CN102794186A - Oxyhalide photo-catalytic material and preparation method thereof - Google Patents

Abstract

The invention relates to an oxyhalide photocatalytic material and a preparation method thereof, belonging to the field of photocatalytic materials. The present invention utilizes a solid-phase or liquid-phase method to prepare an oxyhalide photocatalytic material, which is characterized in that its chemical composition is BiOX, X=Cl, Br, I, [Bi ₂ O ₂ ] and the [X] structural layer along the c-axis direction Alternately stacked on each other to form a layered crystal configuration. The prepared BiOX (X=Cl, Br, I) all have excellent photocatalytic properties, can degrade organic dyes, degrade organic harmful gases, sterilize and produce hydrogen by photolyzing water. The photocatalytic performance of the material can be greatly improved by loading Ag and Pt and other nano-metal particles with strong electron affinity.

Description

Oxyhalide photocatalytic material and preparation method thereof

technical field

The invention relates to an oxyhalide photocatalytic material and a preparation method thereof, and belongs to the field of photocatalytic materials, in particular to the fields of dye degradation, hydrogen production by photolysis of water, degradation of organic harmful gases, sterilization and the like.

Background technique

Since Fujishima and Honda discovered the phenomenon of photoresponsive hydrogen production on the surface of TiO ₂ electrode materials in 1972, photocatalysis has attracted worldwide attention as a potential technology to solve environmental pollution and energy crisis. In the process of semiconductor photocatalysis, light irradiation excites electrons in the valence band to transition to the conduction band, that is, photogenerated electrons are formed on the conduction band and photogenerated holes are formed on the valence band; Under the influence of the environment, complex oxidation and reduction reactions occur. In this way, the strong reduction characteristics of electrons and the oxidation of holes can be used to reduce and oxidize H ⁺ and OH ^- in water to H ₂ and O ₂ respectively; in addition, the electrons and holes that migrate to the surface of the photocatalyst It can react with O ₂ , H ⁺ , OH ^- in the environment to form strong active oxidants such as ·O ₂ ^- , ·OH and HO ₂ ^- , which are used for oxidative degradation and purification of organic pollutants in liquid and gas phases.

In addition to the potential use of photolysis of water to produce hydrogen energy, photocatalysis technology has emerged in the actual solution to environmental pollution problems. At present, the photocatalytic technology based on _TiO2 with low cost and high chemical stability has been used in anti-sun cosmetics, metallic paint for luxury cars and electronics industry, copier industry, high-voltage insulation materials, integrated circuit substrates, fluorescent Tubes and many other fields have been applied. According to reports, this photocatalytic technology can also be widely used in sanitary ceramics, glass products, gas appliances, digital keyboards, and household appliances such as air conditioners, refrigerators, washing machines, etc., which will bring about great changes in building materials, household appliances and people's daily life . According to relevant experts, if this technology is popularized and applied on a large scale, it is expected to become a high-tech weapon to solve the problem of environmental pollution.

At present, most of the research on photocatalysts at home and abroad stays on TiO ₂ and related modifications, such as nanometerization and high specific surface of materials, doping, semiconductor recombination, noble metal and oxide loading, etc. Although these works are very effective, their quantum yield is not high, and it is difficult to be used for hydrogen production by photocatalytic cracking of water. Therefore, finding new high-efficiency photocatalysts has become one of the most important issues in this field. According to the discovered photocatalytic materials, their systems can be classified into oxides, sulfides, oxysulfides, nitrides and oxynitrides, among which oxides often have better (photo) chemical stability; sulfides and Although oxysulfide can show relatively ideal visible light response characteristics, it is prone to photochemical corrosion as a photocatalytic material; nitride and oxynitride also have good visible light absorption characteristics, and the photocatalytic effect of the material itself is not ideal, but in After loading noble metals with strong electron affinity or their oxides, the photocatalytic activity can be greatly improved, such as (GaN) _x (ZnO) _1-x solid solution powder loaded with Rh-Cr nanocomposite oxides in response to photocatalytic cracking of water hydrogen production rate under visible light It can reach the order of mmol/h, but the photocatalytic activity of unloaded powder is extremely poor.

Finding new high-efficiency photocatalysts has always been a long-term and arduous task in the field of photocatalysis technology. It is the core of the large-scale application of photocatalysis technology, especially in the field of photolysis of water to produce hydrogen.

Contents of the invention

The purpose of the present invention is to provide a novel oxyhalide photocatalytic material and various preparation methods.

In the BiOX (X=Cl, Br, I) crystal structure, [Bi ₂ O ₂ ] and [X] structural layers are stacked alternately along the c-axis direction to form this unique layered crystal structure. Using the density functional (DFT) band theory calculation method to calculate the energy band of BiOX (X=Cl, Br, I), the results show that the conduction band is mainly composed of Bi 6p orbitals, and the valence band is mainly composed of Cl 3p (or Br 4p, I5p) composition; BiOX (X=Cl, Br, I) semiconductor is a kind of indirect transition material, Bi6p is more dispersed in the conduction band, which is conducive to the transmission of electrons in the material, improving the electronic conductivity and the corresponding photogenerated electron-space Hole separation ability. The ultraviolet-visible light absorption spectrum shows that the absorption edges of the BiOX (X=Cl, Br, I) material correspond to about 358, 426, and 646nm, respectively, and the optical band gaps correspond to about 3.46, 2.91, and 1.92eV.

We use a variety of methods such as solid phase or liquid to synthesize materials, and test the photocatalytic performance of materials.

1. Material preparation

method one:

Dissolve Bi ₂ O ₃ powder in concentrated halogen acid (HCl, HBr, HI), adjust to pH=2~5 with ammonia water, and filter for many times until no X ^- ions can be detected (tested with silver nitrate solution) , and the precipitate is dried to obtain the finished photocatalytic powder.

The specific process of the supported BiOX (X=Cl, Br, I) photocatalytic material can be: take the BiOX (X=Cl, Br, I) catalyst powder and place it in a beaker containing deionized water, add a sufficient amount of methanol to Hole sacrificial agent and 0.05-5wt% AgNO ₃ or 0.05-5wt% H ₂ PtCl ₆ ·6H ₂ O, irradiated under a mercury lamp for 5-10 hours while vigorously stirring, filtered and washed several times, and dried to obtain nano Photocatalytic materials of Ag or Pt particles.

The obtained BiOX (X=Cl, Br, I) photocatalytic powder has a particle diameter of 5-120 nm, and is loaded with 0.05-5 wt % of Ag or Pt.

Method Two:

The stoichiometric ratio of Bi ₂ O ₃ and BiX ₃ (X=Cl, Br, I) powders is placed in a quartz tube, vacuumized and packaged, and heated at 400-750° C. for 2-24 hours. After cooling, open the tube and grind to get the finished photocatalytic powder.

Method three:

Take deionized water in a beaker, use the corresponding halogen acid to adjust the pH of the solution to less than 1, then heat the solution, and while stirring continuously, slowly add the stoichiometric ratio of bismuth nitrate-halogen acid solution, and at the same time slowly add the concentration of 5 to 20 % NaOH solution to neutralize the HNO ₃ produced by hydrolysis, and maintain the pH value at 2-5, and the whole process lasts for about 0.5-5 hours. During this period, the temperature is kept constant at about 50-90°C, and the stirring is continued for more than 10 minutes, and the finished photocatalytic powder is obtained by cooling, filtering, washing, and drying.

Method four:

adding a stoichiometric ratio of halogen acid and solid bismuth nitrate to mix, then adding 0.5-5% anhydrous sodium sulfate and 0.5-5% sodium dodecylbenzenesulfonate solution based on the weight of the mixture, adding hot water and stirring to obtain a transparent solution, Then put it into a microwave oven and irradiate it with microwaves for 2 to 3 minutes, take it out for rapid cooling, filter, wash and dry to obtain the finished photocatalytic powder.

