CN113145138B - Heat-responsive composite photocatalyst and its preparation method and application - Google Patents
Heat-responsive composite photocatalyst and its preparation method and application Download PDFInfo
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- 229940071125 manganese acetate Drugs 0.000 claims description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
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- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 2
- 229960001471 sodium selenite Drugs 0.000 claims description 2
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- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
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- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域technical field
本发明属于光催化材料技术领域，具体涉及一种富含硫空位的Co0.85Se/Mn0.3Cd0.7S热响应型复合光催化剂的制备方法及其可见光诱导催化分解水产氢应用。The invention belongs to the technical field of photocatalytic materials, and in particular relates to a preparation method of Co 0.85 Se/Mn 0.3 Cd 0.7 S heat-responsive composite photocatalyst rich in sulfur vacancies and its application of visible light-induced catalytic decomposition of water for hydrogen production.
背景技术Background technique
氢能因其环境友好、清洁和可再生性而被广泛认为是新一代能源的理想选择，因此，吸收源源不断的太阳光在半导体材料上直接分解水产氢，实现将太阳能转化为氢能对解决能源危机和治理环境污染具有重要意义。Hydrogen energy is widely considered to be an ideal choice for a new generation of energy because of its environmental friendliness, cleanliness, and renewability. Therefore, absorbing a steady stream of sunlight and directly decomposing water on semiconductor materials to produce hydrogen can realize the conversion of solar energy into hydrogen energy. The energy crisis and the control of environmental pollution are of great significance.
硫化物固溶体由于其带隙宽度可调，在可见光下具有催化活性，已经受到广泛关注。但是其光生载流子的快速重组限制了其实际应用，因此有必要对其进行改性。半导体光催化剂的固有特性（如空位）以及构建半导体异质结可以调节其能带结构、改变载流子浓度和电荷转移效率，从而能够影响光催化活性。另外，相对于单一的光催化，多种能源的协同利用，能进一步提高光催化的效率。Sulfide solid solutions have attracted extensive attention due to their tunable bandgap width and catalytic activity under visible light. However, the rapid recombination of photogenerated carriers limits its practical application, so it is necessary to modify it. The inherent characteristics of semiconductor photocatalysts (such as vacancies) and the construction of semiconductor heterojunctions can adjust their energy band structure, change the carrier concentration and charge transfer efficiency, which can affect the photocatalytic activity. In addition, compared with single photocatalysis, the synergistic utilization of multiple energy sources can further improve the efficiency of photocatalysis.
发明内容Contents of the invention
本发明的目的在于提供一种具有更高效且具有光响应Co0.85Se/Mn0.3Cd0.7S复合光催化剂的制备方法及其可见光诱导催化分解水产氢中的应用。本发明构建了Co0.85Se纳米颗粒与富含硫空位的Mn0.3Cd0.7S纳米棒间紧密的界面接触，充分暴露了反应位点，实现了光生载流子的有效分离/传输并抑制其重组，使其在可见光催化分解水产氢中展现出优异的活性及稳定性并可以实现温度对光催化产氢速率的调控。The purpose of the present invention is to provide a more efficient and photoresponsive Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst preparation method and its application in visible light-induced catalytic decomposition of water for hydrogen production. The present invention constructs a tight interfacial contact between Co 0.85 Se nanoparticles and Mn 0.3 Cd 0.7 S nanorods rich in sulfur vacancies, fully exposes the reaction sites, realizes the effective separation/transport of photogenerated carriers and inhibits their recombination , so that it exhibits excellent activity and stability in the visible light photocatalytic splitting of water for hydrogen production, and can realize the regulation of temperature on the photocatalytic hydrogen production rate.
为实现上述目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种富含硫空位的Co0.85Se/Mn0.3Cd0.7S复合光催化剂，是由富含硫空位的Mn0.3Cd0.7S纳米棒作为载体，在其表面原位生长Co0.85Se纳米颗粒而构成；其中，Co0.85Se纳米颗粒与Mn0.3Cd0.7S纳米棒的质量比为3%-20%。A composite photocatalyst of Co 0.85 Se/Mn 0.3 Cd 0.7 S rich in sulfur vacancies, which is composed of Mn 0.3 Cd 0.7 S nanorods rich in sulfur vacancies as a support, and Co 0.85 Se nanoparticles are grown on the surface in situ ; Wherein, the mass ratio of Co 0.85 Se nanoparticles to Mn 0.3 Cd 0.7 S nanorods is 3%-20%.
