技术领域technical field
本发明属于材料制备及光催化技术领域，具体涉及一种手性石墨相氮化碳聚合物半导体光催化剂及其制备方法和应用。The invention belongs to the technical field of material preparation and photocatalysis, and specifically relates to a chiral graphite phase carbon nitride polymer semiconductor photocatalyst, a preparation method and application thereof.
背景技术Background technique
如果一种物质与它的镜像不重合，我们就称它具有手性，这种物质称为手性物质。手性物质广泛存在于自然界及人工合成的材料和药物中。由于其在材料、催化、传感、分子识别等方面具有重要作用，人工合成手性材料具有重要的意义。目前，人们已经制备了手性的二氧化硅、金属氧化物、金原子簇、分子筛、金属-有机框架材料、有机物、聚合物等等。其中比较典型的例子是手性介孔二氧化硅材料。最近，车顺爱等人成功合成了具有手性螺旋结构的介孔二氧化硅材料(Nature, 2004, 429, 281; Adv. Mater. 2006, 18, 593; Chem. Eur. J. 2008, 14, 6413)。由于手性二氧化硅具有精致的形貌、规则的孔道、大的比表面积和良好的物理化学稳定性，它可以作为一种硬模板来传递手性和合成新的手性材料。If a substance does not coincide with its mirror image, we say it has chirality, and this substance is called a chiral substance. Chiral substances widely exist in natural and synthetic materials and drugs. Because of their important roles in materials, catalysis, sensing, molecular recognition, etc., the artificial synthesis of chiral materials is of great significance. At present, people have prepared chiral silica, metal oxides, gold clusters, molecular sieves, metal-organic framework materials, organics, polymers and so on. A typical example is chiral mesoporous silica material. Recently, Che Shunai and others successfully synthesized mesoporous silica materials with chiral helical structure (Nature, 2004, 429, 281; Adv. Mater. 2006, 18, 593; Chem. Eur. J. 2008, 14 , 6413). Due to the exquisite morphology, regular channels, large specific surface area and good physical and chemical stability of chiral silica, it can be used as a hard template to transfer chirality and synthesize new chiral materials.
近年来，石墨相氮化碳半导体聚合物材料作为一种不含金属的可见光光催化剂，受到科学家和研究者们的关注(Nat. Mater. 2009, 8, 76)。但由于它是体相物质，缺陷多，比表面积小，活性位少，影响了它的量子效率和光催化活性。于是人们希望通过控制氮化碳的结构和形貌来提高其光催化活性。我们课题组在氮化碳的结构和形貌调控上做了大量的工作，如合成SBA-15型有序介孔氮化碳、球状氮化碳等(Adv. Funct. Mater. 2013, doi:10.1002/adfm.201203287; Nature Communications 2012, 3, 1139)。但是将手性和螺旋的微纳结构引入氮化碳的研究工作尚未见报道。对氮化碳进行手性调控，是一种全新的改性修饰手段，有望改变其结构参数及光学、电学、光催化性能。手性螺旋石墨相氮化碳聚合物材料将会在手性光开关、分子识别、选择性吸附分离、传感器和催化等领域中有广泛的应用前景。此外，将手性从无机材料二氧化硅传递到聚合物氮化碳，实现了材料学上的手性复制过程，对于合成手性材料具有重要的指导作用。In recent years, graphitic carbon nitride semiconducting polymer materials have attracted the attention of scientists and researchers as a metal-free visible light photocatalyst (Nat. Mater. 2009, 8, 76). However, because it is a bulk material, it has many defects, small specific surface area, and few active sites, which affects its quantum efficiency and photocatalytic activity. Therefore, it is hoped that the photocatalytic activity of carbon nitride can be improved by controlling the structure and morphology of carbon nitride. Our research group has done a lot of work on the structure and morphology of carbon nitride, such as the synthesis of SBA-15 ordered mesoporous carbon nitride, spherical carbon nitride, etc. (Adv. Funct. Mater. 2013, doi: 10.1002/adfm.201203287; Nature Communications 2012, 3, 1139). However, the research work on introducing chiral and helical micro-nano structures into carbon nitride has not been reported yet. Chiral control of carbon nitride is a new modification method, which is expected to change its structural parameters and optical, electrical, and photocatalytic properties. Chiral helical graphite phase carbon nitride polymer materials will have broad application prospects in the fields of chiral optical switches, molecular recognition, selective adsorption separation, sensors and catalysis. In addition, the transfer of chirality from the inorganic material silica to the polymer carbon nitride has realized the chiral replication process in materials science, which has an important guiding role in the synthesis of chiral materials.
