CN114250473A - Iron oxide based Z-shaped heterojunction composite photo-anode film and preparation method and application thereof - Google Patents

Iron oxide based Z-shaped heterojunction composite photo-anode film and preparation method and application thereof Download PDF

Info

Publication number
CN114250473A
CN114250473A CN202210189801.1A CN202210189801A CN114250473A CN 114250473 A CN114250473 A CN 114250473A CN 202210189801 A CN202210189801 A CN 202210189801A CN 114250473 A CN114250473 A CN 114250473A
Authority
CN
China
Prior art keywords
cuins
solution
photo
anode film
anode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210189801.1A
Other languages
Chinese (zh)
Other versions
CN114250473B (en
Inventor
冯文萱
张小影
于偲怡
王亚伟
贾小玥
刘佳豪
苏祥宇
厉程昊
刘亚坤
郭轩铭
梁瀚文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao University of Technology
Original Assignee
Qingdao University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao University of Technology filed Critical Qingdao University of Technology
Priority to CN202210189801.1A priority Critical patent/CN114250473B/en
Publication of CN114250473A publication Critical patent/CN114250473A/en
Application granted granted Critical
Publication of CN114250473B publication Critical patent/CN114250473B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
    • C23F13/12—Electrodes characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention provides an iron oxide-based Z-shaped heterojunction composite photo-anode film and a preparation method and application thereof, belonging to the technical field of corrosion inhibition of ocean engineering metal materials, wherein the preparation method comprises the following steps: firstly, preprocessing an 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 glycol solution to prepare Fe2O3(ii) a Step three, mixing CuInS2NanocrystalDissolving in mixed solution of n-hexane, thiourea and ethanol to prepare CuInS2Electrostatically spraying the precursor solution; step four, adopting an electrostatic spraying method to perform reaction on Fe2O3Up-atomized CuInS2Electrostatically spraying the precursor solution to obtain a photo-anode material; step five, roasting the photo-anode material to obtain Fe2O3‑CuInS2And (3) compounding the light anode film. The composite photo-anode membrane is of a Z-shaped heterojunction structure, can realize high-efficiency photoelectric cathode protection of an ocean engineering structure, and improves the durability of a structure.

Description

Iron oxide based Z-shaped heterojunction composite photo-anode film 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 an iron oxide-based Z-shaped heterojunction composite photo-anode film as well as a preparation method and application thereof.
Background
As a marine country, China has a lengthy coastline which can reach 32000 km or more including continents and island coastlines. Many cross-sea reinforced concrete bridges are built or built in China, including Hongzhu Macau bridge (49.968 km in service), Hangzhou Bay bridge (36 km in service) and Jiaozhou Bay bridge (36.48 km in service). The offshore bridge is located in a severe sea-land mixed environment, the underwater condition is complex, and the natural weather condition is severe. When chloride ions corrode the interior of the concrete protective layer and the concentration of the chloride ions reaches the threshold value, the reinforcing steel bars are corroded, and therefore the problem that the sea-crossing bridge fails due to insufficient durability is rare.
The cathodic protection is one of the most economic and effective measures in the technology of corrosion protection of marine concrete reinforcing bars. Conventional cathodic protection is classified into cathodic protection of a sacrificial anode and cathodic protection of an applied current. The former consumes active metals (such as zinc, magnesium and the like), thus causing environmental pollution and energy waste; the latter is greatly limited due to high maintenance and management costs. The novel photoelectric cathode protection technology is a new technology which only utilizes solar energy to realize the cathode protection of metal and accords with green sustainable development. However, the single photo-anode used in this technique has low light utilization efficiency and high photo-generated charge recombination rate, which limits its application. Through the construction of the heterojunction, the separation efficiency of the photoproduction electron holes and the utilization rate of sunlight can be obviously improved. 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 an iron oxide-based Z-shaped heterojunction composite photo-anode film and a preparation method and application thereof, and aims to solve the problem that the existing photo-anode material for protecting a photocathode is poor in metal corrosion prevention effect.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of an iron oxide-based Z-shaped heterojunction composite photo-anode film 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, preparing CuInS2Nanocrystalline of CuInS2Dissolving the nano-crystal in a mixed solution of n-hexane, thiourea and ethanol to prepare CuInS2Electrostatically spraying the precursor solution;
step four, adopting an electrostatic spraying method to remove Fe2O3Atomizing CuInS on a ferrous matrix2Electrostatically spraying the precursor solution to obtain a photo-anode material;
step five, roasting the photo-anode material to obtain Fe2O3-CuInS2And (3) compounding the light anode film.
In the above preparation method of the iron oxide-based Z-type heterojunction composite photo-anode film, preferably, in the first step, 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 iron oxide-based Z-type heterojunction composite photo-anode film, 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 preparation method of the iron oxide-based Z-type heterojunction composite photo-anode film, preferably, the anodic oxidation reaction specifically comprises the following steps: 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 constant-voltage reaction time is 1-10 h;
the inert conductive electrode is a glassy carbon electrode, a platinum electrode or a graphite electrode.
In the preparation method of the iron oxide-based Z-type heterojunction composite photo-anode film, preferably, in the third step, CuInS is prepared2Specifically, the nanocrystalline is prepared by putting a copper source, an indium source and a sulfur source into an organic solvent, uniformly stirring to prepare a solution, heating to 200-240 ℃ under the protection of inert gas, reacting for 1-10h, cooling to room temperature, and cleaning by using an organic cleaning solution to obtain CuInS2A nanocrystal;
the copper source is inorganic salt or organic salt containing copper; the indium source is inorganic salt or organic salt containing indium; the sulfur source is sulfur-containing organic matter;
the organic solvent is one or a mixture of oleic acid and octadecylamine;
the organic cleaning solution is one or more of ethanol, acetone, toluene and n-hexane.
In the preparation method of the iron oxide-based Z-type heterojunction composite photo-anode film, preferably, the concentrations of a copper source and an indium source are 1-100mmol/L respectively; the concentration of the sulfur source is 2-500 mmol/L;
the concentration of the copper source, the concentration of the indium source and the concentration of the sulfur source satisfy the following relational expressions: cConcentration of copper source=CConcentration of indium source≤0.5CConcentration of sulfur source。
In the preparation method of the iron oxide-based Z-type heterojunction composite photo-anode film, preferably, CuInS2The concentration of the electrostatic spraying precursor solution is 0.05-0.5 mol/L;
in the fourth step, the electrostatic spraying method comprises the following specific steps: taking the iron matrix obtained in the step two as a negative electrode and filling CuInS2And (3) taking an injector needle of the electrostatic spraying precursor solution as a positive electrode, and controlling the pumping speed to be 1-5mL/h and the spraying time to be 1-10h under the action of voltage of 15-40V to obtain the photoanode material.
In the preparation method of the iron oxide-based Z-shaped heterojunction composite photo-anode film, preferably, in the fifth step, the roasting temperature is controlled to be 250-600 ℃ 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.
The iron oxide based Z-shaped heterojunction composite photo-anode film is prepared by the preparation method of the iron oxide based Z-shaped heterojunction composite photo-anode film.
The application of the iron oxide-based Z-shaped heterojunction composite photo-anode film is used for photo-protecting a photo-anode film of a steel bar in a marine concrete structure.
Has the advantages that:
the invention adopts Z-shaped heterojunction Fe prepared by an electrostatic spraying method2O3-CuInS2The composite photo-anode film has a good crystal structure and good interface contact. Under illumination, the corrosion potential of the steel bar is shifted negatively by about 0.3V. ESR further indicates that the composite film is of a Z-type heterojunction structure, and the separation efficiency of photo-generated electron-hole pairs is effectively improved. The photo-anode film is a novel Z-shaped heterojunction structure, can realize high-efficiency photoelectric cathode protection of an ocean engineering structure, and improves the durability of an ocean 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 is a schematic representation of CuInS prepared in examples 1-4 of the present invention2XRD pattern of the nanocrystal;
FIG. 2 shows Fe prepared in examples 1 to 4 of the present invention2O3-CuInS2The microscopic topography of the composite photo-anode film, a, b, c and d are Fe prepared in the first, second, third and fourth embodiments respectively2O3-CuInS2A composite photo-anode film;
FIG. 3 shows Fe provided in examples 1-4 of the present invention under intermittent illumination2O3-CuInS2A photo-induced Open Circuit Potential (OCP) test result graph of the composite photo-anode film;
FIG. 4 shows Fe prepared in example 1 of the present invention2O3Photoanode film, CuInS2Optical nanocrystals and Fe2O3-CuInS2ESR curve 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-CuInS2The preparation method of the composite photo-anode film comprises the following steps: (1) pretreating an iron matrix; (2) putting the iron matrix obtained after the treatment in the step (1) into a reactor containing NH4Carrying out anodic oxidation reaction in the mixed solution of the solution F and the glycol solution; (3) preparing CuInS by adopting one-pot method2A nanocrystal; (4) preparation of CuInS2Electrostatically spraying the precursor solution; (5) atomizing CuInS on the surface of the ferrous matrix treated in the step (2) by adopting an electrostatic spraying method2Electrostatically spraying the precursor solution to form a photo-anode material; (6) high-temperature roasting treatment of the photo-anode material to obtain Fe2O3-CuInS2And (3) a photoanode film.
The invention relates to Fe for marine construction engineering metal corrosion prevention2O3-CuInS2The composite photo-anode film is prepared by an anodic oxidation method, a one-pot method, electrostatic spraying and high-temperature roasting treatment on the surface of the steel bar, the heterojunction is in a Z-shaped electron transmission mode, the oxidation-reduction property of the composite film can be remarkably improved, the separation efficiency of photo-generated charges is improved, the efficient photoelectric cathode protection of the concrete steel bar of the ocean engineering structure is realized, and the durability of the ocean engineering concrete structure is improved. This is because of Fe2O3And CuInS2With matchingBand structure, CuInS2Has a lower conduction band potential (-0.44V vs. NHE), and Fe2O3Has a positive valence band potential (2.48V vs. NHE) and Fe2O3Has a conduction band potential (0.28V vs. NHE) ratio to CuInS2Lower valence band potential (1.06V vs. NHE), Fe2O3The photo-generated electrons on the conduction band can be transferred to CuInS2In the valence band with CuInS2The photogenerated holes on the valence band recombine to form Z-type electron transport. Under illumination, Fe2O3-CuInS2In CuInS2The 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 at the same time 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 a preparation method of an iron oxide-based Z-shaped heterojunction composite photo-anode film, which comprises the following steps:
step one, preprocessing an iron matrix to obtain the preprocessed iron matrix.
In the specific embodiment of the invention, the iron matrix pretreatment specifically comprises the following steps: polishing an iron matrix with 80-2000 mesh sand paper, sequentially performing ultrasonic treatment with ethanol and water for 5-30min (such as 10min, 15min, 20min and 25 min) respectively (namely performing ultrasonic treatment in ethanol for 5-30min, then placing the iron matrix in water for ultrasonic treatment for 5-30 min), then placing the iron matrix in an acid solution, soaking the iron matrix for 5-50min (such as 10min, 20min, 30min, 40min and 50 min) at 20-80 ℃ (such as 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃), and cleaning and drying to obtain a pretreated iron matrix;
the iron matrix is a steel bar; carbon steel bars or stainless steel bars are preferred; 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.
Preferably, the concentration of the acidic solution is 0.5 to 6mol/L (e.g., 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5 mol/L).
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 0.05-2mol/L (such as 0.1mol/L, 0.2mol/L, 0.5mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 1.8 mol/L); the ethylene glycol solution is an aqueous solution of ethylene glycol, and the concentration of the ethylene glycol solution is 0.05-1mol/L (such as 0.1mol/L, 0.2mol/L, 0.5mol/L, 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, taking an inert conductive electrode as a cathode, and carrying out constant-pressure reaction for 1-10h (such as 1h, 2h, 4h, 6h and 8 h) at the anodic oxidation voltage of 20-60V (such as 30V, 40V, 50V and 60V) and the temperature of 20-80 ℃ (such as 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃); preferably, the inert conductive electrode is a glassy carbon electrode, a platinum electrode, or a graphite electrode.
Step three, preparing CuInS by adopting one-pot method2Nanocrystalline of CuInS2Dissolving the nano-crystal in a mixed solution of n-hexane, thiourea and ethanol to prepare CuInS2And (4) electrostatically spraying the precursor solution.
In a specific embodiment of the invention, CuInS is prepared2Specifically, the nanocrystalline is prepared by putting a copper source, an indium source and a sulfur source into an organic solvent and stirring the mixture uniformlyForming a solution, heating to 200-240 ℃ (such as 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃ and 230 ℃) under the protection of inert gas, reacting for 1-10h (such as 1h, 2h, 4h, 6h and 8 h), then cooling to room temperature, and repeatedly centrifuging and cleaning through organic cleaning liquid to obtain the high-purity CuInS2And (4) nanocrystals.
The copper source is inorganic salt or organic salt containing copper, preferably cuprous chloride, cuprous iodide, cuprous acetate or cuprous acetylacetonate; the indium source is inorganic salt or organic salt containing indium, preferably indium chloride, indium nitrate, indium acetate or indium acetylacetonate; the sulfur source is sulfur-containing organic matter, preferably thiourea, thioacetamide, 3-mercapto-1, 2-propanediol or mercaptan.
The concentrations of the copper source and the indium source are respectively 1-100mmol/L (such as 10mmol/L, 20mmol/L, 40mmol/L, 60mmol/L and 80 mmol/L); the concentration of the sulfur source is 2-500mmol/L (such as 10mmol/L, 20mmol/L, 40mmol/L, 60mmol/L, 80mmol/L, 100mmol/L, 200mmol/L, 300mmol/L, 400 mmol/L);
wherein the concentration of the copper source, the concentration of the indium source and the concentration of the sulfur source satisfy the following relational expressions: cConcentration of copper source=CConcentration of indium source≤0.5CConcentration of sulfur source。
The organic solvent is high boiling point organic solvent, and can be one or mixture of oleic acid and octadecylamine. The use of high-boiling organic solvents allows for the preparation of CuInS2The temperature needs to be raised to 200-240 ℃ in the process of nanocrystalline, and the solvent is ensured not to volatilize in the reaction process.
The organic cleaning solution is one or more of ethanol, acetone, toluene and n-hexane.
In a specific embodiment of the invention, CuInS2The concentration of the electrostatic spraying precursor solution is 0.05-0.5mol/L, namely CuInS2Concentration in the mixed solvent. If CuInS2The spray can be blocked and can not be sprayed out when the concentration of the electrostatic spray precursor liquid is too high; too low a concentration will make film formation less likely.
Step four, adopting an electrostatic spraying method to remove Fe2O3Atomizing CuInS on a ferrous matrix2Electrostatically spraying the precursor solution to obtain the photoanodeA material.
In a specific embodiment of the present invention, the electrostatic spraying method comprises the following specific steps: taking the iron matrix obtained in the step two as a negative electrode and filling CuInS2Taking a syringe needle of the electrostatic spraying precursor solution as a positive electrode, and controlling the pumping speed to be 1-5mL/h (such as 2mL/h, 3mL/h, 4mL/h and 5 mL/h) and the spraying time to be 1-10h (such as 1h, 2h, 4h, 6h and 8 h) under the action of a voltage of 15-40V (such as 20V, 25V, 30V and 35V) to obtain the photoanode material.
Step five, roasting the photo-anode material to obtain Fe2O3-CuInS2And (3) compounding the light anode film.
In the specific embodiment of the invention, the photo-anode material prepared in the fourth step is placed into a vacuum furnace, the roasting temperature is controlled to be 250-; heating rate of 1-20 deg.C/min (such as 2 deg.C/min, 4 deg.C/min, 6 deg.C/min, 8 deg.C/min, 10 deg.C/min, 12 deg.C/min, 15 deg.C/min) during roasting treatment, and naturally cooling to room temperature to obtain Fe2O3-CuInS2And (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 iron oxide-based Z-type heterojunction composite photo-anode film provided by the embodiment comprises the following steps:
(1) steel bar pretreatment:
firstly, carbon steel bars are sequentially polished by 80-2000-mesh sand paper, ethanol and water are respectively used for ultrasonic treatment for 5 minutes, then the polished steel bars are placed in 0.5mol/L hydrochloric acid solution to be soaked for 50 minutes at 80 ℃, and the steel bars are cleaned and dried for standby.
(2) Anodic oxidation reaction:
putting the steel bar treated in the step (1) into NH with a certain concentration of 2mol/L4And (3) carrying out anodic oxidation on the solution F and a 1mol/L ethylene glycol aqueous solution: the steel bar treated in the step (1) is used as an anode and a platinum electrodeAs a cathode, the anodic oxidation voltage is 40V, the temperature is 20 ℃, the constant-voltage reaction time is 5h, and Fe is prepared2O3And (3) a photoanode film.
(3) One-pot method for preparing CuInS2Nano-crystalline:
1mmol/L cuprous chloride, 1mmol/L indium chloride and 5mmol/L thiourea are put into oleic acid and stirred evenly to prepare solution. Under the protection of nitrogen, the temperature is increased to 240 ℃, the reaction is carried out for 10 hours, and the temperature is reduced to the room temperature. Repeatedly centrifugally cleaning by normal hexane to obtain high-purity CuInS2And (4) nanocrystals.
(4) Electrostatic spraying precursor solution:
dissolving the sample obtained in the step (3) in a mixed solution of normal hexane, thiourea and ethanol to prepare 0.05mol/L CuInS2And (4) electrostatically spraying the precursor solution.
(5) Electrostatic spraying:
taking the steel bar obtained in the step (2) as a negative electrode, and filling the CuInS obtained in the step (4)2And (3) taking an injector needle of the electrostatic spraying precursor solution as a positive electrode, and controlling the pumping speed to be 1mL/h and the spraying time to be 10h under the action of positive and negative voltage 40V to obtain the uniformly coated steel bar, namely the photo-anode material.
(6) And (3) high-temperature roasting:
putting the photo-anode material prepared in the step (5) into a vacuum furnace, controlling the roasting temperature to be 250 ℃, the roasting time to be 24h, the heating rate to be 1 ℃/min, and naturally cooling to room temperature to obtain Fe2O3-CuInS2And (3) compounding the light anode film.
For CuInS prepared in the embodiment of the invention2XRD test is carried out on the nano-crystal, crystal structure characterization is carried out, and the test result is shown in figure 1; for Fe2O3-CuInS2And performing SEM test on the composite photo-anode film, and characterizing the morphology structure, wherein the test result is shown as a in figure 2.
Under intermittent illumination, Fe prepared in the embodiment of the invention2O3-CuInS2The composite photo-anode film is subjected to an Open Circuit Potential (OCP) test, and the test result is shown in fig. 3.
For Fe prepared in the examples of the present invention2O3Photoanode film, CuInS2Photoanode film and Fe2O3-CuInS2The ESR test of the composite photo-anode film material is shown in fig. 4.
CuInS in Performance testing2The photo-anodic film being CuInS2And (4) nanocrystals.
As can be seen from FIG. 4, Fe2O3The photoanode film can not capture O2 -Indicates that its conduction band potential is higher than O2 -The potential of (2). CuInS2Because the potential of the conduction band is lower than O2 -Can trap O2 -Yielding a weaker signal strength. And Fe2O3-CuInS2The ESR of the composite photo-anode film shows a strong ESR signal, which shows that the composite photo-anode film can more effectively capture O2 -This indicates that the heterojunction in this invention is a Z-type heterojunction. Because the composite membrane cannot trap O if it is a type II heterojunction2 -And generating a signal. In a Z-type heterojunction, Fe2O3The photo-generated electrons on the conduction band can be transferred to CuInS2Are carried on and react with the valence band of (a) to leave photoproduction electron holes in CuInS respectively2Conduction band and Fe2O3The valence band of the photo-generated electron-hole separation device realizes the high-efficiency separation of photo-generated electrons and holes.
Example 2
The preparation method of the iron oxide-based Z-type heterojunction composite photo-anode film provided by the embodiment comprises the following steps:
(1) steel bar pretreatment:
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 6mol/L nitric acid solution and phosphoric acid solution to be soaked for 5 minutes at the temperature of 20 ℃, and the stainless steel reinforcing steel bars are cleaned and dried for later use.
(2) Anodic oxidation reaction:
adding the steel bar treated in the step (1) into a solution containing 0.05mol/L of NH4And (3) anodizing the solution F and a 0.05mol/L ethylene glycol aqueous solution: the steel bar treated in the step (1) is used as an anodeTaking a graphite electrode as a cathode, performing constant-voltage reaction at 80 ℃ for 10h at an anodic oxidation voltage of 20V to obtain Fe2O3And (3) a photoanode film.
(3) One-pot method for preparing CuInS2Nano-crystalline:
adding 100mmol/L cuprous iodide, 100mmol/L indium nitrate and 500 mmol/L3-mercapto-1, 2-propanediol into octadecylamine, and stirring to obtain solution. Under the protection of nitrogen, the temperature is raised to 230 ℃, the reaction is carried out for 1h, and the temperature is reduced to the room temperature. Repeatedly centrifugally cleaning by toluene to obtain high-purity CuInS2And (4) nanocrystals.
(4) Electrostatic spraying precursor solution:
dissolving the sample obtained in the step (3) in a mixed solution of normal hexane, thiourea and ethanol to prepare 0.5mol/L CuInS2And (4) electrostatically spraying the precursor solution.
(5) Electrostatic spraying:
taking the steel bar obtained in the step (2) as a negative electrode, and filling the CuInS obtained in the step (4)2The needle of the electrostatic spraying precursor liquid injector is used as a positive electrode, and the pumping speed is controlled to be 2mL/h and the spraying time is controlled to be 5h under the action of the voltage of the positive electrode and the negative electrode, so that the uniformly coated steel bar, namely the photo-anode material is obtained.
(6) And (3) high-temperature roasting:
placing the photoanode prepared in the step (5) into a vacuum furnace, controlling the roasting temperature at 600 ℃, the roasting time at 10h and the heating rate at 10 ℃/min, and naturally cooling to room temperature to obtain Fe2O3-CuInS2And (3) compounding the light anode film.
For CuInS prepared in the embodiment of the invention2XRD test is carried out on the nano-crystal, crystal structure characterization is carried out, and the test result is shown in figure 1; for Fe2O3-CuInS2And performing SEM test on the composite photo-anode film, and characterizing the morphology structure, wherein the test result is shown as b in figure 2.
Under intermittent illumination, Fe prepared in the embodiment of the invention2O3-CuInS2The composite photo-anode film is subjected to an Open Circuit Potential (OCP) test, and the test result is shown in fig. 3.
Example 3
The preparation method of the iron oxide-based Z-type heterojunction composite photo-anode film provided by the embodiment comprises the following steps:
(1) steel bar pretreatment:
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 a mixed solution of 3mol/L hydrofluoric acid and sulfuric acid to be soaked for 20 minutes at 60 ℃, and the steel bars are cleaned and dried for later use.
(2) Anodic oxidation reaction:
adding the steel bar treated in the step (1) into a solution containing 1mol/L NH4And (3) carrying out anodic oxidation on the solution F and a 0.1mol/L ethylene glycol aqueous solution: and (2) taking the steel bar treated in the step (1) as an anode, taking a glassy carbon electrode as a cathode, wherein the anode oxidation voltage is 60V, and the constant-voltage reaction time is 1h at the temperature of 40 ℃.
(3) One-pot method for preparing CuInS2Nano-crystalline:
adding 50mmol/L cuprous acetate, 50mmol/L indium acetate and 100mmol/L thioacetamide into the mixed solution of oleic acid and octadecenylamine, and stirring to obtain solution. Under the protection of nitrogen, the temperature is raised to 200 ℃, the reaction is carried out for 8 hours, and the temperature is reduced to the room temperature. Repeatedly centrifugally cleaning by using organic cleaning fluid to obtain high-purity CuInS2And (4) nanocrystals.
(4) Electrostatic spraying precursor solution:
dissolving the sample obtained in the step (3) in a mixed solution of normal hexane, thiourea and ethanol to prepare 0.3mol/L CuInS2And (4) electrostatically spraying the precursor solution.
(5) Electrostatic spraying:
taking the steel bar obtained in the step (2) as a negative electrode, and filling the CuInS obtained in the step (4)2The needle of the electrostatic spraying precursor liquid injector is used as the anode, and the pumping speed is controlled to be 5mL/h and the spraying time is controlled to be 2h under the action of the voltage of 25V of the anode and the cathode, so that the uniformly coated steel bar, namely the photo-anode material is obtained.
(6) And (3) high-temperature roasting:
placing the photoanode prepared in the step (5) into a vacuum furnace, controlling the roasting temperature at 400 ℃, the roasting time at 1h, the heating rate at 20 ℃/min, and naturally cooling toObtaining Fe at room temperature2O3-CuInS2And (3) compounding the light anode film.
For CuInS prepared in the embodiment of the invention2XRD test is carried out on the nano-crystal, crystal structure characterization is carried out, and the test result is shown in figure 1; for Fe2O3-CuInS2And performing SEM test on the composite photo-anode film, and characterizing the morphology structure, wherein the test result is shown as c in figure 2.
Under intermittent illumination, Fe prepared in the embodiment of the invention2O3-CuInS2The composite photo-anode film is subjected to an Open Circuit Potential (OCP) test, and the test result is shown in fig. 3.
Example 4
The preparation method of the iron oxide-based Z-type heterojunction composite photo-anode film provided by the embodiment comprises the following steps:
(1) steel bar pretreatment:
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 20 minutes, then the polished reinforcing steel bars are placed in a mixed solution of 0.1mol/L hydrochloric acid and citric acid to be soaked for 30 minutes at the temperature of 60 ℃, and the stainless steel reinforcing steel bars are cleaned and dried for later use.
(2) Anodic oxidation reaction:
adding the steel bar treated in the step (1) into a solution containing 0.5mol/L NH4And (3) anodizing the solution F and a 0.05mol/L ethylene glycol aqueous solution: and (2) taking the steel bar treated in the step (1) as an anode and a graphite electrode as a cathode, wherein the anode oxidation voltage is 60V, and the constant-voltage reaction time is 1h at the temperature of 60 ℃.
(3) One-pot method for preparing CuInS2Nano-crystalline:
adding 50mmol/L cuprous acetylacetonate, 50mmol/L indium acetylacetonate and 300mmol/L mercaptan into oleic acid, and stirring to obtain solution. Under the protection of nitrogen, the temperature is raised to 200 ℃, the reaction is carried out for 10 hours, and the temperature is reduced to the room temperature. Repeatedly centrifugally cleaning by using organic cleaning fluid to obtain high-purity CuInS2And (4) nanocrystals.
(4) Electrostatic spraying precursor solution:
dissolving the sample obtained in the step (3) in n-hexane, thiourea and ethylene0.1mol/L CuInS is prepared in the mixed solution of alcohol2And (4) electrostatically spraying the precursor solution.
(5) Electrostatic spraying:
taking the steel bar obtained in the step (2) as a negative electrode, and filling the CuInS obtained in the step (4)2The needle of the electrostatic spraying precursor liquid injector is used as the anode, and the pumping speed is controlled to be 5mL/h and the spraying time is controlled to be 1h under the action of the voltage of the anode and the cathode of 35V, so that the uniformly coated steel bar, namely the photo-anode material is obtained.
(6) And (3) high-temperature roasting:
placing the photoanode prepared in the step (5) into a vacuum furnace, controlling the roasting temperature to be 350 ℃, the roasting time to be 3h, the heating rate to be 20 ℃/min, and naturally cooling to room temperature to obtain Fe2O3-CuInS2And (3) compounding the light anode film.
For CuInS prepared in the embodiment of the invention2XRD test is carried out on the nano-crystal, crystal structure characterization is carried out, and the test result is shown in figure 1. The CuInS prepared in examples 1-4 was mixed2The results of crystal structure characterization of the nanocrystals are shown in fig. 1, and the comparison shows that the CuInS prepared by the method2The nano crystals have good crystal structures and are wurtzite structures. In the embodiment, the CuInS is not affected when the treatment is carried out at different temperatures of 200-240 DEG C2The crystal structure of (1).
For Fe prepared in this example2O3-CuInS2And performing SEM test on the composite photo-anode film, and characterizing the morphology structure, wherein the test result is shown as d in figure 2. By analyzing graphs a-d in FIG. 2, the CuInS obtained by the invention2The nanocrystalline is of a hexagonal structure and is uniformly distributed in the Fe2O3On the substrate, the size is about 100-200 nm. c diagram example III CuInS2The thickness of the nanocrystalline thin film is about 13 μm, and Fe can be seen in the d picture2O3Is about 1 μm thick, and Fe2O3-CuInS2There is good contact between the interfaces, which facilitates the transfer between photo-generated charges.
Under intermittent illumination, Fe prepared in the embodiment of the invention2O3-CuInS2Photo-opening of composite photo-anode filmThe results of the path potential (OCP) test are shown in fig. 3. Under intermittent sunlight irradiation, the photoelectric cathode protection performance of different composite photo-anode films on the steel bars is judged by testing the potential change of the prepared composite photo-anode film after the composite photo-anode film is coupled with the steel bars of the concrete structure of the ocean building engineering. As can be seen from FIG. 3, Fe is coupled2O3-CuInS2When the photo-anode film is used, under illumination, the corrosion potential of the steel bar of the four embodiments all generates negative shift, which shows that the potential of the photo-anode film is lower than the self-corrosion potential of the steel bar, and can provide cathodic protection for the steel bar. In the first embodiment, the corrosion potential of the steel bar is negatively shifted from-0.55V in a dark state to-0.9V; in the second embodiment, the corrosion potential of the steel bar is negatively shifted from-0.57V in a dark state to-1.05V; in the third embodiment, the corrosion potential of the steel bar is negatively shifted from-0.6V in a dark state to-1.02V; the self-corrosion potential of the steel bars of example four was shifted negatively from-0.55V to-0.97V in the dark state.
In summary, the following steps: fe prepared by the invention2O3-CuInS2The composite light anode film has a good crystal structure and good interface contact. Under illumination, the corrosion potential of the steel bar is shifted negatively by about 0.3V. ESR further indicates that the composite film is of a Z-type heterojunction structure, and the separation efficiency of photo-generated electron-hole pairs is effectively improved. 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 (10)

1. The preparation method of the iron oxide-based Z-shaped heterojunction composite photo-anode film is characterized by comprising the following steps of:
step one, pretreating an iron matrix to obtain a pretreated iron matrix;
step two, the stepPutting 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, preparing CuInS2Nanocrystals of said CuInS2Dissolving the nano-crystal in a mixed solution of n-hexane, thiourea and ethanol to prepare CuInS2Electrostatically spraying the precursor solution;
step four, adopting an electrostatic spraying method to remove Fe2O3The CuInS is atomized on a ferrous matrix2Electrostatically spraying the precursor solution to obtain a photo-anode material;
fifthly, roasting the photo-anode material to obtain Fe2O3-CuInS2And (3) compounding the light anode film.
2. The method for preparing the iron oxide-based Z-type heterojunction composite photo-anode film according to claim 1, wherein in the first step, 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 a mixture of more of hydrochloric acid solution, nitric acid solution, sulfuric acid solution, phosphoric acid solution, hydrofluoric acid solution and citric acid solution.
3. The method for preparing the iron oxide-based Z-type heterojunction composite photo-anode film as claimed in claim 1, wherein in the second step, NH is added4The 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.
4. The method for preparing the iron oxide-based Z-shaped heterojunction composite photo-anode film according to claim 3, wherein the anodic oxidation reaction specifically comprises: taking the pretreated iron matrix 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 constant-voltage reaction time is 1-10 h;
the inert conductive electrode is a glassy carbon electrode, a platinum electrode or a graphite electrode.
5. The method for preparing the iron oxide-based Z-type heterojunction composite photo-anode film according to claim 1, wherein in the third step, the CuInS is prepared2Specifically, the nanocrystalline is prepared by putting a copper source, an indium source and a sulfur source into an organic solvent, uniformly stirring to prepare a solution, heating to 200-240 ℃ under the protection of inert gas, reacting for 1-10h, cooling to room temperature, and cleaning by using an organic cleaning solution to obtain CuInS2A nanocrystal;
the copper source is an inorganic salt or an organic salt containing copper; the indium source is inorganic salt or organic salt containing indium; the sulfur source is a sulfur-containing organic matter;
the organic solvent is one or a mixture of oleic acid and octadecylamine;
the organic cleaning liquid is one or a mixture of ethanol, acetone, toluene and n-hexane.
6. The method for preparing the iron oxide-based Z-type heterojunction composite photo-anode film as claimed in claim 5, wherein the concentrations of the copper source and the indium source are respectively 1-100 mmol/L; the concentration of the sulfur source is 2-500 mmol/L;
the concentration of the copper source, the concentration of the indium source and the concentration of the sulfur source satisfy the following relational expressions: cConcentration of copper source=CConcentration of indium source≤0.5CConcentration of sulfur source。
7. The method for preparing the iron oxide-based Z-type heterojunction composite photoanode film as claimed in claim 1, wherein the CuInS is2The concentration of the electrostatic spraying precursor solution is 0.05-0.5 mol/L;
in the fourth step, the electrostatic spraying method comprises the following specific steps: taking the iron matrix obtained in the step two as a negative electrode, and filling the CuInS2Electrostatic spray precursorTaking a syringe needle of the liquid as a positive pole, and controlling the pumping speed to be 1-5mL/h and the spraying time to be 1-10h under the action of the voltage of 15-40V to obtain the photo-anode material.
8. The method for preparing the iron oxide-based Z-type heterojunction composite photo-anode film as claimed in claim 1, wherein in the fifth step, the roasting temperature is controlled to be 250-600 ℃ and the roasting time is 1-12h in the roasting treatment process; the heating rate in the roasting treatment process is 1-20 ℃/min.
9. An iron oxide based 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 iron oxide based Z-type heterojunction composite photo-anode film as claimed in any one of claims 1 to 8.
10. The application of the iron oxide-based Z-shaped heterojunction composite photo-anode film as claimed in claim 9, wherein the composite photo-anode film is used for a photo-protection photo-anode film of a steel bar of a marine concrete structure.
CN202210189801.1A 2022-03-01 2022-03-01 Iron oxide based Z-shaped heterojunction composite photo-anode film and preparation method and application thereof Active CN114250473B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210189801.1A CN114250473B (en) 2022-03-01 2022-03-01 Iron oxide based Z-shaped heterojunction composite photo-anode film and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210189801.1A CN114250473B (en) 2022-03-01 2022-03-01 Iron oxide based Z-shaped heterojunction composite photo-anode film and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114250473A true CN114250473A (en) 2022-03-29
CN114250473B CN114250473B (en) 2022-06-07

Family

ID=80797172

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210189801.1A Active CN114250473B (en) 2022-03-01 2022-03-01 Iron oxide based Z-shaped heterojunction composite photo-anode film and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114250473B (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2056609A1 (en) * 1991-11-28 1993-05-29 Ishiang Shih Methods for fabrication of cuinse2 thin films and solar cells
US20050044989A1 (en) * 2003-08-28 2005-03-03 Chung-Pin Liao Method to prevent rusting and general oxidation for metals and nonmetals
CN101054198A (en) * 2007-05-17 2007-10-17 上海交通大学 Method for preparing monodisperse ternary sulfide CuInS2
US20110240108A1 (en) * 2010-04-02 2011-10-06 Matt Law Method To Synthesize Colloidal Iron Pyrite (FeS2) Nanocrystals And Fabricate Iron Pyrite Thin Film Solar Cells
CN103137340A (en) * 2013-01-23 2013-06-05 中国科学院过程工程研究所 Preparation method for counter electrode material one-dimensional copper indium sulfide-zinc sulfide heterojunction nanocrystalline of high-efficient low-cost dye-sensitized solar cell
US20130263918A1 (en) * 2012-04-09 2013-10-10 Fundació Institut De Ciències Fotòniques Photovoltaic nanocomposite comprising solution processed inorganic bulk nano-heterojunctions, solar cell and photodiode devices comprising the nanocomposite
EP2693503A1 (en) * 2012-08-03 2014-02-05 Ecole Polytechnique Fédérale de Lausanne (EPFL) Organo metal halide perovskite heterojunction solar cell and fabrication thereof
CN107723712A (en) * 2017-09-30 2018-02-23 青岛大学 ZnIn for photoproduction cathodic protection2S4/TiO2The preparation method of nanometer tube composite film light anode
CN110148523A (en) * 2019-04-22 2019-08-20 南京邮电大学 A kind of preparation method of indium sulphur nano thin-film

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2056609A1 (en) * 1991-11-28 1993-05-29 Ishiang Shih Methods for fabrication of cuinse2 thin films and solar cells
US20050044989A1 (en) * 2003-08-28 2005-03-03 Chung-Pin Liao Method to prevent rusting and general oxidation for metals and nonmetals
CN101054198A (en) * 2007-05-17 2007-10-17 上海交通大学 Method for preparing monodisperse ternary sulfide CuInS2
US20110240108A1 (en) * 2010-04-02 2011-10-06 Matt Law Method To Synthesize Colloidal Iron Pyrite (FeS2) Nanocrystals And Fabricate Iron Pyrite Thin Film Solar Cells
US20130263918A1 (en) * 2012-04-09 2013-10-10 Fundació Institut De Ciències Fotòniques Photovoltaic nanocomposite comprising solution processed inorganic bulk nano-heterojunctions, solar cell and photodiode devices comprising the nanocomposite
EP2693503A1 (en) * 2012-08-03 2014-02-05 Ecole Polytechnique Fédérale de Lausanne (EPFL) Organo metal halide perovskite heterojunction solar cell and fabrication thereof
CN103137340A (en) * 2013-01-23 2013-06-05 中国科学院过程工程研究所 Preparation method for counter electrode material one-dimensional copper indium sulfide-zinc sulfide heterojunction nanocrystalline of high-efficient low-cost dye-sensitized solar cell
CN107723712A (en) * 2017-09-30 2018-02-23 青岛大学 ZnIn for photoproduction cathodic protection2S4/TiO2The preparation method of nanometer tube composite film light anode
CN110148523A (en) * 2019-04-22 2019-08-20 南京邮电大学 A kind of preparation method of indium sulphur nano thin-film

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
王耀明等: "SrTiO_3/α-Fe_2O_3异质结光阳极光电转换性能", 《发光学报》 *
许颂: "铜铟硫薄膜的静电喷雾法制备及其在DSSC对电极中的应用", 《工程科技I辑》 *

Also Published As

Publication number Publication date
CN114250473B (en) 2022-06-07

Similar Documents

Publication Publication Date Title
CN109402656B (en) Preparation method of cobalt phosphide modified molybdenum-doped bismuth vanadate photoelectrode
CN103400878B (en) A kind of zinc-oxide nano pencil array electrode and its preparation method and application
CN106277228B (en) A kind of method of high catalytic activity electrode preparation and its Electrocatalysis Degradation methyl blue
CN107557789B (en) A kind of optical anode material and its preparation and application
CN108479806A (en) A kind of hetero-junction thin-film being made of same metal and oxygen group elements and its preparation and application
CN108806989A (en) Nuclear shell structure quantum point, preparation method and application and light anode, solar energy electrochemical device with transition zone and application
CN110205634A (en) A kind of ZnO/ZnS/CdS photo-anode film and preparation method thereof
CN108611653A (en) A kind of pucherite composite material of carried magnetic nano particle and its preparation and application
CN114086185B (en) Photoanode film and preparation method and application thereof
CN114059071A (en) Photo-anode film for reinforcing steel bar photo-cathode protection and preparation method and application thereof
CN114250473B (en) Iron oxide based Z-shaped heterojunction composite photo-anode film and preparation method and application thereof
CN113293404B (en) Heterojunction photo-anode material and preparation method and application thereof
CN101956194A (en) Method for preparing TiO2 thin film modified titanium-based beta-PbO2 photoelectrode
CN114214703B (en) Z-type heterojunction composite photo-anode membrane and preparation method and application thereof
CN102543457A (en) Preparation method of zinc sulfide (ZnS)/cadmium telluride (CdTe) quantum dot sensitization titanium dioxide (TiO2) nano film
CN104499010A (en) Preparation process of visible-light responsive nano alpha-ferric oxide membrane electrode
CN114622206B (en) NH (NH) 2 -MIL-101(Cr)/TiO 2 Composite photo-anode and preparation method and application thereof
WO2022188503A1 (en) Photogenerated anti-corrosion electrode material and preparation method and application thereof
CN113293381B (en) SrFeO3/Fe2O3 photoelectrode material, preparation method thereof and application thereof in photo-generated cathode corrosion prevention
CN114277375A (en) MnIn2S4/TiO2Nanotube bundle composite photoanode material and preparation method and application thereof
CN108031477B (en) A kind of photocatalysis film and its preparation method and application of electrochemical treatments phosphorus-molybdenum sulfide codope iron oxide
CN114016082B (en) Method for directly depositing and recovering metal bismuth on conductive substrate by utilizing solar energy
WO2021138961A1 (en) Novel preparation technqiue for lead dioxide electrode modified by tetratitanium heptaoxide nanotube
CN111663140A (en) Preparation of double-layer energy storage type photoelectric anode and application thereof in metal cathode protection
CN114231996B (en) Zinc molybdate-cobalt titanate coaxial fiber photo-anode film and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant