CN109609960A - Optical anode material Bi with optical electro-chemistry cathodic protection effect2S3The preparation method of/ZnO - Google Patents

Optical anode material Bi with optical electro-chemistry cathodic protection effect2S3The preparation method of/ZnO Download PDF

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Publication number
CN109609960A
CN109609960A CN201910053436.XA CN201910053436A CN109609960A CN 109609960 A CN109609960 A CN 109609960A CN 201910053436 A CN201910053436 A CN 201910053436A CN 109609960 A CN109609960 A CN 109609960A
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zno
preparation
source
optical
anode material
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李伟华
包慧
张玉梅
李田雨
毛仔健
何海燕
刘小艳
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Hohai University HHU
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Hohai University HHU
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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
    • C23F13/14—Material for sacrificial anodes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires

Abstract

The present invention discloses a kind of optical anode material Bi with optical electro-chemistry cathodic protection effect2S3The preparation method of/ZnO includes the following steps: zinc nitrate and hexa being mixed to get electrolyte, using three-electrode system, applies certain voltage, set temperature and time using electrochemical workstation, deposits ZnO nano-wire film in FTO conductive glass surface；Using bismuth nitrate solution as the source Bi, sodium sulfide solution is adsorbed on compound Bi on obtained ZnO nano-wire film as the source S, by continuous ionic layer2S3, finally obtain Bi2S3/ ZnO photo-anode material.The optical anode material performance of such preparation method preparation is high, and preparation cost is low, and resource utilization is high, there is application in terms of preferable corrosion protection.

