阅读说明：本技术 一种具有光催化污水处理的微弧氧化膜制备方法 (Preparation method of micro-arc oxidation film with photocatalytic sewage treatment ) 是由 施渊吉 李京晓 何延辉 陈显冰 李伟 于 2021-07-20 设计创作，主要内容包括：本发明涉及表面处理领域,具体涉及一种具有光催化污水处理的微弧氧化膜制备方法,包括如下步骤：S1、采用离子渗氮工艺完成纯钛片表面的渗氮处理；S2、以完成渗氮处理的钛片为载体,选用偏钒酸盐和钨酸盐的混合溶液作为电解液,采用微弧氧化法在钛片表面制备V-2O-5/WO-3/TiO-2膜层；S3、去离子水清洗,即得。本发明首先利用离子渗氮工艺在钛片表面形成一渗氮层,然后采用微弧氧化工艺制备了V-2O-5/WO-3/TiO-2膜层,表面粗糙多孔,孔洞分布均匀,能有效促进光生载流子的分离,具有远优于TiO-2膜层的光催化活性,紫外光下照射2h,所得微弧氧化膜能降解92％以上的罗丹明。(The invention relates to the field of surface treatment, in particular to a preparation method of a micro-arc oxidation film for photocatalytic sewage treatment, which comprises the following steps: s1, nitriding the surface of the pure titanium sheet by adopting an ion nitriding process; s2, preparing V on the surface of the titanium sheet by using the titanium sheet subjected to nitriding treatment as a carrier, selecting a mixed solution of metavanadate and tungstate as an electrolyte and adopting a micro-arc oxidation method 2 O 5 /WO 3 /TiO 2 A film layer; and S3, washing with deionized water to obtain the product. The invention firstly utilizes the ion nitriding process to form a nitriding layer on the surface of the titanium sheet, and then adopts the micro-arc oxidation process to prepare the V 2 O 5 /WO 3 /TiO 2 Film layer, surfaceCoarse and porous, uniformly distributed pores, can effectively promote the separation of photon-generated carriers, and is far superior to TiO 2 The photocatalytic activity of the film layer is 2 hours of irradiation under ultraviolet light, and the obtained micro-arc oxidation film can degrade over 92 percent of rhodamine.)

1. A preparation method of a micro-arc oxidation film with photocatalytic sewage treatment is characterized by comprising the following steps: the method comprises the following steps:

s1, nitriding the surface of the pure titanium sheet by adopting an ion nitriding process;

s2, preparing V on the surface of the titanium sheet by using the titanium sheet subjected to nitriding treatment as a carrier, selecting a mixed solution of metavanadate and tungstate as an electrolyte and adopting a micro-arc oxidation method₂O₅/WO₃/TiO₂A film layer;

and S3, washing with deionized water to obtain the product.

2. The method for preparing a micro-arc oxidation film with photocatalytic sewage treatment according to claim 1, wherein the method comprises the following steps: in the step S1, the titanium sheet after polishing, cleaning and oil removal is placed into a vacuum furnace filled with nitrogen, the furnace is vacuumized to 6-10 Pa, the temperature is raised to 780-820 ℃, the temperature is kept for 30min, the surface of the sample is purified and degassed, then a vacuum pump is closed, nitrogen is introduced into the furnace, the pressure is 0.01-0.03 MPa, the temperature is kept for 30min, then vacuum-pumping diffusion is carried out for 30min, then ventilation and nitridation are carried out, the intermittent ventilation/air-extraction is repeated in the way, periodic nitridation and diffusion are carried out for 8-10 h, and a nitriding layer is formed on the surface of the titanium sheet.

3. The method for preparing a micro-arc oxidation film with photocatalytic sewage treatment according to claim 1, wherein the method comprises the following steps: in step S2, the electrolyte contains: 14.7g/L of sodium metavanadate; 3.66g/L of sodium tungstate; 2g/L of sodium hydroxide; sodium fluoride 1 g/L.

4. The method for preparing a micro-arc oxidation film with photocatalytic sewage treatment according to claim 1, wherein the method comprises the following steps: in the step S2, the frequency is 700-800 HZ, the positive pressure is 300V, the negative pressure is 40V, the duty ratio is 0.3, and the pH value is 10-14; the micro-arc oxidation time is 3min to 5min, and the temperature of the bath solution is controlled below 40 ℃.

Technical Field

The invention relates to the field of surface treatment, in particular to a preparation method of a micro-arc oxidation film for photocatalytic sewage treatment.

Background

In semiconductor photocatalysis, TiO₂Because of unique chemical stability, no toxicity and high photocatalytic activity, the photocatalyst is widely applied to air pollution treatment and organic wastewater purification treatment. However, TiO₂The forbidden band width of the solar cell is 3.2eV, the solar cell can only be excited by an ultraviolet light source, and the utilization rate of sunlight is low; on the other hand, TiO is currently used₂The powder is suspended in the aqueous solution II in a powder form, and when the powder is used, the powder is easy to aggregate and run off, so that the separation and recovery are difficult, and secondary pollution is caused. These defects severely restrict TiO₂The application of the photocatalysis technology in practice. Therefore, improving the reaction activity of the catalyst, expanding the spectral response range and perfecting the catalyst fixing technology are still the research hotspots in the current photocatalysis field.

Disclosure of Invention

In order to solve the problems, the invention provides a preparation method of a micro-arc oxidation film for photocatalytic sewage treatment.

In order to achieve the purpose, the invention adopts the technical scheme that:

a preparation method of a micro-arc oxidation film with photocatalytic sewage treatment comprises the following steps:

s1, nitriding the surface of the pure titanium sheet by adopting an ion nitriding process;

s2, preparing V on the surface of the titanium sheet by using the titanium sheet subjected to nitriding treatment as a carrier, selecting a mixed solution of metavanadate and tungstate as an electrolyte and adopting a micro-arc oxidation method₂O₅/WO₃/TiO₂A film layer;

and S3, washing with deionized water to obtain the product.

Further, in the step S1, the titanium sheet after polishing and cleaning is put into a vacuum furnace filled with nitrogen, the furnace is vacuumized to 6-10 Pa, the temperature is raised to 780-820 ℃, then the temperature is kept for 30min, the surface of the sample is purified and degassed, then the vacuum pump is closed, nitrogen is introduced into the furnace with the pressure of 0.01-0.03 MPa, the temperature is kept for 30min, then the furnace is vacuumized and diffused for 30min, and then the furnace is ventilated and nitrided, so that intermittent air introduction/extraction is repeated, and a nitrided layer is formed on the surface of the titanium sheet after periodic nitriding and diffusion are carried out for 8-10 h.

Further, in step S2, the electrolyte contains: 14.7g/L of sodium metavanadate; 3.66g/L of sodium tungstate; 2g/L of sodium hydroxide; sodium fluoride 1 g/L.

Further, in the step S2, the frequency is 700-800 HZ, the positive pressure is 300V, the negative pressure is 40V, the duty ratio is 0.3, and the pH value is 10-14; the micro-arc oxidation time is 3min to 5min, and the temperature of the bath solution is controlled below 40 ℃.

The invention has the following beneficial effects:

firstly, an ion nitriding process is utilized to form a nitriding layer on the surface of a titanium sheet, and then a micro-arc oxidation process is adopted to prepare V₂O₅/WO₃/TiO₂The film layer has rough and porous surface and uniform pore distribution, can effectively promote the separation of photon-generated carriers, and is far superior to TiO₂The photocatalytic activity of the film layer is 2 hours of irradiation under ultraviolet light, and the obtained micro-arc oxidation film can degrade over 92 percent of rhodamine.

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.

Example 1

A preparation method of a micro-arc oxidation film with photocatalytic sewage treatment comprises the following steps:

s1, putting the polished and cleaned titanium sheet into a vacuum furnace filled with nitrogen, vacuumizing the furnace to 6Pa, heating to 780 ℃, keeping the temperature for 30min, purifying the surface of a sample and degassing, closing a vacuum pump, introducing nitrogen into the furnace at the pressure of 0.01MPa, keeping the temperature for 30min, vacuumizing and diffusing for 30min, ventilating and nitriding, repeating intermittent air introduction/extraction in such a way, performing periodic nitriding and diffusing for 8-10 h, and forming a nitriding layer on the surface of the titanium sheet;

s2, preparing V on the surface of the titanium sheet by using the titanium sheet subjected to nitriding treatment as a carrier, selecting a mixed solution of metavanadate and tungstate as an electrolyte and adopting a micro-arc oxidation method₂O₅/WO₃/TiO₂A film layer; wherein, the electrolyte contains: 14.7g/L of sodium metavanadate; 3.66g/L of sodium tungstate; 2g/L of sodium hydroxide; 1g/L of sodium fluoride; the micro-arc oxidation frequency is 700HZ, the positive pressure is 300V, the negative pressure is 40V, the duty ratio is 0.3, and the pH value is 10-14; the micro-arc oxidation time is 5min, and the temperature of the bath solution is controlled below 40 ℃.

And S3, washing with deionized water to obtain the product.

Example 2

A preparation method of a micro-arc oxidation film with photocatalytic sewage treatment comprises the following steps:

s1, putting the polished and cleaned titanium sheet into a vacuum furnace filled with nitrogen, vacuumizing the furnace to 10Pa, heating to 820 ℃, keeping the temperature for 30min, purifying the surface of a sample and degassing, closing a vacuum pump, introducing nitrogen into the furnace at the pressure of 0.03MPa, keeping the temperature for 30min, vacuumizing and diffusing for 30min, ventilating and nitriding, repeating intermittent air introduction/extraction in such a way, performing periodic nitriding and diffusing for 8-10 h, and forming a nitriding layer on the surface of the titanium sheet;

s2, preparing V on the surface of the titanium sheet by using the titanium sheet subjected to nitriding treatment as a carrier, selecting a mixed solution of metavanadate and tungstate as an electrolyte and adopting a micro-arc oxidation method₂O₅/WO₃/TiO₂A film layer; wherein, the electrolyte contains: 14.7g/L of sodium metavanadate; 3.66g/L of sodium tungstate; 2g/L of sodium hydroxide; 1g/L of sodium fluoride; the micro-arc oxidation frequency is 800HZ, the positive pressure is 300V, the negative pressure is 40V, the duty ratio is 0.3, and the pH value is 10-14; the micro-arc oxidation time is 3min, and the temperature of the bath solution is controlled below 40 ℃.

And S3, washing with deionized water to obtain the product.

Example 3

A preparation method of a micro-arc oxidation film with photocatalytic sewage treatment comprises the following steps:

s1, putting the polished and cleaned titanium sheet into a vacuum furnace filled with nitrogen, vacuumizing the furnace to 8Pa, heating to 800 ℃, keeping the temperature for 30min, purifying the surface of a sample and degassing, closing a vacuum pump, introducing nitrogen into the furnace at the pressure of 0.02MPa, keeping the temperature for 30min, vacuumizing and diffusing for 30min, ventilating and nitriding, repeating intermittent air introduction/extraction in such a way, performing periodic nitriding and diffusing for 8-10 h, and forming a nitriding layer on the surface of the titanium sheet;

s2, preparing V on the surface of the titanium sheet by using the titanium sheet subjected to nitriding treatment as a carrier, selecting a mixed solution of metavanadate and tungstate as an electrolyte and adopting a micro-arc oxidation method₂O₅/WO₃/TiO₂A film layer; wherein, the electrolyte contains: 14.7g/L of sodium metavanadate; 3.66g/L of sodium tungstate; 2g/L of sodium hydroxide; 1g/L of sodium fluoride; the micro-arc oxidation frequency is 750HZ, the positive pressure is 300V, the negative pressure is 40V, the duty ratio is 0.3, and the pH value is 10-14; the micro-arc oxidation time is 4min, and the temperature of the bath solution is controlled below 40 ℃.

And S3, washing with deionized water to obtain the product.

The degradation rate of rhodamine is calculated by placing the micro-arc oxidation film obtained in the embodiment 1, the embodiment 2 and the embodiment 3 into 10mg/L rhodamine water solution, placing the film in the dark for 0.5 hour before an ultraviolet lamp is turned on to reach adsorption balance, vertically irradiating the film by using a 300W ultraviolet lamp with the dominant wavelength of 365mm as a light source for 2 hours, and detecting the absorbance values of the rhodamine solution before and after degradation by using a Shimadzu UV-2550 type UV-Vis spectrophotometer.

The experimental results are as follows: under the irradiation of ultraviolet light for 2 hours, the rhodamine of 92.7 percent, 92.3 percent and 93.1 percent can be degraded in sequence in the examples 1 to 3.

The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.