CN114214703B - Z-type heterojunction composite photo-anode membrane and preparation method and application thereof - Google Patents

Z-type heterojunction composite photo-anode membrane and preparation method and application thereof Download PDF

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CN114214703B
CN114214703B CN202210159394.XA CN202210159394A CN114214703B CN 114214703 B CN114214703 B CN 114214703B CN 202210159394 A CN202210159394 A CN 202210159394A CN 114214703 B CN114214703 B CN 114214703B
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anode
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iron matrix
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CN114214703A (en
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张小影
王晓晴
金祖权
蒋浩森
熊传胜
陈越华
程海洋
唐恒
闫杰
刘佳豪
王亚伟
刘世闯
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Qingdao University of Technology
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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
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    • C—CHEMISTRY; METALLURGY
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    • C23F2201/02—Concrete, e.g. reinforced
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Abstract

The invention provides aA Z-shaped heterojunction composite photo-anode film and a preparation method and application thereof belong to the technical field of corrosion inhibition of ocean engineering metal materials. The preparation method comprises the following steps: step one, pretreating an iron matrix to obtain a pretreated iron matrix; step two, putting the pretreated iron matrix into a reactor containing NH4Carrying out anodic oxidation reaction in the mixed solution of the F solution and the ethylene glycol solution to prepare Fe2O3(ii) a Step three, sequentially putting the iron matrix subjected to the anodic oxidation reaction into a cerium source and a sulfur source for soaking, then taking out and drying, circulating the soaking, taking out and drying steps for several times, and performing ion layer deposition to obtain a photo-anode material; step four, roasting the photo-anode material to obtain Fe2O3‑Ce2S3And (3) compounding the light anode film. The composite photo-anode membrane is a novel Z-shaped heterojunction structure, can realize high-efficiency photoelectric cathode protection of a marine engineering structure, and improves the durability of a marine engineering structure.

Description

Z-type heterojunction composite photo-anode membrane and preparation method and application thereof
Technical Field
The invention belongs to the technical field of corrosion inhibition of metal materials of a marine engineering concrete structure, and particularly relates to a Z-type heterojunction composite photo-anode film as well as a preparation method and application thereof.
Background
In the marine environment, the corrosion of the steel bars caused by the corrosion of chloride ions is a main cause of the deterioration failure of marine reinforced concrete. The corrosion of steel reinforcement presents various maintenance problems to many concrete structures when the predetermined age is not reached, resulting in a significant economic loss. Therefore, the problem of corrosion of the steel bars in the concrete is solved, the service life of the ocean engineering structure is prolonged, and the research on the steel bar corrosion protection technology is not slow.
Among the steel bar corrosion protection technologies, cathodic protection is one of the most economical and effective measures in marine concrete protection technologies. Cathodic protection, which is a cathodic protection method involving a sacrificial anode and a cathodic protection method involving an applied electric current, inhibits the corrosion of reinforcing steel by forcing the reinforcing steel to become a cathode by transporting a sufficient amount of electrons to the surface of the reinforcing steel to prevent the release of electrons from iron atoms. The cathodic protection method of the sacrificial anode adopts metal (such as magnesium, zinc and the like) which is more active than iron in chemistry as the anode and is connected with the protected steel bar, the metal material with stronger reduction characteristic preferentially oxidizes rust, and the steel bar is protected by 'sacrificing' the metal material. The sacrificial anode method provides a limited protection current and is difficult to protect the steel bar for a long time. The cathodic protection principle of impressed current is to utilize an impressed power supply to apply a certain current to the steel bar to promote the steel bar matrix to gather a large amount of free electrons, and all areas of the steel bar are forced to become cathodic areas, thereby avoiding the problem that the steel bar is corroded as an anode. In principle, the impressed current cathodic protection method has the defects of thorough, stable and firm effect, continuous maintenance and management, high operation cost, long service life of the anode and possibility of over-protection, so that the application range of the method is greatly limited.
The photocathode protection is a novel cathode protection technology, which utilizes inexhaustible solar energy to carry out corrosion protection. The principle of the method is that valence band electrons are excited to a conduction band to form separation of photo-generated electron holes under the condition that a semiconductor photo-anode is excited by incident light. If the photo-generated electron potential is lower than the metal self-corrosion potential, they can be transferred to the metal to which they are electrically connected and form an enrichment at the metal surface, thus achieving cathodic protection of the metal. The semiconductor photo-anode is used as a photoelectric conversion center to continuously convert solar energy to generate photo-generated electrons, and electrons are provided without adding electric energy or corroding sacrificial anode materials. Meanwhile, the photo-generated holes can be transferred to the surface of the photo-anode to oxidize substances such as water, organic pollutants, bacteria and the like around the photo-anode, and the purpose of environmental purification can be achieved to a certain extent. Therefore, in view of the harmfulness of metal corrosion and the superiority of photoelectrochemical cathodic protection, the technology is worthy of intensive research and popularization.