所述Mn0.3Cd0.7S纳米棒的长度为150-700 nm，直径为50 nm；所述Co0.85Se纳米颗粒的直径为5-10 nm。The Mn 0.3 Cd 0.7 S nanorods have a length of 150-700 nm and a diameter of 50 nm; the Co 0.85 Se nanoparticles have a diameter of 5-10 nm.
所述富含硫空位的Co0.85Se/Mn0.3Cd0.7S热响应型复合光催化剂的制备方法包括以下步骤：The preparation method of the Co 0.85 Se/Mn 0.3 Cd 0.7 S thermoresponsive composite photocatalyst rich in sulfur vacancies comprises the following steps:
（1）溶剂热法制备富含硫空位的Mn0.3Cd0.7S纳米棒：(1) Mn 0.3 Cd 0.7 S nanorods rich in sulfur vacancies prepared by solvothermal method:
将乙酸镉和乙酸锰溶解于乙二胺和去离子水的混合溶剂中，加入硫代乙酰胺继续搅拌混匀，然后将所得混合溶液转移到高压反应釜中，200 ℃恒温反应24 h，自然冷却至室温，所得沉淀依次用去离子水和乙醇各洗涤三次后于60 ℃真空干燥过夜，得到Mn0.3Cd0.7S粉末。Dissolve cadmium acetate and manganese acetate in a mixed solvent of ethylenediamine and deionized water, add thioacetamide and continue to stir and mix evenly, then transfer the resulting mixed solution to an autoclave, and react at a constant temperature of 200 °C for 24 h, naturally After cooling to room temperature, the obtained precipitate was washed three times with deionized water and ethanol in turn, and then dried under vacuum at 60 °C overnight to obtain Mn 0.3 Cd 0.7 S powder.
（2）溶剂热法制备Co0.85Se/Mn0.3Cd0.7S热响应型复合光催化剂：(2) Preparation of Co 0.85 Se/Mn 0.3 Cd 0.7 S thermoresponsive composite photocatalyst by solvothermal method:
称取步骤（1）中所得的Mn0.3Cd0.7S粉末0.1 g分散于30 ml乙二醇溶液中并搅拌30min，然后在其中加入10 ml氯化钴和***钠（摩尔比为0.85:1）的乙二醇溶液，继续搅拌30 min后转移至高压反应釜中于180 ℃恒温24 h，自然冷却至室温，所得沉淀用去离子水多次洗涤后干燥，得到所得沉淀依次用去离子水和乙醇各洗涤三次后于60 ℃真空干燥过夜，得到所述Co0.85Se/Mn0.3Cd0.7S复合光催化剂。Weigh 0.1 g of Mn 0.3 Cd 0.7 S powder obtained in step (1) and disperse it in 30 ml of ethylene glycol solution and stir for 30 min, then add 10 ml of cobalt chloride and sodium selenite (molar ratio is 0.85: 1) ethylene glycol solution, continue to stir for 30 min, then transfer to a high-pressure reaction kettle at 180 °C for 24 h, cool to room temperature naturally, wash the obtained precipitate with deionized water for several times and then dry it. After washing with water and ethanol three times each, vacuum drying at 60° C. overnight to obtain the Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst.
步骤（1）中所用乙酸锰、乙酸镉和硫代乙酰胺的摩尔比为6:14:25；所述混合溶剂中乙二胺和去离子水的的体积比为1:1。The molar ratio of manganese acetate, cadmium acetate and thioacetamide used in step (1) is 6:14:25; the volume ratio of ethylenediamine and deionized water in the mixed solvent is 1:1.
步骤（2）中Co0.85Se纳米颗粒与Mn0.3Cd0.7S纳米棒的理论质量比为3%-20%。The theoretical mass ratio of Co 0.85 Se nanoparticles to Mn 0.3 Cd 0.7 S nanorods in step (2) is 3%-20%.
在水热处理过程中，Mn0.3Cd0.7S作为载体，在其表面原位生长Co0.85Se纳米颗粒，从而最终形成Co0.85Se/Mn0.3Cd0.7S复合结构。During the hydrothermal treatment, Mn 0.3 Cd 0.7 S was used as a carrier, and Co 0.85 Se nanoparticles were grown in situ on its surface, thereby finally forming a Co 0.85 Se/Mn 0.3 Cd 0.7 S composite structure.
所得富含硫空位的Co0.85Se/Mn0.3Cd0.7S复合光催化剂可用于光催化分解水产氢。The resulting Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst rich in sulfur vacancies can be used for photocatalytic water splitting to produce hydrogen.
本发明的显著优点在于：Significant advantage of the present invention is:
（1）Co0.85Se具有较好的导电性和更易断裂的化学键，有利于促进催化反应的进行，这已经在电催化水分解领域得到应用。本发明通过溶剂热法，首次将Co0.85Se纳米颗粒与富含硫空位的Mn0.3Cd0.7S纳米棒复合，构建了具有紧密界面接触的复合光催化体系。相对于其他钴基，硒基助催化剂，Co0.85Se作为助催化剂展现出更高效的光催化活性。(1) Co 0.85 Se has better electrical conductivity and more easily broken chemical bonds, which is beneficial to promote the catalytic reaction, which has been applied in the field of electrocatalytic water splitting. The present invention combines Co 0.85 Se nanoparticles with Mn 0.3 Cd 0.7 S nanorods rich in sulfur vacancies for the first time through a solvothermal method, and constructs a composite photocatalytic system with close interfacial contact. Compared with other cobalt-based and selenium-based cocatalysts, Co 0.85 Se exhibited more efficient photocatalytic activity as a cocatalyst.
（2）本发明制备的富含硫空位的Co0.85Se/Mn0.3Cd0.7S异质结，有利于加速光生电子-空穴对的有效分离/传输并抑制其重组，具有较高的活性和稳定性，可以有效地将太阳能转化为化学能，在工业上具有很高的实际应用价值。该方法所需原料成本低、易于得到，操作步骤简单易重复，条件温和安全、易于操控，且无需使用贵金属，大大降低了生产成本，有利于工业化推广应用。(2) The Co 0.85 Se/Mn 0.3 Cd 0.7 S heterojunction rich in sulfur vacancies prepared by the present invention is conducive to accelerating the effective separation/transport of photogenerated electron-hole pairs and inhibiting their recombination, with high activity and Stability, can effectively convert solar energy into chemical energy, and has high practical application value in industry. The raw materials required by the method are low in cost and easy to obtain, the operation steps are simple and easy to repeat, the conditions are mild and safe, easy to control, and no precious metals are used, which greatly reduces the production cost and is conducive to industrial promotion and application.
（3）本发明制备的富含硫空位的Co0.85Se/Mn0.3Cd0.7S复合光催化剂具有热响应的特性，热能可以与光能产生协同效应，进一步提高光催化反应效率，以便在实际工业应用中提供更高效稳定的氢能。(3) The Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst rich in sulfur vacancies prepared by the present invention has the characteristics of thermal response, and thermal energy can produce synergistic effects with light energy, further improving the photocatalytic reaction efficiency, so that Provide more efficient and stable hydrogen energy in applications.
附图说明Description of drawings
图1（a）为Mn0.3Cd0.7S 复合光催化剂的X射线衍射图以及CdS、MnS标准XRD卡片，（b）为Mn0.3Cd0.7S、Co0.85Se及实施例1-4所得Co0.85Se/Mn0.3Cd0.7S复合光催化剂的X射线衍射图；Figure 1 (a) is the X-ray diffraction pattern of Mn 0.3 Cd 0.7 S composite photocatalyst and CdS, MnS standard XRD card, (b) is Mn 0.3 Cd 0.7 S, Co 0.85 Se and Co 0.85 Se obtained in Examples 1-4 X-ray diffraction pattern of /Mn 0.3 Cd 0.7 S composite photocatalyst;
图2在Co0.85Se/Mn0.3Cd0.7S合成过程中，不加入Mn0.3Cd0.7S所得的纯Co0.85Se样品的X射线衍射图以及标准XRD卡片；Figure 2 is the X-ray diffraction pattern and standard XRD card of the pure Co 0.85 Se sample obtained without adding Mn 0.3 Cd 0.7 S during the synthesis of Co 0.85 Se/Mn 0.3 Cd 0.7 S;
图3为7 wt% Co0.85Se/Mn0.3Cd0.7S（实施例2）复合光催化剂的（a）扫描电镜图与（b-d）透射电镜图；Figure 3 is the (a) SEM image and (bd) TEM image of the composite photocatalyst with 7 wt% Co 0.85 Se/Mn 0.3 Cd 0.7 S (Example 2);
图4为本发明中7 wt% Co0.85Se/Mn0.3Cd0.7S（实施例2）复合光催化剂的透射电镜选区元素分布图；Fig. 4 is a transmission electron microscope element distribution diagram of a composite photocatalyst of 7 wt% Co 0.85 Se/Mn 0.3 Cd 0.7 S (Example 2) in the present invention;
图5硫空位缺乏Mn0.3Cd0.7S-p与富含硫空位Mn0.3Cd0.7S的电子顺磁共振强度对比图和Fig.5 Comparison of electron paramagnetic resonance intensities of sulfur-vacancy-deficient Mn 0.3 Cd 0.7 Sp and sulfur-vacancy-rich Mn 0.3 Cd 0.7 S and
图6为（a）不同催化剂样品在可见光诱导下光催化分解水产氢活性的对比图；（b）不同Co0.85Se负载量产氢速率图以及（c）不同反应温度7 wt% Co0.85Se/Mn0.3Cd0.7S（实施例2）复合光催化剂的产氢速率；（d）7 wt% Co0.85Se/Mn0.3Cd0.7S（实施例2）复合光催化剂的长时间产氢循环实验图。Fig. 6 is (a) the comparison diagram of the photocatalytic hydrogen production activity of different catalyst samples induced by visible light; (b) the hydrogen production rate diagram of different Co 0.85 Se loadings and (c) the different reaction temperature of 7 wt% Co 0.85 Se/ Hydrogen production rate of Mn 0.3 Cd 0.7 S (Example 2) composite photocatalyst; (d) Long-term hydrogen production cycle experiment diagram of 7 wt% Co 0.85 Se/Mn 0.3 Cd 0.7 S (Example 2) composite photocatalyst.
具体实施方式detailed description
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。In order to make the content of the present invention easier to understand, the technical solutions of the present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited thereto.
实施例1Example 1
（1）溶剂热法制备富含硫空位的Mn0.3Cd0.7S纳米棒(1) Mn 0.3 Cd 0.7 S nanorods rich in sulfur vacancies prepared by solvothermal method
将14 mmol乙酸镉和6 mmol乙酸锰溶解于30 mL乙二胺和30 mL去离子水的混合溶剂中，搅拌20 min，再加入25 mmol硫代乙酰胺并继续搅拌30 min，然后将所得混合溶液转移到100 mL高压反应釜中，200 ℃恒温反应24 h，自然冷却至室温，所得沉淀依次用去离子水和乙醇各洗涤三次后于60 ℃真空干燥过夜，得到Mn0.3Cd0.7S粉末。Dissolve 14 mmol cadmium acetate and 6 mmol manganese acetate in a mixed solvent of 30 mL ethylenediamine and 30 mL deionized water, stir for 20 min, then add 25 mmol thioacetamide and continue stirring for 30 min, then mix the obtained The solution was transferred to a 100 mL autoclave, reacted at a constant temperature of 200 °C for 24 h, and cooled to room temperature naturally. The obtained precipitate was washed with deionized water and ethanol three times in turn, and then dried under vacuum at 60 °C overnight to obtain Mn 0.3 Cd 0.7 S powder.
（2）溶剂热法制备Co0.85Se/Mn0.3Cd0.7S复合光催化剂(2) Preparation of Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst by solvothermal method
称取步骤（1）中所得的Mn0.3Cd0.7S粉末0.1 g分散于30 ml乙二醇溶液中并搅拌30min，然后在其中加入10 ml含19.53 μmol六水合氯化钴和23.05 μmol***钠的乙二醇混合溶液，继续搅拌30 min后转移至高压反应釜中于180 ℃恒温24 h，自然冷却至室温，所得沉淀用去离子水多次洗涤后干燥，得到所得沉淀依次用去离子水和乙醇各洗涤三次后于60℃真空干燥过夜，得到所述Co0.85Se/Mn0.3Cd0.7S热响应复合光催化剂。Weigh 0.1 g of Mn 0.3 Cd 0.7 S powder obtained in step (1), disperse it in 30 ml of ethylene glycol solution and stir for 30 min, then add 10 ml of 19.53 μmol cobalt chloride hexahydrate and 23.05 μmol selenous acid The mixed solution of sodium in ethylene glycol was stirred continuously for 30 min, then transferred to a high-pressure reactor at a constant temperature of 180 °C for 24 h, cooled to room temperature naturally, and the obtained precipitate was washed with deionized water several times and then dried. After each washing with water and ethanol three times, vacuum drying at 60° C. overnight to obtain the Co 0.85 Se/Mn 0.3 Cd 0.7 S thermally responsive composite photocatalyst.