Description

Optical anode material Bi with optical electro-chemistry cathodic protection effect2S3The preparation of/ZnO Method
Technical field
It is the invention belongs to optical electro-chemistry cathodic protection field, in particular to a kind of with optical electro-chemistry cathodic protection effect Optical anode material (Bi2S3/ ZnO) preparation method.
Background technique
According to incompletely statistics, the whole world every year due to metal erosion and can not the material and facility of normal use account for about metal The a quarter of annual output seriously hinders the development of the national economy to one third.Corrosion of metal is that nature is inevitable The phenomenon that, metal material reacts with surrounding medium lose original property in the natural environment, leads to structure damage, function It loses, finally not only results in resource, energy waste, lead to equipment damage, cause economic loss, hinder technological progress, and A large amount of industrial accident will be also caused, the health and safety of the mankind is jeopardized.What environmental pollution and production of renewable energy resources faced chooses War is all the field of scientific study of high activity.In optical electro-chemistry cathodic protection field, one kind have direct band gap be 3.3eV and Excitation combines semiconductor nanocrystal-zinc oxide (ZnO) of energy to be applied.ZnO has excellent performance, such as its with some The high electron mobility of electronic structure, it is room temperature luminous etc..In this regard, the load of multiple catalysts or secondary semiconductor can To improve the catalytic efficiency of ZnO by forming hetero-junctions.
However, ZnO belongs to wide bandgap semiconductor compound, under normal circumstances can only absorbing wavelength it is ultraviolet less than 387nm Light, on the other hand, after the excitation of ZnO light, electron hole pair is short there are the time, and phototransformation efficiency is lower, causes its improper work For visible light activity photochemical catalyst, therefore design the hetero-junctions coupled with zinc oxide to improve zinc oxide in visible light region Sun light absorpting ability is applied to further use it in the field of photocathode protection.
Summary of the invention
The purpose of the present invention is to provide a kind of optical anode material Bi with optical electro-chemistry cathodic protection effect2S3/ZnO Preparation method, the optical anode material performance of preparation is high, and preparation cost is low, and resource utilization is high, there is preferable corrosion protection Aspect application.
In order to achieve the above objectives, solution of the invention is:
A kind of optical anode material Bi with optical electro-chemistry cathodic protection effect2S3The preparation method of/ZnO, including walk as follows It is rapid:
Step 1, nanometer threadiness ZnO is prepared
Zinc nitrate and hexa are mixed to get electrolyte, using three-electrode system, use electrochemical workstation Apply certain voltage, set temperature and time, deposits ZnO nano-wire film in FTO conductive glass surface；
Step 2, Bi is prepared2S3/ ZnO composite material
Using bismuth nitrate solution as the source Bi, sodium sulfide solution is adsorbed on obtained ZnO by continuous ionic layer and receives as the source S Compound Bi on rice noodles film2S3, finally obtain Bi2S3/ ZnO photo-anode material.
In above-mentioned steps 1, nitric acid zinc concentration is 0.01M, and hexa concentration is 0.03M.
In above-mentioned steps 1, the voltage of application is -1.0V, and the temperature set is 80 DEG C, and the time set is 3h.
In above-mentioned steps 1, the size of FTO electro-conductive glass is 15mm × 10mm, and resistivity is 10 Ω/cm2。
In above-mentioned steps 2, the source Bi solution is by 0.06g Bi (NO3)3·5H2O is dissolved in 25mL ethylene glycol and obtains.
In above-mentioned steps 2, the source S solution is by 0.15g Na2S·9H2O is dissolved in 25mL deionized water and obtains.
In above-mentioned steps 2, continuous ionic layer is adsorbed as obtained ZnO nano-wire film cycle alternation immersing the source Bi and the source S In, 1min is adsorbed, then taking-up is rinsed with deionized water and dries 5min (preferably 80 DEG C) in 75 DEG C -80 DEG C of baking oven, circulation Bi is made in absorption 20 times2S3/ ZnO laminated film light anode.
In above-mentioned steps 2, refer to for circulation absorption 1 time to immerse ZnO film in the source Bi and adsorb 1min, then take out spend from Sub- water rinses and dries in 80 DEG C of baking ovens 5min, then ZnO film is immersed in the source S and adsorbs 1min, then takes out and uses deionized water It rinses and dries 5min in 80 DEG C of baking ovens.
After adopting the above scheme, light anode material performance of the present invention is high, and preparation cost is low, compared with general cathodic protection material Without sacrificial anode, can be recycled.ZnO itself is preferable in ultraviolet light wave section photocatalysis effect, and ultraviolet light is only in sunlight 4% is accounted for, by forming hetero-junctions in conjunction with narrow band gap metal sulfide bismuth sulfide, its photoresponse region is expanded to visible region Domain greatly improves its utilization rate to visible light.Material involved in the present invention can be realized under visible light to 304 stainless steels With the photocathode protective effect of Q235 carbon steel, protecting effect is good.
Detailed description of the invention
Fig. 1 is ZnO and Bi2S3The XRD diagram of/ZnO material；
Fig. 2 is Bi2S3The EDS of/ZnO material schemes；
Fig. 3 is ZnO and Bi2S3The SEM of/ZnO material schemes；
Wherein, (a) is ZnO, (b) is Bi2S3/ZnO；
Fig. 4 is ZnO and Bi2S3The DRS of/ZnO material schemes；
Fig. 5 is ZnO and Bi2S3/ ZnO material performance testing device schematic diagram；
Fig. 6 is ZnO and Bi2S3The OCP comparison diagram of 304 stainless steels is protected in the performance test of/ZnO material；
Fig. 7 is ZnO and Bi2S3The current density comparison diagram of 304 stainless steels is protected in the performance test of/ZnO material；