TiO2、ZnO、g-C3N4、SrTiO3And the like are the most common photocathode-protecting photoanode materials, but a single photo-semiconductor material tends to have a fast rate of recombination of photo-generated electrons and holes, so that fewer photo-generated electrons can be effectively used for photocathode protection. Researches show that the separation efficiency of photo-generated electron holes and the utilization rate of sunlight can be remarkably improved through the construction of the heterojunction. However, most of the currently adopted heterojunction is a type II heterojunction, and although the heterojunction improves the separation efficiency of photo-generated electrons and holes, the heterojunction takes the oxidation-reduction property of a sacrificial semiconductor material as a cost, so that the reduction property of the photo-generated electrons is reduced and the photo-generated electrons are difficult to transfer to a steel bar to be protected; meanwhile, the oxidability of the photo-generated holes is reduced, so that an electron loop cannot be formed, and the cathode protection cannot be provided for the concrete structure reinforcing steel bars of the ocean building engineering or the protection effect is not ideal.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide Z-type heterojunction Fe2O3-Ce2S3The composite photo-anode film and the preparation method and application thereof are used for solving the problem that the existing photo-anode material metal for the protection of the photocathode has poor corrosion prevention effect.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a Z-shaped heterojunction composite photo-anode membrane comprises the following steps:
step one, pretreating an iron matrix to obtain a pretreated iron matrix;
step two, putting the pretreated iron matrix into a reactor containing NH4Carrying out anodic oxidation reaction in the mixed solution of the F solution and the ethylene glycol solution to prepare Fe2O3；
Step three, sequentially putting the iron matrix subjected to the anodic oxidation reaction into a cerium source and a sulfur source for soaking, then taking out and drying, circulating the soaking, taking out and drying steps for several times, and performing ion layer deposition to obtain a photo-anode material;
step four, roasting the photo-anode material to obtain Fe2O3-Ce2S3And (3) compounding the light anode film.
In the above preparation method of the Z-type heterojunction composite photo-anode film, preferably, in the step one, the pretreatment specifically comprises: polishing an iron matrix with sand paper, sequentially performing ultrasonic treatment for 5-30min with ethanol and water respectively, then placing the iron matrix in an acid solution, soaking at 20-80 ℃ for 5-50min, cleaning and drying to obtain a pretreated iron matrix;
the iron matrix is a steel bar;
the acid solution is one or more of hydrochloric acid solution, nitric acid solution, sulfuric acid solution, phosphoric acid solution, hydrofluoric acid solution and citric acid solution.
In the preparation method of the Z-type heterojunction composite photoanode membrane, preferably, in the second step, NH is adopted4The concentration of the F solution is 0.05-2 mol/L; the ethylene glycol solution is an aqueous solution of ethylene glycol, and the concentration of the ethylene glycol solution is 0.05-1 mol/L.
In the above preparation method of the Z-type heterojunction composite photo-anode film, preferably, the anodic oxidation reaction specifically comprises: taking the pretreated iron substrate as an anode and an inert conductive electrode as a cathode, wherein the voltage of anodic oxidation is 20-60V, the temperature is 20-80 ℃, and the reaction time is 10min-10h under constant pressure;
the inert conductive electrode is a glassy carbon electrode, a platinum electrode or a graphite electrode.
Preferably, the third step of the preparation method of the Z-type heterojunction composite photo-anode film is to sequentially put the iron substrate subjected to the anodic oxidation reaction into a cerium source to be soaked for 1-20min, then to be washed by water to remove the redundant adsorption liquid, to be further soaked in a sulfur source for 1-20min, to be washed by water to remove the redundant adsorption liquid, and to be dried for 1-30min at 60-90 ℃, so that the cycle is a cycle with the cycle number of 1-50 times.
In the preparation method of the Z-type heterojunction composite photo-anode film, preferably, the concentration of the cerium source and the concentration of the sulfur source are both 0.1-1 mol/L;
the cerium source is inorganic salt or organic salt containing cerium; the sulfur source is inorganic salt or organic salt containing sulfur.
In the preparation method of the Z-type heterojunction composite photo-anode film, preferably, the roasting temperature is controlled to be 250-900 ℃ in the roasting treatment process, and the roasting time is 1-12 h.
In the preparation method of the Z-type heterojunction composite photo-anode film, preferably, the heating rate in the roasting treatment process is 1-20 ℃/min.
The composite light anode film is prepared by the preparation method of the Z-type heterojunction composite light anode film.
The application of the Z-shaped heterojunction composite photo-anode film is used for a marine concrete structure reinforcing steel bar photoelectric protection photo-anode film.
Has the advantages that:
the Z-shaped heterojunction composite photo-anode film prepared by the invention enables the corrosion potential of the steel bar to be negatively shifted to-1.2V under illumination. The mott schottky curve further illustrates that the composite film is a Z-type heterojunction structure. Photoluminescence spectrum (PL) and alternating current impedance (EIS) curves show that the composite photo-anode film effectively improves the separation efficiency of photo-generated electron-hole pairs. The composite photo-anode membrane is a novel Z-shaped heterojunction structure, can realize high-efficiency photoelectric cathode protection of a marine engineering structure, and improves the durability of a marine engineering structure.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 shows Ce provided in example 1 of the present invention under intermittent illumination2S3Photoanode film and Fe2O3-Ce2S3A photo-induced Open Circuit Potential (OCP) test result graph of the composite photo-anode film;
FIG. 2 shows Fe prepared in example 2 of the present invention2O3Photo-anodic film, Ce2S3Photoanode film and Fe2O3-Ce2S3The mott schottky curve of the composite photo-anode film;
FIG. 3 shows Fe prepared in example 3 of the present invention under irradiation of light2O3Photo-anodic film, Ce2S3Photoanode film and Fe2O3-Ce2S3An alternating current impedance (EIS) curve of the composite photoanode membrane;
FIG. 4 shows Fe prepared in example 4 of the present invention2O3Photo-anodic film, Ce2S3Photoanode film and Fe2O3-Ce2S3Photoluminescence (PL) spectrum of the composite photoanode film.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
Aiming at the problem that the protection effect is not ideal when the II-type heterojunction is used for the cathodic protection of the marine structural steel bar at present, the invention provides Z-type Fe for the metal corrosion prevention of marine building engineering2O3-Ce2S3Of composite anodic filmPreparation method of Fe2O3-Ce2S3The composite photoanode film is used for metal corrosion prevention in marine building engineering, and is formed on the surface of a steel bar through an anodic oxidation method, an ion layer deposition method and high-temperature roasting treatment, wherein Fe is contained in the composite photoanode film2O3-Ce2S3The composite photo-anode membrane belongs to a heterojunction structure, is in a Z-shaped electron transmission mode, can remarkably improve the oxidation-reduction property of the composite membrane, improves the separation efficiency of photo-generated charges, realizes the high-efficiency photoelectric cathode protection of concrete reinforcing bars of ocean engineering structures, and improves the durability of ocean engineering concrete structures. This is because of Fe2O3And Ce2S3With matched band structure, Ce2S3Has a lower conduction band potential (-0.91V vs. NHE), and Fe2O3Has higher valence-band potential (2.48V vs. NHE) and Fe2O3Conduction band potential (0.28V vs. NHE) of Ce2S3Lower valence band potential (1.19V vs. NHE), Fe2O3The photo-generated electrons on the conduction band can be transferred to Ce2S3In the valence band with Ce2S3The photogenerated holes on the valence band recombine to form Z-type electron transport. Under illumination, Fe2O3-Ce2S3At Ce2S3The conduction band is enriched, has high reduction activity, is easy to transfer to the surface of the steel bar which is electrically connected with the conduction band, and provides cathodic protection current for the steel bar. While the photogenerated holes remain in Fe2O3The valence band of the anode has high oxidation activity, and can oxidize surrounding air or water, promote the whole charge movement loop and improve the cathode protection effect.
The invention provides Z-type heterojunction Fe2O3-Ce2S3The preparation method of the composite photo-anode film comprises the following steps:
step one, preprocessing an iron matrix to obtain the preprocessed iron matrix.
In a specific embodiment of the invention, the iron matrix is pretreated by: sequentially polishing an iron matrix by using 80-2000-mesh abrasive paper, sequentially performing ultrasonic treatment for 5-30min by using ethanol and water respectively (namely performing ultrasonic treatment for 5-30min in ethanol and then placing the iron matrix into water for ultrasonic treatment for 5-30 min), placing the iron matrix into an acid solution, soaking for 5-50min at 20-80 ℃, cleaning and drying to obtain a pretreated iron matrix;
the iron matrix is a steel bar, preferably a carbon steel bar or a stainless steel bar; the two reinforcing steel bars are two most commonly used materials in marine structures, and the composite anode film prepared by taking the two reinforcing steel bars as a matrix is more suitable for efficient photoelectric cathode protection of concrete reinforcing steel bars of ocean engineering structures.
The acid solution is one or more of hydrochloric acid solution, nitric acid solution, sulfuric acid solution, phosphoric acid solution, hydrofluoric acid solution and citric acid solution.
Step two, putting the pretreated iron matrix into a reactor containing NH4Carrying out anodic oxidation reaction in the mixed solution of the F solution and the ethylene glycol solution to prepare Fe2O3。
In an embodiment of the present invention, in step two, NH4The concentration of the F solution is 0.05-2 mol/L; the ethylene glycol solution is an aqueous solution of ethylene glycol, and the concentration of the ethylene glycol solution is 0.05-1 mol/L. NH (NH)4The F solution mainly plays a role of a corrosive medium, and the ethylene glycol solution can ensure the stability of anodic oxidation voltage when NH is used4The F solution is not beneficial to Fe when the concentration is too high or too low2O3The film formation, the voltage instability caused by the over-high or over-low concentration of the glycol solution, and the Fe influence2O3The formation of the film prolongs the preparation time and reduces the preparation efficiency.
