WO2019015356A1 - Method for rapidly preparing mica-supported carbon nitride photocatalytic material by means of microwaves - Google Patents

Method for rapidly preparing mica-supported carbon nitride photocatalytic material by means of microwaves Download PDF

Info

Publication number
WO2019015356A1
WO2019015356A1 PCT/CN2018/081339 CN2018081339W WO2019015356A1 WO 2019015356 A1 WO2019015356 A1 WO 2019015356A1 CN 2018081339 W CN2018081339 W CN 2018081339W WO 2019015356 A1 WO2019015356 A1 WO 2019015356A1
Authority
WO
WIPO (PCT)
Prior art keywords
mica
microwave
carbon nitride
dimensional
powder
Prior art date
Application number
PCT/CN2018/081339
Other languages
French (fr)
Chinese (zh)
Inventor
陆春华
张方舒
寇佳慧
许仲梓
熊吉如
袁慧雯
Original Assignee
南京工业大学
南京倍立达新材料***工程股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 南京工业大学, 南京倍立达新材料***工程股份有限公司 filed Critical 南京工业大学
Publication of WO2019015356A1 publication Critical patent/WO2019015356A1/en

Links

Images

Classifications

    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J35/39—

Definitions

  • the invention relates to a method for rapidly preparing a mica-loaded carbon nitride photocatalytic material by microwave.
  • the photocatalytic self-cleaning technology is based on the photocatalytic action of inorganic semiconductor materials, on the one hand, it can degrade organic pollutants on the surface of the substrate; on the other hand, the surface of the substrate is super-hydrophilic, and the surface surface pollutants can be washed away with rainwater.
  • Graphite-like structure carbonitride (gC 3 N 4 ) is a metal element-free semiconductor material with a narrow Eg (2.7 eV), visible light absorption capability, and low cost synthetic raw materials.
  • loading gC 3 N 4 on the mica sheet can effectively prevent the corrosion and embedding of alkaline substances in the cement matrix against gC 3 N 4 . Thereby extending the life cycle of gC 3 N 4 .
  • mica loading gC 3 N 4 is mainly synthesized by thermal polymerization.
  • the method requires high temperature and long time, which increases the production cost in disguise and hinders the progress of industrial production.
  • the preparation of carbon nitride by microwave method has short time, low energy consumption, high production efficiency and simple process, and has wide application prospects.
  • the existing microwave preparation method for carbonation is mainly a container containing an amine compound such as urea. Buried into a large amount of microwave absorbing material, microwave heating to prepare carbon nitride, although this method shortens the preparation time, but consumes a large amount of microwave absorbing material, resulting in waste of resources, and mica and amine-based compounds have no microwave absorption characteristics,
  • the external microwave absorbing medium can only be heated by heat transfer. Due to the short heating time of the microwave, the inside of the accumulated material cannot be sufficiently heated, resulting in poor uniformity of the final product.
  • the object of the present invention is to provide a method for quickly preparing a mica-loaded carbon nitride photocatalytic material by microwave, so that the material itself absorbs microwaves, thereby reducing the amount of external microwave absorbing materials, shortening the preparation time of carbon nitride, and improving product uniformity. Promote its industrial production process and expand its application range.
  • the technical scheme of the invention is: a method for quickly preparing a mica-loaded carbon nitride photocatalytic material by microwave, and the specific steps thereof are as follows:
  • the mica powder is placed in a solvent, wherein the mass percentage of the mica powder is 1% to 20%, stirred until uniform, and ultrasonically dispersed in an ultrasonic wave to obtain a two-dimensional mica suspension;
  • S2 adjusting the pH of the mica flake suspension to 1-2 with hydrochloric acid, heating to 70-80 ° C, adding a certain amount of SnCl 4 ⁇ 5H 2 O and SbCl 3 , wherein the mass ratio of SnCl 4 ⁇ 5H 2 O to mica is 0.5 ⁇ 2, the mass ratio of SbCl 3 to SnCl 4 ⁇ 5H 2 O is 0.05 ⁇ 0.2, adjust the pH of the mixed suspension solution to 1-2 with alkaline solution, stir for 2 ⁇ 4h, centrifuge, wash and dry the powder. Then, the powder is placed in a high temperature furnace, heated to 600-800 ° C, and kept for 2 to 3 hours to obtain a two-dimensional sheet mica coated with antimony-doped tin dioxide;
  • the ultrasonic dispersion in the step S1 has an ultrasonic frequency of 100 W-500 W and an ultrasonic time of 2 to 4 h.
  • the solvent in the step S1 is one or a mixture of deionized water or ethanol.
  • the alkaline solution described in the step S2 is a sodium hydroxide solution or ammonia water.
  • the amine compound described in the step S3 is one or more of urea, melamine or dicyandiamide.
  • the aerogel insulation material described in step S3 is a silica aerogel, a fiber felt aerogel or a silica-fiber mat composite aerogel.
  • the microwave power described in step S3 is 350W-700W.
  • the microwave time described in step S3 is 10 min-30 min.
  • the microwave absorbing material described in step S3 is amorphous carbon, CuO, Fe 3 O 4 , MnO 2 , SnO 2 or WO 3 .
  • Tin dioxide has good microwave absorption characteristics, mixed with amine-based compounds, and expands the depth of microwave action by internal and external microwave bonding, improves the efficiency and uniformity of microwave synthesis of carbon nitride, and greatly reduces the amount of external microwave medium. save resources.
  • 1 is an XRD pattern of a two-dimensional mica-loaded carbonitride photocatalytic material obtained by microwave heating a mixture of mica and urea;
  • FIG. 2 is a graph showing the performance of a two-dimensional mica-loaded carbonitride photocatalytic material for degrading rhodamine B after microwave heating mica and urea mixture.
  • the mica-loaded carbon nitride prepared by the process has better degradation of rhodamine B performance;
  • Figure 3 is a graph showing the degradation of rhodamine B by a two-dimensional mica-loaded carbonitride photocatalytic material after microwave heating mica and melamine mixture.
  • the mica-loaded carbon nitride prepared by the process has better degradation of rhodamine B performance.
  • Figure 4 is a graph showing the degradation of rhodamine B by a two-dimensional mica-loaded carbonitride photocatalytic material after microwave heating mica and dicyandiamide mixture.
  • the mica-loaded carbon nitride prepared by the process has better degradation of rhodamine B performance.
  • Figure 5 is a graph showing the degradation of rhodamine B by two-dimensional mica-loaded carbonitride photocatalytic material after microwave heating mica and urea mixture.
  • the mica-loaded carbon nitride prepared by this process has better degradation of rhodamine B.
  • S2 adjust the pH of the mica flake suspension to 1.5 with hydrochloric acid, heat to 70 ° C, add 5 g of SnCl 4 ⁇ 5H 2 O and 1 g of SbCl 3 , adjust the pH of the mixed solution to 1.5 with NaOH solution, stir for 3 h, suction filtration, washing Drying, then placing the powder in a muffle furnace, heating to 600 ° C, and holding for 3 h to obtain a mica plate coated with antimony-doped tin dioxide;
  • Figure 2 is a graph showing the degradation of rhodamine B in the prepared mica-loaded carbon nitride material. It shows that the prepared mica-loaded carbon nitride material has better degradation performance of rhodamine B, and the degradation rate is more than 95% in one hour.
  • S3 Weigh 0.6 g of two-dimensional mica and 20 g of melamine and mix uniformly; place the mixture in 100 mL of mash, place the mash in 300 mL of mash, and fill in a certain amount of Fe 3 O 4 between the two mashes.
  • the stacking height of Fe 3 O 4 is equal to the stacking height of the mixture in the small crucible, and a layer of silica aerogel insulation material is wrapped outside the 300 mL crucible.
  • 300 mL of ruthenium was placed in a microwave device, microwaved at 550 W for 15 min, and then cooled to room temperature to obtain a two-dimensional mica-supported carbon nitride photocatalytic material.
  • Figure 3 is a graph showing the degradation of rhodamine B in the prepared mica-loaded carbon nitride material, indicating that the prepared mica-loaded carbon nitride material has better degradation properties of rhodamine B, and the degradation rate is 98% in 2 hours.
  • S2 adjust the pH of the mica flake suspension to 1.0 with hydrochloric acid, heat to 80 ° C, add 10 g of SnCl 4 ⁇ 5H 2 O and 0.6 g of SbCl 3 , stir until completely dissolved, and gradually add the mixed solution to the mica suspension.
  • Ammonia solution adjust the pH of the mixed solution to 1.0, stir for 4 hours, centrifuge the powder, wash and dry, then place the powder in a muffle furnace, heat up to 800 ° C, and keep it for 2 h to obtain mica doped with antimony-doped tin dioxide. sheet;
  • Figure 4 is a graph showing the degradation of rhodamine B in the prepared mica-loaded carbon nitride material, indicating that the prepared mica-loaded carbon nitride material has better degradation properties of rhodamine B, and the degradation rate is 98% in 2 hours.
  • S2 adjust the pH of the mica flake suspension to 1.5 with hydrochloric acid, heat to 70 ° C, add a certain amount of 5 g of SnCl 4 ⁇ 5H 2 O and 1 g of SbCl 3 , adjust the pH of the mixed solution to 1.5 with NaOH solution, stir for 2 h, and filter. Washing, drying, and then placing the powder in a muffle furnace, heating to 600 ° C, and holding for 3 h to obtain a mica plate coated with antimony-doped tin dioxide;
  • Figure 5 is a graph showing the degradation of rhodamine B in the prepared mica-loaded carbon nitride material, indicating that the prepared mica-loaded carbon nitride material has better degradation performance of rhodamine B, and the degradation rate of more than 60% in one hour.

