CN114618537B - A kind of red phosphorus/strontium titanate heterojunction photocatalyst and its preparation method and application - Google Patents
A kind of red phosphorus/strontium titanate heterojunction photocatalyst and its preparation method and application Download PDFInfo
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Abstract
本发明公开了一种红磷/钛酸锶异质结光催化剂及制备方法及应用。所述红磷/钛酸锶异质结光催化剂采用红磷和钛酸锶制备，具体是红磷均匀附着在钛酸锶的(110)及(100)晶面上，形成红磷/钛酸锶异质结结构。本发明具有制备方法工艺简单，制备时间短，条件温和，成本低廉，可实现规模性生产，且本发明制备的红磷/钛酸锶异质结光催化剂通过形成异质结结构的方式增强了光生载流子的分离和传输效率，光谱响应拓宽至425nm‑780nm，红磷/钛酸锶异质结光催化剂的光催化水解产氢活性有了大幅度提高，循环稳定性好，异质结的形成，克服了红磷光生电子和光生空穴复合快的缺点，拓宽了钛酸锶的可见光响应范围，提高了光催化活性的有益效果。
The invention discloses a red phosphorus/strontium titanate heterojunction photocatalyst, a preparation method and an application. The red phosphorus/strontium titanate heterojunction photocatalyst is prepared by using red phosphorus and strontium titanate, specifically red phosphorus is evenly attached to the (110) and (100) crystal faces of strontium titanate to form red phosphorus/strontium titanate Strontium heterojunction structure. The invention has the advantages of simple preparation process, short preparation time, mild conditions, low cost, large-scale production can be realized, and the red phosphorus/strontium titanate heterojunction photocatalyst prepared by the invention is enhanced by forming a heterojunction structure The separation and transmission efficiency of photogenerated carriers, the spectral response is broadened to 425nm-780nm, the photocatalytic hydrolysis hydrogen production activity of red phosphorus/strontium titanate heterojunction photocatalyst has been greatly improved, the cycle stability is good, and the heterojunction The formation of the red phosphor overcomes the shortcomings of fast recombination of photogenerated electrons and photogenerated holes, broadens the visible light response range of strontium titanate, and improves the beneficial effect of photocatalytic activity.
Description
技术领域technical field
本发明涉及一种光催化剂，特别是一种红磷/钛酸锶异质结光催化剂及制备方法及应用。The invention relates to a photocatalyst, in particular to a red phosphorus/strontium titanate heterojunction photocatalyst, a preparation method and application.
背景技术Background technique
社会进步需要能源的持续供应，化石能源的过度开采已经给地球带来了环境危机。因此，需要大力发展可再生能源，用可再生能源全面取代化石能源。氢具有较高的能量密度和燃烧值，是一种很有前途的清洁化学燃料。与其他方法相比，光催化分解水制氢是一种成本低、环境友好的方法。而开发高效的光催化剂一直科学界的目标之一。Social progress requires a continuous supply of energy, and the excessive exploitation of fossil energy has brought environmental crisis to the earth. Therefore, it is necessary to vigorously develop renewable energy and fully replace fossil energy with renewable energy. Hydrogen, with its high energy density and combustion value, is a promising clean chemical fuel. Compared with other methods, photocatalytic water splitting for hydrogen production is a low-cost and environmentally friendly method. The development of highly efficient photocatalysts has always been one of the goals of the scientific community.
钛酸锶(SrTiO3)光催化剂是一种钙钛矿型三元氧化物，具有较强的氧化还原能力、良好的物理化学稳定性及环境友好等特点，在光催化各领域得到了广泛应用，如制氢/降解/光电催化等。但钛酸锶的带隙为3.2eV，仅响应紫外光，这极大地限制了钛酸锶在光催化领域的进一步发展。探索具有可见光相应的钛酸锶基光催化剂是满足未来能源需求的一个重要的目标。Strontium titanate (SrTiO 3 ) photocatalyst is a perovskite-type ternary oxide, which has the characteristics of strong redox ability, good physical and chemical stability and environmental friendliness, and has been widely used in various fields of photocatalysis , such as hydrogen production/degradation/photoelectrocatalysis, etc. However, the band gap of strontium titanate is 3.2eV, which only responds to ultraviolet light, which greatly limits the further development of strontium titanate in the field of photocatalysis. Exploring strontium titanate-based photocatalysts with visible light response is an important goal to meet future energy demands.
通过更深入地研究发现，对钛酸锶进行改性处理如构筑异质结，可以拓宽其光响应范围，降低光生电子－空穴复合率，从而提高光催化活性。因此，钛酸锶基光催化剂异质结构具有重要的科学和现实意义。Through more in-depth research, it is found that modification of strontium titanate, such as constructing a heterojunction, can broaden its photoresponse range, reduce the photogenerated electron-hole recombination rate, and thus improve photocatalytic activity. Therefore, the strontium titanate-based photocatalyst heterostructure has important scientific and practical significance.
发明内容Contents of the invention
本发明的目的在于，提供一种红磷/钛酸锶异质结光催化剂及制备方法及应用。本发明具有制备方法工艺简单，制备时间短，条件温和，成本低廉，可实现规模性生产，且本发明制备的红磷/钛酸锶异质结光催化剂通过形成异质结结构的方式增强了光生载流子的分离和传输效率，相较于纯的红磷或纯的钛酸锶，光谱响应拓宽至425nm-780nm，红磷/钛酸锶异质结光催化剂的光催化水解产氢活性有了大幅度提高，循环稳定性好，异质结的形成，克服了红磷光生电子和光生空穴复合快的缺点，拓宽了钛酸锶的可见光响应范围，提高了光催化活性。The purpose of the present invention is to provide a red phosphorus/strontium titanate heterojunction photocatalyst, its preparation method and application. The invention has the advantages of simple preparation method, short preparation time, mild conditions, low cost, large-scale production can be realized, and the red phosphorus/strontium titanate heterojunction photocatalyst prepared by the invention is enhanced by forming a heterojunction structure The separation and transmission efficiency of photogenerated carriers, compared with pure red phosphorus or pure strontium titanate, the spectral response is broadened to 425nm-780nm, and the photocatalytic hydrolysis hydrogen production activity of red phosphorus/strontium titanate heterojunction photocatalyst It has been greatly improved, the cycle stability is good, and the formation of heterojunction overcomes the shortcomings of fast recombination of photogenerated electrons and photogenerated holes of red phosphor, broadens the visible light response range of strontium titanate, and improves the photocatalytic activity.
