CN114618537B - Red phosphorus/strontium titanate heterojunction photocatalyst, and preparation method and application thereof - Google Patents
Red phosphorus/strontium titanate heterojunction photocatalyst, and preparation method and application thereof Download PDFInfo
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 title claims abstract description 136
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- 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 discloses a red phosphorus/strontium titanate heterojunction photocatalyst, a preparation method and application thereof. The red phosphorus/strontium titanate heterojunction photocatalyst is prepared from red phosphorus and strontium titanate, specifically, the red phosphorus is uniformly attached to (110) and (100) crystal faces of the strontium titanate, and a red phosphorus/strontium titanate heterojunction structure is formed. The preparation method has the advantages of simple process, short preparation time, mild conditions and low cost, and can realize large-scale production, the red phosphorus/strontium titanate heterojunction photocatalyst prepared by the preparation method enhances the separation and transmission efficiency of photo-generated carriers in a heterojunction structure forming mode, the spectral response is widened to 425nm-780nm, the photocatalytic hydrolysis hydrogen production activity of the red phosphorus/strontium titanate heterojunction photocatalyst is greatly improved, the circulation stability is good, the formation of a heterojunction is realized, the defect of rapid recombination of red phosphorus photo-generated electrons and photo-generated holes is overcome, the visible light response range of strontium titanate is widened, and the beneficial effect of the photocatalytic activity is improved.
Description
Technical Field
The invention relates to a photocatalyst, in particular to a red phosphorus/strontium titanate heterojunction photocatalyst, a preparation method and application thereof.
Background
The continued supply of energy is required by social progress, and the over exploitation of fossil energy has brought an environmental crisis to the earth. Therefore, there is a need to develop renewable energy sources that fully replace fossil energy sources. Hydrogen has a high energy density and combustion value and is a promising clean chemical fuel. Compared with other methods, the method for preparing hydrogen by photocatalytic water splitting is a low-cost and environment-friendly method. While developing efficient photocatalysts has been one of the goals of the scientific community.
Strontium titanate (SrTiO) 3 ) The photocatalyst is a perovskite type ternary oxide, has the characteristics of strong oxidation-reduction capability, good physicochemical stability, environmental friendliness and the like, and is widely applied to various fields of photocatalysis, such as hydrogen production/degradation/photocatalysis and the like. However, the bandgap of strontium titanate is 3.2eV and only responds to ultraviolet light, which greatly limits the further development of strontium titanate in the field of photocatalysis. It is an important goal to explore strontium titanate-based photocatalysts with visible light correspondence to meet future energy demands.
Through deeper research, the modification treatment of strontium titanate, such as heterojunction construction, can widen the photoresponse range, reduce the photo-generated electron-hole recombination rate and improve the photocatalytic activity. Therefore, the strontium titanate-based photocatalyst heterostructure has important scientific and practical significance.
Disclosure of Invention
The invention aims to provide a red phosphorus/strontium titanate heterojunction photocatalyst, a preparation method and application thereof. The preparation method has the advantages of simple process, short preparation time, mild conditions and low cost, and can realize large-scale production, the red phosphorus/strontium titanate heterojunction photocatalyst prepared by the preparation method enhances the separation and transmission efficiency of photo-generated carriers in a heterojunction structure forming manner, compared with pure red phosphorus or pure strontium titanate, the spectral response is widened to 425nm-780nm, the photocatalytic hydrolysis hydrogen production activity of the red phosphorus/strontium titanate heterojunction photocatalyst is greatly improved, the circulation stability is good, the formation of a heterojunction overcomes the defect of rapid recombination of red phosphorus photo-generated electrons and photo-generated holes, the visible light response range of the strontium titanate is widened, and the photocatalytic activity is improved.
The technical scheme of the invention is as follows: the red phosphorus/strontium titanate heterojunction photocatalyst is prepared from red phosphorus and strontium titanate, and specifically, the red phosphorus is uniformly attached to (110) and (100) crystal faces of the strontium titanate to form a red phosphorus/strontium titanate heterojunction structure.
In the red phosphorus/strontium titanate heterojunction photocatalyst, the red phosphorus/strontium titanate heterojunction photocatalyst comprises: the red phosphorus and strontium titanate are prepared by in-situ synthesis through a hydrothermal method, wherein the molar ratio of the red phosphorus to the strontium titanate is 0.125-1:1.
The preparation method of the red phosphorus/strontium titanate heterojunction photocatalyst comprises the following steps:
(1) Putting red phosphorus into water for ultrasonic dispersion to obtain red phosphorus suspension, wherein the red phosphorus suspension is A;
(2) Tetrabutyl titanate is dissolved in glycol solution to obtain a product B; then adding strontium nitrate solution and sodium hydroxide solution into the product B in sequence under stirring to obtain a product C;
(3) Transferring the product C into a reaction container, performing hydrothermal reaction, naturally cooling, and then adjusting the pH value to obtain a product D;
(4) Adding the product A into the product D under stirring, uniformly mixing to obtain the product E, carrying out hydrothermal reaction on the product E, naturally cooling, washing with deionized water and ethanol, and drying to obtain the red phosphorus/strontium titanate heterojunction photocatalyst.
In the preparation method of the red phosphorus/strontium titanate heterojunction photocatalyst, in the step (1), red phosphorus is placed into water to be dispersed for 5-15min by ultrasonic, so as to obtain red phosphorus suspension, which is A; the concentration of the red phosphorus suspension is 1-2mg/mL.
In the preparation method of the red phosphorus/strontium titanate heterojunction photocatalyst, in the step (2), 3-4g of tetrabutyl titanate is dissolved in 40mL of ethylene glycol solution with the concentration of 98% according to a proportion to obtain a product B; then adding 20mL of strontium nitrate solution with the concentration of 0.44-0.58mol/L and 10mL of sodium hydroxide solution with the concentration of 4.4-5.8mol/L into the product B under magnetic stirring to obtain the product C.
In the preparation method of the red phosphorus/strontium titanate heterojunction photocatalyst, in the step (2), 3.4g of tetrabutyl titanate is dissolved in 40mL of ethylene glycol solution with the concentration of 98% according to a proportion to obtain a product B; then adding 20mL of strontium nitrate solution with the concentration of 0.5mol/L and 10mL of sodium hydroxide solution with the concentration of 5mol/L into the product B in sequence under magnetic stirring to obtain a product C; the strontium nitrate solution is added into the product B in a dropwise manner.
In the preparation method of the red phosphorus/strontium titanate heterojunction photocatalyst, in the step (3), the C product is transferred into a reaction vessel to carry out a hydrothermal reaction, the temperature of the hydrothermal reaction is 120-180 ℃, the time is 12-24h, the product is naturally cooled to 20-30 ℃, and then the pH value is regulated to 6.8-7.2, so that the D product is obtained; the pH is adjusted to 6.8-7.2, specifically HNO of 0.5-1mol/L is adopted 3 The pH of the solution is regulated to 6.8-7.2; concentrated HNO 3 Because red phosphorus is oxidized due to oxidizing property, low-concentration nitric acid must be used to adjust the pH.
In the step (4), adding the product A into the product D under stirring, uniformly mixing to obtain the product E, carrying out a hydrothermal reaction on the product E, wherein the molar ratio of the red phosphorus to the strontium titanate in the product E is 0.125-1:1, the temperature of the hydrothermal reaction is 120-180 ℃, the time is 6-24h, naturally cooling to 20-30 ℃, and washing with deionized water and ethanol and drying to obtain the red phosphorus/strontium titanate heterojunction photocatalyst.
In the preparation method of the red phosphorus/strontium titanate heterojunction photocatalyst, the molar ratio of the red phosphorus to the strontium titanate in the E product is 1:1; the washing with deionized water and ethanol, and the drying is carried out by alternately washing with deionized water and ethanol for 2-4 times, and then vacuum drying at 50-70 ℃ for 10-12h.
The application of the red phosphorus/strontium titanate heterojunction photocatalyst comprises the following steps: the red phosphorus/strontium titanate heterojunction photocatalyst is applied to the photocatalytic decomposition of water to produce hydrogen at the wavelength of 425nm-780nm.
