the titanium oxide nanorod array is grown in the polytetrafluoroethylene by hydrothermal reaction in the third step.
The titanium oxide nanorod array grows on the conductive mica sheet, the titanium oxide generates photo-generated electrons under illumination, the electrons can be quickly conducted to the conductive mica along the axial direction of the nanorods due to the titanium oxide in a one-dimensional nanorod structure, the conductive mica with good conductivity can further conduct the electrons to the protected metal, the potential of the protected metal is lower than the self-corrosion potential of the protected metal, and the effect of photocathode protection is achieved.
The invention has the beneficial effects that:
1. according to the invention, the titanium oxide nanorod array grows on the conductive mica sheet, on one hand, the titanium oxide nanorod array grows on the conductive mica sheet to form a hairbrush-like shape, and the generated steric hindrance effect can effectively prevent the mica sheets from being overlapped and stacked; on the other hand, one-dimensional nanorods have more excellent electron mobility in the axial direction than nanoparticles. Under the illumination condition, electrons generated by the titanium oxide nanorod array can be rapidly conducted to the conductive mica, and then are transferred to a protected metal matrix material, so that the photocathode protection effect is achieved, and the utilization rate of photo-generated electrons and the corrosion resistance of metal are greatly improved.
2. The invention uses the flaky mica as a carrier, and the flaky structure of the mica can effectively shield the permeation of corrosion factors such as water, oxygen, ions and the like, block the permeation path of the corrosion factors and can play a better physical barrier anticorrosion effect.
Drawings
FIG. 1 is a Tafel plot of 304 stainless steel after being connected to the materials prepared in example 4, comparative example 1, comparative example 2, and comparative example 3 by salt bridges; wherein the abscissa is electrode potential V (vs. SCE), and the ordinate is current density (A/cm)2)。
FIG. 2 is a graph of photocurrent after 304 stainless steel was connected to the materials prepared in example 4, comparative example 1, comparative example 2, and comparative example 3 by a salt bridge; wherein the abscissa represents time(s) and the ordinate represents current density (A/cm)2) On represents light and off represents off, i.e. no light.
FIG. 3 is an open circuit potential versus time plot of 304 stainless steel after connection with the materials prepared in example 4, comparative example 1, comparative example 2, and comparative example 3 via a salt bridge; wherein the abscissa represents time(s), the ordinate is electrode potential V (vs. sce), on represents light, and off represents turning off the light source, i.e. no light.
FIG. 4 is a scanning electron microscope image of the composite material prepared by the present invention.
Detailed Description
The invention is described in more detail below with reference to the following examples:
example 1
1) Under the ice-bath condition of-5-0 ℃, adding 30mL of titanium tetrachloride with the concentration of 3mol/L into 50mL of deionized water, stirring for 0.5h to obtain a transparent solution, dispersing 7g of conductive mica powder into the solution under the ice-bath stirring, and stirring for reaction for 0.5h at 70 ℃; filtering, washing with deionized water until the pH value of the filtrate is 5-6, drying the filter cake at 60 ℃ for 4h, and calcining in a muffle furnace at 400 ℃ for 2 h;
2) dispersing 2.5g of the composite powder obtained in the step 1) in 50mL of water, and raising the temperature of the system to 85 ℃; adding 0.2g of sodium stearate anionic surfactant while stirring, stirring for 1h, naturally cooling to room temperature, performing suction filtration, washing, and drying in an oven at 60 ℃ for 4 h;
3) taking 0.1g of the modified powder obtained in the step 2), adding the modified powder into a mixed solution of 1mL of 3mol/L titanium tetrachloride, 30mL of 36 wt% hydrochloric acid and 30mL of deionized water, carrying out hydrothermal treatment at 180 ℃ for 12h, cooling to room temperature, washing with deionized water, and drying at 60 ℃ for 4h to obtain the one-dimensional nano titanium dioxide photocathode protective composite material taking conductive mica as a carrier.