本发明的技术方案：一种红磷/钛酸锶异质结光催化剂，所述红磷/钛酸锶异质结光催化剂采用红磷和钛酸锶制备，具体是红磷均匀附着在钛酸锶的(110)及(100)晶面上，形成红磷/钛酸锶异质结结构。The technical scheme of the present invention: a red phosphorus/strontium titanate heterojunction photocatalyst, the red phosphorus/strontium titanate heterojunction photocatalyst is prepared by red phosphorus and strontium titanate, specifically red phosphorus is evenly attached to titanium The (110) and (100) crystal planes of strontium oxide form a red phosphorus/strontium titanate heterojunction structure.
前述的红磷/钛酸锶异质结光催化剂中，所述红磷/钛酸锶异质结光催化剂：采用红磷和钛酸锶通过水热法原位合成制备，其中红磷与钛酸锶的摩尔比为0.125-1:1。In the aforementioned red phosphorus/strontium titanate heterojunction photocatalyst, the red phosphorus/strontium titanate heterojunction photocatalyst is prepared by in-situ synthesis of red phosphorus and strontium titanate by hydrothermal method, wherein red phosphorus and titanium The molar ratio of strontium acid is 0.125-1:1.
前述的红磷/钛酸锶异质结光催化剂的制备方法，包括有以下步骤：The preparation method of the aforementioned red phosphorus/strontium titanate heterojunction photocatalyst comprises the following steps:
(1)将红磷放入水中超声分散，得红磷悬浮液，为A品；(1) put red phosphorus into water and ultrasonically disperse to obtain red phosphorus suspension, which is product A;
(2)将钛酸四丁酯溶解在乙二醇溶液中，得B品；然后在搅拌下，向B品中依次加入硝酸锶溶液和氢氧化钠溶液，得C品；(2) Dissolving tetrabutyl titanate in ethylene glycol solution to obtain product B; then, under stirring, sequentially add strontium nitrate solution and sodium hydroxide solution to product B to obtain product C;
(3)将C品转移至反应容器中，进行水热反应，自然冷却，然后调节pH，得D品；(3) Transfer product C to a reaction vessel, carry out hydrothermal reaction, cool naturally, and then adjust pH to obtain product D;
(4)在搅拌下，将A品加入D品中，混合均匀后，得E品，将E品进行水热反应，并自然冷却，采用去离子水和乙醇洗涤、干燥，即得红磷/钛酸锶异质结光催化剂。(4) Under stirring, add product A into product D, and after mixing evenly, product E is obtained, and product E is subjected to hydrothermal reaction, and cooled naturally, washed with deionized water and ethanol, and dried to obtain red phosphorus/ Strontium titanate heterojunction photocatalyst.
前述的红磷/钛酸锶异质结光催化剂的制备方法中，所述步骤(1)中，将红磷放入水中超声分散5-15min，得红磷悬浮液，为A品；所述红磷悬浮液的浓度为1-2mg/mL。In the preparation method of the aforementioned red phosphorus/strontium titanate heterojunction photocatalyst, in the step (1), the red phosphorus is put into water and ultrasonically dispersed for 5-15min to obtain a red phosphorus suspension, which is product A; The concentration of red phosphorus suspension is 1-2mg/mL.
前述的红磷/钛酸锶异质结光催化剂的制备方法中，所述步骤(2)中，按比例，将3-4g钛酸四丁酯溶解在40mL浓度为98％的乙二醇溶液中，得B品；然后在磁力搅拌下向B品中依次加入20mL浓度为0.44-0.58mol/L的硝酸锶溶液和10mL浓度为4.4-5.8mol/L的氢氧化钠溶液，得C品。In the preparation method of the aforementioned red phosphorus/strontium titanate heterojunction photocatalyst, in the step (2), in proportion, 3-4g tetrabutyl titanate is dissolved in 40mL concentration of 98% ethylene glycol solution Then, under magnetic stirring, add 20 mL of strontium nitrate solution with a concentration of 0.44-0.58 mol/L and 10 mL of sodium hydroxide solution with a concentration of 4.4-5.8 mol/L to obtain product C under magnetic stirring.
前述的红磷/钛酸锶异质结光催化剂的制备方法中，所述步骤(2)中，按比例，将3.4g钛酸四丁酯溶解在40mL浓度为98％的乙二醇溶液中，得B品；然后在磁力搅拌下向B品中依次加入20mL浓度为0.5mol/L的硝酸锶溶液和10mL浓度为5mol/L的氢氧化钠溶液，得C品；所述向B品中加入硝酸锶溶液时采用逐滴加入的方式。In the preparation method of the aforementioned red phosphorus/strontium titanate heterojunction photocatalyst, in the step (2), in proportion, 3.4g tetrabutyl titanate is dissolved in 40mL concentration of 98% ethylene glycol solution , to obtain product B; then add 20 mL of strontium nitrate solution with a concentration of 0.5 mol/L and 10 mL of sodium hydroxide solution with a concentration of 5 mol/L to product B under magnetic stirring to obtain product C; When adding the strontium nitrate solution, the method of adding dropwise is adopted.
前述的红磷/钛酸锶异质结光催化剂的制备方法中，所述步骤(3)中，将C品转移至反应容器中，进行水热反应，水热反应的温度为120-180℃，时间为12-24h，自然冷却至20-30℃，然后调节pH为6.8-7.2，得D品；所述调节pH为6.8-7.2，具体是采用0.5-1mol/L的HNO3溶液调节pH为6.8-7.2；浓HNO3具有氧化性，会将红磷氧化，所以必须使用低浓度的硝酸来调节pH。In the preparation method of the aforementioned red phosphorus/strontium titanate heterojunction photocatalyst, in the step (3), the product C is transferred to a reaction vessel for hydrothermal reaction, and the temperature of the hydrothermal reaction is 120-180°C , the time is 12-24h, naturally cooled to 20-30°C, and then the pH is adjusted to 6.8-7.2 to obtain product D; the pH is adjusted to 6.8-7.2, specifically, the pH is adjusted by using 0.5-1mol/L HNO3 solution It is 6.8-7.2; concentrated HNO 3 is oxidizing and will oxidize red phosphorus, so low-concentration nitric acid must be used to adjust the pH.