Compared with the prior art, the invention has the following beneficial effects:
1. the red phosphorus/strontium titanate heterojunction photocatalyst is prepared from common chemical reagents, and has wide sources, low cost and easy obtainment; compared with the high-temperature calcination method, the method has the advantages of simple reaction equipment, mild reaction conditions, low synthesis temperature and simple preparation steps, and only carries out a hydrothermal process;
2. the red phosphorus/strontium titanate heterojunction photocatalyst prepared by the invention has high photo-generated carrier separation efficiency and low photoluminescence;
3. compared with the single strontium titanate photocatalytic decomposition water hydrogen production activity, the red phosphorus/strontium titanate heterojunction photocatalyst prepared by the invention has the advantages that the hydrogen production activity is greatly improved; the hydrogen production activity of the red phosphorus/strontium titanate heterojunction photocatalyst in visible light photocatalytic decomposition water can reach 196.75 mu mol/(h.g), which is 9.15 times that of pure red phosphorus, and pure strontium titanate has no hydrogen production activity in visible light; the photocatalytic water decomposition can be realized under the irradiation of light with the wavelength of 425nm-780nm, the ultraviolet-spectroscopic spectrum test shows that the related data can be obtained by using a 300W xenon lamp light source (CEL-HXUV 300-T3) with a lambda not less than 420nm filter for simulating the irradiation of sunlight.
4. The invention utilizes XRD, SEM, TEM and other characterization means to characterize the crystal structure, morphology and light absorption performance, and proves that RP and SrTiO 3 Closely contacted to form a heterostructure for increasing SrTiO 3 Has important significance in overcoming the defect of fast recombination of RP photo-generated electrons and photo-generated vacancies and has the shape of heterojunctionThe method overcomes the defect of fast recombination of red phosphorus photogenerated electrons and photogenerated holes, widens the visible light response range of strontium titanate, and improves the photocatalytic activity.
In conclusion, the preparation method has the advantages of simple process, short preparation time, mild condition and low cost, and can realize large-scale production, the red phosphorus/strontium titanate heterojunction photocatalyst prepared by the method enhances the separation and transmission efficiency of photo-generated carriers in a heterojunction structure forming manner, compared with pure red phosphorus or pure strontium titanate, the spectrum response is widened to 425nm-780nm, the photocatalytic hydrolysis hydrogen production activity of the red phosphorus/strontium titanate heterojunction photocatalyst is greatly improved, the circulation stability is good, the heterojunction is formed, the defect of rapid recombination of red phosphorus photo-generated electrons and photo-generated holes is overcome, the visible light response range of the strontium titanate is widened, and the beneficial effect of the photocatalytic activity is improved.
Drawings
FIG. 1 is a graph showing the activity rate of visible light photocatalytic decomposition of water into hydrogen for examples of the present invention, comparative example 1 and comparative example 2;
FIG. 2 is an X-ray diffraction pattern of examples of the present invention, comparative example 1 and comparative example 2;
FIG. 3 is a graph of instantaneous photocurrents i-t of inventive example 4, comparative example 1 and comparative example 2;
FIG. 4 is an impedance (EIS) graph of example 4, comparative example 1 and comparative example 2 of the present invention;
FIG. 5 is a photoluminescence spectrum of inventive example 4, comparative example 1 and comparative example 2;
FIG. 6 is a graph showing the UV-visible absorption spectra of example 4, comparative example 1 and comparative example 2 of the present invention;
FIG. 7 is a scanning electron microscope image and an EDX mapping image of example 4, comparative example 1 and comparative example 2 of the present invention;
FIG. 8 is a transmission electron microscope image of example 4, comparative example 1 and comparative example 2 of the present invention.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not intended to be limiting.
Example 1. The red phosphorus/strontium titanate heterojunction photocatalyst is prepared from red phosphorus and strontium titanate, and specifically, the red phosphorus is uniformly attached to (110) and (100) crystal faces of the strontium titanate to form a red phosphorus/strontium titanate heterojunction structure.
The red phosphorus/strontium titanate heterojunction photocatalyst comprises: the red phosphorus and strontium titanate are prepared by in-situ synthesis through a hydrothermal method, wherein the molar ratio of the red phosphorus to the strontium titanate is 0.125:1.