In a specific embodiment of the present invention, the anodic oxidation reaction specifically comprises: taking the pretreated iron substrate as an anode and an inert conductive electrode as a cathode, wherein the voltage of anodic oxidation is 20-60V, the temperature is 20-80 ℃, and the reaction time is 10min-10h under constant pressure; preferably, the inert conductive electrode is a glassy carbon electrode, a platinum electrode or a graphite electrode.
And step three, sequentially putting the iron matrix subjected to the anodic oxidation reaction into a cerium source and a sulfur source for soaking, then taking out and drying, circulating the soaking, taking out and drying steps for several times, and performing ion layer deposition to obtain the photo-anode material.
In the specific embodiment of the invention, the iron matrix after the anodic oxidation reaction is sequentially placed into a cerium source to be soaked for 1-20min, then the iron matrix is washed by water to remove the redundant adsorption liquid, then the iron matrix is placed into a sulfur source to be soaked for 1-20min, the redundant adsorption liquid is washed by water to remove, and the iron matrix is dried for 1-30min at the temperature of 60-90 ℃, so that the cycle is a cycle, and the cycle frequency is 1-50 times.
The concentration of the cerium source and the sulfur source is 0.1-1 mol/L;
the cerium source is inorganic salt or organic salt containing cerium; preferably cerium nitrate, cerium chloride, cerium acetate or cerium citrate; the sulfur source is inorganic salt or organic salt containing sulfur; preferably thiourea, thioacetamide, sodium sulfite or ammonium sulfite.
Step four, roasting the photo-anode material to obtain Fe2O3-Ce2S3And (3) compounding the light anode film.
In the specific embodiment of the invention, the third step is specifically that the photo-anode material prepared in the third step is placed into a muffle furnace, the roasting temperature is controlled to be 250-2O3-Ce2S3And (3) compounding the light anode film.
The Z-shaped heterojunction composite photo-anode film prepared by the invention is used for a marine concrete structure reinforcing steel bar photoelectric protection photo-anode film.
Example 1
The preparation method of the Z-type heterojunction composite photo-anode film provided by the embodiment comprises the following steps:
(1) firstly, stainless steel reinforcing steel bars are sequentially polished by No. 80-2000 abrasive paper, ethanol and water are respectively used for ultrasonic treatment for 5 minutes, then the polished reinforcing steel bars are placed in a mixed solution of 0.5mol/L nitric acid and sulfuric acid (the concentration of nitric acid and sulfuric acid solutes in the mixed solution is 0.5mol/L, and H is ensured+Concentration is 0.5 mol/L) is soaked for 50min at 20 ℃, cleaned and dried for standby.
(2) Preparation of a solution containing 0.05mol/L NH4And (2) putting the steel bar treated in the step (1) into the solution to serve as an anode and a glassy carbon electrode to serve as a cathode, wherein the oxidation voltage of the anode is 60V, and reacting for 10 hours at a constant pressure at 20 ℃.
(3) Respectively preparing 0.1mol/L cerium nitrate solution and 0.1mol/L thiourea solution, soaking the sample obtained in the step (2) in the cerium nitrate solution for 20min, then washing with water to remove the redundant adsorption liquid, then soaking in the thiourea solution for 20min, washing with water to remove the redundant adsorption liquid, drying at 90 ℃ for 1min, and circulating for 50 times to obtain the photoanode material.
(4) Putting the photo-anode material prepared in the step (3) into a muffle furnace, calcining at 250 ℃ for 12h, heating at the rate of 1 ℃/min, and naturally cooling to room temperature to obtain Fe2O3-Ce2S3And (3) compounding the light anode film.
To facilitate performance comparison tests, Ce is also provided in this example2S3And (3) a preparation process of the membrane.
(1) Firstly, stainless steel reinforcing steel bars are sequentially polished by No. 80-2000 abrasive paper, ethanol and water are respectively used for ultrasonic treatment for 5 minutes, then the polished reinforcing steel bars are placed in a mixed solution of 0.5mol/L nitric acid and sulfuric acid (wherein the concentration of nitric acid and sulfuric acid solutes in the mixed solution is 0.5mol/L, and H is ensured+Concentration is 0.5 mol/L) is soaked for 50min at 20 ℃, cleaned and dried for standby.
(2) Respectively preparing 0.1mol/L cerium nitrate solution and 0.1mol/L thiourea solution, soaking the sample obtained in the step (1) in the cerium nitrate solution for 20min, then washing with water to remove the redundant adsorption liquid, then soaking in the thiourea solution for 20min, washing with water to remove the redundant adsorption liquid, drying at 90 ℃ for 1min, and circulating for 50 times to obtain the photoanode material.
(3) Putting the photo-anode material prepared in the step (2) into a muffle furnace, calcining for 12h at 250 ℃, heating at the rate of 1 ℃/min, and naturally cooling to room temperature to obtain Ce2S3And (3) a photoanode film.
The prepared metal for ocean building engineeringRotten Fe2O3-Ce2S3Composite photo-anode film and Ce2S3The photo-anode film is used as a photo-anode material for photo-generated cathodic protection test:
fe prepared by testing under intermittent sunlight irradiation2O3-Ce2S3Composite photo-anode film and Ce2S3And the potential of the photo-anode film after being coupled with the concrete structure steel bar of the ocean building engineering changes, so that the photoelectric cathode protection performance of different photo-anode films on the steel bar is judged. As can be seen from FIG. 1, Ce is coupled2S3When the photo-anode film is used, the corrosion potential of the steel bar is negatively shifted from-0.62V in a dark state to-0.88V under illumination, which indicates that Ce is in the illumination2S3Can provide certain cathodic protection effect for carbon steel. And the Fe for the metal corrosion prevention of the marine construction engineering coupled with the embodiment2O3-Ce2S3The corrosion potential of the steel bar of the composite photo-anode membrane is negatively shifted from-0.62V in a dark state to about-1.25V under illumination, and the corrosion potential of the steel bar is negatively shifted by more than 630 millivolts. Fe prepared in this example2O3-Ce2S3The composite photo-anode film has good corrosion prevention effect on the steel bars.
Example 2
The preparation method of the Z-type heterojunction composite photo-anode film provided by the embodiment comprises the following steps:
(1) firstly, stainless steel reinforcing steel bars are sequentially polished by 80-2000-mesh sand paper, ultrasonic treatment is respectively carried out on the stainless steel reinforcing steel bars by ethanol and water for 30 minutes, then the polished reinforcing steel bars are placed in a mixed solution of 6mol/L phosphoric acid, nitric acid, hydrofluoric acid and acetic acid (wherein the concentration of solutes of the phosphoric acid, the nitric acid, the hydrofluoric acid and the acetic acid in the mixed solution is 6mol/L, and H is ensured+Concentration is 6 mol/L) is soaked for 5min at 40 ℃, cleaned and dried for standby.
(2) Preparation of a solution containing 2mol/L NH4And (3) putting the steel bar treated in the step (1) into the solution to serve as an anode and a graphite electrode to serve as a cathode, wherein the solution F and a 1mol/L ethylene glycol aqueous solution react for 5 hours at a constant pressure at 80 ℃ under the condition that the anode oxidation voltage is 20V.
(3) Respectively preparing 1mol/L cerium citrate solution and 1mol/L thioacetamide solution, soaking the sample obtained by the treatment in the step (2) in the cerium citrate solution for 1min, then washing with water to remove the redundant adsorption liquid, then placing the sample in the thioacetamide solution for soaking for 1min, washing with water to remove the redundant adsorption liquid, drying at 70 ℃ for 15 min, and circulating for 1 time to obtain the photoanode material.
(4) Putting the photo-anode material prepared in the step (3) into a muffle furnace, calcining for 1h at 900 ℃, heating at the rate of 20 ℃/min, and naturally cooling to room temperature to obtain Fe2O3-Ce2S3And (3) a composite photo-anode film.
To facilitate performance comparison tests, Ce is also provided in this example2S3Film and Fe2O3And (3) a preparation process of the membrane.
Ce2S3The membrane was prepared as follows:
(1) firstly, stainless steel reinforcing steel bars are sequentially polished by 80-2000-mesh sand paper, ultrasonic treatment is respectively carried out on the stainless steel reinforcing steel bars by ethanol and water for 30 minutes, then the polished reinforcing steel bars are placed in a mixed solution of 6mol/L phosphoric acid, nitric acid, hydrofluoric acid and acetic acid (wherein the concentration of solutes of the phosphoric acid, the nitric acid, the hydrofluoric acid and the acetic acid in the mixed solution is 6mol/L, and H is ensured+Concentration is 6 mol/L) is soaked for 5min at 40 ℃, cleaned and dried for standby.
(2) Respectively preparing 1mol/L cerium citrate solution and 1mol/L thioacetamide solution, soaking the sample obtained by the treatment in the step (1) in the cerium citrate solution for 1min, then washing with water to remove the redundant adsorption liquid, then placing the sample in the thioacetamide solution for soaking for 1min and washing with water to remove the redundant adsorption liquid, drying at 70 ℃ for 15 min, and circulating for 1 time, namely only performing the soaking, taking out and drying steps once to obtain the photo-anode material.
(3) Putting the photo-anode material prepared in the step (2) into a muffle furnace, calcining for 1h at 900 ℃, heating at the rate of 20 ℃/min, and naturally cooling to room temperature to obtain Ce2S3And (3) a photoanode film.
Fe2O3The membrane was prepared as follows:
(1) firstly, stainless steel reinforcing steel bars are sequentially polished by 80-2000-mesh sand paper, ultrasonic treatment is respectively carried out on the stainless steel reinforcing steel bars by ethanol and water for 30 minutes, then the polished reinforcing steel bars are placed in a mixed solution of 6mol/L phosphoric acid, nitric acid, hydrofluoric acid and acetic acid (wherein the concentration of solutes of the phosphoric acid, the nitric acid, the hydrofluoric acid and the acetic acid in the mixed solution is 6mol/L, and H is ensured+Concentration is 6 mol/L) is soaked for 5min at 40 ℃, cleaned and dried for standby.
(2) Respectively preparing 1mol/L cerium citrate solution and 1mol/L thioacetamide solution, soaking the sample obtained by the treatment in the step (1) in the cerium citrate solution for 1min, then washing with water to remove the redundant adsorption liquid, then placing the sample in the thioacetamide solution for soaking for 1min, washing with water to remove the redundant adsorption liquid, drying at 70 ℃ for 15 min, and circulating for 1 time to obtain the photoanode material.
(3) Putting the photo-anode material prepared in the step (2) into a muffle furnace, calcining for 1h at 900 ℃, heating at a rate of 20 ℃/min, and naturally cooling to room temperature to obtain Fe2O3And (3) a photoanode film.
For the obtained Fe2O3Photo-anodic film, Ce2S3Photoanode film and Fe2O3-Ce2S3The flat band potential and Mott Schottky result of the composite photo-anode film is shown in FIG. 2
As can be seen from fig. 2: fe2O3、Ce2S3And Fe2O3-Ce2S3The slope of the mott schottky curves of (a) are all positive values, indicating that they are all n-type semiconductors. At the same time, Fe2O3-Ce2S3The flat band potential of (A) is-0.98V vs. SCE, Ce2S3And Fe2O3The flat band potentials of the composite material are respectively-0.7V vs. SCE and-0.1V vs. SCE, which shows that the composite material retains a lower conduction band potential, so that the heterojunction is a Z-type heterojunction. The flat potential is far lower than the self-corrosion potential of the steel bar, so that the cathode protection can be provided for the steel bar in the concrete structure of the ocean building engineering under the illumination.
Example 3
The preparation method of the Z-type heterojunction composite photo-anode film provided by the embodiment includes the following steps:
(1) firstly, carbon steel bars are sequentially polished by 80-2000-mesh sand paper, ethanol and water are respectively used for ultrasonic treatment for 15 minutes, then the polished steel bars are placed in 3mol/L phosphoric acid solution to be soaked for 20 minutes at 80 ℃, and the steel bars are cleaned and dried for standby.
(2) Preparation of a solution containing 1mol/L NH4F and 0.5mol/L ethylene glycol aqueous solution, putting the steel bar treated in the step (1) into the solution to be used as an anode, using a platinum electrode as a cathode, and reacting at constant voltage of 40V at 80 ℃ for 10 min.
(3) Respectively preparing 0.5mol/L cerium chloride solution and 0.5mol/L sodium sulfite solution, soaking the sample obtained in the step (2) in the cerium chloride solution for 5min, then washing with water to remove the redundant adsorption liquid, then soaking in the sodium sulfite solution for 5min, washing with water to remove the redundant adsorption liquid, drying at 60 ℃ for 30min, and circulating for 20 times.
(4) Putting the photo-anode prepared in the step (3) into a muffle furnace, calcining for 10h at 450 ℃, heating at a rate of 10 ℃/min, and naturally cooling to room temperature to obtain Fe2O3-Ce2S3And (3) compounding the light anode film.
To facilitate performance comparison tests, Ce is also provided in this example2S3Film and Fe2O3And (3) a preparation process of the membrane.
Ce2S3The membrane was prepared as follows:
(1) firstly, carbon steel bars are sequentially polished by 80-2000-mesh sand paper, ethanol and water are respectively used for ultrasonic treatment for 15 minutes, then the polished steel bars are placed in 3mol/L phosphoric acid solution to be soaked for 20 minutes at 80 ℃, and the steel bars are cleaned and dried for standby.
(2) Respectively preparing 0.5mol/L cerium chloride solution and 0.5mol/L sodium sulfite solution, soaking the sample obtained in the step (1) in the cerium chloride solution for 5min, then washing with water to remove the redundant adsorption liquid, then soaking in the sodium sulfite solution for 5min, washing with water to remove the redundant adsorption liquid, drying at 60 ℃ for 30min, and circulating for 20 times.
(3) Putting the photo-anode prepared in the step (2) into a muffle furnace, calcining for 10h at 450 ℃, heating at the rate of 10 ℃/min, and naturally cooling to room temperature to obtain Ce2S3And (3) a photoanode film.
Fe2O3The membrane was prepared as follows:
(1) firstly, carbon steel bars are sequentially polished by 80-2000-mesh sand paper, ethanol and water are respectively used for ultrasonic treatment for 15 minutes, then the polished steel bars are placed in 3mol/L phosphoric acid solution to be soaked for 20 minutes at 80 ℃, and the steel bars are cleaned and dried for standby.
(2) Preparation of a solution containing 1mol/L NH4F and 0.5mol/L ethylene glycol aqueous solution, putting the steel bar treated in the step (1) into the solution to be used as an anode, using a platinum electrode as a cathode, and reacting at constant voltage of 40V at 80 ℃ for 10 min.
(3) Putting the sample prepared in the step (2) into a muffle furnace, calcining for 10h at 450 ℃, heating at the rate of 10 ℃/min, and naturally cooling to room temperature to obtain Fe2O3And (3) a photoanode film.
For Fe prepared in the examples of the present invention2O3Photo-anodic film, Ce2S3Photoanode film and Fe2O3-Ce2S3The composite photoanode membrane was subjected to EIS testing, as shown in FIG. 3. Fe2O3-Ce2S3The impedance of the composite photo-anode film is far lower than that of pure Fe2O3Photoanode film and Ce2S3Photo-anodic film, description Fe2O3-Ce2S3The construction of the Z-shaped heterojunction of the composite photo-anode membrane obviously enhances the separation efficiency of photo-generated electrons and holes.
Example 4
The preparation method of the Z-type heterojunction composite photo-anode film provided by the embodiment includes the following steps:
(1) firstly, carbon steel bars are sequentially polished by 80-2000-mesh sand paper, ethanol and water are respectively used for ultrasonic treatment for 25 minutes, then the polished steel bars are placed in 1mol/L hydrochloric acid solution to be soaked for 40 minutes at 60 ℃, and the steel bars are washed and dried by deionized water for later use.
(2) Preparation of a solution containing 1mol/L NH4And (2) putting the steel bar treated in the step (1) into the solution to serve as an anode and a glassy carbon electrode to serve as a cathode, wherein the oxidation voltage of the anode is 50V, and reacting for 5 hours at a constant pressure at 50 ℃.
(3) Respectively preparing 0.5mol/L cerium citrate solution and 0.5mol/L ammonium sulfite solution, soaking the sample obtained in the step (2) in the cerium citrate solution for 10min, then washing with water to remove the redundant adsorption liquid, then soaking in the ammonium sulfite solution for 10min, washing with water to remove the redundant adsorption liquid, drying at 60 ℃ for 30min, and circulating for 10 times to obtain the photo-anode material.
(4) Putting the photo-anode material prepared in the step (3) into a muffle furnace, calcining for 10h at 450 ℃, heating at a rate of 10 ℃/min, and naturally cooling to room temperature to obtain Fe2O3-Ce2S3And (3) compounding the light anode film.
To facilitate performance comparison tests, Ce is also provided in this example2S3Film and Fe2O3And (3) a preparation process of the membrane.
Ce2S3The membrane was prepared as follows:
(1) firstly, carbon steel bars are sequentially polished by 80-2000-mesh sand paper, ethanol and water are respectively used for ultrasonic treatment for 25 minutes, then the polished steel bars are placed in 1mol/L hydrochloric acid solution to be soaked for 40 minutes at 60 ℃, and the steel bars are washed and dried by deionized water for later use.
(2) Respectively preparing 0.5mol/L cerium citrate solution and 0.5mol/L ammonium sulfite solution, soaking the sample obtained in the step (2) in the cerium citrate solution for 10min, then washing with water to remove the redundant adsorption liquid, then soaking in the ammonium sulfite solution for 10min, washing with water to remove the redundant adsorption liquid, drying at 60 ℃ for 30min, and circulating for 10 times to obtain the photo-anode material.
(3) Putting the photo-anode material prepared in the step (2) into a muffle furnace, calcining for 10h at 450 ℃, and raising the temperature rateCooling to room temperature at a rate of 10 deg.C/min to obtain Ce2S3And (3) a photoanode film.
Fe2O3The membrane was prepared as follows:
(1) firstly, carbon steel bars are sequentially polished by 80-2000-mesh sand paper, ethanol and water are respectively used for ultrasonic treatment for 25 minutes, then the polished steel bars are placed in 1mol/L hydrochloric acid solution to be soaked for 40 minutes at 60 ℃, and the steel bars are washed and dried by deionized water for later use.
(2) Preparation of a solution containing 1mol/L NH4And (2) putting the steel bar treated in the step (1) into the solution to serve as an anode and a glassy carbon electrode to serve as a cathode, wherein the oxidation voltage of the anode is 50V, and reacting for 5 hours at a constant pressure at 50 ℃.
(3) Putting the sample prepared in the step (2) into a muffle furnace, calcining for 10h at 450 ℃, heating at the rate of 10 ℃/min, and naturally cooling to room temperature to obtain Fe2O3And (3) a photo-anode film.
For Fe obtained in this example2O3Photo-anodic film, Ce2S3Photoanode film and Fe2O3-Ce2S3The photoluminescence spectrum (PL) of the composite photo-anode film material is tested, and the test result is shown in FIG. 4. As can be seen from FIG. 4, Fe2O3-Ce2S3The strength of the composite photo-anode film is far lower than that of single Fe2O3And Ce2S3Description of Fe2O3And Ce2S3Having a band structure of Fe2O3The photo-generated electrons on the conduction band can be transferred to Ce2S3Are carried on and react with the valence band of (A) to leave photoproduction electron holes respectively in Ce2S3Conduction band and Fe2O3The valence band of the photo-generated electron-hole separation device realizes the high-efficiency separation of photo-generated electrons and holes.
In summary, the following steps: the Z-shaped heterojunction composite photo-anode film prepared by the invention enables the corrosion potential of the steel bar to be negatively shifted to-1.2V under illumination. The mott schottky curve further illustrates that the composite film is a Z-type heterojunction structure. Photoluminescence spectrum (PL) and alternating current impedance (EIS) curves show that the composite photo-anode film effectively improves the separation efficiency of photo-generated electron-hole pairs. The composite photo-anode membrane is a novel Z-shaped heterojunction structure, can realize high-efficiency photoelectric cathode protection of a marine engineering structure, and improves the durability of a marine engineering structure.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A preparation method of a Z-type heterojunction composite photo-anode membrane is characterized by comprising the following steps:
step one, pretreating an iron matrix to obtain a pretreated iron matrix; the pretreatment specifically comprises the following steps: polishing an iron matrix by using sand paper, sequentially performing ultrasonic treatment for 5-30min by using ethanol and water respectively, then placing the iron matrix in an acid solution, soaking for 5-50min at 20-80 ℃, cleaning and drying to obtain a pretreated iron matrix; the iron matrix is a steel bar; the acid solution is one or a mixture of hydrochloric acid solution, nitric acid solution, sulfuric acid solution, phosphoric acid solution, hydrofluoric acid solution and citric acid solution
Secondly, putting the pretreated iron matrix into a reactor containing NH4Carrying out anodic oxidation reaction in the mixed solution of the F solution and the ethylene glycol solution to prepare Fe2O3(ii) a The NH4The concentration of the F solution is 0.05-2 mol/L; the ethylene glycol solution is an aqueous solution of ethylene glycol, and the concentration of the ethylene glycol solution is 0.05-1 mol/L;
step three, sequentially putting the iron matrix subjected to the anodic oxidation reaction into a cerium source and a sulfur source for soaking, then taking out and drying, circulating the soaking, taking out and drying steps for several times, and performing ion layer deposition to obtain a photo-anode material;
step four, roasting the photo-anode material to obtain Fe2O3-Ce2S3A composite photo-anode film; the roasting temperature is controlled to be 250-900 ℃ in the roasting treatment process, and the roasting time is 1-12 h; the heating rate in the roasting treatment process is 1-20 ℃/min.
2. The method for preparing the Z-type heterojunction composite photo-anode film as claimed in claim 1, wherein the anodic oxidation reaction specifically comprises: taking the pretreated iron substrate as an anode and an inert conductive electrode as a cathode, wherein the voltage of anodic oxidation is 20-60V, the temperature is 20-80 ℃, and the reaction time is 10min-10h under constant pressure;
the inert conductive electrode is a glassy carbon electrode, a platinum electrode or a graphite electrode.
3. The method for preparing the Z-type heterojunction composite photoanode membrane as claimed in claim 1, wherein the step three is to sequentially put the iron substrate after the anodic oxidation reaction into a cerium source to soak for 1-20min, then wash with water to remove the excess adsorption liquid, then put into a sulfur source to soak for 1-20min, wash with water to remove the excess adsorption liquid, and dry at 60-90 ℃ for 1-30min, thereby forming a cycle with the cycle number of 1-50.
4. The method for preparing a Z-type heterojunction composite photo-anode film as claimed in claim 3, wherein the concentration of the cerium source and the concentration of the sulfur source are both 0.1-1 mol/L;
the cerium source is inorganic salt or organic salt containing cerium; the sulfur source is inorganic salt or organic salt containing sulfur.
5. A Z-type heterojunction composite photo-anode film, which is characterized in that the composite photo-anode film is prepared by the preparation method of the Z-type heterojunction composite photo-anode film as claimed in any one of claims 1 to 4.
6. The application of the Z-shaped heterojunction composite photo-anode film as claimed in claim 5, wherein the composite photo-anode film is used for a marine concrete structure reinforcing steel bar photoelectric protection photo-anode film.
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