WO2019109597A1 - Sulfur-doped s-c3n4 ammonia synthesis catalyst with graphene-like structure and preparation method therefor - Google Patents

Sulfur-doped s-c3n4 ammonia synthesis catalyst with graphene-like structure and preparation method therefor Download PDF

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WO2019109597A1
WO2019109597A1 PCT/CN2018/087120 CN2018087120W WO2019109597A1 WO 2019109597 A1 WO2019109597 A1 WO 2019109597A1 CN 2018087120 W CN2018087120 W CN 2018087120W WO 2019109597 A1 WO2019109597 A1 WO 2019109597A1
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sulfur
porcelain boat
catalyst
preparation
graphene
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许海峰
毛强
赫保明
叶吾梅
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宿州学院
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/026—Preparation of ammonia from inorganic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • the invention relates to the technical field of photocatalytic synthesis of ammonia, in particular to a sulfur-doped graphene-like structure S-C 3 N 4 high-efficiency visible light synthetic ammonia catalyst and a preparation method thereof.
  • Ammonia is one of the important inorganic chemical products.
  • the synthetic ammonia industry plays an important role in the national economy. With the development of the economy and the increase of population, nitrogen fertilizers used in agriculture such as urea, ammonium nitrate, ammonium phosphate, ammonium chloride and various nitrogen-containing compound fertilizers all use ammonia as raw material.
  • Synthetic ammonia is a large-scale chemical product. The annual production of synthetic ammonia in the world has reached more than 100 million tons, of which about 80% is used for chemical fertilizers and 20% is used as raw materials for other chemical products. Ammonia, as a clean, high energy density energy source, is the most ideal energy source.
  • ammonia For the utilization of ammonia, its large-scale preparation is the basis for the utilization of ammonia.
  • the ammonia method is mainly to directly synthesize ammonia by using nitrogen and hydrogen.
  • the high-temperature and high-pressure ammonia method has large energy consumption and serious pollution, and is not conducive to the sustainable acquisition of ammonia energy.
  • the use of water and nitrogen as raw materials to prepare ammonia by means of photocatalysis is safer, more efficient, environmentally friendly and sustainable.
  • the technical problem to be solved by the present invention is to provide a sulfur-doped graphene-like S-C 3 N 4 high-efficiency visible-light ammonia catalyst and a preparation method thereof, and the prepared sulfur-doped graphene-like structure S-C 3 N 4 has a high catalytic activity.
  • the present invention provides a method for preparing a sulfur-doped graphene-like S-C 3 N 4 high-efficiency visible-light ammonia catalyst, comprising the following steps:
  • the high temperature porcelain boat was placed in a muffle furnace and calcined in a gas atmosphere to obtain a sulfur-doped graphene-like structure S-C 3 N 4 catalyst.
  • the mass ratio of the thiourea to urea is (1 to 10):1.
  • the mixing treatment is one or more of grinding, ball milling and mechanical agitation.
  • the muffle furnace has a heating rate of 5 to 10 ° C / min.
  • the calcination temperature is 400 to 600 °C.
  • the calcination time is calcination for 1 to 6 hours.
  • the gas atmosphere is one or more of oxygen, air, nitrogen, and argon.
  • the high temperature porcelain boat is made of quartz, Al 2 O 3 , Si 3 N 4 or BN.
  • the invention utilizes a high temperature limited field combustion method to form an atmosphere rich in nitrogen, sulfur and carbon compounds, and reacts nitrogen, sulfur and carbon active substances uniformly and rapidly to form a uniform sulfur-doped graphene-like structure S-C 3 .
  • N 4 high efficiency catalyst The high temperature inert environment promotes the rapid reaction, and also increases the active area of the photocatalytic ammonia production catalytic reaction and the catalytic reaction site.
  • the above preparation method provided by the invention has simple equipment and only needs porcelain boat and the most common chemical raw materials to be mass-produced, and the degree of pollution of the products and raw materials to the environment is low.
  • the present invention also provides a sulfur-doped graphene-like structure S-C 3 N 4 catalyst prepared by the above preparation method.
  • Figure 1 is a diffraction pattern obtained by XRD analysis of a sample prepared by the present invention
  • Figure 3 is a UV-visible absorption spectrum of a sample prepared by the present invention.