Fig. 8 is ZnO and Bi2S3The OCP comparison diagram of/ZnO material performance test protection Q235 carbon steel；
Fig. 9 is ZnO and Bi2S3The current density comparison diagram of/ZnO material performance test protection Q235 carbon steel.
Specific embodiment
Below with reference to attached drawing, technical solution of the present invention and beneficial effect are described in detail.
It is Bruker-AXS SMART APEX- II that XRD, which detects used instrument,；
Instrument used in EDS analysis and SEM morphology observation is Hitachi S-4800；
DRS is tested using Varian Cary 5000；
The used electrochemical workstation of performance test is Shanghai Chen Hua CHI760E, and simulated visible light light source is that Beijing pool is luxuriant and rich with fragrance Lay PLS-SXE300.
(1) FTO electro-conductive glass is immersed in detergent, grease stain, the sweat stain on substrate is taken out, then with absorbent cotton by glass The dirt and impurity particle of glass on piece are wiped, and are rinsed with deionized water.Then by substrate successively isopropanol, ethyl alcohol, go from It is cleaned by ultrasonic 10min in sub- water, is repeated 3 times, make noresidue impurity particle on sheet glass, finally uses baking oven at 70 DEG C of heat it Manage 30min.
(2) 0.01M Zn (NO is prepared3)2Electrolyte is placed on magnetic stirring apparatus by the electrolyte of+0.03M hexa Upper to be uniformly mixed, setting temperature is 80 DEG C.Using three-electrode system, reference electrode is saturated calomel electrode, auxiliary electrode Pt Electrode.Working electrode is adjusted to submerge in electrolytic cell the position of liquid level of solution just and three electrodes of electrochemical workstation Clip is clipped in respectively on corresponding three electrodes of electrolytic cell.Then open the test software of electrochemical workstation, setting deposition electricity Position is -1.0V, and the time is that 3h carries out film growth.
(3) after testing, sample is taken out, sample is rinsed with a large amount of deionized waters, puts it into thermostatic drying chamber and dry It is dry.Obtain ZnO nano-wire film.
(4) 0.06g Bi (NO is taken3)3·5H2O is dissolved in 25mL ethylene glycol the source Bi that is configured to, and takes 0.15g Na2S· 9H2O is dissolved in 25mL deionized water the source S that is configured to.Obtained ZnO film cycle alternation is immersed in the source Bi and the source S, absorption 1min, taking-up is rinsed with deionized water and dries 5min in 80 DEG C of baking ovens after absorption every time, will immerse the source Bi and the source S as one Circulation absorption 20 times, Bi is made in circulation2S3/ ZnO laminated film light anode.
(5) by ZnO and Bi2S3/ ZnO carries out XRD test, and surface sweeping range is 20 ° -90 °, as shown in Figure 1.The result shows that institute The material of preparation is really ZnO and Bi2S3/ZnO。
(6) by Bi2S3/ ZnO carries out EDS analysis, as shown in Figure 2.The result shows that prepared material is really Bi2S3/ ZnO。
(7) by ZnO and Bi2S3/ ZnO carries out SEM morphology observation, as shown in Figure 3.The result shows that prepared ZnO is length The about nano wire of 300nm, Bi2S3Uniform modification is less than the nanoparticle of 50nm for average diameter on its surface.
(8) by ZnO and Bi2S3/ ZnO carries out DRS characterization, as shown in Figure 4.The result shows that prepared ZnO absorption maximum Wavelength is about 390nm, by Kubleka-Munk formula calculate its forbidden bandwidth is about 3.2eV, Bi2S3The absorption maximum of/ZnO Wavelength is significantly improved, calculate its forbidden bandwidth is about 2.6eV, show Bi2S3The range of ZnO after modification to photoresponse It is expanded by UV light region to visible light region.
(9) according to Fig.5, performance testing device schematic diagram to ZnO and Bi2S3/ ZnO material is tested for the property, and is made Electrochemical workstation is Shanghai Chen Hua CHI760E, and simulated visible light light source is that luxuriant and rich with fragrance Lay PLS-SXE300, test knot are moored in Beijing Fruit is as shown in Figures 6 to 9.After irradiating visible light, it is then stable in certain electricity that the mixed potential of coupling electrode bears rapidly shifting Position, photopotential have certain negative shifting (Fig. 6, Fig. 8) relative to the spontaneous potential of 304 stainless steels and Q235 carbon steel. It is preferable to the protecting effect of 304SS, ZnO and Bi2S3The mixed potential of/ZnO is negative move stablize after have dropped respectively about 70mV and 420mV, Bi2S3Photopotential after/ZnO coupling has reached -930mV (vs.SCE).In comparison, prepared film pair Q235 carbon steel protecting effect is less better, because of Q235 carbon steel corrosion potential ratio 304SS stainless steel, ZnO and Bi2S3/ ZnO's The negative shifting of mixed potential has dropped about 20mV and 180mV, Bi after stablizing respectively2S3/ ZnO coupling after photopotential reached- 900mV(vs.SCE).Illustrate Bi2S3Photo-generated carrier has better separative efficiency in/ZnO optoelectronic pole, that is to say, that optoelectronic pole On light induced electron can be transferred to metal surface, therefore play the role of to it photocathode protection.It is corresponding, illumination Afterwards, electron-hole pair efficiently separates, and photoelectron is sharply increased to result in current density (Fig. 7, Fig. 9) and shuffle and then be tended towards stability. When film photoelectric electrode and metal (304 stainless steels and Q235 carbon steel) couple, Bi2S3Photogenerated current density (the 94.35 μ A/ of/ZnO cm2With 107.10 μ A/cm2) than ZnO (32.00 μ A/cm2With 17.80 μ A/cm2) height, this is consistent with OCP test result.As a result Show that compound film optoelectronic pole can play good photocathode protective effect to 304 stainless steels and Q235 carbon steel.
The above examples only illustrate the technical idea of the present invention, and this does not limit the scope of protection of the present invention, all According to the technical idea provided by the invention, any changes made on the basis of the technical scheme each falls within the scope of the present invention Within.

