CN108220973A - A kind of preparation method and application of clay-based photo-catelectrode protection material - Google Patents
A kind of preparation method and application of clay-based photo-catelectrode protection material Download PDFInfo
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- CN108220973A CN108220973A CN201810052834.5A CN201810052834A CN108220973A CN 108220973 A CN108220973 A CN 108220973A CN 201810052834 A CN201810052834 A CN 201810052834A CN 108220973 A CN108220973 A CN 108220973A
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- 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
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Abstract
The invention belongs to photo-catelectrode protection Material Fields, and in particular to a kind of preparation method and application of clay-based photo-catelectrode protection material.The photo-catelectrode protection material can be the composite material of clay or clay, i.e. cadmium sulfide/cerium oxide/clay photo-catelectrode protection composite material.The photo-catelectrode protection material is coated on 304 stainless steel electrodes, corrosion of metal current potential has very big negative offset under light illumination, far below its corrosion potential, plays significant photocathode anti-corrosion effect.
Description
Technical field
The invention belongs to photo-catelectrode protection Material Fields, and in particular to a kind of preparation side of clay-based photo-catelectrode protection material
Method and application.
Background technology
Corrosion of metal protected working has been to be concerned by more and more people and payes attention in actual production life.Traditional the moon
There are two types of pole anti-corrosions：Sacrificial protection and external impressed current method.Sacrificial protection needs often update anode material, and
And a large amount of anode materials of consumption generate harmful substance, cause environmental pollution；External impressed current method needs to continue supplying DC power source, disappears
A large amount of electric energy are consumed, it is not energy-efficient, of high cost.Photo-catelectrode protection is that a kind of utilization sun semiconductor materials with optical excitation generates electronics biography
The novel cathode aseptic technic to prevent it from corroding on metal is led, easy to operate because having, film covering requires low and energy-saving ring
The advantages that guarantor, in recent years as research hotspot.
The material for being presently used for photo-catelectrode protection is mainly TiO2、SrTiO3, ZnO, general character existing for these semiconductors asks
Topic is that light induced electron and hole-recombination probability are higher, causes light induced electron utilization rate low；It can not be to metal under dark condition
Play cathodic protection effect.Therefore, it is necessary to develop the compound light of a kind of at low cost, electronics utilization rate height and energy stored electrons
Cathodic protection material.
Invention content
The present invention provides a kind of applications of photo-catelectrode protection material：Photo-catelectrode protection material is coated on metal surface,
And the metal after coating is placed under ultraviolet light or visible light environment,
The photo-catelectrode protection material can be the composite material of clay or clay, i.e. cadmium sulfide/cerium oxide/viscous
Native photo-catelectrode protection composite material,
Wherein, combination of the clay for one or more of attapulgite, kaolin, montmorillonite and galapectite,
The preparation method of cadmium sulfide/cerium oxide/clay photo-catelectrode protection composite material includes the following steps：
(1) cadmium salt soln and sodium hexametaphosphate solution are mixed, then adds in clay, be stirred, vulcanization is then added dropwise
Sodium solution centrifuges after continuing stirring, dries 8~12h after filter cake is washed at 40~60 DEG C, you can cadmium sulfide/clay is made
Composite material,
Cadmium salt can be one kind in caddy, cadmium acetate,
Clay can be one kind in attapulgite, kaolin, montmorillonite and galapectite,
A concentration of 0.1mol/L of cadmium salt soln, a concentration of 0.1mol/L of sodium hexametaphosphate solution, sodium sulfide solution are a concentration of
0.1mol/L,
Cadmium salt soln is 2~5 with sodium sulfide solution volume ratio:1, sodium sulfide solution is with sodium hexametaphosphate solution volume ratio
1:10~15；The cadmium sulfide and the quality of clay formed is 0.005~0.05:1；
(2) cadmium sulfide/clay composite material obtained by step (1) is scattered in the aqueous solution of cerous nitrate, heating is stirred
It mixes, ammonium hydroxide is then added dropwise and continues to stir, with salt acid for adjusting pH, is centrifuged after cooling, after filter cake is washed dry 8 at 40~60 DEG C
~12h, you can cadmium sulfide/cerium oxide/clay photo-catelectrode protection composite material is made,
A length of 0.5~1h during heating stirring, the NH of dropwise addition3·H2The mass ratio of O and cerous nitrate is 5.8~7:1, ammonia is added dropwise
Water to dispersion liquid continues to stir 2h after becoming yellow, and it is 0.1mol/L to adjust concentration of hydrochloric acid used in pH, and pH is adjusted to 2-6,
The mass ratio of the cerium oxide formed and cadmium sulfide/clay composite material is 0.5~1:1.