发明内容Contents of the invention
本发明的目的在于提供一种手性石墨相氮化碳聚合物半导体光催化剂及其制备方法和应用。本发明制备的手性石墨相氮化碳具有手性螺旋棒状形貌和微纳结构，与传统的体相氮化碳相比，表现出特殊的圆二色性和光学活性，具有更大的比表面积和更强的光吸收性能，在可见光下展示出良好的光催化产氢性能。The object of the present invention is to provide a chiral graphite phase carbon nitride polymer semiconductor photocatalyst and its preparation method and application. The chiral graphitic carbon nitride prepared by the present invention has a chiral helical rod-like morphology and a micro-nano structure. Compared with the traditional bulk carbon nitride, it exhibits special circular dichroism and optical activity, and has a greater The specific surface area and stronger light absorption performance show good photocatalytic hydrogen production performance under visible light.
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:
一种手性石墨相氮化碳聚合物半导体光催化剂为具有手性螺旋棒状的形貌和微纳结构的半导体聚合物，化学式为C3N4，且为类石墨相，比表面积为50-100 m2/g，吸收可见光，光吸收带边在450-600 nm，并具有光催化分解水制取氢气的性能，可作为一种光催化剂，同时具有特殊的圆二色性和光学活性。A chiral graphitic phase carbon nitride polymer semiconductor photocatalyst is a semiconductor polymer with a chiral helical rod shape and a micro-nano structure, the chemical formula is C3 N4 , and it is a graphite-like phase with a specific surface area of 50- 100 m2 /g, absorbs visible light, the light absorption band edge is at 450-600 nm, and has the performance of photocatalytic water splitting to produce hydrogen, can be used as a photocatalyst, and has special circular dichroism and optical activity.
制备如上所述的手性石墨相氮化碳聚合物半导体光催化剂的方法是以氰胺为前驱物和手性介孔二氧化硅为硬模板，进行热聚合，除去模板，得到手性石墨相氮化碳聚合物。包括以下步骤：The method for preparing the above-mentioned chiral graphite phase carbon nitride polymer semiconductor photocatalyst is to use cyanamide as a precursor and chiral mesoporous silica as a hard template, carry out thermal polymerization, remove the template, and obtain a chiral graphite phase carbon nitride polymer. Include the following steps:
（1）合成手性介孔二氧化硅(Adv. Mater. 2006, 18, 593; Chem. Eur. J. 2008, 14, 6413)。将L-丙氨酸(或D-丙氨酸)、氢氧化钠溶液、30%的丙酮溶液混合，在0℃下分别滴加十四烷基酰氯和NaOH溶液，维持pH 12，反应结束后，加入HCl溶液调节pH 1~pH5，搅拌，洗涤，烘干，得到C14-L-AlaA(或C14-D-AlaA)。取0.3g~1g C14-L-AlaA(或C14-D-AlaA)加1g~15g水和1g~10g NaOH(0.1mol/L)溶液，室温搅拌溶解，再加入1g~10gHCl (0.01mol/L)溶液，22℃下搅拌1h，加入0.23g~5.46g 3-氨丙基三乙氧基硅烷和1.46g~6.23g正硅酸乙酯的混合物，搅拌0.5h，静置1~3天，离心，水洗，烘干。(1) Synthesis of chiral mesoporous silica (Adv. Mater. 2006, 18, 593; Chem. Eur. J. 2008, 14, 6413). Mix L-alanine (or D-alanine), sodium hydroxide solution, and 30% acetone solution, add tetradecyl chloride and NaOH solution dropwise at 0°C, and maintain the pH at 12. After the reaction , adding HCl solution to adjust pH 1~pH5, stirring, washing and drying to obtain C14 -L-AlaA (or C14 -D-AlaA). Take 0.3g~1g C14 -L-AlaA (or C14 -D-AlaA), add 1g~15g water and 1g~10g NaOH (0.1mol/L) solution, stir at room temperature to dissolve, then add 1g~10gHCl (0.01mol /L) solution, stirred at 22°C for 1h, added a mixture of 0.23g~5.46g 3-aminopropyltriethoxysilane and 1.46g~6.23g ethyl orthosilicate, stirred for 0.5h, and stood for 1~3 day, centrifuged, washed and dried.
（2）将手性介孔二氧化硅于450℃~600℃焙烧1~10h，研磨，加入1 mol/L HCl，80℃搅拌，离心，烘干，研磨。(2) Calcinate chiral mesoporous silica at 450°C~600°C for 1~10h, grind, add 1 mol/L HCl, stir at 80°C, centrifuge, dry, and grind.
（3）在圆底烧瓶中，加入质量比为8:1~6:1的氰胺和步骤（2）的手性介孔二氧化硅，抽真空、加热和超声，60℃~90℃搅拌；水洗，取沉淀，烘干，研磨；将固体粉末于N2气氛中450℃~600℃焙烧1h ~10h；焙烧后的固体中加入4 mol/L氟化氢铵溶液，洗涤，烘干，即得手性石墨相氮化碳聚合物。 (3) In a round bottom flask, add cyanamide with a mass ratio of 8:1~6:1 and chiral mesoporous silica from step (2), vacuumize, heat and sonicate, and stir at 60°C~90°C ; wash with water, take the precipitate, dry and grind; roast the solid powder at 450°C~600°C for 1h~10h inN2 atmosphere; add 4 mol/L ammonium bifluoride solution to the roasted solid, wash, dry, and get it graphite phase carbon nitride polymer.
所述的手性石墨相氮化碳聚合物应用于可见光下光催化分解水制取氢气，且产氢速率是体相石墨相氮化碳的7倍。The chiral graphitic carbon nitride polymer is applied to the photocatalytic decomposition of water under visible light to produce hydrogen, and the hydrogen production rate is 7 times that of bulk graphitic carbon nitride.
本发明的显著优点在于：Significant advantage of the present invention is:
（1）本发明首次合成了具有手性形貌和纳米结构的石墨相氮化碳聚合物，并表现出有别于传统氮化碳材料的特殊的圆二色性和光学活性。(1) The present invention synthesized a graphitic carbon nitride polymer with chiral morphology and nanostructure for the first time, and exhibited special circular dichroism and optical activity different from traditional carbon nitride materials.
（2）本发明合成的手性石墨相氮化碳聚合物不含金属，具有廉价、环保、稳定、质轻等优点。(2) The chiral graphitic phase carbon nitride polymer synthesized by the present invention does not contain metal, and has the advantages of low cost, environmental protection, stability, and light weight.
（3）本发明的制备方法能够有效地将二氧化硅的手性复制到氮化碳中，并适用于合成其他形貌和微纳结构的氮化碳，具有良好的可调控性和广谱性。(3) The preparation method of the present invention can effectively copy the chirality of silica to carbon nitride, and is suitable for the synthesis of carbon nitride with other morphology and micro-nano structure, and has good controllability and broad spectrum sex.
（4）本发明首次将手性螺旋聚合物材料应用于光催化制取氢气，发现手性调控有利于提高氮化碳的光催化产氢性能，而且手性氮化碳具有良好的活性稳定性。(4) For the first time in the present invention, chiral helical polymer materials are applied to photocatalytic production of hydrogen, and it is found that chiral regulation is beneficial to improve the photocatalytic hydrogen production performance of carbon nitride, and chiral carbon nitride has good activity stability .
附图说明Description of drawings
图1为实施例1所得的手性石墨相氮化碳的X射线粉末衍射(XRD)图。Fig. 1 is the X-ray powder diffraction (XRD) pattern of the chiral graphite phase carbon nitride obtained in Example 1.
图2为实施例1所得的手性石墨相氮化碳的固体13C核磁共振(13C NMR)图。Fig. 2 is a solid13 C nuclear magnetic resonance (13 C NMR) diagram of the chiral graphite phase carbon nitride obtained in Example 1.
图3为实施例1所得的手性石墨相氮化碳的扫描电镜(SEM)图。Fig. 3 is the scanning electron microscope (SEM) figure of the chiral graphite phase carbon nitride obtained in Example 1.
图4为实施例1所得的手性石墨相氮化碳的透射电镜(TEM)图。Fig. 4 is the transmission electron microscope (TEM) figure of the chiral graphite phase carbon nitride obtained in Example 1.
图5为实施例1所得的手性石墨相氮化碳的固体漫反射圆二色性光谱(DRCD)和紫外可见吸收光谱图, 并与传统的体相氮化碳进行对比。Figure 5 shows the solid diffuse reflectance circular dichroism spectrum (DRCD) and UV-Vis absorption spectrum of the chiral graphitic carbon nitride obtained in Example 1, and compares it with the traditional bulk carbon nitride.
图6为实施例1所得的手性石墨相氮化碳与传统的体相氮化碳进行光催化分解水制取氢气的性能比较图。Fig. 6 is a comparison diagram of the performance of the chiral graphitic carbon nitride obtained in Example 1 and the traditional bulk carbon nitride for photocatalytic water splitting to produce hydrogen.
在上述图中，a表示所制备的手性石墨相氮化碳；b表示传统的体相氮化碳。In the above figure, a represents the prepared chiral graphitic carbon nitride; b represents the traditional bulk carbon nitride.
具体实施方式Detailed ways
以下是本发明的几个实施例，进一步说明本发明，但是本发明不仅限于此。Below are several embodiments of the present invention to further illustrate the present invention, but the present invention is not limited thereto.
实施例1Example 1
将L-丙氨酸、氢氧化钠溶液、30%的丙酮溶液混合，在0℃下分别滴加十四烷基酰氯和NaOH溶液，维持pH 12，反应结束后，加入HCl溶液调节pH 1，搅拌，洗涤，烘干，得到C14-L-AlaA。取0.3g C14-L-AlaA加10g水和10g NaOH(0.1mol/L)溶液，室温搅拌溶解，再加入10g HCl (0.01mol/L)溶液，22℃下搅拌1h，加入0.23g 3-氨丙基三乙氧基硅烷和1.46g正硅酸乙酯的混合物，搅拌0.5h，静置1天，离心，水洗，烘干。将手性介孔二氧化硅于550℃焙烧6h，研磨，加入1 mol/L HCl，80℃搅拌，离心，烘干，研磨。在圆底烧瓶中，加入氰胺和处理过的手性介孔二氧化硅(质量比为6:1)，抽真空、加热和超声，60℃搅拌。水洗，取沉淀，烘干，研磨。将固体粉末于N2气氛中550℃焙烧4h。焙烧后的固体加入4 mol/L氟化氢铵溶液，洗涤，烘干，就合成了手性氮化碳。Mix L-alanine, sodium hydroxide solution, and 30% acetone solution, add tetradecyl chloride and NaOH solution dropwise at 0°C, and maintain the pH at 12. After the reaction, add HCl solution to adjust the pH to 1. Stirring, washing and drying to obtain C14 -L-AlaA. Take 0.3g C14 -L-AlaA, add 10g water and 10g NaOH (0.1mol/L) solution, stir at room temperature to dissolve, then add 10g HCl (0.01mol/L) solution, stir at 22°C for 1h, add 0.23g 3- The mixture of aminopropyltriethoxysilane and 1.46g ethyl orthosilicate was stirred for 0.5h, allowed to stand for 1 day, centrifuged, washed with water, and dried. Chiral mesoporous silica was calcined at 550°C for 6h, ground, added 1 mol/L HCl, stirred at 80°C, centrifuged, dried, and ground. In a round bottom flask, add cyanamide and treated chiral mesoporous silica (mass ratio: 6:1), vacuumize, heat and sonicate, and stir at 60°C. Wash with water, take the precipitate, dry and grind. The solid powder was calcined at 550 °C for 4 h in N2 atmosphere. Add 4 mol/L ammonium bifluoride solution to the calcined solid, wash it, and dry it to synthesize chiral carbon nitride.
实施例2Example 2
将L-丙氨酸、氢氧化钠溶液、30%的丙酮溶液混合，在0℃下分别滴加十四烷基酰氯和NaOH溶液，维持pH 12，反应结束后，加入HCl溶液调节pH 1，搅拌，洗涤，烘干，得到C14-L-AlaA。取0.3g C14-L-AlaA加10g水和10g NaOH(0.1mol/L)溶液，室温搅拌溶解，再加入10g HCl (0.01mol/L)溶液，22℃下搅拌1h，加入0.23g 3-氨丙基三乙氧基硅烷和1.46g正硅酸乙酯的混合物，搅拌0.5h，静置1天，离心，水洗，烘干。将手性介孔二氧化硅于550℃焙烧6h，研磨，加入1 mol/L HCl，80℃搅拌，离心，烘干，研磨。在圆底烧瓶中，加入氰胺和处理过的手性介孔二氧化硅(质量比为7:1)，抽真空、加热和超声，60℃搅拌。水洗，取沉淀，烘干，研磨。将固体粉末于N2气氛中550℃焙烧4h。焙烧后的固体加入4 mol/L氟化氢铵溶液，洗涤，烘干，就合成了手性氮化碳。Mix L-alanine, sodium hydroxide solution, and 30% acetone solution, add tetradecyl chloride and NaOH solution dropwise at 0°C, and maintain the pH at 12. After the reaction, add HCl solution to adjust the pH to 1. Stirring, washing and drying to obtain C14 -L-AlaA. Take 0.3g C14 -L-AlaA, add 10g water and 10g NaOH (0.1mol/L) solution, stir at room temperature to dissolve, then add 10g HCl (0.01mol/L) solution, stir at 22°C for 1h, add 0.23g 3- The mixture of aminopropyltriethoxysilane and 1.46g ethyl orthosilicate was stirred for 0.5h, allowed to stand for 1 day, centrifuged, washed with water, and dried. Chiral mesoporous silica was calcined at 550°C for 6h, ground, added 1 mol/L HCl, stirred at 80°C, centrifuged, dried, and ground. In a round-bottomed flask, add cyanamide and treated chiral mesoporous silica (mass ratio: 7:1), vacuumize, heat and sonicate, and stir at 60°C. Wash with water, take the precipitate, dry and grind. The solid powder was calcined at 550 °C for 4 h in N2 atmosphere. Add 4 mol/L ammonium bifluoride solution to the calcined solid, wash it, and dry it to synthesize chiral carbon nitride.
实施例3 Example 3
将L-丙氨酸、氢氧化钠溶液、30%的丙酮溶液混合，在0℃下分别滴加十四烷基酰氯和NaOH溶液，维持pH 12，反应结束后，加入HCl溶液调节pH 1，搅拌，洗涤，烘干，得到C14-L-AlaA。取0.3g C14-L-AlaA加10g水和10g NaOH(0.1mol/L)溶液，室温搅拌溶解，再加入10g HCl (0.01mol/L)溶液，22℃下搅拌1h，加入0.23g 3-氨丙基三乙氧基硅烷和1.46g正硅酸乙酯的混合物，搅拌0.5h，静置1天，离心，水洗，烘干。将手性介孔二氧化硅于550℃焙烧6h，研磨，加入1 mol/L HCl，80℃搅拌，离心，烘干，研磨。在圆底烧瓶中，加入氰胺和处理过的手性介孔二氧化硅(质量比为8:1)，抽真空、加热和超声，60℃搅拌。水洗，取沉淀，烘干，研磨。将固体粉末于N2气氛中550℃焙烧4h。焙烧后的固体加入4 mol/L氟化氢铵溶液，洗涤，烘干，就合成了手性氮化碳。Mix L-alanine, sodium hydroxide solution, and 30% acetone solution, add tetradecyl chloride and NaOH solution dropwise at 0°C, and maintain the pH at 12. After the reaction, add HCl solution to adjust the pH to 1. Stirring, washing and drying to obtain C14 -L-AlaA. Take 0.3g C14 -L-AlaA, add 10g water and 10g NaOH (0.1mol/L) solution, stir at room temperature to dissolve, then add 10g HCl (0.01mol/L) solution, stir at 22°C for 1h, add 0.23g 3- The mixture of aminopropyltriethoxysilane and 1.46g ethyl orthosilicate was stirred for 0.5h, allowed to stand for 1 day, centrifuged, washed with water, and dried. Chiral mesoporous silica was calcined at 550°C for 6h, ground, added 1 mol/L HCl, stirred at 80°C, centrifuged, dried, and ground. In a round bottom flask, add cyanamide and treated chiral mesoporous silica (mass ratio: 8:1), vacuumize, heat and sonicate, and stir at 60°C. Wash with water, take the precipitate, dry and grind. The solid powder was calcined at 550 °C for 4 h in N2 atmosphere. Add 4 mol/L ammonium bifluoride solution to the calcined solid, wash it, and dry it to synthesize chiral carbon nitride.
实施例4Example 4
将D-丙氨酸、氢氧化钠溶液、30%的丙酮溶液混合，在0℃下分别滴加十四烷基酰氯和NaOH溶液，维持pH 12，反应结束后，加入HCl溶液调节pH 1，搅拌，洗涤，烘干，得到C14-D-AlaA。取0.3g C14-D-AlaA加10g水和10g NaOH(0.1mol/L)溶液，室温搅拌溶解，再加入10g HCl (0.01mol/L)溶液，22℃下搅拌1h，加入0.23g 3-氨丙基三乙氧基硅烷和1.46g正硅酸乙酯的混合物，搅拌0.5h，静置1天，离心，水洗，烘干。将手性介孔二氧化硅于550℃焙烧6h，研磨，加入1 mol/L HCl，80℃搅拌，离心，烘干，研磨。在圆底烧瓶中，加入氰胺和处理过的手性介孔二氧化硅(质量比为6:1)，抽真空、加热和超声，60℃搅拌。水洗，取沉淀，烘干，研磨。将固体粉末于N2气氛中550℃焙烧4h。焙烧后的固体加入4 mol/L氟化氢铵溶液，洗涤，烘干，就合成了手性氮化碳。Mix D-alanine, sodium hydroxide solution, and 30% acetone solution, add tetradecyl chloride and NaOH solution dropwise at 0°C, and maintain the pH at 12. After the reaction, add HCl solution to adjust the pH to 1. Stir, wash, and dry to obtain C14 -D-AlaA. Take 0.3g C14 -D-AlaA, add 10g water and 10g NaOH (0.1mol/L) solution, stir at room temperature to dissolve, then add 10g HCl (0.01mol/L) solution, stir at 22°C for 1h, add 0.23g 3- The mixture of aminopropyltriethoxysilane and 1.46g ethyl orthosilicate was stirred for 0.5h, allowed to stand for 1 day, centrifuged, washed with water, and dried. Chiral mesoporous silica was calcined at 550°C for 6h, ground, added 1 mol/L HCl, stirred at 80°C, centrifuged, dried, and ground. In a round bottom flask, add cyanamide and treated chiral mesoporous silica (mass ratio: 6:1), vacuumize, heat and sonicate, and stir at 60°C. Wash with water, take the precipitate, dry and grind. The solid powder was calcined at 550 °C for 4 h in N2 atmosphere. Add 4 mol/L ammonium bifluoride solution to the calcined solid, wash it, and dry it to synthesize chiral carbon nitride.