Example 2
1) Under the ice-bath condition of-5-0 ℃, adding 20mL of titanium tetrachloride with the concentration of 4mol/L into 60mL of deionized water, stirring for 1h to obtain a transparent solution, dispersing 9.6g of conductive mica powder into the solution under the ice-bath stirring, and stirring for reacting for 2h at 50 ℃; filtering, washing with deionized water until the pH value of the filtrate is 5-6, drying the filter cake at 40 ℃ for 8h, and calcining in a muffle furnace at 550 ℃ for 1 h;
2) dispersing 7g of the composite powder obtained in the step 1) in 70mL of water, and raising the temperature of the system to 90 ℃; adding 0.45g of sodium laurate anionic surfactant while stirring, stirring for 0.5h, naturally cooling to room temperature, filtering, washing, and drying in an oven at 40 ℃ for 8 h;
3) taking 0.2g of the modified powder obtained in the step 2), adding the modified powder into a mixed solution of 1mL of 4mol/L titanium tetrachloride, 30mL of 36 wt% hydrochloric acid and 30mL of deionized water, carrying out hydrothermal treatment at 210 ℃ for 4h, cooling to room temperature, washing with deionized water, and drying in an oven at 40 ℃ for 8h to obtain the one-dimensional nano titanium dioxide photocathode protective composite material taking conductive mica as a carrier.
Example 3
1) Under the ice-bath condition of-5-0 ℃, adding 10mL of titanium tetrachloride with the concentration of 5mol/L into 70mL of deionized water, stirring for 45min to obtain a transparent solution, dispersing 11g of conductive mica powder into the solution under the ice-bath stirring, and stirring and reacting for 1.5h at the temperature of 60 ℃; filtering, washing with deionized water until the pH value of the filtrate is 5-6, drying the filter cake at 50 ℃ for 6h, and calcining in a muffle furnace at 500 ℃ for 1.5 h;
2) dispersing 7g of the composite powder obtained in the step 1) in 90mL of water, and raising the temperature of the system to 90 ℃; adding 0.52g of sodium laurate anionic surfactant while stirring, stirring for 1h, naturally cooling to room temperature, filtering, washing, and drying in an oven at 50 ℃ for 6 h;
3) taking 0.2g of the modified powder obtained in the step 2), adding the modified powder into a mixed solution of 1mL of 5mol/L titanium tetrachloride, 30mL of 36 wt% hydrochloric acid and 30mL of deionized water, carrying out hydrothermal treatment at 200 ℃ for 8h, cooling to room temperature, washing with deionized water, and drying in an oven at 60 ℃ for 6h to obtain the one-dimensional nano titanium dioxide photocathode protective composite material taking conductive mica as a carrier.
Example 4
1) Under the ice-bath condition of-5-0 ℃, adding 1mL of titanium tetrachloride with the concentration of 3.75mol/L into 70mL of deionized water, stirring for 75min to obtain a transparent solution, dispersing 5g of conductive mica powder into the solution under the ice-bath stirring, and stirring and reacting for 1.5h at the temperature of 60 ℃; filtering, washing with deionized water until the pH value of the filtrate is 5-6, drying the filter cake at 60 ℃ for 6h, and calcining in a muffle furnace at 500 ℃ for 1 h;
2) dispersing 4g of the composite powder obtained in the step 1) in 90mL of water, and raising the temperature of the system to 90 ℃; adding 0.52g of sodium laurate anionic surfactant while stirring, stirring for 1h, naturally cooling to room temperature, filtering, washing, and drying in an oven at 50 ℃ for 6 h;
3) taking 0.15g of the modified powder obtained in the step 2), adding the modified powder into a mixed solution of 1mL of 3.75mol/L titanium tetrachloride, 30mL of 36 wt% hydrochloric acid and 30mL of deionized water, carrying out hydrothermal reaction at 200 ℃ for 8h, cooling to room temperature, washing with deionized water, and drying in an oven at 60 ℃ for 6h to obtain the one-dimensional nano titanium dioxide photocathode protective composite material taking conductive mica as a carrier.