Method five:

Take the stoichiometric ratio bismuth nitrate-halogen acid solution, add an excess ratio of alkali metal halide (corresponding to the halogen acid) while stirring continuously, then adjust the pH to 2-5 with dilute ammonia water, stir, filter, wash, and dry. The finished photocatalytic powder is obtained.

Method six:

Dissolve bismuth nitrate in sufficient amount of glacial acetic acid, quickly add the mixed solution of sodium carbonate and alkali metal halide while stirring, the molar ratio of sodium carbonate and alkali metal halide is 1: (0.5～1.5), after vigorous stirring, Filter, wash and dry to get the finished photocatalytic powder.

2. Performance evaluation (photocatalytic performance)

Select P25-TiO ₂ photocatalyst to qualitatively evaluate the photocatalytic activity of BiOX (X=Cl, Br, I), and the experiment process is the same as that of BiOX (X=Cl, Br, I).

(1) Dye degradation and hydrogen production by photolysis of water

The sample powder obtained in the present invention is used in a self-made reactor to carry out photocatalytic degradation of organic dyes (methyl orange) and photocatalytic decomposition of water to produce hydrogen. The light source is a 500W high-pressure mercury lamp. During the catalytic experiment, the concentration of the dye is: 10mg/L, and the amount of the powder in the dye solution or pure water is: 0.2g/100mL.

(2) Harmful gas degradation

The sample powder obtained in the present invention is carried out in a self-made reactor for photocatalytic degradation of representative harmful gas formaldehyde. The photocatalytic reaction was carried out in a self-made cylindrical stainless steel photocatalytic reactor, and the light source was an 8W ultraviolet lamp (PHILIPS company). The photocatalyst is evenly coated with water on a square glass sheet of 70mm×70mm×2mm, and after drying, it is suspended between the ultraviolet lamp and the axial flow fan in the reactor. Vacuumize the reaction system first, and the reactor is a closed container. After vacuuming, dry air was introduced until atmospheric pressure was reached. Then a certain amount of solid paraformaldehyde is vaporized and injected into the reaction vessel. Turn off the UV light source at the beginning of the experiment, turn on the UV lamp when the formaldehyde content in the system no longer decreases and reaches the adsorption equilibrium, and perform UV irradiation. Use a gas chromatograph to detect the concentration of formaldehyde gas in the system every 20 minutes, and calculate the light according to ΔC/C ₀ Degradation rate of catalytic oxidative decomposition of formaldehyde.

(3) Sterilization test

Escherichia coli E.coli and Staphylococcus aureus were selected as the test strains. Bacteria were propagated with beef extract peptone medium. Use a hemocytometer to directly count and measure the amount of bacteria contained in the solution under a microscope to determine the bactericidal efficiency of the powder.

From the test results, the ability of BiOX (X=Cl, Br, I) to degrade organic pollutants is better than that of nano P25-TiO ₂ , and the hydrogen production rate of photolysis water under ultraviolet light response reaches the order of 10-100 μmol/h, which is better than that of nano P25-TiO ₂ , BiOX can also degrade harmful gas formaldehyde, and the effect of killing Escherichia coli and Staphylococcus aureus is better than that of nano-sized P25-TiO ₂ .

Description of drawings

Figure 1 is the layered crystal structure of BiOX;

Figure 2 is the energy band structure of BiOCl;

Figure 3 shows the partial density of states and the total density of states of BiOCl;

Fig. 4 is BiOX (X=Cl, Br, I) ultraviolet-visible absorption spectrum;

Fig. 5 is BiOX (X=Cl, Br, I) and P25-TiO The activity of _{photocatalytic} degradation dye methyl orange;

6 is a field emission scanning electron microscope image of BiOCl prepared in Example 1.

Detailed ways

Examples of the present invention will be described below, but the present invention is by no means limited to the examples.

