技术领域technical field
本发明属于纳米材料制备的技术领域，特别涉及了一种高催化活性的氮化碳纳米催化材料的制备方法，该方法主要通过对温度梯度的控制，成功的制备出蓬松的高催化活性的石墨相氮化碳。The invention belongs to the technical field of nanomaterial preparation, and in particular relates to a method for preparing a carbon nitride nanocatalytic material with high catalytic activity. The method mainly successfully prepares fluffy graphite with high catalytic activity by controlling the temperature gradient phase carbon nitride.
背景技术Background technique
自从1989年Liu和M.L.Cohen在理论上预言，β-C3N4可能是一种比金刚石还要硬的新型超硬材料[1,2]。1996年Tete等则采用第一性原理赝势计算方法计算出了氮化碳的理论结构，认为该化合物可能存在五种物相，即：α相、β相、立方相，类立方相和类石墨相[3]。类石墨相氮化碳因具有类似石墨的层状结构而得名，因此也叫做石墨相氮化碳，是这五种物相中最稳定的晶相。于是人们开始了对这种新型碳氮材料的研究热潮。国内外上千个实验室都被吸引到此项研究中，他们利用已知的各种可实现的实验方法来合成这种材料。2009年Wang等人首次报道，成功的热解单氰胺制备出石墨相C3N4并在可见光下(λ>420nm)分解水制氢[4]。此后，有关氮化碳光催化的研究相继拉开了序幕。Since Liu and ML Cohen theoretically predicted in 1989, β-C3 N4 may be a new type of superhard material harder than diamond[1,2] . In 1996, Tete et al. calculated the theoretical structure of carbon nitride by using the first-principle pseudopotential calculation method, and believed that the compound may have five phases, namely: α phase, β phase, cubic phase, quasi-cubic phase and quasi-cubic phase. Graphite phase[3] . Graphite-like carbon nitride is named for its graphite-like layered structure, so it is also called graphite-phase carbon nitride, which is the most stable crystal phase among the five phases. So people began to study this new type of carbon-nitrogen material. Thousands of laboratories at home and abroad are attracted to this research, and they synthesize this material by using various known and achievable experimental methods. In 2009, Wang et al. reported for the first time that the successful pyrolysis of cyanamide produced graphite phase C3 N4 and decomposed water to produce hydrogen under visible light (λ>420nm)[4] . Since then, the research on carbon nitride photocatalysis has started one after another.
石墨相氮化碳的制备方法主要有两种：溶剂热合成法和高温聚合法。溶剂热合成法是指在密闭的容器中，溶剂作为反应介质，在高温和高压(溶剂变成蒸汽时所产生的压力)的条件下制备纳米材料的一种非均相合成方法，是制备粉体的湿化学法之一。近年来，该合成方法已被广泛应用，1999年，Montigaud等以三聚氰胺为原料，以NH2NH2为溶剂，在压力为3GPa、温度800℃-850℃之间的条件下合成出石墨相的氮化碳[5]。Bai等人在没有使用任何催化剂的前提下，采用NH4C1和CCl4在400℃溶剂热反应中得到了石墨相氮化碳纳米晶，XRD和TEM给出的平均晶粒尺寸约为11nm，并有少量的单晶产生[6]。There are two main methods for the preparation of graphitic carbon nitride: solvothermal synthesis and high temperature polymerization. Solvothermal synthesis refers to a heterogeneous synthesis method for preparing nanomaterials under conditions of high temperature and high pressure (the pressure generated when the solvent turns into steam) in a closed container with a solvent as the reaction medium. One of the wet chemical methods of body. In recent years, this synthesis method has been widely used. In 1999, Montigaud et al. used melamine as raw material and NH2 NH2 as solvent to synthesize graphitic phase at a pressure of 3 GPa and a temperature between 800°C and 850°C. Carbon Nitride[5] . Bai et al. used NH4 C1 and CCl4 in a solvothermal reaction at 400°C to obtain graphitic carbon nitride nanocrystals without using any catalyst. The average grain size given by XRD and TEM is about 11nm. And a small amount of single crystal produced[6] .