Abstract

Disclosed is a method for rapidly preparing a mica-supported carbon nitride photocatalytic material by means of microwaves, wherein the mica-supported carbon nitride photocatalytic material is prepared by coating the surface of a two-dimensional flaky mica as a support with a layer of microwave-absorbing material, i.e., stannic oxide, and subjecting same to a microwave method with an amino compound as a material for the synthesis of a graphite-like carbon nitride. Stannic oxide has a very good microwave-absorbing property. By mixing same with the amino compound and by means of the microwave effect heating from outside in, the depth of the microwave action is expanded, the efficiency and uniformity of the microwave synthesis of the mica-supported carbon nitride are improved, the preparation time is reduced, the usage amount of the external microwave medium is greatly reduced, and resources are saved.

Description

微波快速制备云母负载氮化碳光催化材料的方法Method for rapidly preparing mica-loaded carbon nitride photocatalytic material by microwave 技术领域Technical field
本发明涉及一种微波快速制备云母负载氮化碳光催化材料的方法。The invention relates to a method for rapidly preparing a mica-loaded carbon nitride photocatalytic material by microwave.
背景技术Background technique
光催化自清洁技术是基于无机半导体材料的光催化作用，一方面可降解基体表面的有机污染物；另一方面，使得基体表面超亲水，基体表面污染物可随雨水冲洗掉。类石墨结构氮化碳(g-C 3N 4)是一种不含金属元素的半导体材料，该材料的Eg较窄(2.7eV)，具有可见光吸收能力，且其合成原材料价格低廉，容易获取，具有很大的应用前景。为了更好将g-C 3N 4应用在以水泥为基础材料的建筑外墙上，将g-C 3N 4负载于云母片上可有效防止水泥基体中碱性物质对g-C 3N 4的腐蚀、包埋，从而延长g-C 3N 4的使用周期。 The photocatalytic self-cleaning technology is based on the photocatalytic action of inorganic semiconductor materials, on the one hand, it can degrade organic pollutants on the surface of the substrate; on the other hand, the surface of the substrate is super-hydrophilic, and the surface surface pollutants can be washed away with rainwater. Graphite-like structure carbonitride (gC 3 N 4 ) is a metal element-free semiconductor material with a narrow Eg (2.7 eV), visible light absorption capability, and low cost synthetic raw materials. Great application prospects. In order to better apply gC 3 N 4 on the exterior wall of cement-based materials, loading gC 3 N 4 on the mica sheet can effectively prevent the corrosion and embedding of alkaline substances in the cement matrix against gC 3 N 4 . Thereby extending the life cycle of gC 3 N 4 .
目前云母负载g-C 3N 4主要以热聚合法合成为主，该方法所需温度较高，且所需时间长，变相增加其生产成本，阻碍其工业生产的进度。微波法制备氮化碳，时间短、能耗小、生产效率高且工艺简单，具有广泛的应用前景，但现有的微波制备氮化碳方法主要是将装有胺基化合物，如尿素的容器埋入大量的微波吸收物质内，通过微波加热制备氮化碳，此法虽然缩短了制备时间，但要消耗大量的微波吸收物质，造成资源浪费，且云母及胺基化合物均无微波吸收特性，只能由外部微波吸收介质通过热传递进行加热，由于微波加热时间较短，使得堆积的物料内部不能充分被加热，从而导致最终产品均匀性较差。 