The preparation method of the red phosphorus/strontium titanate heterojunction photocatalyst comprises the following steps:
(1) Putting red phosphorus into water, and performing ultrasonic dispersion for 5min to obtain red phosphorus suspension serving as a product A; the concentration of the red phosphorus suspension is 1mg/mL;
(2) In the step (2), 3g of tetrabutyl titanate is dissolved in 40mL of ethylene glycol solution with the concentration of 98% according to the proportion to obtain a product B; then adding 20mL of strontium nitrate solution with the concentration of 0.44mol/L and 10mL of sodium hydroxide solution with the concentration of 4.4mol/L into the product B under magnetic stirring to obtain a product C;
(3) Transferring the product C into a reaction container, performing hydrothermal reaction at 120 ℃ for 12 hours, naturally cooling to 20 ℃, and then adjusting the pH value to 6.8 to obtain a product D; the pH is adjusted to 6.8, in particular to 0.5mol/L HNO is adopted 3 The pH of the solution is regulated to 6.8;
(4) Adding the product A into the product D under stirring, uniformly mixing to obtain a product E, carrying out a hydrothermal reaction on the product E, wherein the molar ratio of red phosphorus to strontium titanate in the product E is 0.125:1, the temperature of the hydrothermal reaction is 120 ℃, the time is 6h, naturally cooling to 20 ℃, alternately washing for 2 times by adopting deionized water and ethanol, and then carrying out vacuum drying at 50 ℃ for 10h to obtain the red phosphorus/strontium titanate heterojunction photocatalyst, wherein the mark is P 0.125 /STO。
Example 2. The red phosphorus/strontium titanate heterojunction photocatalyst is prepared from red phosphorus and strontium titanate, and specifically, the red phosphorus is uniformly attached to (110) and (100) crystal faces of the strontium titanate to form a red phosphorus/strontium titanate heterojunction structure.
The red phosphorus/strontium titanate heterojunction photocatalyst comprises: the red phosphorus and strontium titanate are prepared by in-situ synthesis through a hydrothermal method, wherein the molar ratio of the red phosphorus to the strontium titanate is 0.25:1.
The preparation method of the red phosphorus/strontium titanate heterojunction photocatalyst comprises the following steps:
(1) Putting red phosphorus into water, and performing ultrasonic dispersion for 10min to obtain red phosphorus suspension serving as a product A; the concentration of the red phosphorus suspension is 1.5mg/mL;
(2) In the step (2), 3.4g of tetrabutyl titanate is dissolved in 40mL of ethylene glycol solution with the concentration of 98% according to a proportion to obtain a product B; then adding 20mL of strontium nitrate solution with the concentration of 0.5mol/L and 10mL of sodium hydroxide solution with the concentration of 5mol/L into the product B in sequence under magnetic stirring to obtain a product C;
(3) Transferring the product C into a reaction container, performing hydrothermal reaction at 150 ℃ for 20 hours, naturally cooling to 25 ℃, and then adjusting the pH value to 7 to obtain a product D; the pH is adjusted to 7, in particular to 0.8mol/L HNO 3 The pH of the solution is regulated to 7;
(4) Adding the product A into the product D under stirring, uniformly mixing to obtain a product E, carrying out hydrothermal reaction on the product E, wherein the molar ratio of red phosphorus to strontium titanate in the product E is 0.25:1, the temperature of the hydrothermal reaction is 150 ℃, the time is 18h, naturally cooling to 25 ℃, alternately washing 3 times by adopting deionized water and ethanol, and then carrying out vacuum drying at 60 ℃ for 11h to obtain the red phosphorus/strontium titanate heterojunction photocatalyst, and the red phosphorus/strontium titanate heterojunction photocatalyst is marked as P 0.25 /STO。
Example 3. The red phosphorus/strontium titanate heterojunction photocatalyst is prepared from red phosphorus and strontium titanate, and specifically, the red phosphorus is uniformly attached to (110) and (100) crystal faces of the strontium titanate to form a red phosphorus/strontium titanate heterojunction structure.
The red phosphorus/strontium titanate heterojunction photocatalyst comprises: the red phosphorus and strontium titanate are prepared by in-situ synthesis through a hydrothermal method, wherein the molar ratio of the red phosphorus to the strontium titanate is 0.5:1.