前述的红磷/钛酸锶异质结光催化剂的制备方法中，所述步骤(4)中，在搅拌下，将A品加入D品中，混合均匀后，得E品，E品中红磷与钛酸锶的摩尔比为0.125-1:1，将E品进行水热反应，水热反应的温度为120-180℃，时间为6-24h，并自然冷却至20-30℃，采用去离子水和乙醇洗涤、干燥，即得红磷/钛酸锶异质结光催化剂。In the preparation method of the aforementioned red phosphorus/strontium titanate heterojunction photocatalyst, in the step (4), under stirring, the product A is added to the product D, and after mixing evenly, the product E is obtained, and the product E is red The molar ratio of phosphorus to strontium titanate is 0.125-1:1. The product E is subjected to a hydrothermal reaction. The temperature of the hydrothermal reaction is 120-180°C, the time is 6-24h, and it is naturally cooled to 20-30°C. The red phosphorus/strontium titanate heterojunction photocatalyst is obtained by washing with deionized water and ethanol and drying.
前述的红磷/钛酸锶异质结光催化剂的制备方法中，所述E品中红磷与钛酸锶的摩尔比为1:1；所述采用去离子水和乙醇洗涤、干燥具体是用去离子水和乙醇交替洗涤2-4次，然后在50-70℃下真空干燥10-12h。In the preparation method of the aforementioned red phosphorus/strontium titanate heterojunction photocatalyst, the mol ratio of red phosphorus and strontium titanate in the E product is 1:1; the described washing and drying with deionized water and ethanol are specifically Alternately wash 2-4 times with deionized water and ethanol, and then vacuum dry at 50-70°C for 10-12h.
前述的红磷/钛酸锶异质结光催化剂的应用：是将所述红磷/钛酸锶异质结光催化剂在425nm-780nm波长的光催化分解水产氢中的应用。The application of the aforementioned red phosphorus/strontium titanate heterojunction photocatalyst is the application of the red phosphorus/strontium titanate heterojunction photocatalyst in the photocatalytic decomposition of water with a wavelength of 425nm-780nm to produce hydrogen.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1、本发明红磷/钛酸锶异质结光催化剂的原料均为常用化学试剂，且来源广泛，价廉易得；且与高温煅烧法相比，反应设备简单，反应条件温和，同时只进行水热过程，合成温度低，制备步骤简单；1. The raw materials of the red phosphorus/strontium titanate heterojunction photocatalyst of the present invention are common chemical reagents, and the source is wide, cheap and easy to get; and compared with the high-temperature calcination method, the reaction equipment is simple, the reaction conditions are mild, and only Hydrothermal process, low synthesis temperature, simple preparation steps;
2、本发明制得的红磷/钛酸锶异质结光催化剂光生载流子分离效率高，光致发光低；2. The red phosphorus/strontium titanate heterojunction photocatalyst prepared by the present invention has high separation efficiency of photogenerated carriers and low photoluminescence;
3、本发明制得的红磷/钛酸锶异质结光催化剂相较于单一钛酸锶光催化分解水产氢活性有较大提高；本发明红磷/钛酸锶异质结光催化剂在可见光光催化分解水产氢活性可高达196.75μmol/(h·g)，是纯红磷的9.15倍，而纯钛酸锶在可见光下无产氢活性；在425nm-780nm波长的光照射下能实现光催化分解水，通过紫外-分光光谱测试可以看出，并且使用配有λ≥420nm滤波片的300W氙灯光源(CEL-HXUV300-T3)模拟太阳光照射光催化评价***测试得出相关数据。3. The red phosphorus/strontium titanate heterojunction photocatalyst prepared by the present invention has a greatly improved hydrogen production activity compared with the single strontium titanate photocatalytic decomposition of water; the red phosphorus/strontium titanate heterojunction photocatalyst of the present invention is in Visible light photocatalytic water splitting hydrogen production activity can be as high as 196.75μmol/(h g), which is 9.15 times that of pure red phosphorus, while pure strontium titanate has no hydrogen production activity under visible light; it can achieve photocatalytic activity under 425nm-780nm wavelength light irradiation Catalytic water splitting can be seen through UV-spectroscopy test, and relevant data are obtained by using a 300W xenon lamp light source (CEL-HXUV300-T3) equipped with a λ≥420nm filter to simulate sunlight irradiation photocatalytic evaluation system.
4、本发明利用XRD、SEM和TEM等多种表征手段对其晶体结构、形貌特征、光吸收性能进行了表征，证明了RP与SrTiO3紧密接触，形成了异质结构，对提高SrTiO3的光吸收和克服RP光生电子和光生空缺复合快的缺点具有重要的意义，异质结的形成，克服了红磷光生电子和光生空穴复合快的缺点，拓宽了钛酸锶的可见光响应范围，提高了光催化活性。4. The present invention uses various characterization methods such as XRD, SEM, and TEM to characterize its crystal structure, morphology, and light absorption properties, and proves that RP and SrTiO 3 are in close contact to form a heterogeneous structure, which is beneficial to improving the SrTiO 3 It is of great significance to overcome the shortcoming of fast recombination of RP photogenerated electrons and photogenerated vacancies. The formation of heterojunction overcomes the shortcoming of fast recombination of red phosphor photogenerated electrons and photogenerated holes, and broadens the visible light response range of strontium titanate. , enhanced photocatalytic activity.
综上所述，本发明具有制备方法工艺简单，制备时间短，条件温和，成本低廉，可实现规模性生产，且本发明制备的红磷/钛酸锶异质结光催化剂通过形成异质结结构的方式增强了光生载流子的分离和传输效率，相较于纯的红磷或纯的钛酸锶，光谱响应拓宽至425nm-780nm，红磷/钛酸锶异质结光催化剂的光催化水解产氢活性有了大幅度提高，循环稳定性好，异质结的形成，克服了红磷光生电子和光生空穴复合快的缺点，拓宽了钛酸锶的可见光响应范围，提高了光催化活性的有益效果。In summary, the present invention has the advantages of simple preparation process, short preparation time, mild conditions, low cost, large-scale production can be realized, and the red phosphorus/strontium titanate heterojunction photocatalyst prepared by the present invention can form a heterojunction The way of structure enhances the separation and transmission efficiency of photogenerated carriers. Compared with pure red phosphorus or pure strontium titanate, the spectral response is broadened to 425nm-780nm, and the photocatalyst of red phosphorus/strontium titanate heterojunction photocatalyst The activity of hydrogen production by catalytic hydrolysis has been greatly improved, the cycle stability is good, and the formation of heterojunction overcomes the shortcomings of fast recombination of photogenerated electrons and photogenerated holes of red phosphorous, broadens the visible light response range of strontium titanate, and improves Beneficial effects of catalytic activity.
附图说明Description of drawings
图1是本发明实施例、对比例1和对比例2的可见光光催化分解水产氢活性速率图；Fig. 1 is the activity rate diagram of visible light photocatalytic decomposition of water for hydrogen production of the embodiment of the present invention, comparative example 1 and comparative example 2;
图2是本发明实施例、对比例1和对比例2的X-射线衍射图；Fig. 2 is the X-ray diffraction figure of the embodiment of the present invention, comparative example 1 and comparative example 2;
图3是本发明实施例4、对比例1和对比例2的瞬时光电流i-t曲线图；Fig. 3 is the instantaneous photoelectric current i-t curve figure of
图4是本发明实施例4、对比例1和对比例2的阻抗(EIS)曲线图；Fig. 4 is the impedance (EIS) curve chart of
图5是本发明实施例4、对比例1和对比例2的光致发光光谱图；Fig. 5 is the photoluminescence spectrogram of
图6是本发明实施例4、对比例1和对比例2的紫外-可见吸收光谱图；Fig. 6 is the ultraviolet-visible absorption spectrogram of
图7是本发明实施例4、对比例1和对比例2的扫描电镜图和EDX mapping图；Fig. 7 is the scanning electron microscope picture and the EDX mapping figure of the
图8是本发明实施例4、对比例1和对比例2的透射电镜图。FIG. 8 is a transmission electron microscope image of Example 4, Comparative Example 1 and Comparative Example 2 of the present invention.
具体实施方式Detailed ways
下面结合附图和实施例对本发明作进一步的说明，但并不作为对本发明限制的依据。The present invention will be further described below in conjunction with the accompanying drawings and embodiments, but not as a basis for limiting the present invention.
实施例1。一种红磷/钛酸锶异质结光催化剂，所述红磷/钛酸锶异质结光催化剂采用红磷和钛酸锶制备，具体是红磷均匀附着在钛酸锶的(110)及(100)晶面上，形成红磷/钛酸锶异质结结构。Example 1. A red phosphorus/strontium titanate heterojunction photocatalyst, the red phosphorus/strontium titanate heterojunction photocatalyst is prepared by using red phosphorus and strontium titanate, specifically red phosphorus is uniformly attached to strontium titanate (110) and (100) crystal plane, forming a red phosphorus/strontium titanate heterojunction structure.
所述红磷/钛酸锶异质结光催化剂：采用红磷和钛酸锶通过水热法原位合成制备，其中红磷与钛酸锶的摩尔比为0.125:1。The red phosphorus/strontium titanate heterojunction photocatalyst is prepared by in-situ synthesis of red phosphorus and strontium titanate by hydrothermal method, wherein the molar ratio of red phosphorus to strontium titanate is 0.125:1.
所述的红磷/钛酸锶异质结光催化剂的制备方法，包括有以下步骤：The preparation method of the described red phosphorus/strontium titanate heterojunction photocatalyst comprises the following steps:
(1)将红磷放入水中超声分散5min，得红磷悬浮液，为A品；所述红磷悬浮液的浓度为1mg/mL；(1) Red phosphorus is put into water and ultrasonically dispersed for 5 minutes to obtain a red phosphorus suspension, which is product A; the concentration of the red phosphorus suspension is 1 mg/mL;
(2)所述步骤(2)中，按比例，将3g钛酸四丁酯溶解在40mL浓度为98％的乙二醇溶液中，得B品；然后在磁力搅拌下向B品中依次加入20mL浓度为0.44mol/L的硝酸锶溶液和10mL浓度为4.4mol/L的氢氧化钠溶液，得C品；(2) In the step (2), according to the proportion, 3g of tetrabutyl titanate was dissolved in 40mL of ethylene glycol solution with a concentration of 98% to obtain product B; 20 mL of strontium nitrate solution with a concentration of 0.44 mol/L and 10 mL of a sodium hydroxide solution with a concentration of 4.4 mol/L to obtain product C;
(3)将C品转移至反应容器中，进行水热反应，水热反应的温度为120℃，时间为12h，自然冷却至20℃，然后调节pH为6.8，得D品；所述调节pH为6.8，具体是采用0.5mol/L的HNO3溶液调节pH为6.8；(3) Transfer product C to a reaction container, and carry out hydrothermal reaction. The temperature of the hydrothermal reaction is 120° C., the time is 12 hours, naturally cool to 20° C., and then adjust the pH to 6.8 to obtain product D; It is 6.8, specifically adopting 0.5mol/L HNO3 solution to adjust the pH to 6.8;
(4)在搅拌下，将A品加入D品中，混合均匀后，得E品，E品中红磷与钛酸锶的摩尔比为0.125:1，将E品进行水热反应，水热反应的温度为120℃，时间为6h，并自然冷却至20℃，采用去离子水和乙醇交替洗涤2次，然后在50℃下真空干燥10h，即得红磷/钛酸锶异质结光催化剂，标记为P0.125/STO。(4) Add product A into product D under stirring, and after mixing evenly, product E is obtained. The molar ratio of red phosphorus to strontium titanate in product E is 0.125:1. The temperature of the reaction is 120°C, the time is 6h, and naturally cooled to 20°C, washed twice with deionized water and ethanol alternately, and then vacuum-dried at 50°C for 10h to obtain the red phosphorus/strontium titanate heterojunction Catalyst, labeled P 0.125 /STO.
实施例2。一种红磷/钛酸锶异质结光催化剂，所述红磷/钛酸锶异质结光催化剂采用红磷和钛酸锶制备，具体是红磷均匀附着在钛酸锶的(110)及(100)晶面上，形成红磷/钛酸锶异质结结构。Example 2. A red phosphorus/strontium titanate heterojunction photocatalyst, the red phosphorus/strontium titanate heterojunction photocatalyst is prepared by using red phosphorus and strontium titanate, specifically red phosphorus is uniformly attached to strontium titanate (110) and (100) crystal plane, forming a red phosphorus/strontium titanate heterojunction structure.
所述红磷/钛酸锶异质结光催化剂：采用红磷和钛酸锶通过水热法原位合成制备，其中红磷与钛酸锶的摩尔比为0.25:1。The red phosphorus/strontium titanate heterojunction photocatalyst is prepared by in-situ synthesis of red phosphorus and strontium titanate by hydrothermal method, wherein the molar ratio of red phosphorus to strontium titanate is 0.25:1.
所述的红磷/钛酸锶异质结光催化剂的制备方法，包括有以下步骤：The preparation method of the described red phosphorus/strontium titanate heterojunction photocatalyst comprises the following steps:
(1)将红磷放入水中超声分散10min，得红磷悬浮液，为A品；所述红磷悬浮液的浓度为1.5mg/mL；(1) Red phosphorus is put into water and ultrasonically dispersed for 10 minutes to obtain a red phosphorus suspension, which is product A; the concentration of the red phosphorus suspension is 1.5 mg/mL;
(2)所述步骤(2)中，按比例，将3.4g钛酸四丁酯溶解在40mL浓度为98％的乙二醇溶液中，得B品；然后在磁力搅拌下向B品中依次加入20mL浓度为0.5mol/L的硝酸锶溶液和10mL浓度为5mol/L的氢氧化钠溶液，得C品；(2) In the step (2), according to the proportion, 3.4g of tetrabutyl titanate is dissolved in 40mL of ethylene glycol solution with a concentration of 98% to obtain product B; Add 20 mL of strontium nitrate solution with a concentration of 0.5 mol/L and 10 mL of a sodium hydroxide solution with a concentration of 5 mol/L to obtain product C;
(3)将C品转移至反应容器中，进行水热反应，水热反应的温度为150℃，时间为20h，自然冷却至25℃，然后调节pH为7，得D品；所述调节pH为7，具体是采用0.8mol/L的HNO3溶液调节pH为7；(3) Transfer product C to a reaction container, and carry out hydrothermal reaction. The temperature of the hydrothermal reaction is 150° C., the time is 20 h, and naturally cool to 25° C., and then adjust the pH to 7 to obtain product D; It is 7, specifically adopting 0.8mol/L HNO solution to adjust the pH to 7;
(4)在搅拌下，将A品加入D品中，混合均匀后，得E品，E品中红磷与钛酸锶的摩尔比为0.25:1，将E品进行水热反应，水热反应的温度为150℃，时间为18h，并自然冷却至25℃，采用去离子水和乙醇交替洗涤3次，然后在60℃下真空干燥11h，即得红磷/钛酸锶异质结光催化剂，标记为P0.25/STO。(4) Under stirring, add product A into product D, and after mixing evenly, product E is obtained. The molar ratio of red phosphorus to strontium titanate in product E is 0.25:1, and product E is subjected to hydrothermal reaction. The temperature of the reaction is 150°C, the time is 18h, and naturally cooled to 25°C, washed with deionized water and ethanol three times alternately, and then vacuum-dried at 60°C for 11h to obtain the red phosphorus/strontium titanate heterojunction Catalyst, labeled P 0.25 /STO.
实施例3。一种红磷/钛酸锶异质结光催化剂，所述红磷/钛酸锶异质结光催化剂采用红磷和钛酸锶制备，具体是红磷均匀附着在钛酸锶的(110)及(100)晶面上，形成红磷/钛酸锶异质结结构。Example 3. A red phosphorus/strontium titanate heterojunction photocatalyst, the red phosphorus/strontium titanate heterojunction photocatalyst is prepared by using red phosphorus and strontium titanate, specifically red phosphorus is uniformly attached to strontium titanate (110) and (100) crystal plane, forming a red phosphorus/strontium titanate heterojunction structure.
所述红磷/钛酸锶异质结光催化剂：采用红磷和钛酸锶通过水热法原位合成制备，其中红磷与钛酸锶的摩尔比为0.5:1。The red phosphorus/strontium titanate heterojunction photocatalyst is prepared by in-situ synthesis of red phosphorus and strontium titanate through a hydrothermal method, wherein the molar ratio of red phosphorus to strontium titanate is 0.5:1.
所述的红磷/钛酸锶异质结光催化剂的制备方法，包括有以下步骤：The preparation method of the described red phosphorus/strontium titanate heterojunction photocatalyst comprises the following steps:
(1)将红磷放入水中超声分散10min，得红磷悬浮液，为A品；所述红磷悬浮液的浓度为1.5mg/mL；(1) Red phosphorus is put into water and ultrasonically dispersed for 10 minutes to obtain a red phosphorus suspension, which is product A; the concentration of the red phosphorus suspension is 1.5 mg/mL;
(2)所述步骤(2)中，按比例，将3.4g钛酸四丁酯溶解在40mL浓度为98％的乙二醇溶液中，得B品；然后在磁力搅拌下向B品中依次加入20mL浓度为0.5mol/L的硝酸锶溶液和10mL浓度为5mol/L的氢氧化钠溶液，得C品；(2) In the step (2), according to the proportion, 3.4g of tetrabutyl titanate is dissolved in 40mL of ethylene glycol solution with a concentration of 98% to obtain product B; Add 20 mL of strontium nitrate solution with a concentration of 0.5 mol/L and 10 mL of a sodium hydroxide solution with a concentration of 5 mol/L to obtain product C;
(3)将C品转移至反应容器中，进行水热反应，水热反应的温度为160℃，时间为18h，自然冷却至26℃，然后调节pH为7.1，得D品；所述调节pH为7.1，具体是采用0.9mol/L的HNO3溶液调节pH为7.1；(3) Transfer product C to a reaction container, and carry out hydrothermal reaction. The temperature of the hydrothermal reaction is 160° C., the time is 18 hours, naturally cool to 26° C., and then adjust the pH to 7.1 to obtain product D; is 7.1, specifically, the pH is adjusted to 7.1 by using 0.9mol/L HNO3 solution;
(4)在搅拌下，将A品加入D品中，混合均匀后，得E品，E品中红磷与钛酸锶的摩尔比为0.5:1，将E品进行水热反应，水热反应的温度为160℃，时间为22h，并自然冷却至27℃，采用去离子水和乙醇交替洗涤3次，然后在60℃下真空干燥12h，即得红磷/钛酸锶异质结光催化剂，标记为P0.5/STO。(4) Under stirring, add product A into product D, and after mixing evenly, product E is obtained. The molar ratio of red phosphorus to strontium titanate in product E is 0.5:1, and product E is subjected to hydrothermal reaction. The temperature of the reaction is 160°C, the time is 22h, and naturally cooled to 27°C, washed with deionized water and ethanol three times alternately, and then vacuum-dried at 60°C for 12h to obtain the red phosphorus/strontium titanate heterojunction light Catalyst, labeled P 0.5 /STO.
实施例4。一种红磷/钛酸锶异质结光催化剂，所述红磷/钛酸锶异质结光催化剂采用红磷和钛酸锶制备，具体是红磷均匀附着在钛酸锶的(110)及(100)晶面上，形成红磷/钛酸锶异质结结构。Example 4. A red phosphorus/strontium titanate heterojunction photocatalyst, the red phosphorus/strontium titanate heterojunction photocatalyst is prepared by using red phosphorus and strontium titanate, specifically red phosphorus is uniformly attached to strontium titanate (110) and (100) crystal plane, forming a red phosphorus/strontium titanate heterojunction structure.
所述红磷/钛酸锶异质结光催化剂：采用红磷和钛酸锶通过水热法原位合成制备，其中红磷与钛酸锶的摩尔比为1:1。The red phosphorus/strontium titanate heterojunction photocatalyst is prepared by in-situ synthesis of red phosphorus and strontium titanate by hydrothermal method, wherein the molar ratio of red phosphorus to strontium titanate is 1:1.
所述的红磷/钛酸锶异质结光催化剂的制备方法，包括有以下步骤：The preparation method of the described red phosphorus/strontium titanate heterojunction photocatalyst comprises the following steps:
(1)将红磷放入水中超声分散15min，得红磷悬浮液，为A品；所述红磷悬浮液的浓度为2mg/mL；(1) Red phosphorus is put into water and ultrasonically dispersed for 15 minutes to obtain a red phosphorus suspension, which is product A; the concentration of the red phosphorus suspension is 2 mg/mL;
(2)所述步骤(2)中，按比例，将4g钛酸四丁酯溶解在40mL浓度为98％的乙二醇溶液中，得B品；然后在磁力搅拌下向B品中依次加入20mL浓度为0.58mol/L的硝酸锶溶液和10mL浓度为5.8mol/L的氢氧化钠溶液，得C品；(2) In the step (2), according to the proportion, 4g of tetrabutyl titanate was dissolved in 40mL of ethylene glycol solution with a concentration of 98% to obtain product B; 20 mL of strontium nitrate solution with a concentration of 0.58 mol/L and 10 mL of a sodium hydroxide solution with a concentration of 5.8 mol/L to obtain product C;
(3)将C品转移至反应容器中，进行水热反应，水热反应的温度为180℃，时间为24h，自然冷却至30℃，然后调节pH为7.2，得D品；所述调节pH为7.2，具体是采用1mol/L的HNO3溶液调节pH为7.2；(3) Transfer product C to a reaction container, and carry out hydrothermal reaction. The temperature of the hydrothermal reaction is 180° C., the time is 24 hours, naturally cool to 30° C., and then adjust the pH to 7.2 to obtain product D; is 7.2, specifically, the pH is adjusted to 7.2 by using 1mol/L HNO3 solution;
(4)在搅拌下，将A品加入D品中，混合均匀后，得E品，E品中红磷与钛酸锶的摩尔比为0.125:1，将E品进行水热反应，水热反应的温度为180℃，时间为24h，并自然冷却至30℃，采用去离子水和乙醇交替洗涤4次，然后在70℃下真空干燥12h，即得红磷/钛酸锶异质结光催化剂，标记为P1.0/STO。(4) Add product A into product D under stirring, and after mixing evenly, product E is obtained. The molar ratio of red phosphorus to strontium titanate in product E is 0.125:1. The temperature of the reaction is 180°C, the time is 24h, and naturally cooled to 30°C, washed with deionized water and ethanol four times alternately, and then vacuum-dried at 70°C for 12h to obtain the red phosphorus/strontium titanate heterojunction light Catalyst, labeled P 1.0 /STO.
对比例1：钛酸锶催化剂Comparative Example 1: Strontium titanate catalyst
在20-30℃条件下，将10mmol钛酸四丁酯溶解在40mL乙二醇溶液中，连续搅拌1h后，形成A液，然后将20mL的106g/L高纯硝酸锶溶液滴加至持续磁力搅拌的A液中，A液中形成白色胶体B；再向A溶液中滴加10mL的200g/L氢氧化钠溶液，溶液逐渐澄清后，继续搅拌30min，得到混合均匀的C液；将C液转移至100mL带不锈钢外壳的聚四氟乙烯反应釜中，在180℃下进行水热反应24h，反应结束后待反应釜自然冷却至20-30℃，然后将所得物经用去离子水和乙醇交替洗涤2-4次，然后在50-70℃下真空干燥10-12h，即制得钛酸锶催化剂，标记为STO。Under the condition of 20-30℃, dissolve 10mmol tetrabutyl titanate in 40mL ethylene glycol solution, and after continuous stirring for 1h, liquid A is formed, then add 20mL of 106g/L high-purity strontium nitrate solution dropwise to the continuous magnetic In the stirred liquid A, a white colloid B is formed in the A liquid; then add 10mL of 200g/L sodium hydroxide solution dropwise to the A solution, and after the solution gradually becomes clear, continue to stir for 30 minutes to obtain a uniformly mixed liquid C; Transfer to a 100mL polytetrafluoroethylene reactor with a stainless steel shell, and conduct a hydrothermal reaction at 180°C for 24 hours. After the reaction, the reactor is naturally cooled to 20-30°C, and then the resultant is washed with deionized water and ethanol Alternately wash 2-4 times, and then vacuum-dry at 50-70°C for 10-12 hours to obtain a strontium titanate catalyst, marked as STO.
对比例2：红磷催化剂Comparative example 2: red phosphorus catalyst
在20-30℃条件下，将市售红磷研磨后用120目筛网筛分，称取3g分散于由55mL水、5mL乙二醇和0.12g氢氧化钠组成的反应液中，搅拌30min后，转移至100mL带不锈钢外壳的聚四氟乙烯反应釜中，在200℃下进行水热反应24h，反应完成后自然冷却至20-30℃，将产物用去离子水和乙醇交替洗涤2-4次，然后在50-70℃下真空干燥10-12h，红磷催化剂，标记为RP。Under the condition of 20-30°C, commercially available red phosphorus was ground and sieved with a 120-mesh sieve, and 3 g was weighed and dispersed in a reaction solution consisting of 55 mL of water, 5 mL of ethylene glycol and 0.12 g of sodium hydroxide, and stirred for 30 min. , transferred to a 100mL polytetrafluoroethylene reactor with a stainless steel shell, and carried out a hydrothermal reaction at 200°C for 24 hours. After the reaction was completed, it was naturally cooled to 20-30°C, and the product was alternately washed with deionized water and ethanol for 2-4 hours. times, and then vacuum-dried at 50-70°C for 10-12h, red phosphorus catalyst, marked as RP.