  • Figure 4 is a graph showing the performance of photocatalytic ammonia production of a sample prepared by the present invention.
  • the prepared samples were analyzed by XRD, and the results are shown in Fig. 1.
  • the synthesized sample is a sulfur-doped graphene-like structure of S-C 3 N 4 , and no impurity peak appears.
  • the prepared sample was subjected to nitrogen adsorption analysis. The results are shown in Fig. 2. It can be seen from Fig. 2 that the S-C 3 N 4 sample has good adsorption performance for nitrogen and is favorable for photocatalytic nitrogen fixation.
  • the prepared sample was subjected to ultraviolet-visible absorption spectroscopy.
  • the results are shown in Fig. 3.
  • the S-C 3 N 4 sample has good absorption of ultraviolet and visible light, and can provide an effective energy source for photocatalysis.
  • the prepared sample was subjected to photocatalytic nitrogen fixation test.
  • the results are shown in Fig. 4.
  • the S-C 3 N 4 sample has stable and efficient photocatalytic nitrogen fixation performance with an efficiency of about 5 mmol.
  • the prepared sample was tested to have a catalytic activity comparable to that of the sample of Example 1.
  • the prepared sample was tested to have a catalytic activity comparable to that of the sample of Example 1.
  • the prepared sample was tested to have a catalytic activity comparable to that of the sample of Example 1.
  • the prepared sample was tested to have a catalytic activity comparable to that of the sample of Example 1.
  • the S-C 3 N 4 high-efficiency visible light synthetic ammonia catalyst prepared by the sulfur-doped graphene-like structure prepared by the invention has high catalytic activity.

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  • Engineering & Computer Science (AREA)
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Abstract

A preparation method for a sulfur-doped S-C3N4 efficient visible light ammonia synthesis catalyst with a graphene-like structure, comprising the following steps: mixing thiourea and urea according to a certain proportion, placing the uniform mixture into a high-temperature porcelain boat and covering the high-temperature porcelain boat with a porcelain boat cover plate; putting the high-temperature porcelain boat into a muffle furnace and calcining under gas atmosphere to obtain the sulfur-doped S-C3N4 catalyst with a graphene-like structure. The prepared sulfur-doped S-C3N4 catalyst with a graphene-like structure has higher visible light ammonia synthesis efficiency. Under normal temperature, normal pressure and visible light or direct solar radiation, the method for reducing N2 into NH3 based on the sulfur-doped S-C3N4 catalyst with a graphene-like structure is a new approach with high potential and promise.

Description

硫掺杂的类石墨烯结构的S‐C 3N 4合成氨催化剂及其制备方法 Sulfur-doped graphene-like structure S-C       3N       4 synthetic ammonia catalyst and preparation method thereof      技术领域Technical field
本发明涉及光催化合成氨技术领域，尤其涉及一种硫掺杂的类石墨烯结构的S‐C 3N 4高效可见光合成氨催化剂及其制备方法。 The invention relates to the technical field of photocatalytic synthesis of ammonia, in particular to a sulfur-doped graphene-like structure S-C 3 N 4 high-efficiency visible light synthetic ammonia catalyst and a preparation method thereof.
背景技术Background technique
能源是人类社会生存和发展的源泉，氨是重要的无机化工产品之一，合成氨工业在国民经济中占有重要地位。随着经济的发展和人口的增多，农业上使用的氮肥如尿素、硝酸铵、磷酸铵、氯化铵以及各种含氮复合肥，都以氨为原料。合成氨是大宗化工产品，世界每年合成氨产量已达1亿吨以上，其中约80％用于化学肥料，20％用作其它化工产品的原料。而氨气，作为一种清洁、高能量密度能源，是最理想的能源。对于氨气的利用来说，其规模化制备是氨气利用的基础。目前制氨气的方法主要为利用氮气与氢气直接合成氨，其中高温高压制氨法的能耗大，污染严重，并不利于可持续性的氨气能源的获取。而以水和氮气为原料利用光催化的方法制备氨气与之相比要更加安全，高效，环保，可持续。Energy is the source of the survival and development of human society. Ammonia is one of the important inorganic chemical products. The synthetic ammonia industry plays an important role in the national economy. With the development of the economy and the increase of population, nitrogen fertilizers used in agriculture such as urea, ammonium nitrate, ammonium phosphate, ammonium chloride and various nitrogen-containing compound fertilizers all use ammonia as raw material. Synthetic ammonia is a large-scale chemical product. The annual production of synthetic ammonia in the world has reached more than 100 million tons, of which about 80% is used for chemical fertilizers and 20% is used as raw materials for other chemical products. Ammonia, as a clean, high energy density energy source, is the most ideal energy source. For the utilization of ammonia, its large-scale preparation is the basis for the utilization of ammonia. At present, the ammonia method is mainly to directly synthesize ammonia by using nitrogen and hydrogen. The high-temperature and high-pressure ammonia method has large energy consumption and serious pollution, and is not conducive to the sustainable acquisition of ammonia energy. The use of water and nitrogen as raw materials to prepare ammonia by means of photocatalysis is safer, more efficient, environmentally friendly and sustainable.