实施例2Example 2
（1）溶剂热法制备富含硫空位的Mn0.3Cd0.7S纳米棒(1) Mn 0.3 Cd 0.7 S nanorods rich in sulfur vacancies prepared by solvothermal method
将14 mmol乙酸镉和6 mmol乙酸锰溶解于30 mL乙二胺和30 mL去离子水的混合溶剂中，搅拌20 min，再加入25 mmol硫代乙酰胺并继续搅拌30 min，然后将所得混合溶液转移到100 mL高压反应釜中，200 ℃恒温反应24 h，自然冷却至室温，所得沉淀依次用去离子水和乙醇各洗涤三次后于60 ℃真空干燥过夜，得到Mn0.3Cd0.7S粉末。Dissolve 14 mmol cadmium acetate and 6 mmol manganese acetate in a mixed solvent of 30 mL ethylenediamine and 30 mL deionized water, stir for 20 min, then add 25 mmol thioacetamide and continue stirring for 30 min, then mix the obtained The solution was transferred to a 100 mL autoclave, reacted at a constant temperature of 200 °C for 24 h, and cooled to room temperature naturally. The obtained precipitate was washed with deionized water and ethanol three times in turn, and then dried under vacuum at 60 °C overnight to obtain Mn 0.3 Cd 0.7 S powder.
（2）溶剂热法制备Co0.85Se/Mn0.3Cd0.7S复合光催化剂(2) Preparation of Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst by solvothermal method
称取步骤（1）中所得的Mn0.3Cd0.7S粉末0.1 g分散于30 ml乙二醇溶液中并搅拌30min，然后在其中加入10 ml含45.71 μmol六水合氯化钴和53.78 μmol***钠的乙二醇混合溶液，继续搅拌30 min后转移至高压反应釜中于180 ℃恒温24 h，自然冷却至室温，所得沉淀用去离子水多次洗涤后干燥，得到所得沉淀依次用去离子水和乙醇各洗涤三次后于60℃真空干燥过夜，得到所述Co0.85Se/Mn0.3Cd0.7S热响应复合光催化剂。Weigh 0.1 g of Mn 0.3 Cd 0.7 S powder obtained in step (1), disperse it in 30 ml of ethylene glycol solution and stir for 30 min, then add 10 ml of 45.71 μmol cobalt chloride hexahydrate and 53.78 μmol selenous acid The mixed solution of sodium in ethylene glycol was stirred continuously for 30 min, then transferred to a high-pressure reactor at a constant temperature of 180 °C for 24 h, cooled to room temperature naturally, and the obtained precipitate was washed with deionized water several times and then dried. After each washing with water and ethanol three times, vacuum drying at 60° C. overnight to obtain the Co 0.85 Se/Mn 0.3 Cd 0.7 S thermally responsive composite photocatalyst.
实施例3Example 3
（1）溶剂热法制备富含硫空位的Mn0.3Cd0.7S纳米棒(1) Mn 0.3 Cd 0.7 S nanorods rich in sulfur vacancies prepared by solvothermal method
将14 mmol乙酸镉和6 mmol乙酸锰溶解于30 mL乙二胺和30 mL去离子水的混合溶剂中，搅拌20 min，再加入25 mmol硫代乙酰胺并继续搅拌30 min，然后将所得混合溶液转移到100 mL高压反应釜中，200 ℃恒温反应24 h，自然冷却至室温，所得沉淀依次用去离子水和乙醇各洗涤三次后于60 ℃真空干燥过夜，得到Mn0.3Cd0.7S粉末。Dissolve 14 mmol cadmium acetate and 6 mmol manganese acetate in a mixed solvent of 30 mL ethylenediamine and 30 mL deionized water, stir for 20 min, then add 25 mmol thioacetamide and continue stirring for 30 min, then mix the obtained The solution was transferred to a 100 mL autoclave, reacted at a constant temperature of 200 °C for 24 h, and cooled to room temperature naturally. The obtained precipitate was washed with deionized water and ethanol three times in turn, and then dried under vacuum at 60 °C overnight to obtain Mn 0.3 Cd 0.7 S powder.
（2）溶剂热法制备Co0.85Se/Mn0.3Cd0.7S复合光催化剂(2) Preparation of Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst by solvothermal method
称取步骤（1）中所得的Mn0.3Cd0.7S粉末0.1 g分散于30 ml乙二醇溶液中并搅拌30min，然后在其中加入10 ml含65.30 μmol六水合氯化钴和76.83 μmol***钠的乙二醇混合溶液，继续搅拌30 min后转移至高压反应釜中于180 ℃恒温24 h，自然冷却至室温，所得沉淀用去离子水多次洗涤后干燥，得到所得沉淀依次用去离子水和乙醇各洗涤三次后于60℃真空干燥过夜，得到所述Co0.85Se/Mn0.3Cd0.7S热响应复合光催化剂。Weigh 0.1 g of Mn 0.3 Cd 0.7 S powder obtained in step (1), disperse it in 30 ml of ethylene glycol solution and stir for 30 min, then add 10 ml of 65.30 μmol cobalt chloride hexahydrate and 76.83 μmol selenous acid The mixed solution of sodium in ethylene glycol was stirred continuously for 30 min, then transferred to a high-pressure reactor at a constant temperature of 180 °C for 24 h, cooled to room temperature naturally, and the obtained precipitate was washed with deionized water several times and then dried. After each washing with water and ethanol three times, vacuum drying at 60° C. overnight to obtain the Co 0.85 Se/Mn 0.3 Cd 0.7 S thermally responsive composite photocatalyst.
实施例4Example 4
（1）溶剂热法制备富含硫空位的Mn0.3Cd0.7S纳米棒(1) Mn 0.3 Cd 0.7 S nanorods rich in sulfur vacancies prepared by solvothermal method
将14 mmol乙酸镉和6 mmol乙酸锰溶解于30 mL乙二胺和30 mL去离子水的混合溶剂中，搅拌20 min，再加入25 mmol硫代乙酰胺并继续搅拌30 min，然后将所得混合溶液转移到100 mL高压反应釜中，200 ℃恒温反应24 h，自然冷却至室温，所得沉淀依次用去离子水和乙醇各洗涤三次后于60 ℃真空干燥过夜，得到Mn0.3Cd0.7S粉末。Dissolve 14 mmol cadmium acetate and 6 mmol manganese acetate in a mixed solvent of 30 mL ethylenediamine and 30 mL deionized water, stir for 20 min, then add 25 mmol thioacetamide and continue stirring for 30 min, then mix the obtained The solution was transferred to a 100 mL autoclave, reacted at a constant temperature of 200 °C for 24 h, and cooled to room temperature naturally. The obtained precipitate was washed with deionized water and ethanol three times in turn, and then dried under vacuum at 60 °C overnight to obtain Mn 0.3 Cd 0.7 S powder.
（2）溶剂热法制备Co0.85Se/Mn0.3Cd0.7S复合光催化剂(2) Preparation of Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst by solvothermal method
称取步骤（1）中所得的Mn0.3Cd0.7S粉末0.1 g分散于30 ml乙二醇溶液中并搅拌30min，然后在其中加入10 ml含130.60 μmol六水合氯化钴和153.66 μmol***钠的乙二醇混合溶液，继续搅拌30 min后转移至高压反应釜中于180 ℃恒温24 h，自然冷却至室温，所得沉淀用去离子水多次洗涤后干燥，得到所得沉淀依次用去离子水和乙醇各洗涤三次后于60 ℃真空干燥过夜，得到所述Co0.85Se/Mn0.3Cd0.7S热响应复合光催化剂。Weigh 0.1 g of Mn 0.3 Cd 0.7 S powder obtained in step (1), disperse it in 30 ml of ethylene glycol solution and stir for 30 min, then add 10 ml of 130.60 μmol cobalt chloride hexahydrate and 153.66 μmol selenous acid The mixed solution of sodium in ethylene glycol was stirred continuously for 30 min, then transferred to a high-pressure reactor at a constant temperature of 180 °C for 24 h, cooled to room temperature naturally, and the obtained precipitate was washed with deionized water several times and then dried. After washing with water and ethanol three times each, vacuum drying at 60°C overnight was obtained to obtain the Co 0.85 Se/Mn 0.3 Cd 0.7 S thermally responsive composite photocatalyst.
图1（a）为Mn0.3Cd0.7S 复合光催化剂的X射线衍射图以及CdS、MnS标准XRD卡片，（b）为Mn0.3Cd0.7S、Co0.85Se及实施例1-4所得Co0.85Se/Mn0.3Cd0.7S复合光催化剂的X射线衍射图。由图1可知，所得Mn0.3Cd0.7S及Co0.85Se/Mn0.3Cd0.7S复合材料的X射线衍射峰与对应标准XRD卡片相匹配，说明了催化剂的成功制备。Figure 1 (a) is the X-ray diffraction pattern of Mn 0.3 Cd 0.7 S composite photocatalyst and CdS, MnS standard XRD card, (b) is Mn 0.3 Cd 0.7 S, Co 0.85 Se and Co 0.85 Se obtained in Examples 1-4 X-ray diffraction patterns of /Mn 0.3 Cd 0.7 S composite photocatalyst. It can be seen from Figure 1 that the X-ray diffraction peaks of the obtained Mn 0.3 Cd 0.7 S and Co 0.85 Se/Mn 0.3 Cd 0.7 S composites match the corresponding standard XRD cards, indicating the successful preparation of the catalyst.
图2是在Co0.85Se/Mn0.3Cd0.7S合成过程中，不加入Mn0.3Cd0.7S所得的纯Co0.85Se样品的X射线衍射图，其衍射峰与Co0.85Se标准卡片相匹配，证明Co0.85Se的成功制备。Figure 2 is the X-ray diffraction pattern of the pure Co 0.85 Se sample obtained without adding Mn 0.3 Cd 0.7 S during the synthesis of Co 0.85 Se/Mn 0.3 Cd 0.7 S. The diffraction peaks match the Co 0.85 Se standard card, proving that Successful preparation of Co0.85Se .
图3为7 wt% Co0.85Se/Mn0.3Cd0.7S（实施例2）复合光催化剂的（a）扫描电镜图与（b-d）透射电镜图。从图中可见，Mn0.3Cd0.7S具有光滑的纳米棒结构，其直径约为50nm，长度为150-700 nm；Co0.85Se纳米颗粒约10nm，成功负载在Mn0.3Cd0.7S纳米棒表面上。0.34和0.25nm的晶格条纹分别归因于Mn0.3Cd0.7S的（002）晶面和Co0.85Se的（101）晶面，进一步证明了Co0.85Se和Mn0.3Cd0.7S的成功制备。Fig. 3 is (a) SEM image and (bd) TEM image of 7 wt% Co 0.85 Se/Mn 0.3 Cd 0.7 S (Example 2) composite photocatalyst. It can be seen from the figure that Mn 0.3 Cd 0.7 S has a smooth nanorod structure with a diameter of about 50 nm and a length of 150-700 nm; Co 0.85 Se nanoparticles of about 10 nm were successfully loaded on the surface of Mn 0.3 Cd 0.7 S nanorods . The lattice fringes of 0.34 and 0.25 nm are attributed to the (002) crystal plane of Mn 0.3 Cd 0.7 S and the (101) crystal plane of Co 0.85 Se, respectively, further proving the successful preparation of Co 0.85 Se and Mn 0.3 Cd 0.7 S.
图4 为7 wt% Co0.85Se/Mn0.3Cd0.7S（实施例2）复合光催化剂的透射电镜选区元素分布图。由图中可见，所制得Co0.85Se纳米颗粒均匀分散附着于Mn0.3Cd0.7S纳米棒表面，并形成紧密接触。Figure 4 is a transmission electron microscope element distribution map of the composite photocatalyst with 7 wt% Co 0.85 Se/Mn 0.3 Cd 0.7 S (Example 2). It can be seen from the figure that the prepared Co 0.85 Se nanoparticles are uniformly dispersed and attached to the surface of Mn 0.3 Cd 0.7 S nanorods, and form close contact.
图5 为硫空位缺乏的Mn0.3Cd0.7S-p和富含硫空位Mn0.3Cd0.7S的电子顺磁共振对比，可以证明硫空位存在于Mn0.3Cd0.7S结构中。Mn0.3Cd0.7S-p合成方法如下：将实施例步骤（1）中硫代乙酰胺的用量替换为20 mmol，其他步骤同实施例，得到缺少硫空位的Mn0.3Cd0.7S（Svacancies-poor Mn0.3Cd0.7S），并将其命名为Mn0.3Cd0.7S-p。Figure 5 is the electron paramagnetic resonance comparison of sulfur vacancy-deficient Mn 0.3 Cd 0.7 Sp and sulfur vacancy-rich Mn 0.3 Cd 0.7 S, which can prove that sulfur vacancies exist in the Mn 0.3 Cd 0.7 S structure. The synthesis method of Mn 0.3 Cd 0.7 Sp is as follows: replace the amount of thioacetamide in the step (1) of the example with 20 mmol, and other steps are the same as in the example to obtain Mn 0.3 Cd 0.7 S lacking sulfur vacancies (Svacancies-poor Mn 0.3 Cd 0.7 S), and named it Mn 0.3 Cd 0.7 Sp.
应用例Application example
1. 将实施例1-4所得Co0.85Se/Mn0.3Cd0.7S复合光催化剂分别用于可见光诱导催化分解水产氢，其具体步骤为：称取5 mg催化剂样品，加入到50 mL含有0.25 M Na2S和0.35 MNa2SO3的水溶液中，将该溶液置于光催化产氢***中，由恒温循环冷凝水控制反应温度，待***抽真空后，开启氙灯光源进行光催化分解水产氢，产生氢气的量通过气相色谱检测。1. The Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalysts obtained in Examples 1-4 were used for visible light-induced catalytic decomposition of water to produce hydrogen. The specific steps were: weigh 5 mg of the catalyst sample and add it to 50 mL In an aqueous solution of Na 2 S and 0.35 MNa 2 SO 3 , the solution is placed in a photocatalytic hydrogen production system, and the reaction temperature is controlled by constant temperature circulating condensed water. After the system is vacuumed, the xenon lamp light source is turned on for photocatalytic decomposition of water to produce hydrogen. The amount of hydrogen gas produced was detected by gas chromatography.
图6（a）为不同催化剂样品在可见光诱导下光催化分解水产氢活性的对比图，具有硫缺陷的催化剂与硫空穴缺乏的样品相比，有更高的产氢活性；暗处理实验表明，25摄氏度下没有热催化产氢的作用，证明热的引入没有引发热催化产氢。Figure 6(a) is a comparison of the photocatalytic hydrogen production activity of different catalyst samples under the induction of visible light. The catalyst with sulfur defects has higher hydrogen production activity than the sample lacking sulfur holes; the dark treatment experiment shows that , there is no effect of thermocatalytic hydrogen production at 25 degrees Celsius, which proves that the introduction of heat does not trigger thermocatalytic hydrogen production.
图6（b）为Mn0.3Cd0.7S、Co0.85Se及实施例1-4所得Co0.85Se/Mn0.3Cd0.7S复合光催化剂在可见光诱导下光催化分解水产氢活性的对比图。由图可知，Co0.85Se/Mn0.3Cd0.7S复合光催化剂的活性较单纯Mn0.3Cd0.7S催化剂活性明显提高，最高产氢速率提升约4倍，证明本发明制备的Co0.85Se/Mn0.3Cd0.7S复合光催化剂具有高效的光催化产氢活性。Figure 6(b) is a comparison diagram of the photocatalytic hydrogen production activity of Mn 0.3 Cd 0.7 S, Co 0.85 Se and the Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst obtained in Examples 1-4 under the induction of visible light. It can be seen from the figure that the activity of the Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst is significantly higher than that of the pure Mn 0.3 Cd 0.7 S catalyst, and the highest hydrogen production rate is increased by about 4 times, which proves that the Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst has high photocatalytic hydrogen production activity.
图6（c）为不同温度下7 wt% Co0.85Se/Mn0.3Cd0.7S（实施例2）复合光催化剂的产氢速率。由图可见，提高温度可以显著提高光催化的产氢速率，说明本发明制备的复合催化剂对于温度具有明显的响应，可以通过调整温度实现对光催化产氢速率的控制。Figure 6(c) shows the hydrogen production rate of 7 wt% Co 0.85 Se/Mn 0.3 Cd 0.7 S (Example 2) composite photocatalyst at different temperatures. It can be seen from the figure that increasing the temperature can significantly increase the photocatalytic hydrogen production rate, indicating that the composite catalyst prepared by the present invention has a significant response to temperature, and the photocatalytic hydrogen production rate can be controlled by adjusting the temperature.
图6（d）为7 wt% Co0.85Se/Mn0.3Cd0.7S复合光催化剂的长时间产氢循环实验图。由图中可见，在四个光照反应循环（共16 h）后，复合催化剂的活性仅略有下降，表明该催化剂具有较好的稳定性。Figure 6(d) is the long-term hydrogen production cycle experiment diagram of 7 wt% Co 0.85 Se/Mn 0.3 Cd 0.7 S composite photocatalyst. It can be seen from the figure that after four light reaction cycles (16 h in total), the activity of the composite catalyst only slightly decreased, indicating that the catalyst has good stability.
表1Table 1
表1为本发明与近期报道的相关光催化剂的活性对比，本发明的光催化剂具有明显较高的产氢活性。Table 1 is a comparison of the activity of the present invention and related photocatalysts reported recently, and the photocatalyst of the present invention has significantly higher hydrogen production activity.
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。The above descriptions are only preferred embodiments of the present invention, and all equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope of the present invention.
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