实验证明：Experiments prove that:
对本发明实施例1-4中所制得的红磷/钛酸锶异质结光催化剂，以及对比例1所得的钛酸锶催化剂(STO)、对比例2所得的红磷催化剂(RP)进行光催化分解水产氢活性评价，具体操作步骤为：The red phosphorus/strontium titanate heterojunction photocatalyst obtained in Examples 1-4 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 carried out Activity evaluation of photocatalytic decomposition of water for hydrogen production, the specific operation steps are as follows:
取一定量的催化剂样品分散在特定体积分数的Na2S和Na2SO3混合溶液中。实验Na2S和Na2SO3混合溶液采用作为牺牲试剂以消耗光生空穴，抑制其与光生电子的复合，帮助改善催化剂的光催化产氢活性。并超声分散10min。将其置于光催化反应***中，整个***用真空泵抽至真空，以去除反应液中的空气，使实验数据更准确，而恒温冷却***确保整个产氢过程处于室温状态。活性测试采用外照式300W氙灯作为光源进行产氢实验测试，在光源上添加滤波片(λ≥420nm)得到可见光照射，产生的氢气通过封闭的气体循环***，进入带有热导检测器的在线气相色谱仪(GC-7900)中进行测量，每间隔一个小时测量一次氢气，测得的5组数据最后进行拟合得到平均产氢量。采用单位时间内、一定剂量的光催化剂产生的氢气量来表示光催化分解水产氢的光催化剂的活性高低。在光催化产氢前要先进行标基线，用于确定实际测得的产氢量。Take a certain amount of catalyst sample and disperse it in the mixed solution of Na 2 S and Na 2 SO 3 with specific volume fraction. In the experiment, the mixed solution of Na 2 S and Na 2 SO 3 was used as a sacrificial reagent to consume photogenerated holes, inhibit their recombination with photogenerated electrons, and help improve the photocatalytic hydrogen production activity of the catalyst. And ultrasonically dispersed for 10min. It is placed in a photocatalytic reaction system, and the whole system is evacuated to vacuum with a vacuum pump to remove the air in the reaction solution to make the experimental data more accurate, and the constant temperature cooling system ensures that the entire hydrogen production process is at room temperature. The activity test uses an externally illuminated 300W xenon lamp as the light source for the hydrogen production experiment test. A filter (λ≥420nm) is added to the light source to obtain visible light irradiation. The gas chromatograph (GC-7900) is used for measurement, and the hydrogen gas is measured every hour. The 5 sets of data measured are finally fitted to obtain the average hydrogen production. The amount of hydrogen produced by a certain dose of photocatalyst per unit time is used to indicate the activity of the photocatalyst for photocatalytic decomposition of water to produce hydrogen. Before photocatalytic hydrogen production, a baseline should be carried out to determine the actual measured hydrogen production.
图1为本发明实施例1-4、对比例1和对比例2的光催化分解水产氢速率图。可以看到本发明所有实施例的光催化分解水产氢活性均高于对比例，且P1.0/STO产氢速率约为196.75μmol/(h·g)，是RP的9.15倍，而STO在可见光下无产氢活性。Fig. 1 is a diagram of the hydrogen production rate of photocatalytic water splitting in Examples 1-4, Comparative Example 1 and Comparative Example 2 of the present invention. It can be seen that the hydrogen production activity of photocatalytic water splitting in all examples of the present invention is higher than that of the comparative examples, and the hydrogen production rate of P 1.0 /STO is about 196.75 μmol/(h g), which is 9.15 times that of RP. no hydrogen production activity.
图2为本发明实施例1-4、对比例1和对比例2的X射线衍射图谱，与标准卡片(SrTiO3：JCPDS:35-0734，RP:PDF:44-0609)对比可知，本发明实施例均存在钛酸锶和红磷两种物质，结晶良好，且不存在其他杂相，同时随着红磷加入量的增加，红磷的衍射峰逐渐增强；对比例1的STO为纯的钛酸锶，对比例2的RP为纯的红磷。Fig. 2 is the X-ray diffraction patterns of Examples 1-4, Comparative Example 1 and Comparative Example 2 of the present invention, compared with the standard card (SrTiO 3 : JCPDS: 35-0734, RP: PDF: 44-0609), it can be known that the present invention There are two kinds of substances, strontium titanate and red phosphorus, in the examples, and the crystallization is good, and there are no other impurity phases. At the same time, with the increase of the amount of red phosphorus added, the diffraction peak of red phosphorus is gradually enhanced; the STO of comparative example 1 is pure Strontium titanate, the RP of Comparative Example 2 is pure red phosphorus.
图3为本发明实施例4、对比例1和对比例2的瞬时光电流i-t曲线图，瞬时光电流i-t曲线能够反映光生电子空穴对的分离能力。所有的样品，在光照射时能够迅速产生可重复的光电流响应，与STO和RP相比，P1.0/STO对光更为敏感且电流密度更高，表明拥有异质结结构的红磷/钛酸锶复合材料具有更强的光电转换能力。FIG. 3 is the instantaneous photocurrent it curves of Example 4, Comparative Example 1 and Comparative Example 2 of the present invention. The instantaneous photocurrent it curve can reflect the separation ability of photogenerated electron-hole pairs. All samples can rapidly produce reproducible photocurrent responses when light is irradiated. Compared with STO and RP, P 1.0 /STO is more sensitive to light and has a higher current density, indicating that red phosphorus/STO with a heterojunction structure Strontium titanate composites have stronger photoelectric conversion capabilities.