At present, mica loading gC 3 N 4 is mainly synthesized by thermal polymerization. The method requires high temperature and long time, which increases the production cost in disguise and hinders the progress of industrial production. The preparation of carbon nitride by microwave method has short time, low energy consumption, high production efficiency and simple process, and has wide application prospects. However, the existing microwave preparation method for carbonation is mainly a container containing an amine compound such as urea. Buried into a large amount of microwave absorbing material, microwave heating to prepare carbon nitride, although this method shortens the preparation time, but consumes a large amount of microwave absorbing material, resulting in waste of resources, and mica and amine-based compounds have no microwave absorption characteristics, The external microwave absorbing medium can only be heated by heat transfer. Due to the short heating time of the microwave, the inside of the accumulated material cannot be sufficiently heated, resulting in poor uniformity of the final product.
发明内容Summary of the invention
本发明的目的是提供一种微波快速制备云母负载氮化碳光催化材料的方法，使材料本身吸收微波，从而减少外界微波吸收物质用量，同时缩短氮化碳的制备时间，提高产品均匀性，推进其工业生产进程，扩大其应用范围。The object of the present invention is to provide a method for quickly preparing a mica-loaded carbon nitride photocatalytic material by microwave, so that the material itself absorbs microwaves, thereby reducing the amount of external microwave absorbing materials, shortening the preparation time of carbon nitride, and improving product uniformity. Promote its industrial production process and expand its application range.
本发明的技术方案为：微波快速制备云母负载氮化碳光催化材料的方法，其具体步骤如下：The technical scheme of the invention is: a method for quickly preparing a mica-loaded carbon nitride photocatalytic material by microwave, and the specific steps thereof are as follows:
S1：将云母粉置于溶剂中，其中云母粉的质量百分含量占1％～20％，搅拌 至均匀，置于超声波中超声分散，得到二维云母片悬浮液；S1: The mica powder is placed in a solvent, wherein the mass percentage of the mica powder is 1% to 20%, stirred until uniform, and ultrasonically dispersed in an ultrasonic wave to obtain a two-dimensional mica suspension;
S2：用盐酸将云母片悬浮液pH调节至1～2，加热至70～80℃，加入一定量SnCl 4·5H 2O和SbCl 3，其中，SnCl 4·5H 2O与云母的质量比为0.5～2，SbCl 3与SnCl 4·5H 2O质量比为0.05～0.2，用碱性溶液将混合悬浮液溶液pH调至1～2，搅拌2～4h，将粉体离心、洗涤、烘干，然后将粉体置于高温炉中，升温至600～800℃，保温2～3h，获得掺锑二氧化锡包覆的二维片状云母； S2: adjusting the pH of the mica flake suspension to 1-2 with hydrochloric acid, heating to 70-80 ° C, adding a certain amount of SnCl 4 ·5H 2 O and SbCl 3 , wherein the mass ratio of SnCl 4 ·5H 2 O to mica is 0.5～2, the mass ratio of SbCl 3 to SnCl 4 ·5H 2 O is 0.05～0.2, adjust the pH of the mixed suspension solution to 1-2 with alkaline solution, stir for 2~4h, centrifuge, wash and dry the powder. Then, the powder is placed in a high temperature furnace, heated to 600-800 ° C, and kept for 2 to 3 hours to obtain a two-dimensional sheet mica coated with antimony-doped tin dioxide;
S3：将二维云母和胺基化合物均匀混合，其中二维云母和胺基化合物的质量比为0.01～0.12:1；将放有二维云母和胺基化合物的坩埚置于更大的坩埚内，两坩埚之间填入微波吸收物质，在坩埚外部包裹一层气凝胶保温材料，将大坩埚放入微波装置中，在一定微波功率下，加热一段时间后，冷却得到云母负载氮化碳光催化材料。S3: uniformly mixing two-dimensional mica and an amine compound, wherein the mass ratio of the two-dimensional mica to the amine compound is 0.01 to 0.12:1; and the ruthenium containing the two-dimensional mica and the amine compound is placed in a larger crucible The microwave absorbing material is filled between the two crucibles, and a layer of aerogel insulation material is wrapped outside the crucible, and the big crucible is placed in a microwave device, and after heating for a certain period of time under microwave power, the mica-loaded carbon nitride is cooled. Photocatalytic material.
优选步骤S1中的超声分散的超声频率为100W-500W，超声时间为2～4h。Preferably, the ultrasonic dispersion in the step S1 has an ultrasonic frequency of 100 W-500 W and an ultrasonic time of 2 to 4 h.
优选步骤S1中的溶剂为去离子水或乙醇中的一种或两种混合液。Preferably, the solvent in the step S1 is one or a mixture of deionized water or ethanol.
优选步骤S2中所述的碱性溶液为氢氧化钠溶液或氨水。Preferably, the alkaline solution described in the step S2 is a sodium hydroxide solution or ammonia water.
优选步骤S3中所述的胺基化合物为尿素、三聚氰胺或双氰胺中的一种或多种。Preferably, the amine compound described in the step S3 is one or more of urea, melamine or dicyandiamide.
优选步骤S3中所述的气凝胶保温材料为二氧化硅气凝胶、纤维毡气凝胶或二氧化硅-纤维毡复合气凝胶。Preferably, the aerogel insulation material described in step S3 is a silica aerogel, a fiber felt aerogel or a silica-fiber mat composite aerogel.
优选步骤S3中所述的微波功率350W-700W。Preferably, the microwave power described in step S3 is 350W-700W.
优选步骤S3中所述的微波时间10min-30min。Preferably, the microwave time described in step S3 is 10 min-30 min.
优选步骤S3中所述的微波吸收物质为无定型炭、CuO、Fe 3O 4、MnO 2、SnO 2或WO 3。 Preferably, the microwave absorbing material described in step S3 is amorphous carbon, CuO, Fe 3 O 4 , MnO 2 , SnO 2 or WO 3 .
有益效果：Beneficial effects:
二氧化锡具有很好的微波吸收特性，与胺基化合物混合，通过内外微波结合的方法，扩大微波作用的深度，提高微波合成氮化碳的效率和均匀性，大大减少外部微波介质的用量，节约资源。Tin dioxide has good microwave absorption characteristics, mixed with amine-based compounds, and expands the depth of microwave action by internal and external microwave bonding, improves the efficiency and uniformity of microwave synthesis of carbon nitride, and greatly reduces the amount of external microwave medium. save resources.
附图说明DRAWINGS
图1为微波加热云母与尿素混合物后得到二维云母负载氮化碳光催化材料的XRD图；1 is an XRD pattern of a two-dimensional mica-loaded carbonitride photocatalytic material obtained by microwave heating a mixture of mica and urea;
图2为微波加热云母与尿素混合物后得到二维云母负载氮化碳光催化材料降解罗丹明B性能图，该工艺制备的云母负载氮化碳具有较好的降解罗丹明B性能；2 is a graph showing the performance of a two-dimensional mica-loaded carbonitride photocatalytic material for degrading rhodamine B after microwave heating mica and urea mixture. The mica-loaded carbon nitride prepared by the process has better degradation of rhodamine B performance;
图3为微波加热云母与三聚氰胺混合物后得到二维云母负载氮化碳光催化材料降解罗丹明B性能图，该工艺制备的云母负载氮化碳具有较好的降解罗丹明B性能；Figure 3 is a graph showing the degradation of rhodamine B by a two-dimensional mica-loaded carbonitride photocatalytic material after microwave heating mica and melamine mixture. The mica-loaded carbon nitride prepared by the process has better degradation of rhodamine B performance.
图4为微波加热云母与双氰胺混合物后得到二维云母负载氮化碳光催化材料降解罗丹明B性能图，该工艺制备的云母负载氮化碳具有较好的降解罗丹明B性能；Figure 4 is a graph showing the degradation of rhodamine B by a two-dimensional mica-loaded carbonitride photocatalytic material after microwave heating mica and dicyandiamide mixture. The mica-loaded carbon nitride prepared by the process has better degradation of rhodamine B performance.
图5为微波加热云母与尿素混合物后得到二维云母负载氮化碳光催化材料降解罗丹明B性能图，该工艺制备的云母负载氮化碳具有较好的降解罗丹明B性能。Figure 5 is a graph showing the degradation of rhodamine B by two-dimensional mica-loaded carbonitride photocatalytic material after microwave heating mica and urea mixture. The mica-loaded carbon nitride prepared by this process has better degradation of rhodamine B.
具体实施方式Detailed ways
下面结合附图和四个实施例，对本发明的技术方案作进一步的介绍The technical solution of the present invention is further introduced in the following with reference to the accompanying drawings and the four embodiments.
实施例1Example 1
本实施案例所述的微波快速制备二维云母负载类石墨氮化碳的制备方法，包括以下步骤：The method for preparing a two-dimensional mica-loaded graphite carbon nitride by microwave in the present embodiment includes the following steps:
S1：将5g云母粉置于200mL乙醇，云母粉的质量百分含量为3％，搅拌至均匀，置于400W超声波中，超声2h，得到二维云母片悬浮液；S1: 5g of mica powder is placed in 200mL of ethanol, the mass percentage of mica powder is 3%, stirred until uniform, placed in 400W ultrasonic wave, ultrasonic 2h, to obtain a two-dimensional mica suspension;
S2：用盐酸将云母片悬浮液pH调节至1.5，加热至70℃，加入5g SnCl 4·5H 2O和1g SbCl 3，用NaOH溶液将混合溶液pH调至1.5，搅拌3h，抽滤、洗涤、干燥，然后将粉体置于马弗炉中，升温至600℃，保温3h，获得掺锑二氧化锡包覆的云母片； S2: adjust the pH of the mica flake suspension to 1.5 with hydrochloric acid, heat to 70 ° C, add 5 g of SnCl 4 ·5H 2 O and 1 g of SbCl 3 , adjust the pH of the mixed solution to 1.5 with NaOH solution, stir for 3 h, suction filtration, washing Drying, then placing the powder in a muffle furnace, heating to 600 ° C, and holding for 3 h to obtain a mica plate coated with antimony-doped tin dioxide;
S3：称取0.2g二维云母和20g尿素均匀混合；将混合物置于100mL坩埚中，将100mL坩埚置于300mL坩埚中，两坩埚之间填入一定量CuO，两坩埚之间CuO的堆积高度等于小坩埚内混合物的堆积高度，在300mL坩埚外部包裹一层纤维毡子气凝胶保温材料。将300mL坩埚置于微波装置中，在550w功率下微波15min，冷却至室温得到二维云母负载氮化碳光催化材料。S3: Weigh 0.2g two-dimensional mica and 20g urea uniformly; put the mixture in 100mL sputum, place 100mL sputum in 300mL sputum, fill a certain amount of CuO between the two sputum, and stack height of CuO between two sputum It is equal to the stacking height of the mixture in the small crucible, and a layer of fiber felt aerogel insulation material is wrapped outside the 300 mL crucible. A 300 mL crucible was placed in a microwave device, microwaved at 550 W for 15 min, and cooled to room temperature to obtain a two-dimensional mica-loaded carbonitride photocatalytic material.