The preparation method of the red phosphorus/strontium titanate heterojunction photocatalyst comprises the following steps:
(1) Putting red phosphorus into water, and performing ultrasonic dispersion for 10min to obtain red phosphorus suspension serving as a product A; the concentration of the red phosphorus suspension is 1.5mg/mL;
(2) In the step (2), 3.4g of tetrabutyl titanate is dissolved in 40mL of ethylene glycol solution with the concentration of 98% according to a proportion to obtain a product B; then adding 20mL of strontium nitrate solution with the concentration of 0.5mol/L and 10mL of sodium hydroxide solution with the concentration of 5mol/L into the product B in sequence under magnetic stirring to obtain a product C;
(3) Transferring the product C into a reaction container, performing hydrothermal reaction at 160 ℃ for 18 hours, naturally cooling to 26 ℃, and then adjusting the pH value to 7.1 to obtain a product D; the pH is adjusted to 7.1, in particular to 0.9mol/L HNO is adopted 3 The pH of the solution is regulated to 7.1;
(4) Adding the product A into the product D under stirring, uniformly mixing to obtain a product E, carrying out a hydrothermal reaction on the product E, wherein the molar ratio of red phosphorus to strontium titanate in the product E is 0.5:1, the temperature of the hydrothermal reaction is 160 ℃, the time is 22h, naturally cooling to 27 ℃, alternately washing 3 times by adopting deionized water and ethanol, and then carrying out vacuum drying at 60 ℃ for 12h to obtain the red phosphorus/strontium titanate heterojunction photocatalyst, and the red phosphorus/strontium titanate heterojunction photocatalyst is marked as P 0.5 /STO。
Example 4. The red phosphorus/strontium titanate heterojunction photocatalyst is prepared from red phosphorus and strontium titanate, and specifically, the red phosphorus is uniformly attached to (110) and (100) crystal faces of the strontium titanate to form a red phosphorus/strontium titanate heterojunction structure.
The red phosphorus/strontium titanate heterojunction photocatalyst comprises: the red phosphorus and strontium titanate are prepared by in-situ synthesis through a hydrothermal method, wherein the molar ratio of the red phosphorus to the strontium titanate is 1:1.
The preparation method of the red phosphorus/strontium titanate heterojunction photocatalyst comprises the following steps:
(1) Putting red phosphorus into water, and performing ultrasonic dispersion for 15min to obtain red phosphorus suspension serving as a product A; the concentration of the red phosphorus suspension is 2mg/mL;
(2) In the step (2), 4g of tetrabutyl titanate is dissolved in 40mL of ethylene glycol solution with the concentration of 98% according to a proportion to obtain a product B; then adding 20mL of strontium nitrate solution with the concentration of 0.58mol/L and 10mL of sodium hydroxide solution with the concentration of 5.8mol/L into the product B under magnetic stirring to obtain a product C;
(3) Transferring the product C into a reaction container, performing hydrothermal reaction at 180 ℃ for 24 hours, naturally cooling to 30 ℃, and then adjusting the pH value to 7.2 to obtain a product D; the pH is adjusted to 7.2, in particular 1mol/L HNO is adopted 3 The pH of the solution is regulated to 7.2;
(4) Adding the product A into the product D under stirring, uniformly mixing to obtain a product E, carrying out hydrothermal reaction on the product E, wherein the molar ratio of red phosphorus to strontium titanate in the product E is 0.125:1, the temperature of the hydrothermal reaction is 180 ℃, the time is 24 hours, naturally cooling to 30 ℃, alternately washing for 4 times by adopting deionized water and ethanol, and then carrying out vacuum drying at 70 ℃ for 12 hours to obtain the red phosphorus/strontium titanate heterojunction photocatalyst, and the red phosphorus/strontium titanate heterojunction photocatalyst is marked as P 1.0 /STO。
Comparative example 1: strontium titanate catalyst
Dissolving 10mmol of tetrabutyl titanate in 40mL of glycol solution at 20-30 ℃, continuously stirring for 1h to form solution A, and then dropwise adding 20mL of 106g/L high-purity strontium nitrate solution into the solution A which is continuously magnetically stirred, so as to form white colloid B; then, dropwise adding 10mL of 200g/L sodium hydroxide solution into the solution A, and continuously stirring for 30min after the solution is gradually clarified to obtain uniformly mixed solution C; transferring the solution C into a 100mL polytetrafluoroethylene reaction kettle with a stainless steel shell, performing hydrothermal reaction at 180 ℃ for 24 hours, naturally cooling the reaction kettle to 20-30 ℃ after the reaction is finished, washing the obtained product with deionized water and ethanol alternately for 2-4 times, and then performing vacuum drying at 50-70 ℃ for 10-12 hours to obtain the strontium titanate catalyst, namely STO.