The present invention is by lower-cost clay for photo-catelectrode protection, this is not reported in photocathode corrosion-resistant field, by this
Photo-catelectrode protection material is coated on 304 stainless steels (304SS) electrode, and corrosion of metal current potential has very big negative bias under light illumination
It moves, far below its corrosion potential, plays significant photocathode anti-corrosion effect；
The energy gap of the present invention cadmium sulfide sensitization clay and cerium oxide, clay and cerium oxide is wider, is 3 points several
EV can only have response to ultraviolet light substantially；And cadmium sulfide band gap is narrow, can only there is response to visible ray substantially, but this patent is sent out
It is existing, after cadmium sulfide is sensitized clay and cerium oxide, not only make the response enhancing of clay/cerium oxide composite material under visible light,
It also is able to significantly strengthen the clay/response of cerium oxide composite material under ultraviolet light, improves the utilization rate of light；
Cadmium sulfide and cerium oxide in the present invention are supported on surface of clay, form II type hetero-junctions, reduce light induced electron-
The recombination rate in hole makes more electronics be transmitted to by protection metal, improves electronics utilization rate；
Cerium oxide has oxidation-reduction quality in the present invention, and part light induced electron is with Ce4+It is reduced to Ce3+Form storage
In cerium oxide, the lower Ce of dark3+It is oxidized to Ce4+Release electronics continues as metal and provides electronics, can be carried under dark for metal
For protection.
Description of the drawings
Fig. 1 is that the material that 304 stainless steels are prepared with kaolin and embodiment 2, comparative example 1, comparative example 2 and comparative example 3 leads to
Supersalt bridging connect after Tafel curve,
Wherein, abscissa is electrode potential V (vs.SCE), and ordinate is current density (A/cm2)。
Fig. 2 is that the material that 304 stainless steels are prepared with kaolin and embodiment 2, comparative example 1, comparative example 2 and comparative example 3 leads to
Supersalt bridging connect after photocurrent curve,
Wherein, abscissa represents the time (s), and ordinate represents current density (A/cm2), on represents illumination, and off, which is represented, to close
Black out source, that is, no light condition.
Fig. 3 is that the material that 304 stainless steels are prepared with kaolin and embodiment 2, comparative example 1, comparative example 2 and comparative example 3 leads to
Supersalt bridging connect after open circuit potential-time graph,
Wherein, abscissa represents the time (s), and ordinate is electrode potential V (vs.SCE), and on represents illumination, and off, which is represented, to close
Black out source, that is, no light condition.
Specific embodiment
Embodiment 1
(1) take 5mL 0.1mol/L cadmium chloride solution and 25mL 0.1mol/L sodium hexametaphosphate solution in flask,
7.2g attapulgites are added in, 0.5h is mixed；Then the sodium sulfide solution of 2.5mL 0.1mol/L is added dropwise to, after being added dropwise to complete
Stirring 1h is simultaneously centrifuged, and filter cake is washed and dry abundant at 40 DEG C, you can cadmium sulfide/clay composite material is made；
(2) by cadmium sulfide/clay composite material obtained by 2g steps (1) and 2.5g Ce (NO3)3·6H2O is added in
In 250mL flasks, and 100mL deionized waters are added in, 60 DEG C are heated under stirring, be slowly added dropwise into 16mL Solute mass hundred
Point than the ammonium hydroxide for 25%, system color is become continuing after yellow to stir 2h from blackish green, with 0.1mol/L hydrochloric acid solution tune pH
Be 6, centrifuged after cooling, after filter cake is washed in 60 DEG C of vacuum drying chambers fully dry cadmium sulfide/cerium oxide/clay time
Protect composite material in pole.