到目前为止利用光催化产氨需要的催化剂大部分都是通过实验室小规模合成制备得到的，其主要合成方法有水热法、高温煅烧、气相沉积等制备途径。这些方法大多耗能较高或者产量太小，无法进行大规模的运用。同时，氮气是非常稳定的一种单质—它是一种惰性气体。氮气的三根化学键(两个π键和一个σ键)非常难断裂，导致固氮的效率非常低。Most of the catalysts required for photocatalytic ammonia production have been prepared by small-scale laboratory synthesis. The main synthetic methods include hydrothermal method, high temperature calcination, vapor deposition and other preparation routes. Most of these methods consume a lot of energy or the output is too small to be used on a large scale. At the same time, nitrogen is a very stable element - it is an inert gas. The three chemical bonds of nitrogen (two π bonds and one sigma bond) are very difficult to break, resulting in very low nitrogen fixation efficiency.
发明内容Summary of the invention
有鉴于此，本发明要解决的技术问题在于提供一种硫掺杂的类石墨烯结构的S‐C 3N 4高效可见光合成氨催化剂及其制备方法，制备的硫掺杂的类石墨烯结构的S‐C 3N 4具有较高的催化活性。 In view of the above, the technical problem to be solved by the present invention is to provide a sulfur-doped graphene-like S-C 3 N 4 high-efficiency visible-light ammonia catalyst and a preparation method thereof, and the prepared sulfur-doped graphene-like structure S-C 3 N 4 has a high catalytic activity.
为解决以上问题，本发明提供了一种硫掺杂的类石墨烯结构的S‐C 3N 4高效可见光合成氨催化剂的制备方法，包括以下步骤： In order to solve the above problems, the present invention provides a method for preparing a sulfur-doped graphene-like S-C 3 N 4 high-efficiency visible-light ammonia catalyst, comprising the following steps:
将硫脲与尿素按一定比例混合，在高温瓷舟中放置均匀混合之后的混合物，然后用瓷舟盖板盖住高温瓷舟；Mixing thiourea and urea in a certain ratio, placing the mixture after uniform mixing in a high temperature porcelain boat, and then covering the high temperature porcelain boat with a porcelain boat cover;
将所述高温瓷舟置于马弗炉中，在气体气氛中进行煅烧，得到硫掺杂的类石墨烯结构的S‐C 3N 4催化剂。 The high temperature porcelain boat was placed in a muffle furnace and calcined in a gas atmosphere to obtain a sulfur-doped graphene-like structure S-C 3 N 4 catalyst.
所述的硫脲与尿素的质量比为(1～10)：1。The mass ratio of the thiourea to urea is (1 to 10):1.
所述的混合处理的方式为研磨、球磨和机械搅拌中的一种或多种。The mixing treatment is one or more of grinding, ball milling and mechanical agitation.
所述的马弗炉升温速度为5～10℃/min。The muffle furnace has a heating rate of 5 to 10 ° C / min.
所述的煅烧温度为400～600℃。The calcination temperature is 400 to 600 °C.
所述的煅烧时间为煅烧1～6小时。The calcination time is calcination for 1 to 6 hours.
所述的气体气氛为氧气、空气、氮气和氩气中的一种或多种。The gas atmosphere is one or more of oxygen, air, nitrogen, and argon.
所述的高温瓷舟为石英、Al 2O 3、Si 3N 4或BN材质。 The high temperature porcelain boat is made of quartz, Al 2 O 3 , Si 3 N 4 or BN.
本发明利用高温限域燃烧法，形成富含氮、硫、碳化合物的气氛，让氮、硫、碳活性物质均匀快速地发生反应，生成均匀硫掺杂的类石墨烯结构的S‐C 3N 4高效催化剂。高温惰性环境促进了反应快速进行，同时也增加了光催化产氨催化反应的活性面积以及催化反应活性位点。 The invention utilizes a high temperature limited field combustion method to form an atmosphere rich in nitrogen, sulfur and carbon compounds, and reacts nitrogen, sulfur and carbon active substances uniformly and rapidly to form a uniform sulfur-doped graphene-like structure S-C 3 . N 4 high efficiency catalyst. The high temperature inert environment promotes the rapid reaction, and also increases the active area of the photocatalytic ammonia production catalytic reaction and the catalytic reaction site.
本发明提供的上述制备方法使用设备简单，只需要瓷舟、及最普遍的化工原料即可进行批量生产，产物与原料对于环境的污染程度低。The above preparation method provided by the invention has simple equipment and only needs porcelain boat and the most common chemical raw materials to be mass-produced, and the degree of pollution of the products and raw materials to the environment is low.
本发明还提供了上述制备方法制备的硫掺杂的类石墨烯结构的S‐C 3N 4催化剂。 The present invention also provides a sulfur-doped graphene-like structure S-C 3 N 4 catalyst prepared by the above preparation method.
附图说明DRAWINGS
图1为本发明制备的样品进行XRD分析所获得的衍射花样；Figure 1 is a diffraction pattern obtained by XRD analysis of a sample prepared by the present invention;
图2对本发明制备的样品进行氮吸附分析所获得的吸附‐脱附曲线；2 is an adsorption-desorption curve obtained by performing nitrogen adsorption analysis on a sample prepared by the present invention;
图3为本发明制备的样品的紫外可见吸收光谱图；Figure 3 is a UV-visible absorption spectrum of a sample prepared by the present invention;
图4为本发明制备的样品的光催化产氨的性能图；Figure 4 is a graph showing the performance of photocatalytic ammonia production of a sample prepared by the present invention;
具体实施方式Detailed ways
为了进一步说明本发明，下面结合实施例对本发明提供的一种硫掺杂的类石墨烯结构的S‐C 3N 4高效可见光合成氨催化剂及其制备方法进行详细描述。 In order to further illustrate the present invention, a sulfur-doped graphene-like structure of S-C 3 N 4 high-efficiency visible light synthetic ammonia catalyst and a preparation method thereof according to the present invention will be described in detail below with reference to the examples.
实施例1：Example 1:
将硫脲与尿素按质量比1:1的比例混合，在高温瓷舟中放置均匀混合之后的混合物，然后用瓷舟盖板盖住高温瓷舟；将所述高温瓷舟置于马弗炉中，在氮气气氛中进行煅烧，煅烧温度为550摄氏度,煅烧时间为2小时,得到硫掺杂的类石墨烯结构的S‐C 3N 4催化剂。称取50克得到的催化剂,分散在100mL去离子水中,向水中持续鼓入氮气,利用300W的氙灯光源进行照射,每隔20分钟取3mL反应溶液,进行离心,去除催化剂,对上清液利用购自市场的阳离子色谱对产物进行检测,得到水溶液中铵根离子的浓度. Mixing thiourea and urea in a ratio of 1:1 by mass ratio, placing the mixture after uniform mixing in a high temperature porcelain boat, and then covering the high temperature porcelain boat with a porcelain boat cover; placing the high temperature porcelain boat in the muffle furnace The calcination was carried out in a nitrogen atmosphere at a calcination temperature of 550 ° C and a calcination time of 2 hours to obtain a sulfur-doped graphene-like structure of S-C 3 N 4 catalyst. Weigh 50 g of the obtained catalyst, disperse it in 100 mL of deionized water, continue to bubble nitrogen into the water, irradiate with a 300 W xenon lamp source, take 3 mL of the reaction solution every 20 minutes, centrifuge, remove the catalyst, and use the supernatant. The product is detected by cation chromatography purchased from the market to obtain the concentration of ammonium ions in the aqueous solution.
采用XRD对制备的样品进行分析，结果见图1。由图1可知，所合成的样品是硫掺杂的类石墨烯结构的S‐C 3N 4，没有杂峰出现。 The prepared samples were analyzed by XRD, and the results are shown in Fig. 1. As can be seen from Fig. 1, the synthesized sample is a sulfur-doped graphene-like structure of S-C 3 N 4 , and no impurity peak appears.
对制备的样品进行氮气吸附分析，结果见图2，由图2可知S‐C 3N 4样品对氮气具有良好的吸附性能,有利于光催化固氮的反应。 The prepared sample was subjected to nitrogen adsorption analysis. The results are shown in Fig. 2. It can be seen from Fig. 2 that the S-C 3 N 4 sample has good adsorption performance for nitrogen and is favorable for photocatalytic nitrogen fixation.
对制备的样品进行紫外可见吸收光谱分析，结果见图3，由图3可知,S‐C 3N 4样品对紫外和可见光具有良好的吸收,可为光催化提供有效的能量来源。 The prepared sample was subjected to ultraviolet-visible absorption spectroscopy. The results are shown in Fig. 3. As can be seen from Fig. 3, the S-C 3 N 4 sample has good absorption of ultraviolet and visible light, and can provide an effective energy source for photocatalysis.
对制备的样品进行光催化固氮的测试,结果见图4,由图4可知,S‐C 3N 4样品具有稳定高效的光催化固氮性能,效率约为5毫摩尔每小时。 The prepared sample was subjected to photocatalytic nitrogen fixation test. The results are shown in Fig. 4. As can be seen from Fig. 4, the S-C 3 N 4 sample has stable and efficient photocatalytic nitrogen fixation performance with an efficiency of about 5 mmol.
实施例2：Example 2:
将硫脲与尿素按质量比1:3的比例混合，在高温瓷舟中放置均匀混合之后的混合物，然后用瓷舟盖板盖住高温瓷舟；将所述高温瓷舟置于马弗炉中，在氮气气氛中进行煅烧，煅烧温度为550摄氏度,煅烧时间为2小时,得到硫掺杂的类石墨烯结构的S‐C 3N 4催化剂。称取50克得到的催化剂,分散在100mL去离子水中,向水中持续鼓入氮气,利用300W的氙灯光源进行照射,每隔20分钟取3mL反应溶液,进行离心,去除催化剂,对上清液利用购自市场的阳离子色谱对产物进行检测,得到水溶液中铵根离子的浓度. Mixing thiourea and urea at a mass ratio of 1:3, placing the mixture after uniform mixing in a high temperature porcelain boat, and then covering the high temperature porcelain boat with a porcelain boat cover; placing the high temperature porcelain boat in a muffle furnace The calcination was carried out in a nitrogen atmosphere at a calcination temperature of 550 ° C and a calcination time of 2 hours to obtain a sulfur-doped graphene-like structure of S-C 3 N 4 catalyst. Weigh 50 g of the obtained catalyst, disperse it in 100 mL of deionized water, continue to bubble nitrogen into the water, irradiate with a 300 W xenon lamp source, take 3 mL of the reaction solution every 20 minutes, centrifuge, remove the catalyst, and use the supernatant. The product is detected by cation chromatography purchased from the market to obtain the concentration of ammonium ions in the aqueous solution.
经检测，制备的样品具有和实施例1样品相当的催化活性。The prepared sample was tested to have a catalytic activity comparable to that of the sample of Example 1.
实施例3：Example 3:
将硫脲与尿素按质量比2:1的比例混合，在高温瓷舟中放置均匀混合之后 的混合物，然后用瓷舟盖板盖住高温瓷舟；将所述高温瓷舟置于马弗炉中，在氮气气氛中进行煅烧，煅烧温度为550摄氏度,煅烧时间为2小时,得到硫掺杂的类石墨烯结构的S‐C 3N 4催化剂。称取50克得到的催化剂,分散在100mL去离子水中,向水中持续鼓入氮气,利用300W的氙灯光源进行照射,每隔20分钟取3mL反应溶液,进行离心,去除催化剂,对上清液利用购自市场的阳离子色谱对产物进行检测,得到水溶液中铵根离子的浓度. Mixing thiourea and urea in a ratio of 2:1 by mass, placing the mixture after uniform mixing in a high temperature porcelain boat, and then covering the high temperature porcelain boat with a porcelain boat cover; placing the high temperature porcelain boat in the muffle furnace The calcination was carried out in a nitrogen atmosphere at a calcination temperature of 550 ° C and a calcination time of 2 hours to obtain a sulfur-doped graphene-like structure of S-C 3 N 4 catalyst. Weigh 50 g of the obtained catalyst, disperse it in 100 mL of deionized water, continue to bubble nitrogen into the water, irradiate with a 300 W xenon lamp source, take 3 mL of the reaction solution every 20 minutes, centrifuge, remove the catalyst, and use the supernatant. The product is detected by cation chromatography purchased from the market to obtain the concentration of ammonium ions in the aqueous solution.
经检测，制备的样品具有和实施例1样品相当的催化活性。The prepared sample was tested to have a catalytic activity comparable to that of the sample of Example 1.
实施例4：Example 4:
将硫脲与尿素按质量比1:5的比例混合，在高温瓷舟中放置均匀混合之后的混合物，然后用瓷舟盖板盖住高温瓷舟；将所述高温瓷舟置于马弗炉中，在氮气气氛中进行煅烧，煅烧温度为550摄氏度,煅烧时间为2小时,得到硫掺杂的类石墨烯结构的S‐C 3N 4催化剂。称取50克得到的催化剂,分散在100mL去离子水中,向水中持续鼓入氮气,利用300W的氙灯光源进行照射,每隔20分钟取3mL反应溶液,进行离心,去除催化剂,对上清液利用购自市场的阳离子色谱对产物进行检测,得到水溶液中铵根离子的浓度. Mixing thiourea and urea at a mass ratio of 1:5, placing the mixture after uniform mixing in a high temperature porcelain boat, and then covering the high temperature porcelain boat with a porcelain boat cover; placing the high temperature porcelain boat in a muffle furnace The calcination was carried out in a nitrogen atmosphere at a calcination temperature of 550 ° C and a calcination time of 2 hours to obtain a sulfur-doped graphene-like structure of S-C 3 N 4 catalyst. Weigh 50 g of the obtained catalyst, disperse it in 100 mL of deionized water, continue to bubble nitrogen into the water, irradiate with a 300 W xenon lamp source, take 3 mL of the reaction solution every 20 minutes, centrifuge, remove the catalyst, and use the supernatant. The product is detected by cation chromatography purchased from the market to obtain the concentration of ammonium ions in the aqueous solution.
经检测，制备的样品具有和实施例1样品相当的催化活性。The prepared sample was tested to have a catalytic activity comparable to that of the sample of Example 1.
实施例5：Example 5:
将硫脲与尿素按质量比5:1的比例混合，在高温瓷舟中放置均匀混合之后的混合物，然后用瓷舟盖板盖住高温瓷舟；将所述高温瓷舟置于马弗炉中，在氮气气氛中进行煅烧，煅烧温度为550摄氏度,煅烧时间为2小时,得到硫掺杂的类石墨烯结构的S‐C 3N 4催化剂。称取50克得到的催化剂,分散在100mL去离子水中,向水中持续鼓入氮气,利用300W的氙灯光源进行照射,每隔20分钟取3mL反应溶液,进行离心,去除催化剂,对上清液利用购自市场的阳离子色谱对产物进行检测,得到水溶液中铵根离子的浓度. Mixing thiourea and urea in a ratio of mass ratio of 5:1, placing the mixture after uniform mixing in a high temperature porcelain boat, and then covering the high temperature porcelain boat with a porcelain boat cover; placing the high temperature porcelain boat in the muffle furnace The calcination was carried out in a nitrogen atmosphere at a calcination temperature of 550 ° C and a calcination time of 2 hours to obtain a sulfur-doped graphene-like structure of S-C 3 N 4 catalyst. Weigh 50 g of the obtained catalyst, disperse it in 100 mL of deionized water, continue to bubble nitrogen into the water, irradiate with a 300 W xenon lamp source, take 3 mL of the reaction solution every 20 minutes, centrifuge, remove the catalyst, and use the supernatant. The product is detected by cation chromatography purchased from the market to obtain the concentration of ammonium ions in the aqueous solution.
经检测，制备的样品具有和实施例1样品相当的催化活性。The prepared sample was tested to have a catalytic activity comparable to that of the sample of Example 1.
由上述实施例可知，本发明制备的硫掺杂的类石墨烯结构的S‐C 3N 4高效可见光合成氨催化剂具有较高的催化活性。 It can be seen from the above examples that the S-C 3 N 4 high-efficiency visible light synthetic ammonia catalyst prepared by the sulfur-doped graphene-like structure prepared by the invention has high catalytic activity.
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要 求的保护范围内。The above description of the embodiments is merely to assist in understanding the method of the present invention and its core idea. It should be noted that those skilled in the art can make various modifications and changes to the present invention without departing from the spirit and scope of the invention.

Claims (10)

  1. 一种硫掺杂的类石墨烯结构的S‐C 3N 4高效可见光合成氨催化剂的制备方法，其特征在于，包括以下步骤： A method for preparing a sulfur-doped graphene-like structure of S-C 3 N 4 high-efficiency visible light synthetic ammonia catalyst, comprising the steps of:
    将硫脲与尿素按一定比例混合，在高温瓷舟中放置均匀混合之后的混合物，然后用瓷舟盖板盖住高温瓷舟；Mixing thiourea and urea in a certain ratio, placing the mixture after uniform mixing in a high temperature porcelain boat, and then covering the high temperature porcelain boat with a porcelain boat cover;
    将所述高温瓷舟置于马弗炉中，在气体气氛中进行煅烧，得到硫掺杂的类石墨烯结构的S‐C 3N 4催化剂。 The high temperature porcelain boat was placed in a muffle furnace and calcined in a gas atmosphere to obtain a sulfur-doped graphene-like structure S-C 3 N 4 catalyst.
  2. 根据权利要求1所述的制备方法，其特征在于，所述硫脲与尿素的质量比为(1～10)：1。The production method according to claim 1, wherein the mass ratio of the thiourea to urea is (1 to 10):1.
  3. 根据权利要求1所述的制备方法，其特征在于，所述混合处理的方式为研磨、球磨和机械搅拌中的一种或多种。The preparation method according to claim 1, wherein the mixing treatment is one or more of grinding, ball milling, and mechanical agitation.
  4. 根据权利要求1所述的制备方法，其特征在于，所述马弗炉升温速度为5～10℃/min。The preparation method according to claim 1, wherein the muffle furnace is heated at a rate of 5 to 10 ° C / min.
  5. 根据权利要求1所述的制备方法，其特征在于，所述煅烧温度为400～600℃。The production method according to claim 1, wherein the calcination temperature is from 400 to 600 °C.
  6. 根据权利要求1所述的制备方法，其特征在于，所述煅烧时间为煅烧1～6小时。The preparation method according to claim 1, wherein the calcination time is calcination for 1 to 6 hours.
  7. 根据权利要求1所述的制备方法，其特征在于，所述气体气氛为氧气、空气、氮气和氩气中的一种或多种。The preparation method according to claim 1, wherein the gas atmosphere is one or more of oxygen, air, nitrogen, and argon.
  8. 根据权利要求1所述的制备方法，其特征在于，所述高温瓷舟为石英、Al 2O 3、Si 3N 4或BN材质。 The preparation method according to claim 1, wherein the high temperature porcelain boat is made of quartz, Al 2 O 3 , Si 3 N 4 or BN.
  9. 权利要求1～8任一项所述的制备方法制备的硫掺杂的类石墨烯结构的S‐C 3N 4催化剂。 A sulfur-doped graphene-like structure S-C 3 N 4 catalyst prepared by the production method according to any one of claims 1 to 8.
  10. 权利要求1～9任一项所述的制备方法制备的硫掺杂的类石墨烯结构的S‐C 3N 4催化剂可用于高效可见光合成氨。 The sulfur-doped graphene-like structure S-C 3 N 4 catalyst prepared by the preparation method according to any one of claims 1 to 9 can be used for high-efficiency visible light synthesis of ammonia.
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