Comparative example 2: red phosphorus catalyst
Grinding commercial red phosphorus at 20-30 ℃, sieving with a 120-mesh screen, weighing 3g of the ground red phosphorus, dispersing in a reaction solution consisting of 55mL of water, 5mL of ethylene glycol and 0.12g of sodium hydroxide, stirring for 30min, transferring into a 100mL polytetrafluoroethylene reaction kettle with a stainless steel shell, carrying out hydrothermal reaction at 200 ℃ for 24h, naturally cooling to 20-30 ℃ after the reaction is finished, alternately washing the product with deionized water and ethanol for 2-4 times, and then carrying out vacuum drying at 50-70 ℃ for 10-12h, wherein the red phosphorus catalyst is marked as RP.
Experiments prove that:
the red phosphorus/strontium titanate heterojunction photocatalysts prepared in examples 1 to 4 of the present invention, the strontium titanate catalyst (STO) obtained in comparative example 1, and the red phosphorus catalyst (RP) obtained in comparative example 2 were subjected to photocatalytic decomposition to produce hydrogen activity evaluation, and the specific operation steps were:
taking a certain amount of catalyst sample to disperse in Na with a specific volume fraction 2 S and Na 2 SO 3 And (3) mixing the solution. Experiment Na 2 S and Na 2 SO 3 The mixed solution is used as a sacrificial reagent to consume photo-generated holes, inhibit the recombination of photo-generated electrons and help improve the photo-catalytic hydrogen production activity of the catalyst. And dispersed by ultrasound for 10min. The method is placed in a photocatalytic reaction system, the whole system is pumped to vacuum by a vacuum pump so as to remove air in reaction liquid, experimental data are more accurate, and a constant-temperature cooling system ensures that the whole hydrogen production process is in a room temperature state. The activity test adopts an external illumination type 300W xenon lamp as a light source to carry out hydrogen production experimental test, a filter (lambda is more than or equal to 420 nm) is added on the light source to obtain visible light irradiation, the generated hydrogen enters an on-line gas chromatograph (GC-7900) with a thermal conductivity detector to carry out measurement through a closed gas circulation system, the hydrogen is measured once every one hour, and finally, the measured 5 groups of data are fitted to obtain the average hydrogen production. The activity of the photocatalyst for decomposing the water into hydrogen by photocatalysis is expressed by the hydrogen amount generated by a certain amount of photocatalyst in unit time. A baseline standard is performed prior to photocatalytic hydrogen production for determining the actual measured hydrogen production.
FIG. 1 is a graph showing the hydrogen production rate of photocatalytic decomposition water according to examples 1 to 4, comparative example 1 and comparative example 2 of the present invention. It can be seen that the photocatalytic decomposition of water to produce hydrogen activity is higher than that of the comparative example in all the examples of the present invention, and P 1.0 The hydrogen production rate of STO is about 196.75. Mu. Mol/(h.g) which is 9.15 times that of RP, whereas STO is not hydrogen producing active under visible light.
FIG. 2 is an X-ray diffraction pattern of examples 1-4, comparative example 1 and comparative example 2 according to the present invention, and a standard card (SrTiO 3 ：JCPDS:35-0734，RP:PDF:44-0609), the embodiment of the invention has two substances of strontium titanate and red phosphorus, has good crystallization and no other impurity phase, and the diffraction peak of the red phosphorus is gradually enhanced along with the increase of the addition amount of the red phosphorus; STO of comparative example 1 was pure strontium titanate and RP of comparative example 2 was pure red phosphorus.
Fig. 3 is a graph showing instantaneous photocurrents i-t of example 4, comparative example 1 and comparative example 2 according to the present invention, which can reflect the separation capability of photo-generated electron-hole pairs. All samples, when irradiated with light, rapidly produced a repeatable photocurrent response, P compared to STO and RP 1.0 The STO is more sensitive to light and has higher current density, which shows that the red phosphorus/strontium titanate composite material with the heterojunction structure has stronger photoelectric conversion capability.
FIG. 4 is a graph showing impedance (EIS) curves of example 4, comparative example 1 and comparative example 2 according to the present invention, composite sample P 1.0 The STO has smaller Nyquist incomplete semicircle radius compared with RP and STO, which shows that after the formation of the compound heterojunction, the charge transfer resistance becomes smaller, the photocurrent response is stronger, the effective separation of the photo-generated electron-hole pair and the rapid transfer of interface charge of the red phosphorus/strontium titanate heterojunction photocatalyst are shown, the service life of photo-generated carriers is prolonged, and the heterojunction is proved to improve the photocatalytic activity.