Embodiment 2
(1) take 5mL 0.1mol/L cadmium chloride solution and 15mL 0.1mol/L sodium hexametaphosphate solution in flask,
0.29g kaolin is added in, 0.5h is mixed；Then the sodium sulfide solution of 1mL 0.1mol/L is added dropwise to, is stirred after being added dropwise to complete
It mixes 1h and centrifuges, filter cake is washed and dry abundant at 60 DEG C, you can cadmium sulfide/clay composite material is made；
(2) by cadmium sulfide/clay composite material obtained by 2g steps (1) and 5g Ce (NO3)3·6H2O adds in 250mL
In flask, and 100mL deionized waters are added in, 60 DEG C are heated under stirring, be slowly added dropwise into 32mL Solute mass percentages
For 25% ammonium hydroxide, system color from it is blackish green become yellow after continue to stir 2h, be 2 with 0.1mol/L hydrochloric acid solution tune pH,
It is centrifuged after cooling, it is fully dry that cadmium sulfide/cerium oxide/clay photocathode is protected in 60 DEG C of vacuum drying chambers after filter cake is washed
Protect composite material.
Embodiment 3
(1) take 9mL 0.1mol/L cadmium chloride solution and 36mL 0.1mol/L sodium hexametaphosphate solution in flask,
4.3g montmorillonites are added in, 0.5h is mixed；Then the sodium sulfide solution of 3mL 0.1mol/L is added dropwise to, is stirred after being added dropwise to complete
1h is simultaneously centrifuged, and filter cake is washed and dry abundant at 50 DEG C, you can cadmium sulfide/clay composite material is made；
(2) by cadmium sulfide/clay composite material obtained by 2.5g steps (1) and 4g Ce (NO3)3·6H2O is added in
In 250mL flasks, and 100mL deionized waters are added in, 60 DEG C are heated under stirring, be slowly added dropwise into 25.6mL Solute mass
Percentage is 25% ammonium hydroxide, and system color is become continuing after yellow to stir 2h from blackish green, with 0.1mol/L hydrochloric acid solution tune
PH is 5, is centrifuged after cooling, after filter cake is washed in 60 DEG C of vacuum drying chambers fully dry cadmium sulfide/cerium oxide/clay light
Cathodic protection composite material.
Embodiment 4
(1) take 8mL 0.1mol/L cadmium chloride solution and 22mL 0.1mol/L sodium hexametaphosphate solution in flask,
0.96g galapectites are added in, 0.5h is mixed；Then the sodium sulfide solution of 2mL 0.1mol/L is added dropwise to, is stirred after being added dropwise to complete
It mixes 1h and centrifuges, filter cake is washed and dry abundant at 50 DEG C, you can cadmium sulfide/clay composite material is made；
(2) by cadmium sulfide/clay composite material obtained by 3.53g steps (1) and 7.5g Ce (NO3)3·6H2O is added in
In 250mL flasks, and 100mL deionized waters are added in, 60 DEG C are heated under stirring, be slowly added dropwise into 48mL Solute mass hundred
Point than the ammonium hydroxide for 25%, system color is become continuing after yellow to stir 2h from blackish green, with 0.1mol/L hydrochloric acid solution tune pH
Be 4, centrifuged after cooling, after filter cake is washed in 60 DEG C of vacuum drying chambers fully dry cadmium sulfide/cerium oxide/clay time
Protect composite material in pole.
Embodiment 5
(1) take 6mL 0.1mol/L cadmium chloride solution and 30mL 0.1mol/L sodium hexametaphosphate solution in flask,
14.45g attapulgites are added in, 0.5h is mixed；Then the sodium sulfide solution of 3mL 0.1mol/L is added dropwise to, after being added dropwise to complete
Stirring 1h is simultaneously centrifuged, and filter cake is washed and dry abundant at 50 DEG C, you can cadmium sulfide/clay composite material is made；
(2) by cadmium sulfide/clay composite material obtained by 1.5g steps (1) and 3g Ce (NO3)3·6H2O is added in
In 250mL flasks, and 100mL deionized waters are added in, 60 DEG C are heated under stirring, be slowly added dropwise into 48mL Solute mass hundred
Point than the ammonium hydroxide for 25%, system color is become continuing after yellow to stir 2h from blackish green, with 0.1mol/L hydrochloric acid solution tune pH
Be 4, centrifuged after cooling, after filter cake is washed in 60 DEG C of vacuum drying chambers fully dry cadmium sulfide/cerium oxide/clay time
Protect composite material in pole.
Comparative example 1
With reference to the method for embodiment 2, the photo-catelectrode protection composite material without cadmium sulfide is prepared.
Comparative example 2
With reference to the method for embodiment 2, the photo-catelectrode protection composite material of not oxidation-containing cerium is prepared.
Comparative example 3
With reference to the method for embodiment 2, photo-catelectrode protection composite material not argillaceous is prepared.
Photocathode antiseptic property is tested
It takes in 40mg above example 2 and is scattered in 1mL water as the kaolin for preparing raw material, ultrasonic disperse 30min is used
Liquid-transfering gun pipettes the 50 uniform dispersion liquids of μ L in being smeared uniformly on Ti electrode, and naturally dry is for use,
The sample of each embodiments of 40mg or comparative example is taken respectively, is equally scattered in 1mL water, ultrasonic disperse 30min, with shifting
Liquid rifle pipettes the 50 uniform dispersion liquids of μ L in being smeared uniformly on Ti electrode, and naturally dry is for use.
Photocathode is protected and is tested, using double-electrolyzer system, it is 3.5wt% to corrode the electrolyte used in pond
NaCl aqueous solutions, and the electrolyte used in photo cathode is 1mol/L Na2S aqueous solutions, they are connected by salt bridge.In light
In electrochemical test cell, three-electrode system, using 304SS as working electrode, Hg/Hg are used2Cl2As with reference to electrode, platinum filament
As to electrode.Ti electrode after drying is put into light anode battery and is wired to working electrode.It is used during test
For 300W mercury lamps as light source, effective irradiated area of light anode and 304SS are 1cm2, the part asphalt mixtures modified by epoxy resin except effective area
Fat seals.The variation of polarization curve, current curve and open circuit potential is measured with CHI 660D electrochemical workstations, it is specific such as attached drawing
It is shown.
Claims (8)
1. a kind of application of photo-catelectrode protection material, it is characterised in that：The photo-catelectrode protection material includes clay；Described
Using for the photo-catelectrode protection material is coated on metal surface, and the metal after coating is placed in ultraviolet light or visible ray
Under environment.
2. the application of photo-catelectrode protection material as described in claim 1, it is characterised in that：The clay for attapulgite,
The combination of one or more of kaolin, montmorillonite and galapectite.
3. the application of photo-catelectrode protection material as described in claim 1, it is characterised in that：The photo-catelectrode protection material packet
Include cadmium sulfide, cerium oxide and clay.
4. the application of photo-catelectrode protection material as claimed in claim 3, it is characterised in that：Described includes cadmium sulfide, oxidation
The preparation method of the photo-catelectrode protection material of cerium and clay is,
(1) cadmium salt soln and sodium hexametaphosphate solution are mixed, then adds in clay, be stirred, it is molten that vulcanized sodium is then added dropwise
Liquid centrifuges after continuing stirring, and filter cake is washed, dry, you can cadmium sulfide/clay composite material is made；
(2) cadmium sulfide/clay composite material obtained by step (1) is scattered in the aqueous solution of cerous nitrate, heating stirring, so
Ammonium hydroxide is added dropwise afterwards to continue to stir, with salt acid for adjusting pH, is centrifuged after cooling, filter cake is washed, dry, you can cadmium sulfide/oxygen is made
Change cerium/clay photo-catelectrode protection composite material.
5. the application of photo-catelectrode protection material as claimed in claim 4, it is characterised in that：Cadmium salt described in step (1) is
One kind in caddy, cadmium acetate.
6. the application of photo-catelectrode protection material as claimed in claim 4, it is characterised in that：In step (1), cadmium salt soln and sulphur
It is 2~5 to change sodium solution volume ratio:1, sodium sulfide solution is 1 with sodium hexametaphosphate solution volume ratio:10~15.
7. the application of photo-catelectrode protection material as claimed in claim 4, it is characterised in that：In step (2), hydrochloric acid used in pH is adjusted
A concentration of 0.1mol/L, pH are adjusted to 2-6.
8. the application of photo-catelectrode protection material as claimed in claim 4, it is characterised in that：In step (2), cerium oxide and vulcanization
The mass ratio of cadmium/clay composite material is 0.5~1:1.
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| CN201810052834.5A CN108220973B (en) | 2018-01-19 | 2018-01-19 | Preparation method and application of clay-based photocathode protection material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108930041A (en) * | 2018-08-02 | 2018-12-04 | 常州大学盱眙凹土研发中心 | A kind of TiO2Quantum dot/carbonitride/attapulgite composite material preparation method and its application in photocathode anti-corrosion |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2018
- 2018-01-19 CN CN201810052834.5A patent/CN108220973B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108930041A (en) * | 2018-08-02 | 2018-12-04 | 常州大学盱眙凹土研发中心 | A kind of TiO2Quantum dot/carbonitride/attapulgite composite material preparation method and its application in photocathode anti-corrosion |
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