Comparative example 1
Putting 50mL of water into a three-neck flask, adding 1mL of titanium tetrachloride solution into ice water under ice-bath stirring, and continuously stirring to obtain a transparent solution; carrying out ultrasonic treatment on FTO conductive glass in acetone, ethanol and deionized water for 15min, immersing an FTO substrate in the titanium tetrachloride solution, and keeping the temperature in an oven at 70 ℃ for 1 h; naturally cooling, and washing with deionized water; then calcining the mixture for 1.5h in a muffle furnace at 500 ℃; placing an FTO substrate with a titanium oxide seed crystal layer in a polytetrafluoroethylene lining at an oblique angle of 80 degrees, adding 1mL of titanium tetrachloride solution, 30mL of 36 wt% hydrochloric acid and 30mL of deionized water, carrying out hydrothermal treatment at 180 ℃ for 8h, cooling to room temperature, washing with deionized water, and drying in an oven at 70 ℃ for 6h to obtain the titanium oxide nanorod array composite material.
Comparative example 2
Adding 60mL of 2.5mol/L sodium hydroxide solution into 20mL of 2.5mol/L titanium tetrachloride solution dropwise under stirring at room temperature, continuing to stir for 0.5h after the dropwise addition is finished, then adding 4g of conductive mica into the solution, continuing to stir for 0.5h, heating the system to 85 ℃ and maintaining the temperature for 2h, adjusting the pH to 5-6 by using 2mol/L hydrochloric acid after the reaction is finished, performing suction filtration, washing, and drying at 60 ℃ to obtain the titanium oxide nanoparticle/conductive mica composite material.
Comparative example 3
1) Under the ice-bath condition of-5-0 ℃, adding 1mL of titanium tetrachloride with the concentration of 3.75mol/L into 70mL of deionized water, stirring for 75min to obtain a transparent solution, dispersing 5g of conductive mica powder into the solution under the ice-bath stirring, and stirring and reacting for 1.5h at the temperature of 60 ℃; filtering, washing with deionized water until the pH value of the filtrate is 5-6, drying the filter cake at 60 ℃ for 6h, and calcining in a muffle furnace at 500 ℃ for 1 h;
2) taking 0.15g of the composite powder obtained in the step 1), adding the composite powder into a mixed solution of 1mL of 3.75mol/L titanium tetrachloride, 30mL of 36 wt% hydrochloric acid and 30mL of deionized water, carrying out hydrothermal reaction at 200 ℃ for 8h, cooling to room temperature, washing with deionized water, and drying in an oven at 60 ℃ for 6h to obtain the titanium dioxide/conductive mica photocathode protective composite material.
Testing of photocathode corrosion resistance
40mg of samples of the examples and the comparative examples are dissolved in 1mL of water, ultrasonic dispersion is carried out for 30min, 50 mu L of solution is transferred to a titanium electrode by a liquid transfer gun, the solution is evenly coated, and the solution is naturally dried for standby.
For the photocathode protection test, a two-cell system was used, the electrolyte used in the corrosion cell was a 3.5 wt% aqueous NaCl solution, and the electrolyte used in the photoanode was 1mol/L Na2S aqueous solution, which are linked by salt bridges. In a photoelectrochemical test cell, a three electrode system was used with 304SS as the working electrode, Hg/Hg2Cl2As a reference electrode, a platinum wire as a counter electrode. And putting the dried titanium electrode into a photo-anode cell and connecting the titanium electrode to a working electrode through a lead. In the test, a 300W mercury lamp was used as a light source, and the effective irradiation areas of the photo-anode and 304SS were 1cm2And the rest area is sealed by epoxy resin. The changes in the polarization curve, current curve and open circuit potential were measured with the CHI 660D electrochemical workstation.
