CN108220973B - Preparation method and application of clay-based photocathode protection material - Google Patents
Preparation method and application of clay-based photocathode protection material Download PDFInfo
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- CN108220973B CN108220973B CN201810052834.5A CN201810052834A CN108220973B CN 108220973 B CN108220973 B CN 108220973B CN 201810052834 A CN201810052834 A CN 201810052834A CN 108220973 B CN108220973 B CN 108220973B
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- 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
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- 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
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Abstract
The invention belongs to the field of photocathode protection materials, and particularly relates to a preparation method and application of a clay-based photocathode protection material. The photocathode protective material can be clay or a composite material of the clay, namely a cadmium sulfide/cerium oxide/clay photocathode protective composite material. When the photocathode protection material is coated on a 304 stainless steel electrode, the corrosion potential of metal under illumination has large negative offset which is far lower than the self-corrosion potential, and the photocathode protection material has obvious photocathode corrosion prevention effect.
Description
Technical Field
The invention belongs to the field of photocathode protection materials, and particularly relates to a preparation method and application of a clay-based photocathode protection material.
Background
The work of corrosion protection of metals is more and more concerned and valued by people in the actual production life. There are two types of traditional cathodic corrosion protection: sacrificial anode protection method and external current method. The sacrificial anode protection method needs to frequently update the anode material, consumes a large amount of anode material to generate harmful substances, and causes environmental pollution; the external current method needs to continuously supply a direct current power supply, consumes a large amount of electric energy, and is not energy-saving and high in cost. The photocathode protection is a novel cathode corrosion prevention technology which utilizes sunlight to excite a semiconductor material to generate electrons to be conducted to metal so as to prevent the semiconductor material from being corroded, and has the advantages of simplicity and convenience in operation, low requirement on film covering, energy conservation, environmental protection and the like, so that the photocathode protection becomes a research hotspot in recent years.
At present, the material used for photocathode protection is mainly TiO2、SrTiO3ZnO, the common problem of the semiconductors is that the recombination probability of photo-generated electrons and holes is high, so that the utilization rate of the photo-generated electrons is low; the metal can not be protected by the cathode under dark conditions. Therefore, it is necessary to develop a composite photocathode protective material which is low in cost, high in electron utilization rate and capable of storing electrons.
Disclosure of Invention
The invention provides an application of a photocathode protection material, which comprises the following steps: coating the photocathode protective material on the surface of metal, placing the coated metal in an ultraviolet light or visible light environment,
the photocathode protective material can be clay or a composite material of the clay, namely a cadmium sulfide/cerium oxide/clay photocathode protective composite material,
wherein the clay is one or more of attapulgite, kaolin, montmorillonite and halloysite,
the preparation method of the cadmium sulfide/cerium oxide/clay photocathode protection composite material comprises the following steps:
(1) mixing the cadmium salt solution and the sodium hexametaphosphate solution, then adding clay, stirring and mixing, then dropwise adding the sodium sulfide solution, continuously stirring and centrifuging, washing a filter cake, drying for 8-12 h at 40-60 ℃ to obtain the cadmium sulfide/clay composite material,
the cadmium salt can be one of cadmium chloride and cadmium acetate,
the clay may be one of attapulgite, kaolin, montmorillonite and halloysite,
the concentration of the cadmium salt solution is 0.1mol/L, the concentration of the sodium hexametaphosphate solution is 0.1mol/L, the concentration of the sodium sulfide solution is 0.1mol/L,
the volume ratio of the cadmium salt solution to the sodium sulfide solution is 2-5: 1, and the volume ratio of the sodium sulfide solution to the sodium hexametaphosphate solution is 1: 10-15; the mass of the formed cadmium sulfide and clay is 0.005-0.05: 1;
(2) dispersing the cadmium sulfide/clay composite material prepared in the step (1) in an aqueous solution of cerium nitrate, heating and stirring, then dropwise adding ammonia water, continuously stirring, adjusting the pH value by hydrochloric acid, cooling, centrifuging, washing a filter cake, and drying at 40-60 ℃ for 8-12 hours to obtain the cadmium sulfide/cerium oxide/clay photocathode protection composite material,
the heating and stirring time is 0.5-1 h, and dropwise adding NH3·H2The mass ratio of O to cerium nitrate is 5.8-7: 1, ammonia water is dripped until the dispersion turns yellow, the mixture is continuously stirred for 2 hours, the concentration of hydrochloric acid used for adjusting the pH is 0.1mol/L, the pH is adjusted to 2-6,
the mass ratio of the formed cerium oxide to the cadmium sulfide/clay composite material is 0.5-1: 1.
According to the invention, clay with low cost is used for photocathode protection, which is not reported in the field of photocathode corrosion prevention, when the photocathode protection material is coated on a 304 stainless steel (304SS) electrode, the corrosion potential of metal has large negative offset under illumination and is far lower than the self-corrosion potential, and a remarkable photocathode corrosion prevention effect is achieved;
the invention uses cadmium sulfide to sensitize clay and cerium oxide, the forbidden bandwidths of the clay and the cerium oxide are wider, both are 3-point and several eV, and the clay and the cerium oxide can only respond to ultraviolet basically; the cadmium sulfide has a narrow band gap and basically only can respond to visible light, but the patent finds that after the clay and the cerium oxide are sensitized by the cadmium sulfide, the response of the clay/cerium oxide composite material under the visible light is enhanced, the response of the clay/cerium oxide composite material under ultraviolet light can be obviously enhanced, and the light utilization rate is improved;
the cadmium sulfide and the cerium oxide are loaded on the surface of the clay to form a II-type heterojunction, so that the recombination rate of photoproduction electrons and holes is reduced, more electrons are conducted to protected metal, and the utilization rate of the electrons is improved;
the cerium oxide has oxidation-reduction property, and part of photogenerated electrons are Ce4+Is reduced to Ce3+Stored in cerium oxide in the dark Ce3+Is oxidized into Ce4+The released electrons continue to provide electrons for the metal, and the metal can be protected in the dark.
Drawings
FIG. 1 is a Tafel plot of 304 stainless steel and kaolin and the materials prepared in example 2, comparative example 1, comparative example 2 and comparative example 3 after they are connected by a salt bridge,
wherein the abscissa is electrode potential V (vs. SCE), and the ordinate is current density (A/cm)2)。
FIG. 2 is a graph showing photocurrent curves of 304 stainless steel and kaolin and materials prepared in example 2, comparative example 1, comparative example 2 and comparative example 3 after they are connected 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 and kaolin and the materials prepared in example 2, comparative example 1, comparative example 2 and comparative example 3 after they are connected by 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.
Detailed Description
Example 1
(1) 5mL of 0.1mol/L cadmium chloride solution and 25mL of 0.1mol/L sodium hexametaphosphate solution are put into a flask, 7.2g of attapulgite is added, and the mixture is mixed and stirred for 0.5 h; then dropwise adding 2.5mL of 0.1mol/L sodium sulfide solution, stirring for 1h after dropwise adding, centrifuging, washing a filter cake, and fully drying at 40 ℃ to obtain the cadmium sulfide/clay composite material;
(2) 2g of the cadmium sulfide/clay composite material prepared in the step (1) and 2.5g of Ce (NO)3)3·6H2Adding O into a 250mL flask, adding 100mL deionized water, heating to 60 ℃ under a stirring state, slowly dropwise adding 16mL ammonia water with 25% solute by mass, continuously stirring for 2h after the system color is changed from dark green to yellow, adjusting the pH to 6 by using 0.1mol/L hydrochloric acid solution, cooling, centrifuging, washing a filter cake, and fully drying in a vacuum drying oven at 60 ℃ to obtain the cadmium sulfide/cerium oxide/clay photocathode protection composite material.
Example 2
(1) Taking 5mL of 0.1mol/L cadmium chloride solution and 15mL of 0.1mol/L sodium hexametaphosphate solution into a flask, adding 0.29g of kaolin, mixing and stirring for 0.5 h; then dropwise adding 1mL of 0.1mol/L sodium sulfide solution, stirring for 1h after dropwise adding, centrifuging, washing a filter cake, and fully drying at 60 ℃ to obtain the cadmium sulfide/clay composite material;
(2) 2g of the cadmium sulfide/clay composite material prepared in the step (1) and 5g of Ce (NO)3)3·6H2Adding O into a 250mL flask, adding 100mL deionized water, heating to 60 ℃ under stirring, slowly dropwise adding 32mL ammonia water with 25% solute by mass, continuously stirring for 2h after the system color changes from dark green to yellow, adjusting the pH to 2 by using 0.1mol/L hydrochloric acid solution, cooling, centrifuging, washing a filter cake, and putting the filter cake in a 60 ℃ vacuum drying ovenFully drying to obtain the cadmium sulfide/cerium oxide/clay photocathode protection composite material.
Example 3
(1) Adding 4.3g of montmorillonite into 9mL of 0.1mol/L cadmium chloride solution and 36mL of 0.1mol/L sodium hexametaphosphate solution in a flask, and mixing and stirring for 0.5 h; then dropwise adding 3mL of 0.1mol/L sodium sulfide solution, stirring for 1h after dropwise adding, centrifuging, washing a filter cake, and fully drying at 50 ℃ to obtain the cadmium sulfide/clay composite material;
(2) 2.5g of the cadmium sulfide/clay composite material obtained in step (1) and 4g of Ce (NO)3)3·6H2Adding O into a 250mL flask, adding 100mL deionized water, heating to 60 ℃ under a stirring state, slowly dropwise adding 25.6mL ammonia water with 25% solute by mass, continuously stirring for 2h after the system color is changed from dark green to yellow, adjusting the pH to 5 by using 0.1mol/L hydrochloric acid solution, cooling, centrifuging, washing a filter cake, and fully drying in a vacuum drying oven at 60 ℃ to obtain the cadmium sulfide/cerium oxide/clay photocathode protective composite material.
Example 4
(1) Adding 0.96g halloysite into 8mL of 0.1mol/L cadmium chloride solution and 22mL of 0.1mol/L sodium hexametaphosphate solution in a flask, mixing and stirring for 0.5 h; then dropwise adding 2mL of 0.1mol/L sodium sulfide solution, stirring for 1h after dropwise adding, centrifuging, washing a filter cake, and fully drying at 50 ℃ to obtain the cadmium sulfide/clay composite material;
(2) mixing 3.53g of the cadmium sulfide/clay composite obtained in step (1) with 7.5g of Ce (NO)3)3·6H2Adding O into a 250mL flask, adding 100mL deionized water, heating to 60 ℃ under a stirring state, slowly dropwise adding 48mL ammonia water with the solute mass percent of 25%, continuously stirring for 2h after the system color is changed from dark green to yellow, adjusting the pH to 4 by using 0.1mol/L hydrochloric acid solution, cooling, centrifuging, washing a filter cake, and fully drying in a vacuum drying oven at 60 ℃ to obtain the cadmium sulfide/cerium oxide/clay photocathode protection composite material.
Example 5
(1) Putting 6mL of 0.1mol/L cadmium chloride solution and 30mL of 0.1mol/L sodium hexametaphosphate solution into a flask, adding 14.45g of attapulgite, and mixing and stirring for 0.5 h; then dropwise adding 3mL of 0.1mol/L sodium sulfide solution, stirring for 1h after dropwise adding, centrifuging, washing a filter cake, and fully drying at 50 ℃ to obtain the cadmium sulfide/clay composite material;
(2) mixing 1.5g of the cadmium sulfide/clay composite material prepared in step (1) with 3g of Ce (NO)3)3·6H2Adding O into a 250mL flask, adding 100mL deionized water, heating to 60 ℃ under a stirring state, slowly dropwise adding 48mL ammonia water with the solute mass percent of 25%, continuously stirring for 2h after the system color is changed from dark green to yellow, adjusting the pH to 4 by using 0.1mol/L hydrochloric acid solution, cooling, centrifuging, washing a filter cake, and fully drying in a vacuum drying oven at 60 ℃ to obtain the cadmium sulfide/cerium oxide/clay photocathode protection composite material.
Comparative example 1
With reference to the procedure of example 2, a photocathode protective composite material free of cadmium sulfide was prepared.
Comparative example 2
Referring to the method of example 2, a photocathode protective composite material not containing cerium oxide was prepared.
Comparative example 3
A photocathode protective composite not containing clay was prepared by referring to the method of example 2.
Testing of photocathode corrosion resistance
40mg of kaolin used as a raw material in the above example 2 is dispersed in 1mL of water, ultrasonically dispersed for 30min, 50 muL of uniform dispersion liquid is transferred by a liquid transfer gun to be uniformly coated on a titanium electrode, and the titanium electrode is naturally dried for standby,
40mg of each sample of the examples or the comparative examples are dispersed in 1mL of water, ultrasonically dispersed for 30min, 50 mu L of uniform dispersion liquid is transferred by a liquid transfer gun to be uniformly coated on the titanium electrode, and the titanium electrode 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 photoelectrochemical test cells, a three-electrode system is used, to304SS as 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 1cm2The portion other than the effective area is sealed with epoxy resin. The changes in the polarization curve, current curve and open circuit potential were measured with the CHI 660D electrochemical workstation, as shown in the figure.
Claims (3)
1. The application of the photocathode protective material is characterized in that: the photocathode protective material comprises cadmium sulfide, cerium oxide and clay; the application is that the photocathode protection material is coated on the surface of metal, and the coated metal is placed in an ultraviolet light or visible light environment;
the preparation method of the photocathode protection material comprises the following steps,
(1) mixing the cadmium salt solution and the sodium hexametaphosphate solution, then adding clay, stirring and mixing, then dropwise adding the sodium sulfide solution, continuously stirring and centrifuging, and washing and drying a filter cake to obtain the cadmium sulfide/clay composite material;
the cadmium salt is one of cadmium chloride and cadmium acetate;
the volume ratio of the cadmium salt solution to the sodium sulfide solution is 2-5: 1, and the volume ratio of the sodium sulfide solution to the sodium hexametaphosphate solution is 1: 10-15;
the concentration of the cadmium salt solution is 0.1mol/L, the concentration of the sodium hexametaphosphate solution is 0.1mol/L, and the concentration of the sodium sulfide solution is 0.1 mol/L;
(2) dispersing the cadmium sulfide/clay composite material prepared in the step (1) in a cerous nitrate aqueous solution, heating and stirring, then dropwise adding ammonia water, continuously stirring, adjusting the pH value by using hydrochloric acid, cooling, centrifuging, washing and drying a filter cake, and thus obtaining the cadmium sulfide/cerium oxide/clay photocathode protection composite material;
the mass ratio of the cerium oxide to the cadmium sulfide/clay composite material is 0.5-1: 1.
2. Use of a photocathode protective material according to claim 1, characterized in that: the clay is one or a combination of more of attapulgite, kaolin, montmorillonite and halloysite.
3. Use of a photocathode protective material according to claim 1, characterized in that: in the step (2), the concentration of hydrochloric acid used for adjusting the pH is 0.1mol/L, and the pH is adjusted to 2-6.
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| CN101891283A (en) * | 2010-06-25 | 2010-11-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Photoelectrocatalysis water electrolysis method, device and application thereof |
| CN105419413A (en) * | 2015-12-25 | 2016-03-23 | 常州大学 | Anti-corrosion coating containing grapheme/zinc oxide/titanium oxide composite material and preparation method thereof |
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| CN101891283A (en) * | 2010-06-25 | 2010-11-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Photoelectrocatalysis water electrolysis method, device and application thereof |
| CN105419413A (en) * | 2015-12-25 | 2016-03-23 | 常州大学 | Anti-corrosion coating containing grapheme/zinc oxide/titanium oxide composite material and preparation method thereof |
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