CN103769213A - Preparation method for phosphor-doped graphite-phase carbon nitride visible-light catalyst - Google Patents

Preparation method for phosphor-doped graphite-phase carbon nitride visible-light catalyst Download PDF

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CN103769213A
CN103769213A CN201410006789.1A CN201410006789A CN103769213A CN 103769213 A CN103769213 A CN 103769213A CN 201410006789 A CN201410006789 A CN 201410006789A CN 103769213 A CN103769213 A CN 103769213A
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carbon nitride
visible light
phase carbon
phosphorus
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王德松
张鑫鑫
罗青枝
李雪艳
安静
殷蓉
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Hebei University of Science and Technology
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Abstract

本发明属于环境净化光催化材料制备技术领域,公开了一种磷掺杂石墨相氮化碳可见光催化剂的制备方法,所述该方法由下述步骤进行:将三聚氰胺分散于稀磷酸溶液中,使磷酸分子均匀吸附分散在三聚氰胺微粒表面,然后加热除去溶剂水,在充分干燥后经程序升温至520℃,使三聚氰胺发生热缩聚反应,产物经冷却、研磨,得到磷掺杂石墨相氮化碳可见光催化剂。本发明原料来源广泛,制备方法简单,不需要复杂设备,适于大规模生产,所制备的磷掺杂石墨相氮化碳复合可见光催化剂具有优异的可见光催化性能和良好的催化稳定性。

The invention belongs to the technical field of preparation of photocatalytic materials for environmental purification, and discloses a method for preparing a phosphorus-doped graphite phase carbon nitride visible light catalyst. The method is carried out by the following steps: dispersing melamine in dilute phosphoric acid solution, making Phosphoric acid molecules are uniformly adsorbed and dispersed on the surface of melamine particles, then heated to remove solvent water, and then heated to 520°C after being fully dried to cause thermal condensation reaction of melamine, and the product is cooled and ground to obtain phosphorus-doped graphite phase carbon nitride visible light catalyst. The invention has wide sources of raw materials, simple preparation method, does not need complex equipment, and is suitable for large-scale production. The prepared phosphorus-doped graphite phase carbon nitride composite visible light catalyst has excellent visible light catalytic performance and good catalytic stability.

Description

一种磷掺杂石墨相氮化碳可见光催化剂的制备方法A kind of preparation method of phosphorus-doped graphite phase carbon nitride visible light catalyst

技术领域technical field

本发明具体涉及一种磷掺杂石墨相氮化碳可见光催化剂的制备方法,属于环境净化光催化剂材料制备技术领域。The invention specifically relates to a preparation method of a phosphorus-doped graphite-phase carbon nitride visible light catalyst, which belongs to the technical field of preparation of photocatalyst materials for environmental purification.

背景技术Background technique

光催化技术是一种在能源领域有着重要应用前景的绿色技术,光催化氧化技术以半导体为催化剂,以光能为能源,将有机污染物降解为二氧化碳和水。自1972年发现纳米二氧化钛能在光照下分解水,纳米半导体光催化技术引起了世界的广泛关注,并被认为是最具发展前途和应用前景的环境净化技术。近年来,许多国内外学者对金属氧化物、硫化物、氮化物等多种类型的纳米半导体材料进行了深入而广泛的研究,但光催化剂的量子效率低、太阳光利用率低等问题仍未得到根本解决,制约着光催化技术的广泛应用,因此寻找和合成新型的可见光诱导的高效光催化材料一直是光催化领域的重要课题。Photocatalytic technology is a green technology with important application prospects in the energy field. Photocatalytic oxidation technology uses semiconductors as catalysts and light energy as energy to degrade organic pollutants into carbon dioxide and water. Since the discovery in 1972 that nano-titanium dioxide can split water under light, nano-semiconductor photocatalysis technology has attracted worldwide attention and is considered to be the most promising and promising environmental purification technology. In recent years, many scholars at home and abroad have conducted in-depth and extensive research on various types of nano-semiconductor materials such as metal oxides, sulfides, and nitrides, but the problems of low quantum efficiency of photocatalysts and low utilization of sunlight have not yet been solved. The fundamental solution restricts the wide application of photocatalytic technology. Therefore, finding and synthesizing new visible light-induced high-efficiency photocatalytic materials has always been an important topic in the field of photocatalysis.

最近,王心晨等(Xinchen Wang et al.,A metal-free polymeric photocatalyst forhydrogen production from water under visible light.Nature Materials,2009,8:76-80)发现石墨相氮化碳在可见光照射下能分解水制氢,并且具有稳定性好、廉价易得、结构易于调控等优点,是一类有潜力的新型可见光光催化材料。但受其结构及带隙限制,纯石墨相氮化碳在实际应用过程中有着自身无法突破的局限性,如禁带宽度较大(2.7eV),光吸收主要集中在可见光区(λ<450nm),对太阳光的利用率较低;光激发后产生的光生电子和空穴易于复合,光生载流子的效率低,光催化性能差等。Recently, Xinchen Wang et al. (Xinchen Wang et al., A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nature Materials, 2009, 8:76-80) found that graphite phase carbon nitride can decompose water under visible light irradiation Hydrogen, and has the advantages of good stability, cheap and easy to obtain, easy to adjust the structure, etc., is a class of potential new visible light photocatalytic materials. However, limited by its structure and band gap, pure graphite phase carbon nitride has its own limitations that cannot be broken through in the actual application process, such as a large forbidden band width (2.7eV), and light absorption is mainly concentrated in the visible light region (λ<450nm ), the utilization rate of sunlight is low; the photogenerated electrons and holes generated after photoexcitation are easy to recombine, the efficiency of photogenerated carriers is low, and the photocatalytic performance is poor.

为了改善石墨相氮化碳的可见光催化活性和催化稳定性,研究人员开展了一系列石墨相氮化碳的改性研究。Shubin Yang(Shubin Yang et al.,Exfoliatedgraphitic carbon nitride nanosheets as efficient catalysts for hydrogen evolution undervisible light.Advanced Materials,2013,25:2452-2456)采用剥层法合成的石墨相氮化碳薄层厚约2nm,有较大的长宽比,较高的比表面积和碳氮比,这不仅有利于提供更多的制氢活性中心,并且能增加电荷传输和减少光激电荷载体的重组能力。Guigang Zhang(Guigang Zhang,Polycondensation of thiourea into carbonnitride semiconductors as visible light photocatalysts.Journal of Materials Chemistry,2012,22:8083-8091)用杂原子调控热聚合合成的硫掺杂石墨相氮化碳半导体材料,增大了比表面积,硫的引入可以控制石墨相氮化碳网状结构的合成,加速石墨相氮化碳聚合的进程,控制加热温度可以生成纳米尺寸,能合成有较好结构、电子和光学性质的氮化碳半导体材料。王心晨等(中国发明专利CN103272639A)制备了聚合改性石墨相氮化碳纳米片可见光催化剂,该催化剂具有高比表面积,窄的带隙宽度,快速的光生载流子分离、迁移能力。上述改性的可见光催化剂有效地提高了石墨相氮化碳比表面积、提供了更多的活性位置,改善对可见光的利用率、但是也限制了可见光的吸收与利用,对降解污染物的光催化活性提高有限。In order to improve the visible light catalytic activity and catalytic stability of graphitic carbon nitride, researchers have carried out a series of modification studies on graphitic carbon nitride. Shubin Yang (Shubin Yang et al., Exfoliated graphitic carbon nitride nanosheets as efficient catalysts for hydrogen evolution undervisible light. Advanced Materials, 2013, 25: 2452-2456) synthesized the graphitic carbon nitride thin layer by the exfoliation method with a thickness of about 2nm. It has larger aspect ratio, higher specific surface area and carbon-nitrogen ratio, which is not only beneficial to provide more active centers for hydrogen production, but also can increase charge transport and reduce the recombination ability of photoexcited charge carriers. Guigang Zhang (Guigang Zhang, Polycondensation of thiourea into carbonnitride semiconductors as visible light photocatalysts. Journal of Materials Chemistry, 2012, 22:8083-8091) Sulfur-doped graphite phase carbon nitride semiconductor materials synthesized by heteroatom-regulated thermal polymerization, increased Larger specific surface area, the introduction of sulfur can control the synthesis of graphite phase carbon nitride network structure, accelerate the process of graphite phase carbon nitride polymerization, control the heating temperature can generate nanometer size, can synthesize better structure, electronic and optical properties carbon nitride semiconductor material. Wang Xinchen et al. (Chinese invention patent CN103272639A) prepared a polymerized modified graphite phase carbon nitride nanosheet visible light catalyst, which has a high specific surface area, a narrow band gap width, and rapid separation and migration of photogenerated carriers. The above-mentioned modified visible light catalyst effectively increases the specific surface area of graphitic carbon nitride, provides more active sites, and improves the utilization rate of visible light, but also limits the absorption and utilization of visible light. The improvement in activity is limited.

发明内容Contents of the invention

本发明要解决的技术问题在于提供一种磷掺杂石墨相氮化碳可见光催化剂的制备方法。本发明制备的磷掺杂石墨相氮化碳具有良好的光催化活性及光催化稳定性,以此法制备的可见光催化剂将在环境净化光催化领域有广阔的应用前景。The technical problem to be solved by the present invention is to provide a preparation method of phosphorus-doped graphite phase carbon nitride visible light catalyst. The phosphorus-doped graphite phase carbon nitride prepared by the invention has good photocatalytic activity and photocatalytic stability, and the visible light catalyst prepared by the method will have broad application prospects in the field of environmental purification and photocatalysis.

为解决上述技术问题本发明的技术方案为,首先将三聚氰胺微粒分散于稀磷酸水溶液中,使磷酸分子均匀吸附在三聚氰胺微粒表面,然后加热除去水,干燥后混合物经程序升温至520℃,使其发生缩聚等系列反应后,产物经冷却、研磨,得到磷掺杂石墨相氮化碳可见光催化剂。In order to solve the above-mentioned technical problems, the technical scheme of the present invention is as follows: firstly, the melamine particles are dispersed in the dilute phosphoric acid aqueous solution, so that the phosphoric acid molecules are evenly adsorbed on the surface of the melamine particles, and then the water is removed by heating, and the mixture is heated to 520° C. after drying to make it After a series of reactions such as polycondensation, the product is cooled and ground to obtain a phosphorus-doped graphite phase carbon nitride visible light catalyst.

所述一种磷掺杂石墨相氮化碳可见光催化剂的制备方法主要包括下述步骤:The preparation method of the phosphorus-doped graphite phase carbon nitride visible light catalyst mainly comprises the following steps:

a.量取85%的浓磷酸2mL~8mL移入100mL容量瓶中,加去离子水配成浓度为0.292mol/L~1.17mol/L的稀磷酸溶液;a. Measure 2mL-8mL of 85% concentrated phosphoric acid into a 100mL volumetric flask, add deionized water to make a dilute phosphoric acid solution with a concentration of 0.292mol/L-1.17mol/L;

b.移取步骤a所述稀磷酸溶液0.25mL~3.0mL加入到含有5mL去离子水的烧杯中,搅拌5min~10min,之后在搅拌下将5.00g三聚氰胺固体粉末缓慢加入该稀磷酸溶液中,使溶液中磷酸与三聚氰胺的摩尔比为1:100~1:20,继续搅拌20min~60min,使磷酸均匀吸附分散在三聚氰胺微粒表面。然后将所得悬浮液在搅拌下加热至60℃~80℃除去溶剂水,再于60℃~80℃烘箱中干燥1h~3h;b. Pipette 0.25mL-3.0mL of the dilute phosphoric acid solution described in step a into a beaker containing 5mL of deionized water, stir for 5min-10min, then slowly add 5.00g of melamine solid powder into the dilute phosphoric acid solution under stirring, Make the molar ratio of phosphoric acid and melamine in the solution 1:100-1:20, and continue to stir for 20-60 minutes, so that phosphoric acid is evenly adsorbed and dispersed on the surface of melamine particles. Then heat the obtained suspension to 60°C-80°C under stirring to remove the solvent water, and then dry it in an oven at 60°C-80°C for 1h-3h;

c.将步骤b所得混合物置于坩埚中,盖好坩埚盖后放入马弗炉中,将马弗炉程序升温至520℃进行煅烧,平均升温速度为1.3℃/min~1.5℃/min,并在520℃保温2h,待自然冷却后将所得固体研磨;c. Put the mixture obtained in step b in a crucible, cover the crucible and put it into a muffle furnace, program the temperature of the muffle furnace to 520°C for calcination, with an average heating rate of 1.3°C/min to 1.5°C/min, And keep it warm at 520°C for 2 hours, and grind the obtained solid after natural cooling;

d.将步骤c所得固体粉末再次放入到坩埚中,敞口放入马弗炉中,以5.0℃/min~6.0℃/min的平均速度程序升温至520℃进行煅烧,并在520℃保温2h,自然冷却后取出产物,研磨后得到磷掺杂石墨相氮化碳可见光催化剂。d. Put the solid powder obtained in step c into the crucible again, put it into the muffle furnace with the open mouth, program the temperature to 520°C at an average speed of 5.0°C/min to 6.0°C/min for calcination, and keep it at 520°C After 2 hours, the product was taken out after natural cooling, and the phosphorus-doped graphite phase carbon nitride visible light catalyst was obtained after grinding.

优选的,步骤a中所述稀磷酸溶液的浓度为0.793mol/L,三聚氰胺固体粉末的量为5.00g,所述磷酸与三聚氰胺的摩尔比为1:100,1:50,1:20。Preferably, the concentration of the dilute phosphoric acid solution in step a is 0.793mol/L, the amount of melamine solid powder is 5.00g, and the molar ratio of phosphoric acid to melamine is 1:100, 1:50, 1:20.

优选的,步骤b中所得悬浮液在机械搅拌条件下加热至70℃~80℃除去溶剂水。Preferably, the suspension obtained in step b is heated to 70°C to 80°C under mechanical stirring to remove the solvent water.

优选的,步骤c中马弗炉程序升温步骤为,先在15min内升温至300℃,恒温1h,然后升温至350℃,恒温1h,再升温至400℃,恒温1h,之后升温至480℃,恒温1h,接着升温至500℃,恒温1h,最后升温至520℃,控制每次加热升温时间为5min~7min,升温至520℃后保温2h。Preferably, the muffle furnace temperature programming step in step c is to first raise the temperature to 300°C within 15 minutes, keep the temperature for 1h, then raise the temperature to 350°C, keep the temperature for 1h, then raise the temperature to 400°C, keep the temperature for 1h, and then raise the temperature to 480°C, Keep the temperature constant for 1 hour, then raise the temperature to 500°C, keep the temperature constant for 1 hour, and finally raise the temperature to 520°C, control the heating time for each heating to 5min-7min, raise the temperature to 520°C and then keep it warm for 2h.

优选的,步骤d中马弗炉程序升温步骤为,首先加热20min~30min升温至450℃,恒温1h,再经5min~10min升温至520℃,然后再保温2h。Preferably, the temperature programming step of the muffle furnace in step d is as follows: first heating for 20 minutes to 30 minutes to 450° C., keeping the temperature for 1 hour, then raising the temperature to 520° C. for 5 minutes to 10 minutes, and then keeping the temperature for 2 hours.

本发明的优点在于,原料来源广泛,制备方法简单,不需要复杂设备,适于大规模生产,所制备的磷掺杂石墨相氮化碳复合可见光催化剂具有优异的可见光催化性能和良好的催化稳定性。The invention has the advantages of wide sources of raw materials, simple preparation method, no need for complex equipment, suitable for large-scale production, and the prepared phosphorus-doped graphite phase carbon nitride composite visible light catalyst has excellent visible light catalytic performance and good catalytic stability sex.

附图说明Description of drawings

图1为磷掺杂石墨相氮化碳可见光催化剂的X射线衍射图谱;Fig. 1 is the X-ray diffraction spectrum of phosphorus-doped graphite phase carbon nitride visible photocatalyst;

图2为石墨相氮化碳的X射线光电子光谱;Fig. 2 is the X-ray photoelectron spectrum of graphite phase carbon nitride;

图3为磷掺杂石墨相氮化碳光催化降解不同时间时罗丹明B降解产物的高压液相色谱图;Fig. 3 is the high pressure liquid chromatogram of rhodamine B degradation product when photocatalytic degradation of phosphorus-doped graphite phase carbon nitride differs in time;

图4为磷掺杂石墨相氮化碳可见光催化降解罗丹明B的循环实验结果图。Fig. 4 is a graph showing the cycle experiment results of visible light catalytic degradation of rhodamine B by phosphorus-doped graphite phase carbon nitride.

具体实施方式Detailed ways

实施例1Example 1

移取浓度为0.793mol/L的稀磷酸溶液1mL加入到含有5mL去离子水的烧杯中,搅拌10min,之后在搅拌下将5.00g三聚氰胺固体粉末缓慢加入该稀磷酸溶液中,继续搅拌50min,使磷酸均匀吸附分散在三聚氰胺微粒表面。将所得悬浮液在搅拌下加热至80℃除去溶剂水,再于80℃烘箱中干燥2h。将干燥后的混合物置于坩埚中,盖好坩埚盖后放入马弗炉中,先在15min内升温至300℃,恒温1h,然后升温至350℃,恒温1h,再升温至400℃,恒温1h,之后升温至480℃,恒温1h,接着升温至500℃,恒温1h,最后升温至520℃,控制每次加热升温时间为5min,升温至520℃后保温2h,待自然冷却后将所得固体研磨;将所得固体粉末再次放入到坩埚中,敞口放入马弗炉中,先加热20min升温至450℃,恒温1h,再经10min升温至520℃,然后再保温2h,自然冷却后取出产物,研磨后得到磷掺杂石墨相氮化碳可见光催化剂。Pipette 1 mL of dilute phosphoric acid solution with a concentration of 0.793 mol/L and add it to a beaker containing 5 mL of deionized water, stir for 10 min, then slowly add 5.00 g of melamine solid powder into the dilute phosphoric acid solution under stirring, and continue stirring for 50 min to make Phosphoric acid is uniformly adsorbed and dispersed on the surface of melamine particles. The resulting suspension was heated to 80°C with stirring to remove the solvent water, and then dried in an oven at 80°C for 2h. Put the dried mixture in a crucible, cover the crucible and put it into a muffle furnace. First, heat up to 300°C within 15 minutes, keep the temperature constant for 1 hour, then raise the temperature to 350°C, keep the temperature constant for 1 hour, then raise the temperature to 400°C, keep the temperature constant 1h, then raise the temperature to 480°C, keep the temperature for 1h, then raise the temperature to 500°C, keep the temperature for 1h, and finally raise the temperature to 520°C, control the heating time of each heating to 5min, heat up to 520°C and keep it for 2h, after natural cooling, the obtained solid Grinding; Put the obtained solid powder into the crucible again, put it into the muffle furnace with the open mouth, heat it up to 450°C for 20 minutes, keep the temperature for 1 hour, then raise the temperature to 520°C in 10 minutes, then keep it warm for 2 hours, take it out after natural cooling The product is ground to obtain a phosphorus-doped graphite phase carbon nitride visible light catalyst.

本实施例中所制备的磷掺杂石墨相氮化碳可见光催化剂的X射线衍射图谱如图1所示。从图1可以看出,所制备样品在27.4°和13.2°有两个明显的特征衍射峰,分别对应石墨相氮化碳的(002)和(100)晶面,证明制得的样品为石墨相氮化碳。图2为所制备的磷掺杂石墨相氮化碳的X射线光电子光谱,从图2中可以看出磷掺杂石墨相氮化碳可见光催化剂在133.5eV处有磷元素峰出现,证明制备的可见光催化剂中确实掺杂进了磷元素。The X-ray diffraction pattern of the phosphorus-doped graphite phase carbon nitride catalyst prepared in this example is shown in FIG. 1 . It can be seen from Figure 1 that the prepared sample has two distinct characteristic diffraction peaks at 27.4° and 13.2°, corresponding to the (002) and (100) crystal planes of graphite-phase carbon nitride respectively, proving that the prepared sample is graphite phase carbon nitride. Figure 2 is the X-ray photoelectron spectrum of the prepared phosphorus-doped graphite phase carbon nitride, it can be seen from Figure 2 that the phosphorus-doped graphite phase carbon nitride visible photocatalyst has a phosphorus element peak at 133.5eV, proving that the prepared Phosphorus is indeed doped into the visible photocatalyst.

所制备的磷掺杂石墨相氮化碳可见光催化剂的性能测试如下:在敞口反应器中加入0.150g所制备催化剂和150mL浓度为4mg/L的罗丹明B溶液,在黑暗条件下搅拌2h达吸附平衡后,开启可见光源(300W碘钨灯并加盖滤光片滤除了400nm以下光)照射,在一定时间间隔内从反应体系中取样,经高速离心分离光催化剂后,取上层清液用分光光度计在554nm波长下测定吸光度,得到溶液中罗丹明B的浓度变化情况。实验结果表明,在可见光照射60min时,磷掺杂石墨相氮化碳可见光催化剂对罗丹明B的可见光催化降解率为97.3%,而相同条件下制备的纯石墨相氮化碳对罗丹明B的可见光催化降解率仅为49.7%。The performance test of the prepared phosphorus-doped graphite phase carbon nitride catalyst is as follows: add 0.150 g of the prepared catalyst and 150 mL of rhodamine B solution with a concentration of 4 mg/L in an open reactor, and stir for 2 h in the dark for up to After the adsorption balance, turn on the visible light source (300W iodine tungsten lamp and add a filter to filter out light below 400nm) to irradiate, take samples from the reaction system within a certain time interval, and after high-speed centrifugation to separate the photocatalyst, take the supernatant for use A spectrophotometer measures the absorbance at a wavelength of 554nm to obtain the concentration change of rhodamine B in the solution. The experimental results show that the visible photocatalytic degradation rate of rhodamine B by phosphorus-doped graphite-phase carbon nitride catalyst is 97.3% when irradiated by visible light for 60 min, while the pure graphite-phase carbon nitride prepared under the same conditions has a degrading rate of rhodamine B. The catalytic degradation rate of visible light is only 49.7%.

所制备的磷掺杂石墨相氮化碳光催化降解不同时间时罗丹明B降解产物的高压液相色谱图如图3所示。图3中横坐标为保留时间/min,纵坐标为相对强度,由图3可以看出,在所制备的磷掺杂石墨相氮化碳催化及可见光照射下,罗丹明B可迅速降解形成小分子中间产物,且中间产物也能被迅速降解,75min时罗丹明B及其中间产物就基本被完全降解,说明磷掺杂石墨相氮化碳具有高效的可见光催化活性。The high-pressure liquid chromatograms of the degradation products of rhodamine B during the photocatalytic degradation of the prepared phosphorus-doped graphite phase carbon nitride at different times are shown in Fig. 3 . In Fig. 3, the abscissa is the retention time/min, and the ordinate is the relative intensity. As can be seen from Fig. 3, Rhodamine B can be rapidly degraded to form small Molecular intermediates, and the intermediates can also be rapidly degraded. Rhodamine B and its intermediates were basically completely degraded in 75 minutes, indicating that phosphorus-doped graphitic carbon nitride has efficient visible light catalytic activity.

实施例2Example 2

移取浓度为0.793mol/L的稀磷酸溶液0.5mL加入到含有5mL去离子水的烧杯中,搅拌5min,之后在搅拌下将5.00g三聚氰胺固体粉末缓慢加入该稀磷酸溶液中,继续搅拌30min,使磷酸均匀吸附分散在三聚氰胺微粒表面。将所得悬浮液在搅拌下加热至80℃除去溶剂水后,再于80℃烘箱中干燥2h。将干燥后的混合物置于坩埚中,盖好坩埚盖后放入马弗炉中,先在15min内升温至300℃,恒温1h,然后升温至350℃,恒温1h,再升温至400℃,恒温1h,之后升温至480℃,恒温1h,接着升温至500℃,恒温1h,最后升温至520℃,控制每次加热升温时间为6min,升温至520℃后保温2h,待自然冷却后将所得固体研磨;将所得固体粉末再次放入到坩埚中,敞口放入马弗炉中,先加热20min升温至450℃,恒温1h,再经10min升温至520℃,然后再保温2h,自然冷却后取出产物,研磨后得到磷掺杂石墨相氮化碳可见光催化剂。实验测得在可见光照射60min时上述磷掺杂石墨相氮化碳可见光催化剂对罗丹明B的光催化降解率为96.0%,明显高于纯石墨相氮化碳对罗丹明B的可见光催化降解率(49.7%)。Pipette 0.5 mL of dilute phosphoric acid solution with a concentration of 0.793 mol/L and add it to a beaker containing 5 mL of deionized water, stir for 5 min, then slowly add 5.00 g of melamine solid powder into the dilute phosphoric acid solution under stirring, and continue stirring for 30 min. Make phosphoric acid evenly adsorbed and dispersed on the surface of melamine particles. The resulting suspension was heated to 80°C with stirring to remove the solvent water, and then dried in an oven at 80°C for 2 h. Put the dried mixture in a crucible, cover the crucible and put it into a muffle furnace. First, heat up to 300°C within 15 minutes, keep the temperature constant for 1 hour, then raise the temperature to 350°C, keep the temperature constant for 1 hour, then raise the temperature to 400°C, keep the temperature constant 1h, then raise the temperature to 480°C, keep the temperature for 1h, then raise the temperature to 500°C, keep the temperature for 1h, and finally raise the temperature to 520°C, control the heating time of each heating to 6min, raise the temperature to 520°C and keep it for 2h, after natural cooling, the obtained solid Grinding; Put the obtained solid powder into the crucible again, put it into the muffle furnace with the open mouth, heat it up to 450°C for 20 minutes, keep the temperature for 1 hour, then raise the temperature to 520°C in 10 minutes, then keep it warm for 2 hours, take it out after natural cooling The product is ground to obtain a phosphorus-doped graphite phase carbon nitride visible light catalyst. The experiment shows that the photocatalytic degradation rate of rhodamine B by the phosphorus-doped graphite phase carbon nitride visible light catalyst is 96.0% when the visible light is irradiated for 60 minutes, which is significantly higher than the visible light catalytic degradation rate of rhodamine B by pure graphite phase carbon nitride. (49.7%).

实施例3Example 3

移取浓度为0.793mol/L的稀磷酸溶液2.5mL加入到含有5mL去离子水的烧杯中,搅拌10min,之后在搅拌下将5.00g三聚氰胺固体粉末缓慢加入该稀磷酸溶液中,继续搅拌60min,使磷酸均匀吸附分散在三聚氰胺微粒表面。将所得悬浮液在搅拌条件下加热至80℃除去溶剂水后,再于80℃烘箱中干燥2h。将干燥后的混合物置于坩埚中,盖好坩埚盖后放入马弗炉中,先在15min内升温至300℃,恒温1h,然后升温至350℃,恒温1h,再升温至400℃,恒温1h,之后升温至480℃,恒温1h,接着升温至500℃,恒温1h,最后升温至520℃,控制每次加热升温时间为5min,升温至520℃后保温2h,待自然冷却后将所得固体研磨;将所得固体粉末再次放入到坩埚中,敞口放入马弗炉中,先加热20min升温至450℃,恒温1h,再经10min升温至520℃,然后再保温2h,自然冷却后取出产物,研磨后得到磷掺杂石墨相氮化碳可见光催化剂。实验测得在可见光照射60min时上述磷掺杂石墨相氮化碳可见光催化剂对罗丹明B的降率为90.5%。Pipette 2.5 mL of dilute phosphoric acid solution with a concentration of 0.793 mol/L into a beaker containing 5 mL of deionized water, stir for 10 min, then slowly add 5.00 g of melamine solid powder into the dilute phosphoric acid solution while stirring, and continue stirring for 60 min. Make phosphoric acid evenly adsorb and disperse on the surface of melamine particles. The resulting suspension was heated to 80°C with stirring to remove the solvent water, and then dried in an oven at 80°C for 2 h. Put the dried mixture in a crucible, cover the crucible and put it into a muffle furnace. First, heat up to 300°C within 15 minutes, keep the temperature constant for 1 hour, then raise the temperature to 350°C, keep the temperature constant for 1 hour, then raise the temperature to 400°C, keep the temperature constant 1h, then raise the temperature to 480°C, keep the temperature for 1h, then raise the temperature to 500°C, keep the temperature for 1h, and finally raise the temperature to 520°C, control the heating time of each heating to 5min, heat up to 520°C and keep it for 2h, after natural cooling, the obtained solid Grinding; Put the obtained solid powder into the crucible again, put it into the muffle furnace with the open mouth, heat it up to 450°C for 20 minutes, keep the temperature for 1 hour, then raise the temperature to 520°C in 10 minutes, then keep it warm for 2 hours, take it out after natural cooling The product is ground to obtain a phosphorus-doped graphite phase carbon nitride visible light catalyst. The experimental results show that the reduction rate of rhodamine B by the phosphorus-doped graphite phase carbon nitride visible light catalyst is 90.5% when the visible light is irradiated for 60 minutes.

实施例4Example 4

选取实施例1所制备的磷掺杂石墨相氮化碳可见光催化剂在可见光下进行循环降解罗丹明B实验以考察其光催化稳定性。在循环实验中,磷掺杂石墨相氮化碳光催化剂被用来重复降解罗丹明B溶液,光照75min后,催化剂经离心分离,水洗,干燥后进行下一次降解罗丹明B溶液测试。由附图4所示的磷掺杂石墨相氮化碳可见光催化降解罗丹明B的循环实验结果图可以看出,经9次循环重复使用后该光催化剂仍保持高效的光催化活性,表明该光催化剂具有良好的光催化稳定性,附图4中的横坐标为时间/min,纵坐标为百分比降解率。The phosphorus-doped graphite phase carbon nitride visible light catalyst prepared in Example 1 was selected to conduct a cycle degradation experiment of rhodamine B under visible light to investigate its photocatalytic stability. In the cycle experiment, the phosphorus-doped graphite phase carbon nitride photocatalyst was used to repeatedly degrade Rhodamine B solution. After 75 minutes of light irradiation, the catalyst was centrifuged, washed with water, and dried for the next Rhodamine B solution degradation test. As can be seen from the cyclic experiment result diagram of phosphorus-doped graphite phase carbon nitride visible light catalytic degradation of rhodamine B shown in accompanying drawing 4, the photocatalyst still maintains high-efficiency photocatalytic activity after 9 cycles of repeated use, indicating that the The photocatalyst has good photocatalytic stability. The abscissa in Figure 4 is time/min, and the ordinate is the percentage degradation rate.

Claims (5)

1.一种磷掺杂石墨相氮化碳可见光催化剂的制备方法,其特征在于,它以磷酸为磷源,以三聚氰胺为前驱体,制备磷元素掺杂石墨相氮化碳可见光催化剂,具体包括以下步骤:1. A method for preparing a phosphorus-doped graphite phase carbon nitride visible light catalyst, characterized in that it uses phosphoric acid as a phosphorus source and melamine as a precursor to prepare a phosphorus element doped graphite phase carbon nitride visible light catalyst, specifically comprising The following steps: a.量取浓度为85%的磷酸2mL~8mL移入100mL容量瓶中,加去离子水配成浓度为0.292mol/L~1.17mol/L的稀磷酸溶液;a. Measure 2mL-8mL of phosphoric acid with a concentration of 85% and transfer it into a 100mL volumetric flask, add deionized water to make a dilute phosphoric acid solution with a concentration of 0.292mol/L-1.17mol/L; b.移取步骤a所述稀磷酸溶液0.25mL~3.0mL加入到含有5mL去离子水的烧杯中,搅拌5min~10min,之后在搅拌下将5.00g三聚氰胺固体粉末缓慢加入该稀磷酸溶液中,使溶液中磷酸与三聚氰胺的摩尔比为1:100~1:20,继续搅拌20min~60min,使磷酸均匀吸附分散在三聚氰胺微粒表面,然后将所得悬浮液在搅拌下加热至60℃~80℃,除去溶剂水,再于60℃~80℃烘箱中干燥1h~3h;得混合物;b. Pipette 0.25mL-3.0mL of the dilute phosphoric acid solution described in step a into a beaker containing 5mL of deionized water, stir for 5min-10min, then slowly add 5.00g of melamine solid powder into the dilute phosphoric acid solution under stirring, Make the molar ratio of phosphoric acid and melamine in the solution 1:100-1:20, continue to stir for 20-60 minutes, so that phosphoric acid is evenly adsorbed and dispersed on the surface of melamine particles, and then the obtained suspension is heated to 60-80°C under stirring, Remove the solvent water, and then dry in an oven at 60°C to 80°C for 1h to 3h; the mixture is obtained; c.将步骤b所得混合物置于坩埚中,盖好坩埚盖后放入马弗炉中,将马弗炉程序升温至520℃进行煅烧,平均升温速度为1.3℃/min~1.5℃/min,并在520℃保温2h,待自然冷却后将所得固体研磨,得固体粉末;c. Put the mixture obtained in step b in a crucible, cover the crucible and put it into a muffle furnace, program the temperature of the muffle furnace to 520°C for calcination, with an average heating rate of 1.3°C/min to 1.5°C/min, And keep it at 520°C for 2 hours, and after natural cooling, grind the obtained solid to obtain solid powder; d.将步骤c所得固体粉末再次放入到坩埚中,敞口放入马弗炉中,以5.0℃/min~6.0℃/min的平均速度程序升温至520℃进行煅烧,并在520℃保温2h,自然冷却后取出产物,研磨后得到磷掺杂石墨相氮化碳可见光催化剂。d. Put the solid powder obtained in step c into the crucible again, put it into the muffle furnace with the open mouth, program the temperature to 520°C at an average speed of 5.0°C/min to 6.0°C/min for calcination, and keep it at 520°C After 2 hours, the product was taken out after natural cooling, and the phosphorus-doped graphite phase carbon nitride visible light catalyst was obtained after grinding. 2.如权利要求1所述的磷掺杂石墨相氮化碳可见光催化剂的制备方法,其特征在于,2. the preparation method of phosphorus-doped graphite phase carbon nitride visible light catalyst as claimed in claim 1, is characterized in that, 所述磷酸与三聚氰胺的摩尔比为1:50。The molar ratio of phosphoric acid to melamine is 1:50. 3.如权利要求1所述的磷掺杂石墨相氮化碳可见光催化剂的制备方法,其特征在于,步骤b中所得悬浮液在机械搅拌条件下加热至70℃~80℃除去溶剂水。3 . The method for preparing phosphorus-doped graphite-phase carbon nitride visible light catalyst according to claim 1 , wherein the suspension obtained in step b is heated to 70° C. to 80° C. under mechanical stirring to remove solvent water. 4 . 4.如权利要求1所述的磷掺杂石墨相氮化碳可见光催化剂的制备方法,其特征在于,步骤c所述马弗炉升温程序步骤为,先在15min内升温至300℃,恒温1h,然后升温至350℃,恒温1h,再升温至400℃,恒温1h,之后升温至480℃,恒温1h,接着升温至500℃,恒温1h,最后升温至520℃,控制每次加热升温时间为5min~10min,升温至520℃后保温2h。4. The preparation method of phosphorus-doped graphite phase carbon nitride visible light catalyst as claimed in claim 1, characterized in that, the step of the muffle furnace heating program described in step c is to first heat up to 300 ° C within 15 min, and keep the temperature constant for 1 h , then raise the temperature to 350°C, hold the temperature for 1 hour, then raise the temperature to 400°C, hold the temperature for 1 hour, then raise the temperature to 480°C, hold the temperature for 1 hour, then raise the temperature to 500°C, hold the temperature for 1 hour, and finally raise the temperature to 520°C, control the heating time for each heating 5min to 10min, heat up to 520°C and keep warm for 2h. 5.如权利要求1所述的磷掺杂石墨相氮化碳可见光催化剂的制备方法,其特征在于,步骤d中所述马弗炉程序升温步骤为,首先加热20min~30min升温至450℃,恒温1h,再经5min~10min升温至520℃,然后再保温2h。5. The preparation method of phosphorus-doped graphite-phase carbon nitride visible light catalyst as claimed in claim 1, characterized in that, the muffle furnace temperature programming step described in step d is, first heating to 450° C. for 20 minutes to 30 minutes, Keep the temperature constant for 1 hour, then raise the temperature to 520°C over 5 minutes to 10 minutes, and then keep the temperature for 2 hours.
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