FIG. 1 is a Tafel plot of 304 stainless steel after connection to the materials prepared in example 4, comparative example 1, comparative example 2, and comparative example 3 via salt bridges, and it can be seen from FIG. 1 that the corrosion potential of uncoated 304SS is-199 mV (vs. SCE), corresponding to a current density of 1.66 × 10-6mA cm2(ii) a Under the condition of illumination, the corrosion potential after coating the material is all compared with that of the materialUnder illumination, the corrosion potential of the electrode coated with the titanium oxide nanorod array of comparative example 1 was reduced to-331 mV (vs. SCE) under illumination, corresponding to a current density of 2.24 × 10-5mA cm2The corrosion potential of the electrode coated with the titanium oxide nanoparticle/conductive mica composite material of comparative example 2 was reduced to-379 mV (vs. SCE) under illumination, the electrode coated with comparative example 3 was very similar to the electrode coated with comparative example 2, indicating that the titanium oxide nanorods did not grow well on the mica plates without modification, whereas the corrosion potential of the electrode coated with the titanium oxide nanorod array/conductive mica composite material of example 4 was reduced by the maximum amount (-474mV (vs. SCE)) under illumination, and the corresponding current density was increased by 2 orders of magnitude (1.58 × 10-4 mA.cm. cm. the corrosion potential of the electrode coated with the titanium oxide nanorod array/conductive mica composite material of example 4 was reduced by the maximum amount (-474 mV) under illumination)2) The effect is significantly better than in comparative example 1, comparative example 2 and comparative example 3. In the dark, the electrode potential of the coated material becomes more positive due to the barrier effect of the material. As can be seen from the figure, the potential of the electrodes coated with the titanium oxide nanoparticle/conductive mica composite material and the electrodes coated with the one-dimensional nano titanium dioxide photocathode protection composite material taking conductive mica as a carrier are more positive than that of the electrodes coated with the titanium oxide nanorod array, mainly because the flaky mica can play a better role in blocking; the electrode potential of the one-dimensional nano titanium dioxide photocathode protection composite material coated with the conductive mica as the carrier is more positive than that of the titanium oxide nano particle/conductive mica composite material, and the steric hindrance effect generated by the titanium oxide nano rod array mainly prevents mica sheets from being overlapped and stacked, so that the mica is more uniformly paved on the protected metal, and a better barrier effect is achieved.
FIG. 2 is a graph of photocurrent after 304 stainless steel was connected to the materials prepared in example 4, comparative example 1, comparative example 2, and comparative example 3 by a salt bridge; as can be seen from fig. 2: photocurrent was generated under illumination, demonstrating that photoelectrons generated by the semiconductor were transferred from the photo-anode to the 304SS electrode, thus providing protection. As can be seen from the figure, the photocurrent density generated by the electrode coated with the one-dimensional nano titanium dioxide photocathode protection composite material using conductive mica as a carrier in example 4 is much greater than that of the titanium oxide nanorod array, the titanium oxide nanoparticle/conductive mica composite material and the unmodified titanium oxide/conductive mica in comparative example 3. The titanium oxide nanorod array has high electron conduction capacity, and the conductive mica has good conductivity, so that the electron utilization rate of the composite material is improved.
FIG. 3 is an open circuit potential versus time plot of 304 stainless steel after connection with the materials prepared in example 4, comparative example 1, comparative example 2, and comparative example 3 via a salt bridge; as can be seen in fig. 3: naked 304SS has an OCP of-187 mV in the dark; the 304SS electrode of the coated material, under illumination, drops suddenly in potential and remains at a more negative potential due to the generation of photo-generated electrons, and when the illumination is turned off, the electrode potential rises rapidly to the initial position. Consistent with the results of fig. 1: before the lamp is turned on, the electrode potential of the one-dimensional nano titanium dioxide photocathode protection composite material coated with the conductive mica as the carrier is in a positive state, and after the lamp is turned on, because a large number of electrons are injected onto 304SS, the electrode potential is more negative.