Claims (8)

1. a kind of optical anode material Bi with optical electro-chemistry cathodic protection effect2S3The preparation method of/ZnO, it is characterised in that packet Include following steps:
Step 1, nanometer threadiness ZnO is prepared
Zinc nitrate and hexa are mixed to get electrolyte, using three-electrode system, applied using electrochemical workstation Certain voltage, set temperature and time deposit ZnO nano-wire film in FTO conductive glass surface；
Step 2, Bi is prepared2S3/ ZnO composite material
Using bismuth nitrate solution as the source Bi, sodium sulfide solution is adsorbed on obtained ZnO nano-wire as the source S, by continuous ionic layer Compound Bi on film2S3, finally obtain Bi2S3/ ZnO photo-anode material.
2. preparation method as described in claim 1, it is characterised in that: in the step 1, nitric acid zinc concentration is 0.01M, and six is sub- Tetramine concentration is 0.03M.
3. preparation method as described in claim 1, it is characterised in that: in the step 1, the voltage of application is -1.0V, setting Temperature be 80 DEG C, the time set is 3h.
4. preparation method as described in claim 1, it is characterised in that: in the step 1, the size of FTO electro-conductive glass is 15mm × 10mm, resistivity are 10 Ω/cm2。
5. preparation method as described in claim 1, it is characterised in that: in the step 2, the source Bi solution is by 0.06g Bi (NO3)3·5H2O is dissolved in 25mL ethylene glycol and obtains.
6. preparation method as described in claim 1, it is characterised in that: in the step 2, the source S solution is by 0.15g Na2S· 9H2O is dissolved in 25mL deionized water and obtains.
7. preparation method as described in claim 1, it is characterised in that: in the step 2, continuous ionic layer is adsorbed as to be made ZnO nano-wire film cycle alternation immerses in the source Bi and the source S, adsorbs 1min, then taking-up rinsed with deionized water and 75 DEG C- 5min is dried in 80 DEG C of baking oven, and circulation absorption 20 times, Bi is made2S3/ ZnO laminated film light anode.
8. preparation method as claimed in claim 7, it is characterised in that: in the step 2, refer to for circulation absorption 1 time ZnO is thin Film, which immerses in the source Bi, adsorbs 1min, and 5min is rinsed with deionized water and dried in 75 DEG C -80 DEG C of baking oven in then taking-up, then will ZnO film, which immerses in the source S, adsorbs 1min, and then taking-up is rinsed with deionized water and dries 5min in 75 DEG C -80 DEG C of baking oven.
CN201910053436.XA 2019-01-21 2019-01-21 Optical anode material Bi with optical electro-chemistry cathodic protection effect2S3The preparation method of/ZnO Pending CN109609960A (en)

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CN110016709A (en) * 2018-11-15 2019-07-16 暨南大学 Zn@P nano-deposit with photoproduction cathodic protection effect and preparation method thereof
CN110205634A (en) * 2019-05-24 2019-09-06 中山大学 A kind of ZnO/ZnS/CdS photo-anode film and preparation method thereof
CN114085043A (en) * 2022-01-18 2022-02-25 青岛理工大学 Composite film for photoelectric cathode protection and preparation method and application thereof
CN114686893A (en) * 2022-03-03 2022-07-01 青岛理工大学 Cathodic protection Z-type photo-anode material, and ionic layer deposition preparation method and application
CN115433943A (en) * 2022-09-09 2022-12-06 中国科学院海洋研究所 Energy storage type semiconductor composite photo-anode for metal corrosion protection

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110016709A (en) * 2018-11-15 2019-07-16 暨南大学 Zn@P nano-deposit with photoproduction cathodic protection effect and preparation method thereof
CN110205634A (en) * 2019-05-24 2019-09-06 中山大学 A kind of ZnO/ZnS/CdS photo-anode film and preparation method thereof
CN110205634B (en) * 2019-05-24 2021-04-20 中山大学 ZnO/ZnS/CdS photo-anode film and preparation method thereof
CN114085043A (en) * 2022-01-18 2022-02-25 青岛理工大学 Composite film for photoelectric cathode protection and preparation method and application thereof
CN114686893A (en) * 2022-03-03 2022-07-01 青岛理工大学 Cathodic protection Z-type photo-anode material, and ionic layer deposition preparation method and application
CN114686893B (en) * 2022-03-03 2023-10-20 青岛理工大学 Cathode protection Z-type photo-anode material, ion layer deposition preparation method and application
CN115433943A (en) * 2022-09-09 2022-12-06 中国科学院海洋研究所 Energy storage type semiconductor composite photo-anode for metal corrosion protection
CN115433943B (en) * 2022-09-09 2023-10-20 中国科学院海洋研究所 Energy storage type semiconductor composite photo-anode for metal corrosion protection

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Application publication date: 20190412