图4为本发明为实施例4、对比例1和对比例2的阻抗(EIS)曲线图，复合样品P1.0/STO与RP和STO相比具有更小的尼奎斯特不完全半圆半径，这表明了复合物异质结形成之后，电荷转移电阻变小，光电流响应更强的，表明红磷/钛酸锶异质结光催化剂的光生电子-空穴对的有效分离和界面电荷的快速转移，延长了光生载流子的寿命，证明了异质结提高了光催化的活性。Fig. 4 is that the present invention is the impedance (EIS) curve chart of
图5为本发明实施例4、对比例1和对比例2的光致发光光谱图，由于光致发光光谱发射信号是来源于光生电子-空穴对复合时所释放的能量，因此可以用来研究半导体催化剂中载流子的转移和分离，进而来表征半导体中被激发的光生载流子的寿命，P1.0/STO的光谱强度比STO及RP光谱强度均有所下降，揭示了RP颗粒能够有效的捕获光生电子，进而抑制光生电子-空穴对的直接复合，延长了载流子电荷的寿命，表现出更高的光催化分解水产氢活性。Fig. 5 is the photoluminescence spectrum graph of the
图6为本发明实施例4、对比例1和对比例2的紫外-可见吸收光谱图，STO的吸收边在400nm左右，RP的吸收边在750nm附近。然而，制备的P1.0/STO吸收带边明显红移，光谱响应拓宽至425nm-780nm，拓宽了可见光吸收范围，优于纯RP和SrTiO3。同时可以看出P1.0/SrTiO3复合材料的吸收阈值较SrTiO3的吸收阈值大，比RP的吸收阈值小，但是光吸收强度要比RP的大，这是因为RP和SrTiO3复合后形成的异质结使光生载流子得到有效地分离，说明P1.0/SrTiO3异质结有很好的可见光光解水制氢性能。Fig. 6 is the ultraviolet-visible absorption spectra of Example 4, Comparative Example 1 and Comparative Example 2 of the present invention, the absorption edge of STO is around 400nm, and the absorption edge of RP is around 750nm. However, the absorption band edge of the prepared P 1.0 /STO is obviously red-shifted, and the spectral response is broadened to 425nm-780nm, broadening the visible light absorption range, which is better than that of pure RP and SrTiO 3 . At the same time, it can be seen that the absorption threshold of the P 1.0 /SrTiO 3 composite is larger than that of SrTiO 3 and smaller than that of RP, but the light absorption intensity is larger than that of RP. This is because the composite formed by RP and SrTiO 3 The heterojunction can effectively separate the photogenerated carriers, which shows that the P 1.0 /SrTiO 3 heterojunction has a good performance of visible light photo-splitting of water for hydrogen production.
图7是本发明实施例4、对比例1和对比例2的扫描电镜图以及EDX mapping图，纳米片状的钛酸锶和颗粒状的红磷已经复合到一起，且分布均匀，复合后P1.0/STO异质结的EDXmapping分布图，可以观察到Ti、O、Sr、P等元素。Figure 7 is the scanning electron microscope and EDX mapping diagrams of Example 4, Comparative Example 1 and Comparative Example 2 of the present invention. The nanosheet-like strontium titanate and granular red phosphorus have been compounded together, and the distribution is uniform. After compounding, P 1.0 /STO heterojunction EDXmapping distribution map, Ti, O, Sr, P and other elements can be observed.
图8是本发明实施例4、对比例1和对比例2的透射电镜图，SrTiO3为纳米薄片结构且生长均匀，HRTEM图像显示样品晶格间距为0.27nm和0.395nm，分别对应钙钛矿SrTiO3的(110)和(100)晶面。而RP属于无定形结构没有晶格条纹，复合材料中形成了清晰的接触界面表明两者紧密接触，形成了异质结构。纳米片状的钛酸锶和颗粒状的红磷已经复合到一起，红磷均匀附着在钛酸锶的(110)和(100)晶面上。综合XRD、SEM和EDX谱图可以得出，本发明的SrTiO3和RP复合可以形成分散均匀的异质结。Figure 8 is the TEM images of Example 4, Comparative Example 1 and Comparative Example 2 of the present invention. SrTiO 3 is a nano-flake structure and grows uniformly. The HRTEM image shows that the sample lattice spacing is 0.27nm and 0.395nm, corresponding to perovskite respectively. (110) and (100) crystal planes of SrTiO3 . However, RP has an amorphous structure without lattice fringes, and a clear contact interface is formed in the composite material, indicating that the two are in close contact and form a heterostructure. The nanosheet-like strontium titanate and granular red phosphorus have been compounded together, and the red phosphorus is evenly attached to the (110) and (100) crystal planes of the strontium titanate. Based on XRD, SEM and EDX spectra, it can be concluded that the composite of SrTiO 3 and RP of the present invention can form a uniformly dispersed heterojunction.
综合XRD以及SEM、TEM的结果P1.0/STO异质结材料复合比较均匀，本申请人还对其它实施例制得的P0.125/STO、P0.25/STO、P0.5/STO催化剂进行了上诉3-8的实验表征测试和分析，所得的结果与上述的测试及分析结果相当。Based on the results of XRD, SEM, and TEM, the composite of P 1.0 /STO heterojunction materials is relatively uniform, and the applicant also appealed to the P 0.125 /STO, P 0.25 /STO, and P 0.5 /STO catalysts prepared in other examples3 -8 experimental characterization test and analysis, the obtained results are equivalent to the above test and analysis results.
综上所述，本发明提供一种红磷/钛酸锶异质结光催化剂及制备方法及应用，所述红磷/钛酸锶异质结光催化剂采用红磷和钛酸锶制备，具体是红磷均匀附着在钛酸锶的(110)和(100)晶面上，形成红磷/钛酸锶异质结结构；红磷和钛酸锶的独特相互作用增强了催化剂对光的吸收性能并加快光生载流子的输运过程，减小了电子-空穴对的复合几率，进而有效提高其光催化产氢特性，相较于纯的红磷或纯的钛酸锶，光谱响应拓宽至425nm-780nm。在可见光照射下，本发明提供的红磷/钛酸锶异质结光催化剂具有较高的产氢速率，并且制备方法工艺简单，条件温和，成本低廉，可实现规模性生产。In summary, the present invention provides a red phosphorus/strontium titanate heterojunction photocatalyst and its preparation method and application. The red phosphorus/strontium titanate heterojunction photocatalyst is prepared by using red phosphorus and strontium titanate, specifically Red phosphorus is evenly attached to the (110) and (100) crystal planes of strontium titanate to form a red phosphorus/strontium titanate heterojunction structure; the unique interaction between red phosphorus and strontium titanate enhances the light absorption of the catalyst performance and speed up the transport process of photogenerated carriers, reducing the recombination probability of electron-hole pairs, thereby effectively improving its photocatalytic hydrogen production characteristics. Compared with pure red phosphorus or pure strontium titanate, the spectral response Widen to 425nm-780nm. Under visible light irradiation, the red phosphorus/strontium titanate heterojunction photocatalyst provided by the invention has a relatively high hydrogen production rate, and the preparation method is simple, the conditions are mild, and the cost is low, and large-scale production can be realized.
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