Although the preferred embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above-described embodiments, which are merely illustrative and not restrictive, and those skilled in the art can make various changes and modifications within the spirit and scope of the present invention without departing from the spirit and scope of the appended claims.
Claims (1)
1. A preparation method of a one-dimensional nanometer titanium dioxide photocathode protection composite material taking conductive mica as a carrier is characterized by comprising the following steps: the method comprises the following steps:
(1) under the ice bath condition of-5-0 ℃, adding a titanium tetrachloride solution into deionized water, stirring for 0.5-1 h to obtain a transparent solution, dispersing conductive mica powder into the solution while stirring under the ice bath, and stirring and reacting for 0.5-2 h at the temperature of 50-70 ℃; filtering and washing with deionized water until the pH of the filtrate is = 5-6, drying the filter cake at 40-60 ℃ for 4-8 h, and calcining in a muffle furnace at 400-550 ℃ for 1-2 h to obtain composite powder;
the volume ratio of the titanium tetrachloride solution to the deionized water is 0.06-0.1: 1; conductive mica powder and TiO2The mass ratio of (A) to (B) is 0.05-2: 1; the molar concentration of the titanium tetrachloride solution is 3-5 mol/L;
(2) dispersing the composite powder obtained in the step (1) in deionized water, and raising the system temperature to 85-90 ℃; adding an anionic surfactant under the stirring condition, stirring for 0.5-1 h, naturally cooling to room temperature, performing suction filtration, washing, and drying at 40-60 ℃ for 4-8 h to obtain modified powder;
the anionic surfactant is one of sodium stearate or sodium laurate; the dosage of the composite powder is 5-15% of the total mass of the composite powder;
the mass ratio of the composite powder to the deionized water is 0.05-0.2: 1;
(3) adding the modified powder obtained in the step (2) into a mixed solution of titanium tetrachloride and hydrochloric acid, carrying out hydrothermal reaction for 4-12 h at 180-210 ℃, cooling to room temperature, carrying out suction filtration and washing, and drying for 4-8 h at 40-60 ℃ to obtain a one-dimensional nano titanium dioxide photocathode protective composite material taking conductive mica as a carrier;
the mass concentration of the hydrochloric acid solution is 36-38%;
the mass ratio of the modified powder to the titanium salt solution is 0.1-0.2: 1, and the volume ratio of the titanium salt solution to the hydrochloric acid solution is 1: 30.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810190036.9A CN108359994B (en) | 2018-03-08 | 2018-03-08 | Preparation method of one-dimensional nano titanium dioxide photocathode protection composite material with conductive mica as carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810190036.9A CN108359994B (en) | 2018-03-08 | 2018-03-08 | Preparation method of one-dimensional nano titanium dioxide photocathode protection composite material with conductive mica as carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108359994A CN108359994A (en) | 2018-08-03 |
| CN108359994B true CN108359994B (en) | 2020-10-09 |
Family
ID=63003847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810190036.9A Active CN108359994B (en) | 2018-03-08 | 2018-03-08 | Preparation method of one-dimensional nano titanium dioxide photocathode protection composite material with conductive mica as carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108359994B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110965066B (en) * | 2019-11-22 | 2022-04-26 | 常州纳欧新材料科技有限公司 | Molybdenum disulfide/tin dioxide/mica composite material for photoproduction cathodic protection and preparation method thereof |
| CN110975856B (en) * | 2019-12-18 | 2023-01-03 | 常州纳欧新材料科技有限公司 | Titanium oxide/conductive potassium titanate composite desulfurization photocatalytic material and preparation method thereof |
