CN114632513B - Preparation method and application of monoatomic Au-loaded strontium titanate/titanium dioxide composite photocatalyst - Google Patents

Preparation method and application of monoatomic Au-loaded strontium titanate/titanium dioxide composite photocatalyst Download PDF

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CN114632513B
CN114632513B CN202210289809.5A CN202210289809A CN114632513B CN 114632513 B CN114632513 B CN 114632513B CN 202210289809 A CN202210289809 A CN 202210289809A CN 114632513 B CN114632513 B CN 114632513B
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解伟誉
符琼月
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Hainan University
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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Abstract

Preparation method and application of monoatomic Au-loaded strontium titanate/titanium dioxide composite photocatalyst, and the invention aims to solve the problem of the existing TiO 2 The photo-generated electrons and holes of the photocatalyst are easy to be combined, and the photocatalytic activity is low. The preparation method comprises the following steps: 1. TiO is mixed with 2 Placing the powder in acid liquor for dipping and acidizing treatment; 2. towards Sr (OH) 2 Adding acidified TiO into the solution 2 Carrying out hydrothermal reaction on the powder under alkaline conditions to obtain composite powder; 3. SrTiO 3 /TiO 2 Dispersing the composite powder in water by ultrasonic, adding chloroauric acid solution, and adding sodium borohydride solution for reduction reaction; 4. and (5) calcining. The invention is realized by controlling Sr (OH) 2 Concentration of solution and reaction time, so that TiO 2 Partial composite SrTiO on particle surface 3 Then loading single-atom Au, thereby improving SrTiO 3 /TiO 2 Photocatalytic decomposition of the composite photocatalyst water to hydrogen performance.

Description

Preparation method and application of monoatomic Au-loaded strontium titanate/titanium dioxide composite photocatalyst
Technical Field
The invention belongs to the field of photocatalyst materials, and in particular relates to SrTiO 3 /TiO 2 A preparation method and application of a composite photocatalyst.
Background
Titanium dioxide is an important n-type wide forbidden band semiconductor, and has the unique properties of higher photocatalytic activity, good hydrophilicity, better thermal stability, no toxicity, no secondary pollution and the like, so that the titanium dioxide becomes the most potential green photocatalyst in recent years. However, titanium dioxide photocatalysis also has a number of problems that limit its application, two of the most critical problems: firstly, photo-generated electrons and photo-generated holes generated by the excitation of titanium dioxide by ultraviolet light are very easy to be combined, so that TiO 2 Quantum efficiency and photocatalytic activity of (C)Low; secondly, the band gap of titanium dioxide is wider (3.0-3.2 eV), and only the ultraviolet part with the solar spectrum range less than 5% can be utilized.
The photocatalytic hydrogen production reaction utilizes the reducibility of electrons, and the photo-generated electrons react with water or hydrogen ions to generate hydrogen, but part of photo-generated electrons and photo-generated holes are combined in the process of migrating to the surface, and heat energy is released. In the reaction of degrading organic pollutants in water body by photocatalysis, the organic pollutants in water body are oxidized by utilizing the strong oxidizing property of the photo-generated holes, which can be expressed as H adsorbed by the surface of the catalyst 2 O or OH-ions are captured and then react with the O or OH-ions to form hydroxyl free radicals with strong oxidability, and the hydroxyl free radicals have the advantages of being capable of carrying out photocatalytic reaction in a water body environment and being in a free state and not selective to pollutants, so that the oxidation reaction of substances is promoted. During the photocatalytic reaction, the life of the photogenerated electrons and the photogenerated holes is a key factor for whether the reaction performance is excellent.
The existing research is that the semiconductor photocatalyst is modified, such as doping of metal anions and cations, sensitization of the photocatalyst and design of a composite photocatalyst, and the modified novel semiconductor photocatalyst is obviously improved in the aspects of visible light absorption and photo-generated electron-hole separation.
Disclosure of Invention
The invention aims to solve the problems of the prior TiO 2 The problems of easy recombination of photo-generated electrons and holes and low photo-catalytic activity of the photocatalyst are solved, and a single-atom Au-loaded SrTiO is provided 3 /TiO 2 A preparation method and application of a composite photocatalyst.
The invention relates to a single-atom Au-loaded SrTiO 3 /TiO 2 The preparation method of the composite photocatalyst is realized according to the following steps:
1. TiO is mixed with 2 Placing the powder into acid liquor for immersion acidification treatment to obtain acidified TiO 2 A powder;
2. sr (OH) 2 Dissolving in water to obtain Sr (OH) with concentration of 2-8 mmol/L 2 Solution to Sr (OH) 2 Adding acid into the solutionTiO of (C) 2 Adding NaOH solution into the powder to adjust the pH value of the system to be 10-12, carrying out hydrothermal reaction at 140-180 ℃, and carrying out acid washing, water washing and drying on a solid phase product to obtain SrTiO 3 /TiO 2 A composite powder;
3. SrTiO 3 /TiO 2 Dispersing the composite powder in water by ultrasonic, adding chloroauric acid solution, stirring, adding sodium borohydride solution to perform reduction reaction on gold ions, continuing ultrasonic dispersion, centrifugally collecting solid phase matters, washing with water and drying to obtain Au-loaded SrTiO 3 /TiO 2 A material;
4. loading SrTiO on Au in a tube furnace at 300-600 DEG C 3 /TiO 2 Calcining the material to obtain single-atom Au-loaded SrTiO 3 /TiO 2 A composite photocatalyst material.
The invention relates to a single-atom Au-loaded SrTiO 3 /TiO 2 The application of the composite photocatalyst is that single-atom Au is loaded on SrTiO 3 /TiO 2 The composite photocatalyst is applied to photocatalytic decomposition of water to hydrogen evolution.
The invention firstly aims at TiO 2 Acidizing the powder, and adding TiO (titanium dioxide) by acidizing 2 Active sites of particles and surface oxygen defects, while also enhancing TiO to some extent 2 Adsorption capacity of the particles, then in TiO by alkaline hydrothermal reaction 2 SrTiO composite on particle surface 3 ,SrTiO 3 Is an n-type semiconductor with perovskite structure, srTiO 3 Is of the forbidden bandwidth of TiO 2 Near, srTiO 3 And TiO 2 The heterojunction is formed at the composite interface of the electron-hole pair, and the photo-generated electrons and the holes can reversely migrate to the two sides of the heterojunction, and the recombination of photo-generated carriers is inhibited due to the special energy band structure and carrier conveying characteristic of the heterojunction, so that the photoelectric performance of quanta is improved. But TiO 2 SrTiO of particle surface 3 Not having the photocatalytic properties of TiO 2 Materials, the invention is also disclosed in SrTiO 3 /TiO 2 The composite material loads single-atom Au by a reduction method, and the Au atoms are taken as electron capturing agents to capture SrTiO simultaneously 3 And TiO 2 The generated photo-generated electrons further improve the electricitySeparation efficiency of the seed and hole, srTiO 3 /TiO 2 The nano Au on the composite material is loaded to generate a plasma resonance effect, and a Schottky barrier drives holes to transfer to the metal surface to form a hole barrier region, so that SrTiO is improved 3 /TiO 2 Photocatalytic properties of the composite material.
The invention is realized by controlling Sr (OH) 2 Concentration of solution and reaction time, so that TiO 2 Partial composite SrTiO on particle surface 3 At the same time expose part of TiO 2 And (3) particles. In TiO 2 Particles and SrTiO 3 The surface of the particle is loaded with single-atom Au at the same time, and the plasma resonance effect of nano Au is utilized to improve SrTiO 3 /TiO 2 Photocatalytic decomposition of the composite photocatalyst water to hydrogen performance.
Drawings
FIG. 1 shows the result of the example 3 /TiO 2 XRD pattern of the composite photocatalyst.
Detailed Description
The first embodiment is as follows: the single-atom Au-supported SrTiO of the present embodiment 3 /TiO 2 The preparation method of the composite photocatalyst is implemented according to the following steps:
1. TiO is mixed with 2 Placing the powder into acid liquor for immersion acidification treatment to obtain acidified TiO 2 A powder;
2. sr (OH) 2 Dissolving in water to obtain Sr (OH) with concentration of 2-8 mmol/L 2 Solution to Sr (OH) 2 Adding acidified TiO into the solution 2 Adding NaOH solution into the powder to adjust the pH value of the system to be 10-12, carrying out hydrothermal reaction at 140-180 ℃, and carrying out acid washing, water washing and drying on a solid phase product to obtain SrTiO 3 /TiO 2 A composite powder;
3. SrTiO 3 /TiO 2 Dispersing the composite powder in water by ultrasonic, adding chloroauric acid solution, stirring, adding sodium borohydride solution to perform reduction reaction on gold ions, continuing ultrasonic dispersion, centrifugally collecting solid phase matters, washing with water and drying to obtain Au-loaded SrTiO 3 /TiO 2 A material;
4. at the position ofThe SrTiO is loaded on Au in a tube furnace at the temperature of 300-600 DEG C 3 /TiO 2 Calcining the material to obtain single-atom Au-loaded SrTiO 3 /TiO 2 A composite photocatalyst material.
The second embodiment is as follows: the difference between the present embodiment and the specific embodiment is that the acid solution in the first step is hydrochloric acid or sulfuric acid with a concentration of 0.5-0.8 mol/L.
And a third specific embodiment: this embodiment differs from the first or second embodiments in that Sr (OH) in step two 2 The concentration of the solution is 4-6 mmol/L.
The present embodiment controls Sr (OH) 2 Controlling the concentration of the solution and controlling the TiO 2 Surface SrTiO 3 The degree of recombination.
The specific embodiment IV is as follows: this embodiment differs from one to three embodiments in that the concentration of the NaOH solution in the second step is 0.1mol/L to 0.2mol/L.
Fifth embodiment: the difference between the first embodiment and the fourth embodiment is that the hydrothermal reaction time in the second step is 8-12 h.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that Sr (OH) in step two 2 And TiO 2 The molar ratio of (2) is 0.6-0.8:1.
Seventh embodiment: the difference between the present embodiment and one of the first to sixth embodiments is that the reduction reaction time in the third step is 2 to 4 hours.
Eighth embodiment: the present embodiment differs from one to seven of the embodiments in that SrTiO is supported by three Au steps 3 /TiO 2 The Au loading in the material is 1-2.5 wt%.
Detailed description nine: the present embodiment differs from one to eight of the embodiments in that the step four loads SrTiO on Au at a temperature of 400 to 500 DEG C 3 /TiO 2 The material was calcined for 1h.
Detailed description ten: the single-atom Au-supported SrTiO of the present embodiment 3 /TiO 2 The application of the composite photocatalyst is that single-atom Au is loaded with SrTiO 3 /TiO 2 The composite photocatalyst is applied to photocatalytic decomposition of water to hydrogen evolution.
Example 1: in this example, srTiO was carried by monoatomic Au 3 /TiO 2 The preparation method of the composite photocatalyst is implemented according to the following steps:
1. TiO is mixed with 2 Immersing the powder in hydrochloric acid with the concentration of 0.8mol/L for acidizing to obtain acidized TiO 2 A powder;
2. sr (OH) 2 Dissolved in water to obtain Sr (OH) with the concentration of 4mmol/L 2 Solution to 20mL of Sr (OH) 2 Adding acidified TiO into the solution 2 Powder, sr (OH) 2 And TiO 2 Adding NaOH solution to adjust the pH value of the system to be 10, carrying out hydrothermal reaction for 10 hours at 160 ℃, and carrying out acid washing, water washing and drying (the drying temperature is 80 ℃) on a solid phase product to obtain SrTiO, wherein the molar ratio of the solid phase product is 0.6:1 3 /TiO 2 A composite powder;
3. SrTiO 3 /TiO 2 Dispersing the composite powder in 50mL of water by ultrasonic, adding 2mL of chloroauric acid solution with the concentration of 0.03mol/L, stirring, adding 0.4mL of sodium borohydride solution with the concentration of 0.5mol/L to carry out reduction reaction on gold ions, continuing ultrasonic dispersion, centrifugally collecting a solid phase, washing with water and drying to obtain Au-loaded SrTiO 3 /TiO 2 A material;
4. SrTiO was supported on Au at a temperature of 500℃in a tube furnace 3 /TiO 2 Calcining the material for 1h to obtain single-atom Au-loaded SrTiO 3 /TiO 2 Composite photocatalyst material (sample a).
In this example, srTiO was carried by monoatomic Au 3 /TiO 2 The Au loading in the composite photocatalyst material was 1.6wt%.
Step four of the embodiment is calcined at 500 ℃ to obtain anatase phase TiO 2 The material, while the calcination treatment, can increase the thickness of the heterojunction.
Example 2: this example differs from example 1 in that Sr (OH) is present in a concentration of 1mmol/L 2 A solution.
The Au-loaded SrTiO obtained in this example 3 /TiO 2 The composite photocatalyst material is sample B.
Example 3: this example differs from example 1 in that Sr (OH) is present in a concentration of 8mmol/L 2 A solution.
The Au-loaded SrTiO obtained in this example 3 /TiO 2 The composite photocatalyst material is sample C.
Example 4: this example differs from example 1 in that Sr (OH) is present in a concentration of 20mmol/L 2 A solution.
The Au-loaded SrTiO obtained in this example 3 /TiO 2 The composite photocatalyst material was sample D.
Example 5: this example differs from example 1 in that step two was hydrothermally reacted at a temperature of 160℃for 20h.
The Au-loaded SrTiO obtained in this example 3 /TiO 2 The composite photocatalyst material was sample E.
Example 6: this example differs from example 1 in that the calcination treatment of step four is not performed.
The Au-loaded SrTiO obtained in this example 3 /TiO 2 The material was sample F.
Photocatalytic water splitting hydrogen evolution experiment:
0.1g of sample is dispersed in 20mL of mixed solution of anhydrous methanol and 80mL of distilled water, and in a constant temperature vacuum circulation system, a 300W xenon lamp is used as a light source, and a gas chromatograph is used for detecting the hydrogen production amount of the catalyst under the corresponding illumination time. The average hydrogen production rate (mmol/g.h) for 10 hours is shown in Table 1 below.
TABLE 1
Sample numbering Average hydrogen production Rate (mmol/g. H)
Sample A 2.135
Sample B 1.683
Sample C 2.368
Sample D 1.836
Sample E 1.755
Sample F 1.085
This example is achieved by adjusting Sr (OH) 2 Controlling the concentration of the solution and the hydrothermal reaction time, and controlling the TiO 2 Particle surface SrTiO 3 Is a composite state of SrTiO 3 Particle part growth on TiO 2 At the acidification sites of the particle surface, while exposing part of the TiO 2 The surface of the particles is subsequently carried with Au on TiO 2 Particles and SrTiO 3 The particle surface exerts a plasmon resonance effect. As can be seen from Table 1, the photocatalytic activity of sample D decreases with Sr (OH) 2 Further increase of solution concentration (up to 60 mmol/L), tiO 2 The particle surface is coated with SrTiO 3 The particles are completely covered, the photocatalytic activity of the sample is instead reduced, the analytical reason being probably due to the TiO 2 Particle coated SrTiO 3 Particle-coated SrTiO 3 Catalytic properties of the material are inherently inferior to those of TiO 2 Materials, resulting in reduced photocatalytic hydrogen production activity.
This example Au-supported SrTiO 3 /TiO 2 The material has excellent photocatalytic hydrogen production stability, basically has no fluctuation of hydrogen production rate in the 10-hour photocatalytic process, and has stable hydrogen production rate.

Claims (5)

1. The preparation method of the monoatomic Au-loaded strontium titanate/titanium dioxide composite photocatalyst is characterized by comprising the following steps of:
1. TiO is mixed with 2 Placing the powder into acid liquor for immersion acidification treatment to obtain acidified TiO 2 A powder;
2. sr (OH) 2 Dissolving in water to obtain Sr (OH) with concentration of 4-6 mmol/L 2 Solution to Sr (OH) 2 Adding acidified TiO into the solution 2 Adding NaOH solution into the powder to adjust the pH value of the system to be 10-12, carrying out hydrothermal reaction for 8-12 h at the temperature of 140-180 ℃, and carrying out acid washing, water washing and drying on a solid phase product to obtain SrTiO 3 /TiO 2 A composite powder;
3. SrTiO 3 /TiO 2 Dispersing the composite powder in water by ultrasonic, adding chloroauric acid solution, stirring, adding sodium borohydride solution to perform reduction reaction on gold ions for 2-4 h, continuing ultrasonic dispersion, centrifugally collecting solid phase matters, washing with water and drying to obtain Au-loaded SrTiO 3 /TiO 2 A material;
4. loading SrTiO on Au in a tube furnace at 300-600 DEG C 3 /TiO 2 Calcining the material to obtain single-atom Au-loaded SrTiO 3 /TiO 2 A composite photocatalyst material;
wherein in the second step Sr (OH) 2 And TiO 2 The molar ratio of (2) is 0.6-0.8:1; step three Au-loaded SrTiO 3 /TiO 2 The Au loading in the material is 1-2.5 wt%.
2. The method for preparing the single-atom Au-supported strontium titanate/titanium dioxide composite photocatalyst according to claim 1, wherein the acid liquor in the first step is hydrochloric acid or sulfuric acid with the concentration of 0.5-0.8 mol/L.
3. The method for preparing a single-atom Au-supported strontium titanate/titanium dioxide composite photocatalyst according to claim 1, wherein the concentration of the NaOH solution in the second step is 0.1mol/L to 0.2mol/L.
4. The method for preparing a single-atom Au-supported strontium titanate/titanium dioxide composite photocatalyst according to claim 1, characterized in that in the fourth step, srTiO is supported on Au at a temperature of 400-500 DEG C 3 /TiO 2 The material was calcined for 1h.
5. The application of the single-atom Au-supported strontium titanate/titanium dioxide composite photocatalyst prepared by the method of claim 1, which is characterized in that the single-atom Au-supported SrTiO 3 /TiO 2 The composite photocatalyst is applied to photocatalytic decomposition of water to hydrogen evolution.
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CN116173950A (en) * 2023-03-09 2023-05-30 华南理工大学 Preparation method and application of gold nanoparticle-loaded zinc titanate/titanium dioxide composite material
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