Example 1:

Dissolve the Bi ₂ O ₃ powder in the corresponding concentrated halogen acid, adjust the pH to 3 with dilute ammonia water, and filter it several times until no X-ions can be detected (tested with silver nitrate solution), and dry the precipitate at 80°C That is, the finished nanometer photocatalytic powder is obtained.

The specific process of the BiOX (X=Cl, Br, I) photocatalytic material of load can be: get 2g BiOX (X=Cl, Br, I) catalyst powder and insert in the beaker that contains 100ml deionized water, add the methanol of 10ml Hole sacrificial agent and an appropriate amount of AgNO ₃ or H ₂ PtCl ₆ 6H ₂ O, while vigorously stirring in a 300W mercury lamp for 85-10 hours, after several times of filtration and washing, and drying to obtain a photon loaded with nano-Ag or Pt particles. catalytic material.

The photocatalytic degradation of methyl orange, an organic compound, shows that the UV photocatalytic performance of BiOX (X=Cl, Br) is better than that of P25-TiO ₂ . The effect of base orange (MO) is improved; and the effect of loading the same mass fraction of Pt is basically the same as that of Ag loading.

In the photocatalytic cracking of water for hydrogen production, the hydrogen production rate can reach the order of 10 μmol/h, and the order of hydrogen production under the same conditions is: BiOCl>BiOBr>BiOI. The effect of loading Pt is better than that of loading Ag, and the hydrogen production rate increases to the order of 100 μmol/h, and the order of hydrogen production is still: BiOCl>BiOBr>BiOI. However, pure P25-TiO ₂ does not have the ability to photocatalytically split water to produce hydrogen.

In the experiment of degrading organic harmful gas formaldehyde, the degradation rate of BiOX (X=Cl, Br, I) exceeded 90% after photocatalysis for 2 hours. The order of degradation rate is BiOCl>BiOBr>BiOI, while the degradation rate of pure P25- _TiO2 is 81%.

In the bactericidal experiment, after 10 hours of photocatalysis, the order of the bactericidal rate of BiOX (X=Cl, Br, I) was BiOCl>BiOBr>BiOI, and the bactericidal rate exceeded 70%. And the pure P25-TiO ₂ bactericidal rate is 55%.

Example 2:

The stoichiometric ratio of Bi ₂ O ₃ and BiX ₃ (X=Cl, Br, I) was placed in a quartz tube, vacuumized, packaged, and heated at 550° C. for 12 hours. After cooling, open the tube and grind to get the finished photocatalytic powder.

Photocatalytic degradation of dye methyl orange, photolysis of water to produce hydrogen, degradation of harmful substance formaldehyde and bactericidal test results are about 40% of those in Embodiment 1, which may be due to the smaller specific surface area of the sample prepared by the solid phase method.

Example 3:

Take 100ml of deionized water in a beaker, adjust the pH of the solution to less than 1 with the corresponding halogen acid, then heat the solution to about 70°C, while stirring continuously, slowly add 1mol of bismuth nitrate-halogen acid solution, and at the same time slowly add 15% NaOH The solution is used to neutralize the HNO ₃ produced by hydrolysis, and the pH value is maintained at about 2, and the whole process lasts for about 1 hour. During this period, the temperature was kept constant at about 75°C, continued to stir for 10 minutes, cooled, filtered, washed, and dried at 80°C to obtain the finished photocatalytic powder.

The performance test result is basically the same as that of Example 1.

Example 4:

Add a sufficient amount of 3mol halide acid, 1mol solid bismuth nitrate, 2wt% anhydrous sodium sulfate and 1wt% sodium dodecylbenzenesulfonate solution, then add hot water at 75°C and stir to obtain a transparent solution, making the total volume 200ml, Then put it into a microwave oven for 2-3 minutes of irradiation, take it out for rapid cooling, filter, wash, and dry at 80°C to obtain the finished photocatalytic powder.

Performance test result is slightly higher than embodiment 1.