| CN110961092B (en) * | 2019-12-23 | 2023-02-07 | 常州纳欧新材料科技有限公司 | Carbon quantum dot/titanium oxide/conductive mica composite degradable tetracycline hydrochloride photocatalytic material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101322944A (en) * | 2008-07-28 | 2008-12-17 | 吉林大学 | Composite photocatalyst prepared from stephanoporate mineral and method thereof |
| CN104388923A (en) * | 2014-10-17 | 2015-03-04 | 山东科技大学 | Making method of graphene modified titanium oxide metal anticorrosion coating |
-
2018
- 2018-03-08 CN CN201810190036.9A patent/CN108359994B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101322944A (en) * | 2008-07-28 | 2008-12-17 | 吉林大学 | Composite photocatalyst prepared from stephanoporate mineral and method thereof |
| CN104388923A (en) * | 2014-10-17 | 2015-03-04 | 山东科技大学 | Making method of graphene modified titanium oxide metal anticorrosion coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108359994A (en) | 2018-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108359994B (en) | Preparation method of one-dimensional nano titanium dioxide photocathode protection composite material with conductive mica as carrier | |
| CN107723712B (en) | ZnIn for photoproduction cathodic protection2S4/TiO2Preparation method of nanotube composite film photo-anode | |
| Liu et al. | A highly efficient reduced graphene oxide/SnO2/TiO2 composite as photoanode for photocathodic protection of 304 stainless steel | |
| Lei et al. | ZnFe2O4/TiO2 nanocomposite films for photocathodic protection of 304 stainless steel under visible light | |
| Chen et al. | Hydrothermal synthesis of Fe 2 O 3/ZnO heterojunction photoanode for photoelectrochemical water splitting | |
| Shao et al. | Synthesis and photocathodic protection properties of nanostructured SnS/TiO2 composites | |
| Sangamesha et al. | Preparation and characterization of nanocrystalline CuS thin films for dye-sensitized solar cells | |
| Shen et al. | Enhancing efficiency of CdS/TiO2 nanorod arrays solar cell through improving the hydrophilicity of TiO2 nanorod surface | |
| CN108314085B (en) | The preparation method of tungstic trioxide nano-slice complex light anode | |
| Yan et al. | Fabrication of BiVO4/Bi12O15Cl6 heterojunction photocatalyst with enhanced photocatalytic performance under visible light | |
| Han et al. | Simultaneous manipulation of ion doping and cocatalyst loading into Mn 0.3 Cd 0.7 S nanorods toward significantly improved H 2 evolution | |
| Yao et al. | Fe2O3 nanothorns sensitized two-dimensional TiO2 nanosheets for highly efficient solar energy conversion | |
| CN108511198A (en) | Ni-doped BiVO4Thin-film photoelectric anode, preparation method and application thereof | |
| Manikandan et al. | Ternary composite based on NiCo2O4/rGO/PANI as an efficient Pt free tri-iodide reducing agent for dye-sensitized solar cell application | |
| CN114016039A (en) | Semiconductor composite light anode, preparation method and application | |
| CN109972149B (en) | Bi2Te3/Bi2O3/TiO2Preparation method of ternary heterojunction film | |
| CN111834128B (en) | Silver-iron oxide composite structure film and preparation method and application thereof | |
| KR20160134298A (en) | Dye-sensitized solar cell | |
| CN105304338B (en) | It is a kind of for quantum dot sensitized solar battery to electrode and preparation method thereof | |
| Lin et al. | Manipulation of inter-particle interactions between TiO2 and CdTe: an effective method to enhance the performance of quantum dot sensitized solar cells | |
| Li et al. | Drop-dry deposition of Co3O4 and fabrication of heterojunction solar cells with electrochemically deposited ZnO | |
| Cheng et al. | Optimization of PEC and photocathodic protection performance of TiO2/CuInS2 heterojunction photoanodes | |
| CN114277375A (en) | MnIn2S4/TiO2Nanotube bundle composite photoanode material and preparation method and application thereof | |
| Li et al. | Electrochemical preparation and photoelectric properties of Cu 2 O-loaded TiO 2 nanotube arrays | |
| CN108264242B (en) | Nano-structure cuprous oxide photoelectric conversion film and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |