CN104437589B - A kind of silver/graphene oxide/carbonitride composite photocatalyst material and preparation method thereof - Google Patents

A kind of silver/graphene oxide/carbonitride composite photocatalyst material and preparation method thereof Download PDF

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CN104437589B
CN104437589B CN201410621933.2A CN201410621933A CN104437589B CN 104437589 B CN104437589 B CN 104437589B CN 201410621933 A CN201410621933 A CN 201410621933A CN 104437589 B CN104437589 B CN 104437589B
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graphene oxide
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CN104437589A (en
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秦洁玲
杨小飞
李�荣
唐华
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Jiangsu University
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Abstract

本发明涉及一种银/氧化石墨烯/氮化碳复合光催化材料及其制备方法。将氧化石墨烯分散于去离子水中超声得到氧化石墨烯分散液；将硝酸银溶液在磁力搅拌下滴加到上述氧化石墨烯分散液中，得到混合溶液A；在磁力搅拌的条件下将二氰二胺分散液逐滴缓慢加入混合前驱体溶液A中，滴加完毕后得到的混合溶液继续搅拌后静置过夜，所得产物抽滤后用无水乙醇和去离子水反复洗涤多次后真空干燥；将得到的产物装入合适的坩埚盖好后放到高温气氛炉中，在氮气保护的条件下烧结得到粉末状样品；其在可见光激发下作用下对有机染料罗丹明B表现出较强的降解活性；该复合光催化材料在异质结光催化材料的制备技术领域和污水处理领域具有广泛地实用价值和应用前景。

The invention relates to a silver/graphene oxide/carbon nitride composite photocatalytic material and a preparation method thereof. Disperse graphene oxide in deionized water and ultrasonically obtain a graphene oxide dispersion; add the silver nitrate solution dropwise to the above graphene oxide dispersion under magnetic stirring to obtain a mixed solution A; The diamine dispersion liquid is slowly added to the mixed precursor solution A drop by drop, and the mixed solution obtained after the dropwise addition is continued to be stirred and left to stand overnight, and the obtained product is suction-filtered, washed repeatedly with absolute ethanol and deionized water for several times, and then vacuum-dried ; put the obtained product into a suitable crucible and cover it in a high-temperature atmosphere furnace, and sinter it under the condition of nitrogen protection to obtain a powder sample; it exhibits strong activity to the organic dye rhodamine B under the action of visible light excitation Degradation activity; the composite photocatalytic material has extensive practical value and application prospect in the technical field of preparation of heterojunction photocatalytic materials and the field of sewage treatment.

Description

一种银/氧化石墨烯/氮化碳复合光催化材料及其制备方法A kind of silver/graphene oxide/carbon nitride composite photocatalytic material and preparation method thereof

技术领域technical field

本发明涉及一种银/氧化石墨烯/氮化碳复合光催化材料及其制备方法，特别是指一种用水溶液中离子交换法制备银/氧化石墨烯/氮化碳复合光催化材料的方法，属于复合材料、光催化技术和水污染治理领域。The invention relates to a silver/graphene oxide/carbon nitride composite photocatalytic material and a preparation method thereof, in particular to a method for preparing silver/graphene oxide/carbon nitride composite photocatalytic material by ion exchange in aqueous solution , which belongs to the field of composite materials, photocatalytic technology and water pollution control.

背景技术Background technique

近年来石墨相氮化碳g-C3N4由于其优异的化学稳定性、特殊的电子能带结构、不含金属组分、对可见光响应等特点引起研究人员的极大兴趣；但由于聚合物的本征特性，氮化碳作为光催化材料存在比表面积小、产生光生载流子的结合能高、光生电子-空穴复合严重、量子效率低、禁带宽度较大等不足，严重制约其在能源和环境领域的大规模推广应用。In recent years, graphitic carbon nitride gC 3 N 4 has attracted great interest of researchers due to its excellent chemical stability, special electronic band structure, no metal components, and response to visible light; Intrinsic characteristics, as a photocatalytic material, carbon nitride has shortcomings such as small specific surface area, high binding energy for photogenerated carriers, severe photogenerated electron-hole recombination, low quantum efficiency, and large forbidden band width, which seriously restrict its application in Large-scale promotion and application in the field of energy and environment.

石墨烯是一种由碳原子构成的单层片状结构的新材料，单层碳原厚度不仅使其不仅适合功能纳米材料的生长，而且具有良好的电子传导性，已经被公认为是催化剂的理想载体材料；实验以氧化石墨烯作为前体材料，在反应的过程中控制磷酸银成核和生长，使最终生成的氧化锌/磷酸银/石墨烯复合光催化材料具有均一的形貌和较小的尺寸；石墨烯的高透光率、高的比表面积使所制得的复合光催化材料在溶液中具有很好的分散性和吸附性；其高的电导性进一步加速光生电子对的分离，延长活性组分的寿命，增强了复合光催化材料的催化活性；目前，以二氰二胺或三聚氰胺、氧化石墨烯、硝酸银为原料，运用水溶液中离子交换法合成具有异质结结构的银/氧化石墨烯/氮化碳复合光催化材料并用于光催化降解有机污染物和净化水资源未见报道。Graphene is a new material with a single-layer sheet structure composed of carbon atoms. The thickness of a single-layer carbon source not only makes it suitable for the growth of functional nanomaterials, but also has good electronic conductivity. It has been recognized as a catalyst. Ideal carrier material; graphene oxide is used as the precursor material in the experiment, and the nucleation and growth of silver phosphate are controlled during the reaction, so that the final zinc oxide/silver phosphate/graphene composite photocatalytic material has a uniform morphology and relatively Small size; graphene's high light transmittance and high specific surface area make the prepared composite photocatalytic material have good dispersibility and adsorption in solution; its high electrical conductivity further accelerates the separation of photogenerated electron pairs , prolong the life of the active components, and enhance the catalytic activity of the composite photocatalytic material; currently, dicyandiamine or melamine, graphene oxide, and silver nitrate are used as raw materials to synthesize photocatalysts with heterojunction structures by ion exchange in aqueous solution. Silver/graphene oxide/carbon nitride composite photocatalytic materials and their use in photocatalytic degradation of organic pollutants and purification of water resources have not been reported.

发明内容Contents of the invention

本发明的目的在于提供一种流程简单、环境友好、成本低廉制备可控形貌、均一分布的异质结结构的银/氧化石墨烯/氮化碳复合光催化材料的方法，制备的复合光催化材料具有广泛的可见光响应特性和卓越的光催化降解污染物性能。The purpose of the present invention is to provide a method for preparing a silver/graphene oxide/carbon nitride composite photocatalytic material with a controllable morphology and a uniformly distributed heterojunction structure with a simple process, environmentally friendly, and low cost. Catalytic materials have a wide range of visible light response characteristics and excellent photocatalytic degradation of pollutants.

实现本发明所采用的技术方案为：以氧化石墨烯为前体材料，通过离子交换法制备氧化银/氧化石墨烯/氮化碳复合光催化材料，其具体制备方法步骤如下：The technical solution adopted to realize the present invention is: use graphene oxide as a precursor material, and prepare silver oxide/graphene oxide/carbon nitride composite photocatalytic material by ion exchange method, and its specific preparation method steps are as follows:

(1) 将氧化石墨烯溶于去离子水中超声分散，得到氧化石墨烯分散液。(1) Graphene oxide is dissolved in deionized water and ultrasonically dispersed to obtain a graphene oxide dispersion.

(2) 将硝酸银溶于去离子水中搅拌，得到硝酸银溶液；将硝酸银溶液在磁力搅拌条件下滴加到上述氧化石墨烯分散液中，滴加完毕后溶液在室温下继续搅拌，得到混合前驱体溶液A。(2) Dissolve silver nitrate in deionized water and stir to obtain a silver nitrate solution; the silver nitrate solution is added dropwise to the above-mentioned graphene oxide dispersion under magnetic stirring conditions, and after the dropwise addition, the solution continues to stir at room temperature to obtain Mix precursor solution A.

(3) 将二氰二胺或三聚氰胺溶于去离子水中超声分散，得到二氰二胺或三聚氰胺分散液。(3) Dissolving dicyandiamine or melamine in deionized water and ultrasonically dispersing to obtain a dicyandiamine or melamine dispersion.

(4) 在磁力搅拌的条件下将步骤(3)制备的二氰二胺或三聚氰胺分散液逐滴缓慢加入步骤(2)制备的混合前驱体溶液A中，滴加完毕后得到的混合溶液继续搅拌后静置过夜，所得产物抽滤后用无水乙醇和去离子水反复洗涤多次后真空干燥。(4) Slowly add the dicyandiamide or melamine dispersion prepared in step (3) dropwise to the mixed precursor solution A prepared in step (2) under the condition of magnetic stirring, and the mixed solution obtained after the dropwise addition is continued After stirring, let it stand overnight, and the obtained product was filtered with suction, washed repeatedly with absolute ethanol and deionized water for several times, and then dried in vacuum.

(5) 将得到的产物装入合适的坩埚盖好后放到高温气氛炉中，在氮气保护的条件下烧结一段时间，得到粉末状样品。(5) Put the obtained product into a suitable crucible and cover it, put it in a high-temperature atmosphere furnace, and sinter it for a period of time under nitrogen protection to obtain a powder sample.

步骤（1）中超声分散的时间为5h，每升水中加入0.1-4g氧化石墨烯。The time for ultrasonic dispersion in step (1) is 5 hours, and 0.1-4 g of graphene oxide is added per liter of water.

步骤（2）中搅拌的时间为10min，硝酸银的浓度为0.3 mol/L，继续搅拌的时间为6h；硝酸银与氧化石墨烯的质量比为254：1-40。The stirring time in step (2) was 10 minutes, the concentration of silver nitrate was 0.3 mol/L, and the stirring time was continued for 6 hours; the mass ratio of silver nitrate to graphene oxide was 254:1-40.

步骤（3）中超声分散的时间为30 min；所述二氰二胺或三聚氰胺与硝酸银的摩尔比为1:1。The time for ultrasonic dispersion in step (3) is 30 min; the molar ratio of dicyandiamide or melamine to silver nitrate is 1:1.

步骤（4）中的混合溶液继续搅拌的时间为6h。The time for the mixed solution in step (4) to continue stirring is 6h.

步骤（5）中产物在高温气氛炉通过4小时从室温匀速上升到550度，保温烧结4h后，自然冷却到室温。In step (5), the product is raised from room temperature to 550 degrees at a constant speed in a high-temperature atmosphere furnace for 4 hours, and after sintering for 4 hours, it is naturally cooled to room temperature.

本发明与现有的技术相比具有以下优点：Compared with the prior art, the present invention has the following advantages:

(a) 通过银与氮化碳以及氧化石墨烯三者之间的协同效应，所制得的复合光催化材料具有增强有可见光响应范围和利用效率。(a) Through the synergistic effect between silver, carbon nitride and graphene oxide, the prepared composite photocatalytic material has enhanced visible light response range and utilization efficiency.

(b) 将氧化石墨烯作为前驱体，氧化石墨烯表面的活性附着点能够有效的调控银纳米颗粒以及氮化碳的尺寸及形貌，增强三者这件的界面复合效果。(b) Using graphene oxide as a precursor, the active attachment points on the surface of graphene oxide can effectively regulate the size and shape of silver nanoparticles and carbon nitride, and enhance the interfacial recombination effect of the three.

(c）氧化石墨烯较大的比表面积有利于对污染物的吸附，光催化过程者三种材料之间快速的光生电子-空穴分离效果和电子迁移能力使复合光催化材料具有高效的光催化活性。(c) The large specific surface area of graphene oxide is conducive to the adsorption of pollutants. The rapid photogenerated electron-hole separation effect and electron migration ability between the three materials in the photocatalytic process make the composite photocatalytic material have an efficient photocatalytic process. catalytic activity.

(d）制备的工艺简单、成本低廉、节能环保并且材料的性能优越。(d) The preparation process is simple, the cost is low, energy saving and environmental protection, and the performance of the material is superior.

附图说明Description of drawings

图1为银/氧化石墨烯/氮化碳复合光催化材料的扫描电子显微镜图。Figure 1 is a scanning electron microscope image of silver/graphene oxide/carbon nitride composite photocatalytic material.

图2为银/氧化石墨烯/氮化碳复合光催化材料的X射线衍射图。Figure 2 is the X-ray diffraction pattern of silver/graphene oxide/carbon nitride composite photocatalytic material.

图3为银/氧化石墨烯/氮化碳复合光催化材料的紫外可见漫反射光谱图。Fig. 3 is the ultraviolet-visible diffuse reflectance spectrum of the silver/graphene oxide/carbon nitride composite photocatalytic material.

图4为银/氧化石墨烯/氮化碳复合光催化材料在可见光条件下对罗丹明B的光催化降解曲线图。Fig. 4 is a graph showing the photocatalytic degradation curve of rhodamine B by the silver/graphene oxide/carbon nitride composite photocatalytic material under visible light conditions.

图5为氮化碳的半导体能带结构图。Fig. 5 is a semiconductor energy band structure diagram of carbon nitride.

具体实施方式detailed description

下面将结合具体实施例进一步阐明本发明的内容，但这些实施例并不限制本发明的保护范围。The content of the present invention will be further clarified below in conjunction with specific examples, but these examples do not limit the protection scope of the present invention.

实施例1Example 1

将10 mg氧化石墨烯分散于100 ml去离子水中超声5小时得到氧化石墨烯分散液；称取15mmol（2.54 g）硝酸银溶于50 ml去离子水中搅拌10 min后，得到硝酸银溶液；将硝酸银溶液在磁力搅拌下滴加到上述氧化石墨烯分散液中，滴加完毕后溶液在室温下继续搅拌6h，得到混合前驱体溶液A；称取15 mmol(1.26 g) 二氰二胺溶于50 ml去离子水中，得到二氰二胺分散液；磁力搅拌的条件下将二氰二胺分散液逐滴缓慢加入混合前驱体溶液A中，滴加完毕后得到的混合溶液继续搅拌6 h后静置过夜，所得产物抽滤后用无水乙醇和去离子水反复洗涤多次后真空干燥；将得到的产物装入合适的坩埚盖好后放到高温气氛炉中，在氮气保护的条件下，通过4小时从室温匀速上升到550度，保温烧结4h后，自然冷却到室温，得到粉末状样品。Disperse 10 mg of graphene oxide in 100 ml of deionized water and ultrasonically obtain a graphene oxide dispersion for 5 hours; weigh 15 mmol (2.54 g) of silver nitrate in 50 ml of deionized water and stir for 10 min to obtain a silver nitrate solution; The silver nitrate solution was added dropwise to the above-mentioned graphene oxide dispersion under magnetic stirring. After the dropwise addition, the solution was continued to stir at room temperature for 6 h to obtain a mixed precursor solution A; weigh 15 mmol (1.26 g) of dicyandiamide solution Dicyandiamine dispersion was obtained in 50 ml of deionized water; under the condition of magnetic stirring, the dicyandiamine dispersion was slowly added dropwise to the mixed precursor solution A, and the mixed solution obtained after the dropwise addition was continued to stir for 6 h After standing still overnight, the obtained product was suction-filtered, washed repeatedly with absolute ethanol and deionized water, and then vacuum-dried; the obtained product was put into a suitable crucible and covered, and then placed in a high-temperature atmosphere furnace, under the condition of nitrogen protection. Under the condition of 4 hours, the temperature was raised from room temperature to 550 degrees at a constant speed, and after 4 hours of heat preservation and sintering, it was naturally cooled to room temperature to obtain a powder sample.

实施例2Example 2

将20 mg氧化石墨烯分散于100 ml去离子水中超声5小时得到氧化石墨烯分散液；称取15mmol（2.54 g）硝酸银溶于50 ml去离子水中搅拌10 min后，得到硝酸银溶液；将硝酸银溶液在磁力搅拌下滴加到上述氧化石墨烯分散液中，滴加完毕后溶液在室温下继续搅拌6h，得到混合前驱体溶液A；称取15 mmol(1.26 g)二氰二胺溶于50 ml去离子水中，得到二氰二胺分散液；在磁力搅拌的条件下将二氰二胺分散液逐滴缓慢加入混合前驱体溶液A中，滴加完毕后得到的混合溶液继续搅拌6h后静置过夜，所得产物抽滤后用无水乙醇和去离子水反复洗涤多次后真空干燥；将得到的产物装入合适的坩埚盖好后放到高温气氛炉中，在氮气保护的条件下，通过4小时从室温匀速上升到550度，保温烧结4h后，自然冷却到室温，得到粉末状样品。Disperse 20 mg of graphene oxide in 100 ml of deionized water and ultrasonically obtain a graphene oxide dispersion for 5 hours; weigh 15 mmol (2.54 g) of silver nitrate in 50 ml of deionized water and stir for 10 min to obtain a silver nitrate solution; The silver nitrate solution was added dropwise to the above-mentioned graphene oxide dispersion under magnetic stirring. After the dropwise addition, the solution was continued to stir at room temperature for 6 h to obtain a mixed precursor solution A; weigh 15 mmol (1.26 g) of dicyandiamide solution Dicyandiamine dispersion was obtained in 50 ml of deionized water; the dicyandiamine dispersion was slowly added dropwise to the mixed precursor solution A under the condition of magnetic stirring, and the mixed solution obtained after the dropwise addition was continued to stir for 6 hours After standing still overnight, the obtained product was suction-filtered, washed repeatedly with absolute ethanol and deionized water, and then vacuum-dried; the obtained product was put into a suitable crucible and covered, and then placed in a high-temperature atmosphere furnace, under the condition of nitrogen protection. Under the condition of 4 hours, the temperature was raised from room temperature to 550 degrees at a constant speed, and after 4 hours of heat preservation and sintering, it was naturally cooled to room temperature to obtain a powder sample.

实施例3Example 3

将50 mg氧化石墨烯分散于100 ml去离子水中超声5小时得到氧化石墨烯分散液；称取15mmol（2.54 g）硝酸银溶于50 ml去离子水中搅拌10 min后，得到硝酸银溶液；将硝酸银溶液在磁力搅拌下滴加到上述氧化石墨烯分散液中，滴加完毕后溶液在室温下继续搅拌6h，得到混合前驱体溶液A；称取15 mmol(1.26 g)二氰二胺溶于50 ml去离子水中，得到二氰二胺分散液；在磁力搅拌的条件下将二氰二胺分散液逐滴缓慢加入混合前驱体溶液A中，滴加完毕后得到的混合溶液继续搅拌6h后静置过夜，所得产物抽滤后用无水乙醇和去离子水反复洗涤多次后真空干燥；将得到的产物装入合适的坩埚盖好后放到高温气氛炉中，在氮气保护的条件下，通过4小时从室温匀速上升到550度，保温烧结4h后，自然冷却到室温，得到粉末状样品。Disperse 50 mg of graphene oxide in 100 ml of deionized water and ultrasonically obtain a graphene oxide dispersion for 5 hours; weigh 15 mmol (2.54 g) of silver nitrate in 50 ml of deionized water and stir for 10 min to obtain a silver nitrate solution; The silver nitrate solution was added dropwise to the above-mentioned graphene oxide dispersion under magnetic stirring. After the dropwise addition, the solution was continued to stir at room temperature for 6 h to obtain a mixed precursor solution A; weigh 15 mmol (1.26 g) of dicyandiamide solution Dicyandiamine dispersion was obtained in 50 ml of deionized water; the dicyandiamine dispersion was slowly added dropwise to the mixed precursor solution A under the condition of magnetic stirring, and the mixed solution obtained after the dropwise addition was continued to stir for 6 hours After standing still overnight, the obtained product was suction-filtered, washed repeatedly with absolute ethanol and deionized water, and then vacuum-dried; the obtained product was put into a suitable crucible and covered, and then placed in a high-temperature atmosphere furnace, under the condition of nitrogen protection. Under the condition of 4 hours, the temperature was raised from room temperature to 550 degrees at a constant speed, and after 4 hours of heat preservation and sintering, it was naturally cooled to room temperature to obtain a powder sample.

实施例4Example 4

将100 mg氧化石墨烯分散于100 ml去离子水中超声5小时得到氧化石墨烯分散液；称取15mmol（2.54 g）硝酸银溶于50 ml去离子水中搅拌10 min后，得到硝酸银溶液；将硝酸银溶液在磁力搅拌下滴加到上述氧化石墨烯分散液中，滴加完毕后溶液在室温下继续搅拌6h，得到混合前驱体溶液A；称取15 mmol(1.26 g)二氰二胺溶于50 ml去离子水中，得到二氰二胺分散液；在磁力搅拌的条件下将二氰二胺分散液逐滴缓慢加入混合前驱体溶液A中，滴加完毕后得到的混合溶液继续搅拌6h后静置过夜，所得产物抽滤后用无水乙醇和去离子水反复洗涤多次后真空干燥；将得到的产物装入合适的坩埚盖好后放到高温气氛炉中，在氮气保护的条件下，通过4小时从室温匀速上升到550度，保温烧结4h后，自然冷却到室温，得到粉末状样品。Disperse 100 mg of graphene oxide in 100 ml of deionized water and ultrasonically obtain a graphene oxide dispersion for 5 hours; weigh 15 mmol (2.54 g) of silver nitrate in 50 ml of deionized water and stir for 10 min to obtain a silver nitrate solution; The silver nitrate solution was added dropwise to the above-mentioned graphene oxide dispersion under magnetic stirring. After the dropwise addition, the solution was continued to stir at room temperature for 6 h to obtain a mixed precursor solution A; weigh 15 mmol (1.26 g) of dicyandiamide solution Dicyandiamine dispersion was obtained in 50 ml of deionized water; the dicyandiamine dispersion was slowly added dropwise to the mixed precursor solution A under the condition of magnetic stirring, and the mixed solution obtained after the dropwise addition was continued to stir for 6 hours After standing still overnight, the obtained product was suction-filtered, washed repeatedly with absolute ethanol and deionized water, and then vacuum-dried; the obtained product was put into a suitable crucible and covered, and then placed in a high-temperature atmosphere furnace, under the condition of nitrogen protection. Under the condition of 4 hours, the temperature was raised from room temperature to 550 degrees at a constant speed, and after 4 hours of heat preservation and sintering, it was naturally cooled to room temperature to obtain a powder sample.

实施例5Example 5

将200 mg氧化石墨烯分散于100 ml去离子水中超声5小时得到氧化石墨烯分散液；称取15mmol（2.54 g）硝酸银溶于50 ml去离子水中搅拌10 min后，得到硝酸银溶液；将硝酸银溶液在磁力搅拌下滴加到上述氧化石墨烯分散液中，滴加完毕后溶液在室温下继续搅拌6h，得到混合前驱体溶液A；称取15 mmol(1.26 g)二氰二胺溶于50 ml去离子水中，得到二氰二胺分散液；在磁力搅拌的条件下将二氰二胺分散液逐滴缓慢加入混合前驱体溶液A中，滴加完毕后得到的混合溶液继续搅拌6h后静置过夜，所得产物抽滤后用无水乙醇和去离子水反复洗涤多次后真空干燥；将得到的产物装入合适的坩埚盖好后放到高温气氛炉中，在氮气保护的条件下，通过4小时从室温匀速上升到550度，保温烧结4h后，自然冷却到室温，得到粉末状样品。Disperse 200 mg of graphene oxide in 100 ml of deionized water and ultrasonically obtain a graphene oxide dispersion for 5 hours; weigh 15 mmol (2.54 g) of silver nitrate in 50 ml of deionized water and stir for 10 min to obtain a silver nitrate solution; The silver nitrate solution was added dropwise to the above-mentioned graphene oxide dispersion under magnetic stirring. After the dropwise addition, the solution was continued to stir at room temperature for 6 h to obtain a mixed precursor solution A; weigh 15 mmol (1.26 g) of dicyandiamide solution Dicyandiamine dispersion was obtained in 50 ml of deionized water; the dicyandiamine dispersion was slowly added dropwise to the mixed precursor solution A under the condition of magnetic stirring, and the mixed solution obtained after the dropwise addition was continued to stir for 6 hours After standing still overnight, the obtained product was suction-filtered, washed repeatedly with absolute ethanol and deionized water, and then vacuum-dried; the obtained product was put into a suitable crucible and covered, and then placed in a high-temperature atmosphere furnace, under the condition of nitrogen protection. Under the condition of 4 hours, the temperature was raised from room temperature to 550 degrees at a constant speed, and after 4 hours of heat preservation and sintering, it was naturally cooled to room temperature to obtain a powder sample.

实施例6Example 6

将400 mg氧化石墨烯分散于100 ml去离子水中超声5小时得到氧化石墨烯分散液；称取15mmol（2.54 g）硝酸银溶于50 ml去离子水中搅拌10 min后，得到硝酸银溶液；将硝酸银溶液在磁力搅拌下滴加到上述氧化石墨烯分散液中，滴加完毕后溶液在室温下继续搅拌6h，得到混合前驱体溶液A；称取15 mmol(1.26 g)二氰二胺溶于50 ml去离子水中，得到二氰二胺分散液；在磁力搅拌的条件下将二氰二胺分散液逐滴缓慢加入混合前驱体溶液A中，滴加完毕后得到的混合溶液继续搅拌6h后静置过夜，所得产物抽滤后用无水乙醇和去离子水反复洗涤多次后真空干燥；将得到的产物装入合适的坩埚盖好后放到高温气氛炉中，在氮气保护的条件下，通过4小时从室温匀速上升到550度，保温烧结4h后，自然冷却到室温，得到粉末状样品。Disperse 400 mg of graphene oxide in 100 ml of deionized water and sonicate for 5 hours to obtain a graphene oxide dispersion; weigh 15 mmol (2.54 g) of silver nitrate in 50 ml of deionized water and stir for 10 min to obtain a silver nitrate solution; The silver nitrate solution was added dropwise to the above-mentioned graphene oxide dispersion under magnetic stirring. After the dropwise addition, the solution was continued to stir at room temperature for 6 h to obtain a mixed precursor solution A; weigh 15 mmol (1.26 g) of dicyandiamide solution Dicyandiamine dispersion was obtained in 50 ml of deionized water; the dicyandiamine dispersion was slowly added dropwise to the mixed precursor solution A under the condition of magnetic stirring, and the mixed solution obtained after the dropwise addition was continued to stir for 6 hours After standing still overnight, the obtained product was suction-filtered, washed repeatedly with absolute ethanol and deionized water, and then vacuum-dried; the obtained product was put into a suitable crucible and covered, and then placed in a high-temperature atmosphere furnace, under the condition of nitrogen protection. Under the condition of 4 hours, the temperature was raised from room temperature to 550 degrees at a constant speed, and after 4 hours of heat preservation and sintering, it was naturally cooled to room temperature to obtain a powder sample.

此外，本发明所制备出的银/氧化石墨烯/氮化碳复合光催化材料同时被用于有机染料罗丹明B的光催化降解实验，具体过程和步骤如下：In addition, the silver/graphene oxide/carbon nitride composite photocatalytic material prepared by the present invention was also used in the photocatalytic degradation experiment of the organic dye Rhodamine B, the specific process and steps are as follows:

将100 mg的银/氧化石墨烯/氮化碳复合光催化材料分散于100毫升 100 ppm的罗丹明B溶液中后超声10分钟，混合均匀的分散液转移到氙灯光催化反应器中的石英瓶中，黑暗条件下搅拌30分钟使其达到吸附平衡后打开氙灯光源，每隔10分钟用注射器抽取4 mL照射后的混合分散液转移到标记的离心管中，可见光照射一定时间后关闭氙灯光源，将所有的离心管中的样品离心分离，离心后所得到的上层清液进一步转移到石英比色皿中在紫外-可见分光光度计上测定不同光催化时间下的吸光度，从而得到各个时间段下银/氧化石墨烯/氮化碳复合光催化材料在可见光照射下对罗丹明B的光催化降解曲线图。 Disperse 100 mg of silver/graphene oxide/carbon nitride composite photocatalytic material in 100 ml of 100 ppm rhodamine B solution and ultrasonicate for 10 minutes, then transfer the evenly mixed dispersion to a quartz bottle in a xenon light catalytic reactor After stirring for 30 minutes in the dark to reach adsorption equilibrium, turn on the xenon lamp light source, use a syringe to extract 4 mL of the irradiated mixed dispersion every 10 minutes and transfer it to a marked centrifuge tube, and turn off the xenon lamp light source after visible light irradiation for a certain period of time. All the samples in the centrifuge tubes were centrifuged, and the supernatant obtained after centrifugation was further transferred to a quartz cuvette, and the absorbance at different photocatalytic times was measured on a UV-visible spectrophotometer, so as to obtain the Photocatalytic degradation curve of rhodamine B by silver/graphene oxide/carbon nitride composite photocatalytic material under visible light irradiation.

图1为所制备出的银/氧化石墨烯/氮化碳复合材料扫描图，从图1中可以清晰看出复合材料片层状的C3N4和片状氧化石墨烯；采用二氰二胺前驱体所获得的复合材料中银的颗粒相对较小，被包裹在层状的C3N4和片状氧化石墨烯中。Fig. 1 is the scanned image of the prepared silver/graphene oxide/carbon nitride composite material. From Fig. 1, it can be clearly seen that the sheet-like C 3 N 4 and sheet-like graphene oxide of the composite material; The silver particles in the composites obtained from the amine precursors are relatively small and are wrapped in layered C 3 N 4 and flake graphene oxide.

图2为所制备出的银/氧化石墨烯/氮化碳材料的XRD图，经过与JCPDS标准卡片对比可以确认,复合材料中所出现的4个强衍射峰都可以很好的指认为Ag对应的晶面，由于复合材料样品中C3N4与GO的比例较低以及相对于强的银的衍射峰，XRD图谱中无法观察到明显的C3N4与GO衍射峰；而且，图谱中没有出现较强的其他相或元素的衍射峰，说明银的引入并没有改变复合材料的晶体结构。Figure 2 is the XRD pattern of the prepared silver/graphene oxide/carbon nitride material. After comparing with the JCPDS standard card, it can be confirmed that the four strong diffraction peaks in the composite material can be well identified as corresponding to Ag. Due to the low ratio of C 3 N 4 and GO in the composite material sample and the strong silver diffraction peaks, no obvious C 3 N 4 and GO diffraction peaks can be observed in the XRD pattern; moreover, in the There were no strong diffraction peaks of other phases or elements, indicating that the introduction of silver did not change the crystal structure of the composite.

图3为所制备的银/氧化石墨烯/氮化碳复合材料的紫外可见漫反射光谱图，从图中我们可以看出，该复合材料在整个紫外可见光区(200-800 nm)都具有较好的吸收，吸光度超过0.3。Figure 3 is the UV-visible diffuse reflectance spectrum of the prepared silver/graphene oxide/carbon nitride composite material. From the figure, we can see that the composite material has a relatively high density in the entire UV-visible region (200-800 nm). Good absorption, the absorbance is more than 0.3.

图4为所制备出的银/氧化石墨烯/氮化碳复合光催化材料在可见光条件下对罗丹明B的光催化降解曲线图，从图4中可以看出，该复合材料在可见光照射40分钟后对罗丹明B的降解率超过60%，60分钟后对罗丹明B的降解率达80%，光催化降解曲线图表明银/氧化石墨烯/氮化碳复合光催化材料在可见光照射下对有机染料罗丹明B具有较好的光催化降解效果。Fig. 4 is the photocatalytic degradation curve of the prepared silver/graphene oxide/carbon nitride composite photocatalytic material to Rhodamine B under visible light conditions. As can be seen from Fig. 4, the composite material is exposed to visible light for 40 After 60 minutes, the degradation rate of rhodamine B exceeds 60%, and after 60 minutes, the degradation rate of rhodamine B reaches 80%. The photocatalytic degradation curve shows that the silver/graphene oxide/carbon nitride composite photocatalytic material is irradiated by visible light It has good photocatalytic degradation effect on organic dye rhodamine B.

图5为氮化碳的半导体能带结构图；由图可知，其结构中的C、N原子以sp2杂化形成高度离域的π共轭体系；其中，Npz轨道组成g-C3N4的最高占据分子轨道（HOMO），Cpz轨道组成最低未占据分子轨道（LUMO），它们之间的禁带宽度～2.7 eV，可以吸收太阳光谱中波长小于475 nm的蓝紫光。理论计算和实验研究表明，g-C3N4还具有非常合适的半导体带边位置，其HOMO 和LUMO分别位于+1.4 V 和-1.3 V （vs NHE，PH=7），满足光解水产氢、产氧的热力学要求；此外氧化石墨烯具有优良的电子传导能力和较低的费米能级，可以有效捕获光生电子，抑制光生载流子的严重复合；三体系的复合材料，将产生的光生电子注入到宽禁带半导体的导带，在空间上将光生电子和空穴进行分离，快速活化分子氧产生超氧自由基（O2 －）以及光生空穴，实现水相中有机污染物的光催化降解。Figure 5 is a diagram of the semiconductor energy band structure of carbon nitride; it can be seen from the figure that the C and N atoms in the structure are sp 2 hybridized to form a highly delocalized π-conjugated system; among them, the Np z orbitals form gC 3 N 4 The highest occupied molecular orbital (HOMO) of the Cp z orbital forms the lowest unoccupied molecular orbital (LUMO), and the band gap between them is ~2.7 eV, which can absorb blue-violet light with a wavelength less than 475 nm in the solar spectrum. Theoretical calculations and experimental studies show that gC 3 N 4 also has a very suitable semiconductor band edge position, and its HOMO and LUMO are located at +1.4 V and -1.3 V, respectively (vs NHE, PH=7), which meets the photolysis of water to produce hydrogen, produce The thermodynamic requirements of oxygen; in addition, graphene oxide has excellent electron conductivity and low Fermi level, which can effectively capture photogenerated electrons and inhibit the severe recombination of photogenerated carriers; the composite material of the three systems will generate photogenerated electrons Injected into the conduction band of wide-bandgap semiconductors, spatially separate photo-generated electrons and holes, rapidly activate molecular oxygen to generate superoxide radicals (O 2 - ) and photo-generated holes, and realize the photocatalysis of organic pollutants in the water phase. catalytic degradation.

Claims (7)

  1. A kind of 1. silver/graphene oxide/carbonitride composite photocatalyst material, it is characterised in that：The composite photocatalyst material by Three kinds of carbonitride, silver and graphene oxide Material claddings form, and wherein Argent grain is embedded in carbonitride layer structure or sunk Product is on graphene oxide layer surface；The composite photocatalyst material has under excited by visible light to organic dyestuff rhodamine B Efficient photocatalytic degradation effect：To 100ppm 60 minutes degradation rates of rhodamine B solution up to 80%；By silver with carbonitride with And there is enhancing to have visible light-responded scope for the cooperative effect between graphene oxide three, obtained composite photocatalyst material And utilization ratio；It can effectively regulate and control silver using graphene oxide as presoma, the active attachment point of surface of graphene oxide The size and pattern of nano particle and carbonitride, strengthen the Interface composites effect between three；The larger ratio of graphene oxide Surface area is advantageous to the absorption to pollutant, and quick photo-generate electron-hole separates effect between three kinds of materials of photocatalytic process person Fruit and electron transfer capabilities make composite photocatalyst material have efficient photocatalytic activity.
  2. 2. a kind of preparation method of silver/graphene oxide/carbonitride composite photocatalyst material as claimed in claim 1, it is special Sign is that preparation process is as follows：
    (1) graphene oxide is dissolved in ultrasonic disperse in deionized water, obtains graphene oxide dispersion；
    (2) silver nitrate is dissolved in deionized water and stirred, obtain silver nitrate solution；By silver nitrate solution under the conditions of magnetic agitation It is added drop-wise in above-mentioned graphene oxide dispersion, rear solution is added dropwise and continues to stir at room temperature, it is molten obtains mixing presoma Liquid A；
    (3) dicyanodiamine or melamine are dissolved in ultrasonic disperse in deionized water, obtain dicyanodiamine or melamine disperses Liquid；
    (4) dicyanodiamine or melamine dispersion liquid for preparing step (3) under conditions of magnetic agitation are slowly added to dropwise In mixing precursor solution A prepared by step (2), the mixed solution obtained after being added dropwise continues to stand overnight after stirring, institute Obtain and be dried in vacuo after being washed repeatedly repeatedly with absolute ethyl alcohol and deionized water after product filters；
    (5) obtained product is fitted into after suitable crucible covers and be put into high-temperature atmosphere furnace, burnt under conditions of nitrogen protection Knot a period of time, obtain powdered samples.
  3. 3. a kind of preparation method of silver/graphene oxide/carbonitride composite photocatalyst material as claimed in claim 2, it is special Sign is：The time of ultrasonic disperse is 5h in step (1), and 0.1-4g graphene oxides are added in every liter of water.
  4. 4. a kind of preparation method of silver/graphene oxide/carbonitride composite photocatalyst material as claimed in claim 2, it is special Sign is：The time of stirring is 10min in step (2), and the concentration of silver nitrate is 0.3mol/L, and the time for continuing stirring is 6h； The mass ratio of silver nitrate and graphene oxide is 254：1-40.
  5. 5. a kind of preparation method of silver/graphene oxide/carbonitride composite photocatalyst material as claimed in claim 2, it is special Sign is：The time of ultrasonic disperse is 30min in step (3)；The mol ratio of the dicyanodiamine or melamine and silver nitrate For 1:1.
  6. 6. a kind of preparation method of silver/graphene oxide/carbonitride composite photocatalyst material as claimed in claim 2, it is special Sign is：The time that mixed solution in step (4) continues stirring is 6h.
  7. 7. a kind of preparation method of silver/graphene oxide/carbonitride composite photocatalyst material as claimed in claim 2, it is special Sign is：In step (5) product in high-temperature atmosphere furnace by the uniform velocity rising within 4 hours 550 degree from room temperature, after heat preservation sintering 4h, Naturally cool to room temperature.
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