高温聚合法是制备氮化碳较为常用的一种方法。因为氰胺在高温下可发生聚合反应，依次缩聚为双氰胺，三聚氰胺，蜜勒胺，最后得到氮化碳产物。Wang等将单氰胺加热至400℃-600℃之间，并保温4h合成得到了石墨相的氮化碳。Zou等人则是利用一种更为廉价的原料三聚氰胺在常压下分别加热到500℃,520℃,550℃和580℃恒温2h也得到石墨相氮化碳，并发现所制备的氮化碳有较好的性能在光降解亚甲基蓝方面[4]。Niu等人利用双氰胺用两步法烧结制备出了石墨相氮化碳的片层状结构，并且得到比体相石墨相氮化碳具有更高的催化效率[7]。Zou等人以更为廉价的尿素为原料TiO2为催化剂利用，在空气的条件下制备出了石墨相氮化碳[8]。然而，普通烧结方法制备出的石墨相C3N4样品具有较大的晶粒尺寸，微纳米结构的C3N4较难制备，因此，这极大的限制了石墨相C3N4在催化领域、光电导领域和光波导等领域的应用。因而制备出可控的多种形貌并具有微纳结构的石墨相C3N4成为这一材料研究的重点和难点。High-temperature polymerization is a commonly used method for preparing carbon nitride. Because cyanamide can undergo polymerization reaction at high temperature, it is polycondensed into dicyandiamide, melamine, and melem in turn, and finally carbon nitride product is obtained. Wang et al. heated cyanamide to between 400°C and 600°C and kept it warm for 4 hours to synthesize carbon nitride in graphite phase. Zou et al. used a cheaper raw material melamine to heat to 500°C, 520°C, 550°C and 580°C under normal pressure for 2 hours to obtain graphitic carbon nitride, and found that the prepared carbon nitride It has better performance in photodegradation of methylene blue[4] . Niu et al. used dicyandiamide to prepare a lamellar structure of graphite carbon nitride by two-step sintering, and obtained a higher catalytic efficiency than bulk graphite carbon nitride[7] . Zou et al. used cheaper urea as raw material TiO2 as a catalyst to prepare graphitic carbon nitride under air conditions[8] . However, the graphite phase C3 N4 samples prepared by the common sintering method have a large grain size, and the micro-nano structure of C3 N4 is difficult to prepare. Therefore, this greatly limits the graphite phase C3 N4 in the Applications in the fields of catalysis, photoconductivity, and optical waveguides. Therefore, the preparation of graphite phase C3 N4 with controllable various shapes and micro-nano structure has become the focus and difficulty of this material research.
近年来，国内外很多小组都展开了对新型石墨相碳氮材料的探索和研究，材料的制备是从基础研究到实际应用的必由之路，是提高材料质量及降低成本的重要途径。实现材料结构和性能设计及新材料的发现能否获得实际应用，取决于制备工艺和成本。到目前为止，尽管有许多报导声称合成了这种新型相材料，却主要还在实验室探索阶段。可以说，用简单、低成本的方法大量合成高纯度新型碳氮材料材料仍然是研究者面前的热点和难题。In recent years, many groups at home and abroad have carried out exploration and research on new graphitic carbon-nitrogen materials. The preparation of materials is the only way from basic research to practical application, and it is an important way to improve material quality and reduce costs. Whether the material structure and performance design and the discovery of new materials can be practically applied depends on the preparation process and cost. So far, although there are many reports claiming to synthesize this new phase material, it is mainly in the stage of laboratory exploration. It can be said that the large-scale synthesis of high-purity new carbon-nitrogen materials with simple and low-cost methods is still a hot spot and difficult problem for researchers.
参考文献：references:
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发明内容Contents of the invention
本发明的目的是公开一种蓬松高催化活性的石墨相氮化碳材料的大量制备方法，此方法简单易行，重复率高。The purpose of the present invention is to disclose a large-scale preparation method of a fluffy and highly catalytic graphite phase carbon nitride material, which is simple and easy to implement and has a high repetition rate.
本发明的目的是这样实现的，该方法采用廉价的尿素做原料，在长1米、直径25mm的管式炉中按照一定的温度梯度进行高温加热，得到大量片状石墨相氮化碳材料，其具体制备方法如下：The object of the present invention is achieved in that the method adopts cheap urea as a raw material, and heats at a high temperature according to a certain temperature gradient in a tube furnace with a length of 1 meter and a diameter of 25 mm to obtain a large amount of flake graphite phase carbon nitride material, Its specific preparation method is as follows:
将分析纯的尿素原料放入到瓷舟中，然后放入已升温到80℃的干燥箱中，进行干燥，干燥时间为12小时，干燥结束之后将尿素原料取出并放入到石英管的中间区域，并在管式炉中烧结，烧结温度在100℃之前以1.5℃/min速率升温，然后以1℃/min升温到200℃，以2℃/min升温到450℃，以1℃/min升温到550℃，最后在550℃的条件下保温2小时，待冷却到室温，即得到蓬松的高催化活性的氮化碳纳米催化材料。Put the analytically pure urea raw material into a porcelain boat, and then put it into a drying oven that has been heated to 80°C for drying. The drying time is 12 hours. After the drying is completed, take out the urea raw material and put it in the middle of the quartz tube area, and sintered in a tube furnace, the sintering temperature was raised at a rate of 1.5°C/min before 100°C, then at 1°C/min to 200°C, at 2°C/min to 450°C, at 1°C/min Raise the temperature to 550° C., and finally keep the temperature at 550° C. for 2 hours. After cooling to room temperature, a fluffy carbon nitride nano-catalyst material with high catalytic activity is obtained.
本发明具有以下优点和积极效果：The present invention has the following advantages and positive effects:
1、本发明所用的尿素原料价格低廉，只需要前期简单干燥处理，通过控制高温烧结的温度梯度合成出大量的石墨相氮化碳材料，这种材料对罗丹明B染料有明显的吸附及催化作用，而通过三次的循环吸附与催化过程之后对其进行XRD检测，发现本发明的催化剂具有良好的化学稳定性。1. The urea raw material used in the present invention is cheap, and only needs simple drying treatment in the early stage, and a large amount of graphite-phase carbon nitride materials are synthesized by controlling the temperature gradient of high-temperature sintering. This material has obvious adsorption and catalysis for rhodamine B dyes After three cycles of adsorption and catalysis, it was detected by XRD, and it was found that the catalyst of the present invention has good chemical stability.
2、本发明的方法简单、环保、低成本；检测迅速、可重复性高；对工业有机染料废水降解检测有广阔的应用前景。2. The method of the present invention is simple, environmentally friendly, and low-cost; it detects quickly and has high repeatability; it has broad application prospects for the detection of industrial organic dye wastewater degradation.
3、本发明通过物理方法制备，可得大量产物，为新型功能碳氮材料的规模化生产和应用奠定基础。3. The present invention is prepared by a physical method, and a large amount of products can be obtained, which lays the foundation for the large-scale production and application of new functional carbon-nitrogen materials.
附图说明Description of drawings
图1是本发明以尿素为原材料制备出的50mg石墨相氮化碳和以三聚氰胺为原材料制备出的50mg的氮化碳纳米催化材料体积对比图。Fig. 1 is the 50mg graphitic phase carbon nitride that the present invention prepares with urea as raw material and the 50mg carbon nitride nano-catalyst material that prepares with melamine as raw material volume contrast figure.
图2是本发明制备出的石墨相氮化碳的SEM图。Fig. 2 is the SEM picture of the graphite phase carbon nitride prepared by the present invention.
图3是本发明制备的石墨相氮化碳纳米片和以三聚氰胺制备出的体相石墨相氮化碳对罗丹明在可见光下的催化活性对比图。Fig. 3 is a comparison chart of the catalytic activity of graphite phase carbon nitride nanosheets prepared by the present invention and bulk phase graphite phase carbon nitride prepared from melamine to rhodamine under visible light.
图4是本发明制备的氮化碳纳米催化材料和经过多次催化反应之后的氮化碳纳米催化材料的XRD对比图。Fig. 4 is an XRD comparison diagram of the carbon nitride nano-catalytic material prepared by the present invention and the carbon nitride nano-catalytic material after multiple catalytic reactions.
具体实施方式Detailed ways
将50mg分析纯的尿素原料放入到瓷舟中，然后放入已升温到80℃的干燥箱中，进行干燥，干燥时间为12小时，干燥结束之后将尿素取出并放入到石英管（直径25mm，长1000mm）的中间区域，并在管式炉中烧结。烧结温度在100℃之前以1.5℃/min速率升温，然后以1℃/min升温到200℃，以2℃/min升温到450℃，以1℃/min升温到550℃，最后在550℃的条件下保温2小时。待冷却到室温，可以收集到蓬松的高催化活性的氮化碳纳米催化材料，不需要进一步的处理。Put 50mg of analytically pure urea raw material into a porcelain boat, and then put it into a drying oven heated to 80°C for drying. The drying time is 12 hours. After drying, take out the urea and put it into a quartz tube (diameter 25mm, length 1000mm) in the middle area, and sintered in a tube furnace. The sintering temperature is raised at a rate of 1.5°C/min before 100°C, then at 1°C/min to 200°C, at 2°C/min to 450°C, at 1°C/min to 550°C, and finally at 550°C Keep warm for 2 hours. After cooling to room temperature, fluffy carbon nitride nanocatalytic materials with high catalytic activity can be collected without further treatment.
结论：图1所示分别是以三聚氰胺(左)和尿素(右)为原材料制备出的50mg石墨相氮化碳，通过图片对比发现以尿素为原材料制备出的样品在同样50mg的质量下是三聚氰胺的制备出50mg样品体积的5倍，说明以尿素制备出的样品通过对温度梯度的控制，使得样品更加蓬松，不易团聚。Conclusion: Figure 1 shows 50mg of graphitic carbon nitride prepared with melamine (left) and urea (right) as raw materials. Through comparison of pictures, it is found that the samples prepared with urea as raw materials are melamine under the same quality of 50mg. 5 times the volume of the 50 mg sample, indicating that the sample prepared with urea is controlled by the temperature gradient, making the sample more fluffy and less likely to agglomerate.
图2所示为以尿素制备出的样品的SEM图像，通过图像观察可知样品在SEM图像下呈现蓬松的状态，通过高倍的SEM图像可观察到样品呈现卷曲的片状结构，并且片上有大小不一的孔。Figure 2 shows the SEM image of the sample prepared with urea. Through image observation, it can be seen that the sample is in a fluffy state under the SEM image. Through the high-magnification SEM image, it can be observed that the sample presents a curled sheet structure, and there are different sizes on the sheet. a hole.
图3所示为尿素制备出的石墨氮化碳(u-g-C3N4)与三聚氰胺制备出的体相石墨氮化碳(m-g-C3N4)催化性能的对比以及无催化剂罗丹明的自降解(blank)。在过程当中样品u-g-C3N4具有高于60%的对染料的吸附效果并且催化效果稳定而高效，最终在180分钟时染料完全降解。与此进行对比实验的样品m-g-C3N4吸附效果只有35%左右并且催化效果不稳定，尤其是当染料浓度低的时，催化降解缓慢。.空白屋催化剂实验表明染料在可见光下的自我降解可以忽略不计。Figure 3 shows the comparison of the catalytic properties of graphitic carbon nitride (ugC3 N4 ) prepared from urea and bulk graphitic carbon nitride (mgC3 N4 ) prepared from melamine and the self-degradation of rhodamine without catalyst (blank ). During the process, the sample ugC3 N4 has an adsorption effect on the dye higher than 60% and the catalytic effect is stable and efficient, and finally the dye is completely degraded in 180 minutes. Compared with this sample mgC3 N4 adsorption effect is only about 35% and the catalytic effect is unstable, especially when the dye concentration is low, the catalytic degradation is slow. . Blank house catalyst experiments showed negligible self-degradation of the dye under visible light.
图4所示为样品u-g-C3N4在催化反映前（Fresh）后（Used）的XRD图像，通过对比发现样品经过催化反应之后样品的XRD图像的峰位没有发生变化，表明样品具有出色的稳定性。Figure 4 shows the XRD image of the sample ugC3 N4 before (Fresh) and after (Used) catalytic reaction. By comparison, it is found that the peak position of the XRD image of the sample after the catalytic reaction has not changed, indicating that the sample has excellent stability. sex.
本发明在氙灯模拟可见光源下光催化降解罗丹明-B的降解率来评估石墨相氮化碳的活性，反应时间为180min时，其降解率达到97%。In the present invention, the degradation rate of photocatalytic degradation of rhodamine-B under xenon lamp simulating visible light source is used to evaluate the activity of graphite phase carbon nitride, and the degradation rate reaches 97% when the reaction time is 180 minutes.
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