Example 5:

Take 1mol of bismuth nitrate dissolved in a sufficient amount of halogen acid solution, add 2mol of the corresponding sodium halide while stirring constantly, then adjust the pH to 3 with ammonia water, stir vigorously for 30min, filter, wash, and dry at 80°C to obtain the finished photocatalyst powder.

The performance test result is basically the same as that of Example 1.

Embodiment 6:

Dissolve 1 mol of bismuth nitrate in 5 mol of glacial acetic acid, quickly add a mixed solution of 3 mol of sodium carbonate and 2 mol of sodium halide while stirring, stir vigorously for 30 minutes, filter, wash, and dry at 80°C to obtain the finished photocatalytic powder.

The performance test result is basically the same as that of Example 1.

Claims (5)

1. the preparation method of a halogen-oxide photocatalytic material, said halogen-oxide photocatalytic material, its chemical composition is BiOX, X=Cl, Br, I, [Bi ₂O ₂] alternately pile up each other along the c direction of principal axis with [X] structure sheaf, form the layered crystal configuration, it is characterized in that Bi by stoichiometric proportion ₂O ₃And BiX ₃(I) powder places quartz ampoule for X=Cl, Br, vacuumizes the back encapsulation, and 400-750 ℃ of heating 2-24 hour, cooling back open pipe ground.

2. the preparation method of a halogen-oxide photocatalytic material, said halogen-oxide photocatalytic material, its chemical composition is BiOX, X=Cl, Br, I, [Bi ₂O ₂] alternately pile up each other along the c direction of principal axis with [X] structure sheaf; Form the layered crystal configuration, it is characterized in that removing ionized water in beaker, with corresponding hydracid regulator solution pH less than 1; Then solution is heated; When constantly stirring, slowly add the bismuth nitrate-hydracid solution of stoichiometric proportion, slowly adding concentration simultaneously is the HNO that 5～20%NaOH solution produces with neutralizing hydrolysis ₃, keep the pH value 2～5, whole process continues 0.5～5h, and temperature constant continues to stir more than the 10min cooling, filtration, washing, oven dry about 50～90 ℃ therebetween.

3. the preparation method of a halogen-oxide photocatalytic material, said halogen-oxide photocatalytic material, its chemical composition is BiOX, X=Cl, Br, I, [Bi ₂O ₂] alternately pile up each other along the c direction of principal axis with [X] structure sheaf; Form the layered crystal configuration, the hydracid, the solid nitric acid bismuth that it is characterized in that adding stoichiometric proportion mix, and add then to account for mixture weight 0.5～5% anhydrous sodium sulfate and 0.5～5% neopelex solution; Add the hot water stirring again and obtain clear solution; Put into the micro-wave oven microwave irradiation then 2～3 minutes, and took out chilling, filter, wash, dry the photocatalytic powder that gets product.

4. the preparation method of a halogen-oxide photocatalytic material, said halogen-oxide photocatalytic material, its chemical composition is BiOX, X=Cl, Br, I, [Bi ₂O ₂] alternately pile up each other along the c direction of principal axis with [X] structure sheaf; Form the layered crystal configuration; It is characterized in that getting stoichiometric proportion bismuth nitrate-hydracid solution, add the alkali halide (corresponding with hydracid) of excessive ratio when constantly stirring, using weak aqua ammonia to regulate pH then is 2～5; Stir, filter, wash, dry.

5. the preparation method of a halogen-oxide photocatalytic material, said halogen-oxide photocatalytic material, its chemical composition is BiOX, X=Cl, Br, I, [Bi ₂O ₂] alternately pile up each other along the c direction of principal axis with [X] structure sheaf; Form the layered crystal configuration; It is characterized in that bismuth nitrate is dissolved in the capacity glacial acetic acid, add the mixed solution of sodium carbonate and alkali halide in the time of stirring fast, the mol ratio of sodium carbonate and alkali halide is 1: (0.5～1.5); After the vigorous stirring, filter, wash, dry the photocatalytic powder that gets product.

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