实施例5Example 5
将D-丙氨酸、氢氧化钠溶液、30%的丙酮溶液混合，在0℃下分别滴加十四烷基酰氯和NaOH溶液，维持pH 12，反应结束后，加入HCl溶液调节pH 1，搅拌，洗涤，烘干，得到C14-D-AlaA。取0.3g C14-D-AlaA加10g水和10g NaOH(0.1mol/L)溶液，室温搅拌溶解，再加入10g HCl (0.01mol/L)溶液，22℃下搅拌1h，加入0.23g 3-氨丙基三乙氧基硅烷和1.46g正硅酸乙酯的混合物，搅拌0.5h，静置1天，离心，水洗，烘干。将手性介孔二氧化硅于550℃焙烧6h，研磨，加入1 mol/L HCl，80℃搅拌，离心，烘干，研磨。在圆底烧瓶中，加入氰胺和处理过的手性介孔二氧化硅(质量比为7:1)，抽真空、加热和超声，60℃搅拌。水洗，取沉淀，烘干，研磨。将固体粉末于N2气氛中550℃焙烧4h。焙烧后的固体加入4 mol/L氟化氢铵溶液，洗涤，烘干，就合成了手性氮化碳。Mix D-alanine, sodium hydroxide solution, and 30% acetone solution, add tetradecyl chloride and NaOH solution dropwise at 0°C, and maintain the pH at 12. After the reaction, add HCl solution to adjust the pH to 1. Stir, wash, and dry to obtain C14 -D-AlaA. Take 0.3g C14 -D-AlaA, add 10g water and 10g NaOH (0.1mol/L) solution, stir at room temperature to dissolve, then add 10g HCl (0.01mol/L) solution, stir at 22°C for 1h, add 0.23g 3- The mixture of aminopropyltriethoxysilane and 1.46g ethyl orthosilicate was stirred for 0.5h, allowed to stand for 1 day, centrifuged, washed with water, and dried. Chiral mesoporous silica was calcined at 550°C for 6h, ground, added 1 mol/L HCl, stirred at 80°C, centrifuged, dried, and ground. In a round-bottomed flask, add cyanamide and treated chiral mesoporous silica (mass ratio: 7:1), vacuumize, heat and sonicate, and stir at 60°C. Wash with water, take the precipitate, dry and grind. The solid powder was calcined at 550 °C for 4 h in N2 atmosphere. Add 4 mol/L ammonium bifluoride solution to the calcined solid, wash it, and dry it to synthesize chiral carbon nitride.
实施例6Example 6
将D-丙氨酸、氢氧化钠溶液、30%的丙酮溶液混合，在0℃下分别滴加十四烷基酰氯和NaOH溶液，维持pH 12，反应结束后，加入HCl溶液调节pH 1，搅拌，洗涤，烘干，得到C14-D-AlaA。取0.3g C14-D-AlaA加10g水和10g NaOH(0.1mol/L)溶液，室温搅拌溶解，再加入10g HCl (0.01mol/L)溶液，22℃下搅拌1h，加入0.23g 3-氨丙基三乙氧基硅烷和1.46g正硅酸乙酯的混合物，搅拌0.5h，静置1天，离心，水洗，烘干。将手性介孔二氧化硅于550℃焙烧6h，研磨，加入1 mol/L HCl，80℃搅拌，离心，烘干，研磨。在圆底烧瓶中，加入氰胺和处理过的手性介孔二氧化硅(质量比为8:1)，抽真空、加热和超声，60℃搅拌。水洗，取沉淀，烘干，研磨。将固体粉末于N2气氛中550℃焙烧4h。焙烧后的固体加入4 mol/L氟化氢铵溶液，洗涤，烘干，就合成了手性氮化碳。Mix D-alanine, sodium hydroxide solution, and 30% acetone solution, add tetradecyl chloride and NaOH solution dropwise at 0°C, and maintain the pH at 12. After the reaction, add HCl solution to adjust the pH to 1. Stir, wash, and dry to obtain C14 -D-AlaA. Take 0.3g C14 -D-AlaA, add 10g water and 10g NaOH (0.1mol/L) solution, stir at room temperature to dissolve, then add 10g HCl (0.01mol/L) solution, stir at 22°C for 1h, add 0.23g 3- The mixture of aminopropyltriethoxysilane and 1.46g ethyl orthosilicate was stirred for 0.5h, allowed to stand for 1 day, centrifuged, washed with water, and dried. Chiral mesoporous silica was calcined at 550°C for 6h, ground, added 1 mol/L HCl, stirred at 80°C, centrifuged, dried, and ground. In a round bottom flask, add cyanamide and treated chiral mesoporous silica (mass ratio: 8:1), vacuumize, heat and sonicate, and stir at 60°C. Wash with water, take the precipitate, dry and grind. The solid powder was calcined at 550 °C for 4 h in N2 atmosphere. Add 4 mol/L ammonium bifluoride solution to the calcined solid, wash it, and dry it to synthesize chiral carbon nitride.
性能测试Performance Testing
图1为实施例1所得的手性石墨相氮化碳的X射线粉末衍射(XRD)图。从图中可以发现手性氮化碳在13.1 o和27.6 o处出现两个明显的归属于石墨相氮化碳(100)和(002)晶面的XRD衍射峰，证实制备的产物为石墨相氮化碳。Fig. 1 is the X-ray powder diffraction (XRD) pattern of the chiral graphite phase carbon nitride obtained in Example 1. From the figure, it can be found that chiral carbon nitride has two obvious XRD diffraction peaks at 13.1o and 27.6o , which belong to the (100) and (002) crystal planes of graphite phase carbon nitride, confirming that the prepared product is graphite phase carbon nitride.
图2为实施例1所得的手性石墨相氮化碳的固体13C核磁共振(13C NMR)图。从图中可以发现手性氮化碳在155.6 ppm 和164.3 ppm处出现两个明显的核磁共振峰，分别归属于石墨相氮化碳七嗪环结构单元中的C(i)和C(e)的化学位移，证实制备的产物为石墨相氮化碳。Fig. 2 is a solid13 C nuclear magnetic resonance (13 C NMR) diagram of the chiral graphite phase carbon nitride obtained in Example 1. From the figure, it can be found that chiral carbon nitride has two obvious NMR peaks at 155.6 ppm and 164.3 ppm, which belong to C(i) and C(e) in the graphitic carbon heptazine ring structure unit respectively. The chemical shifts confirmed that the prepared product was graphitic carbon nitride.
图3为实施例1所得的手性石墨相氮化碳的扫描电镜(SEM)图。从图中可以发现手性石墨相氮化碳具有均匀的手性螺旋棒状形貌，棒的直径约100~200 nm，长度在0.5~2μm，并同时具有左旋和右旋的棒。Fig. 3 is the scanning electron microscope (SEM) figure of the chiral graphite phase carbon nitride obtained in Example 1. It can be seen from the figure that the chiral graphitic carbon nitride has a uniform chiral helical rod-like morphology, the diameter of the rod is about 100-200 nm, the length is 0.5-2 μm, and there are both left-handed and right-handed rods.
图4为实施例1所得的手性石墨相氮化碳的透射电镜(TEM)图。从图中可以发现手性石墨相氮化碳具有均匀的手性螺旋棒状形貌。Fig. 4 is the transmission electron microscope (TEM) figure of the chiral graphite phase carbon nitride obtained in Example 1. It can be seen from the figure that the chiral graphitic carbon nitride has a uniform chiral helical rod-like morphology.
图5为实施例1所得的手性石墨相氮化碳的固体漫反射圆二色性光谱(DRCD)和紫外可见吸收光谱图。从图中可以发现手性石墨相氮化碳的光吸收范围在200-450 nm, 与体相氮化碳相比，吸收带边发生红移且光吸收强度增加。手性石墨相氮化碳在420nm处有正的科顿效应，表现出圆二色性，进一步证明了其特殊的光学活性和手性。而体相氮化碳在圆二色性光谱中几乎没有信号。Fig. 5 is the solid diffuse reflection circular dichroism spectrum (DRCD) and the ultraviolet-visible absorption spectrum diagram of the chiral graphite phase carbon nitride obtained in Example 1. It can be seen from the figure that the light absorption range of chiral graphitic carbon nitride is in the range of 200-450 nm. Compared with bulk carbon nitride, the absorption band edge is red-shifted and the light absorption intensity increases. Chiral graphitic carbon nitride has a positive Codon effect at 420nm and exhibits circular dichroism, which further proves its special optical activity and chirality. However, bulk carbon nitride has almost no signal in the circular dichroism spectrum.
图6为实施例1所得的手性石墨相氮化碳与体相氮化碳光催化分解水制取氢气的性能比较图。从图中可以发现手性石墨相氮化碳在可见光(λ> 420 nm)下的产氢速率达到74 μmol h-1，与体相氮化碳(10 μmol h-1)相比提高了7倍。同时手性石墨相氮化碳保持了较高的活性稳定性，在长达16 h的反应中未见明显失活。Fig. 6 is a performance comparison diagram of the chiral graphite phase carbon nitride obtained in Example 1 and the bulk phase carbon nitride photocatalytically decomposing water to produce hydrogen. It can be seen from the figure that the hydrogen production rate of chiral graphitic carbon nitride under visible light (λ> 420 nm) reaches 74 μmol h-1 , which is 7 times higher than that of bulk carbon nitride (10 μmol h-1 ). times. At the same time, the chiral graphitic carbon nitride maintained a high activity stability, and no obvious deactivation was observed in the reaction up to 16 h.
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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