FIG. 5 is a photoluminescence spectrum of example 4, comparative example 1 and comparative example 2 of the present invention, which shows that photoluminescence spectrum emission signal is derived from energy released during photo-generated electron-hole pair recombination, and thus can be used to study carrier transfer and separation in semiconductor catalyst, and further to characterize life of excited photo-generated carriers in semiconductor, P 1.0 The spectral intensity ratio of STO to RP is reduced, and the RP particles can effectively capture photo-generated electrons, so that the direct recombination of photo-generated electron-hole pairs is inhibited, the service life of carrier charges is prolonged, and higher activity of photo-catalytic decomposition of water into hydrogen is shown.
FIG. 6 is an ultraviolet-visible absorption spectrum of example 4, comparative example 1 and comparative example 2 of the present invention, the absorption edge of STO is about 400nm, and the absorption edge of RP is about 750 nm. HoweverPrepared P 1.0 The STO absorption band edge is obviously red-shifted, the spectral response is widened to 425nm-780nm, the visible light absorption range is widened, and the method is superior to pure RP and SrTiO 3 . At the same time can see P 1.0 /SrTiO 3 Absorption threshold of the composite material is higher than SrTiO 3 Is larger than the absorption threshold of RP, but the light absorption intensity is larger than that of RP because of RP and SrTiO 3 Heterojunction formed after recombination effectively separates photo-generated carriers, which illustrates P 1.0 /SrTiO 3 The heterojunction has good hydrogen production performance by visible light photolysis of water.
FIG. 7 is a scanning electron microscope image and an EDX mapping image of example 4, comparative example 1 and comparative example 2 of the present invention, wherein nano-sheet strontium titanate and granular red phosphorus have been compounded together and uniformly distributed, and P is obtained after compounding 1.0 Elements such as Ti, O, sr, P can be observed in the EDX mapping profile of the STO heterojunction.
FIG. 8 is a transmission electron micrograph of example 4, comparative example 1 and comparative example 2 of the present invention, srTiO 3 The HRTEM image shows that the lattice spacing of the sample is 0.27nm and 0.395nm, which correspond to perovskite SrTiO respectively 3 The (110) and (100) planes. And RP belongs to an amorphous structure without lattice stripes, and a clear contact interface is formed in the composite material to indicate that the RP and the composite material are in close contact with each other, so that a heterostructure is formed. The nano-sheet strontium titanate and the granular red phosphorus are already compounded together, and the red phosphorus is uniformly attached to the (110) crystal face and the (100) crystal face of the strontium titanate. As can be seen from the comprehensive XRD, SEM and EDX spectra, srTiO of the present invention 3 And RP recombination can form a uniformly dispersed heterojunction.
Results P of comprehensive XRD, SEM and TEM 1.0 The composition of the STO heterojunction material was relatively uniform, and the applicant was also able to produce P for other examples 0.125 /STO、P 0.25 /STO、P 0.5 The STO catalyst was subjected to the experimental characterization test and analysis described above for 3-8, and the results obtained were comparable to those described above.
In summary, the invention provides a red phosphorus/strontium titanate heterojunction photocatalyst, a preparation method and application thereof, wherein the red phosphorus/strontium titanate heterojunction photocatalyst is prepared from red phosphorus and strontium titanate, and particularly, the red phosphorus is uniformly attached to (110) and (100) crystal faces of the strontium titanate to form a red phosphorus/strontium titanate heterojunction structure; the unique interaction of red phosphorus and strontium titanate enhances the light absorption performance of the catalyst, accelerates the transportation process of a photogenerated carrier, reduces the recombination probability of electron-hole pairs, further effectively improves the photocatalytic hydrogen production characteristic of the catalyst, and widens the spectral response to 425nm-780nm compared with pure red phosphorus or pure strontium titanate. Under the irradiation of visible light, the red phosphorus/strontium titanate heterojunction photocatalyst provided by the invention has higher hydrogen production rate, and the preparation method has the advantages of simple process, mild condition and low cost, and can realize large-scale production.
Claims (8)
1. A red phosphorus/strontium titanate heterojunction photocatalyst is characterized in that: the red phosphorus/strontium titanate heterojunction photocatalyst is prepared from red phosphorus and strontium titanate, specifically, the red phosphorus is uniformly attached to (110) and (100) crystal faces of the strontium titanate to form a red phosphorus/strontium titanate heterojunction structure;
the red phosphorus/strontium titanate heterojunction photocatalyst comprises: the preparation method comprises the steps of adopting red phosphorus and strontium titanate to be synthesized in situ by a hydrothermal method, wherein the molar ratio of the red phosphorus to the strontium titanate is 0.125-1:1;
the preparation method of the red phosphorus/strontium titanate heterojunction photocatalyst comprises the following steps:
(1) Putting red phosphorus into water for ultrasonic dispersion to obtain red phosphorus suspension, wherein the red phosphorus suspension is A;
(2) Tetrabutyl titanate is dissolved in glycol solution to obtain a product B; then adding strontium nitrate solution and sodium hydroxide solution into the product B in sequence under stirring to obtain a product C;
(3) Transferring the product C into a reaction container, performing hydrothermal reaction, naturally cooling, and then adjusting the pH value to obtain a product D;
(4) Adding the product A into the product D under stirring, uniformly mixing to obtain the product E, carrying out hydrothermal reaction on the product E, naturally cooling, washing with deionized water and ethanol, and drying to obtain the red phosphorus/strontium titanate heterojunction photocatalyst.
2. The method for preparing the red phosphorus/strontium titanate heterojunction photocatalyst according to claim 1, which is characterized in that: in the step (1), red phosphorus is put into water to be dispersed for 5-15min by ultrasonic, so as to obtain red phosphorus suspension, which is A; the concentration of the red phosphorus suspension is 1-2mg/mL.
3. The method for preparing the red phosphorus/strontium titanate heterojunction photocatalyst according to claim 1, which is characterized in that: in the step (2), 3-4g of tetrabutyl titanate is dissolved in 40mL of ethylene glycol solution with the concentration of 98% according to a proportion to obtain a product B; then adding 20mL of strontium nitrate solution with the concentration of 0.44-0.58mol/L and 10mL of sodium hydroxide solution with the concentration of 4.4-5.8mol/L into the product B under magnetic stirring to obtain the product C.
4. The method for preparing the red phosphorus/strontium titanate heterojunction photocatalyst according to claim 3, wherein the method comprises the following steps: in the step (2), 3.4g of tetrabutyl titanate is dissolved in 40mL of ethylene glycol solution with the concentration of 98% according to a proportion to obtain a product B; then adding 20mL of strontium nitrate solution with the concentration of 0.5mol/L and 10mL of sodium hydroxide solution with the concentration of 5mol/L into the product B in sequence under magnetic stirring to obtain a product C; the strontium nitrate solution is added into the product B in a dropwise manner.
5. The method for preparing the red phosphorus/strontium titanate heterojunction photocatalyst according to claim 1, which is characterized in that: in the step (3), the C product is transferred into a reaction vessel for hydrothermal reaction, the temperature of the hydrothermal reaction is 120-180 ℃, the time is 12-24h, the product is naturally cooled to 20-30 ℃, and then the pH value is regulated to 6.8-7.2, so that the D product is obtained; the pH is adjusted to 6.8-7.2, specifically HNO of 0.5-1mol/L is adopted 3 The pH of the solution is regulated to 6.8-7.2.
6. The method for preparing the red phosphorus/strontium titanate heterojunction photocatalyst according to claim 1, which is characterized in that: in the step (4), adding the product A into the product D under stirring, uniformly mixing to obtain a product E, carrying out a hydrothermal reaction on the product E, wherein the molar ratio of red phosphorus to strontium titanate in the product E is 0.125-1:1, the temperature of the hydrothermal reaction is 120-180 ℃, the time is 6-24h, naturally cooling to 20-30 ℃, washing with deionized water and ethanol, and drying to obtain the red phosphorus/strontium titanate heterojunction photocatalyst.
7. The method for preparing the red phosphorus/strontium titanate heterojunction photocatalyst as claimed in claim 6, wherein: the molar ratio of red phosphorus to strontium titanate in the E product is 1:1; the washing with deionized water and ethanol, and the drying is carried out by alternately washing with deionized water and ethanol for 2-4 times, and then vacuum drying at 50-70 ℃ for 10-12h.
8. Use of a red phosphorus/strontium titanate heterojunction photocatalyst as defined in any one of claims 1 to 7: the red phosphorus/strontium titanate heterojunction photocatalyst is applied to the photocatalytic decomposition of water to produce hydrogen at the wavelength of 425nm-780nm.
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