如图1所示。通过对合成样品进行XRD测试，分析得到合成样品有明显的g-C 3N 4、云母、SnO 2的衍射峰。 As shown in Figure 1. The XRD test of the synthesized samples showed that the synthesized samples had obvious diffraction peaks of gC 3 N 4 , mica and SnO 2 .
图2为制备的云母负载氮化碳材料的降解罗丹明B性能图，说明了所制备的云母负载氮化碳材料具有较好的降解罗丹明B的性能，1小时降解率达95％以上。Figure 2 is a graph showing the degradation of rhodamine B in the prepared mica-loaded carbon nitride material. It shows that the prepared mica-loaded carbon nitride material has better degradation performance of rhodamine B, and the degradation rate is more than 95% in one hour.
实施例2Example 2
S1：将10g云母粉置于100mL溶剂中，溶剂为乙醇与去离子水混合物(乙醇：去离子水＝3:7)，云母粉的质量百分含量约为10％，搅拌至均匀，置于100W超声波中，超声4h，得到二维云母片悬浮液；S1: 10 g of mica powder is placed in 100 mL of solvent, the solvent is a mixture of ethanol and deionized water (ethanol: deionized water = 3:7), the mass percentage of mica powder is about 10%, stirred until uniform, placed 100W ultrasonic wave, ultrasonic for 4h, to obtain a two-dimensional mica suspension;
S2：用盐酸将云母片悬浮液pH调节至2.0，加热至75℃，加入20g SnCl 4·5H 2O和2.4g SbCl 3，搅拌至完全溶解，用氨水将混合溶液pH调至2.0，搅拌3h，抽滤、洗涤、干燥，然后将粉体置于马弗炉中，升温至700℃，保温2h，获得掺锑二氧化锡包覆的云母片； S2: adjust the pH of the mica flake suspension to 2.0 with hydrochloric acid, heat to 75 ° C, add 20 g of SnCl 4 ·5H 2 O and 2.4 g of SbCl 3 , stir until completely dissolved, adjust the pH of the mixed solution to 2.0 with ammonia water, stir for 3 h. , suction filtration, washing, drying, and then the powder is placed in a muffle furnace, heated to 700 ° C, and kept for 2 h to obtain a mica plate coated with antimony-doped tin dioxide;
S3：称取0.6g二维云母和20g三聚氰胺均匀混合；将混合物置于100mL坩埚中，再将此坩埚放入300mL的坩埚中，两坩埚中填入一定量Fe 3O 4，两坩埚之间Fe 3O 4的堆积高度等于小坩埚内混合物的堆积高度，在300mL坩埚外部包裹一层二氧化硅气凝胶保温材料。将300mL坩埚置于微波装置中，在550w功率下微波15min后，冷却至室温得到二维云母负载氮化碳光催化材料。 S3: Weigh 0.6 g of two-dimensional mica and 20 g of melamine and mix uniformly; place the mixture in 100 mL of mash, place the mash in 300 mL of mash, and fill in a certain amount of Fe 3 O 4 between the two mashes. The stacking height of Fe 3 O 4 is equal to the stacking height of the mixture in the small crucible, and a layer of silica aerogel insulation material is wrapped outside the 300 mL crucible. 300 mL of ruthenium was placed in a microwave device, microwaved at 550 W for 15 min, and then cooled to room temperature to obtain a two-dimensional mica-supported carbon nitride photocatalytic material.
图3为制备的云母负载氮化碳材料的降解罗丹明B性能图，说明了所制备的云母负载氮化碳材料具有较好的降解罗丹明B的性能，2小时降解率达98％。Figure 3 is a graph showing the degradation of rhodamine B in the prepared mica-loaded carbon nitride material, indicating that the prepared mica-loaded carbon nitride material has better degradation properties of rhodamine B, and the degradation rate is 98% in 2 hours.
实施例3Example 3
S1：将20g云母粉置于100mL溶剂中，云母粉的质量百分含量为20％溶剂为去离子水，搅拌至均匀，置于500W超声波中，超声3h，得到二维云母片悬浮液；S1: 20g of mica powder is placed in 100mL of solvent, the mass percentage of mica powder is 20% solvent is deionized water, stirred until uniform, placed in 500W ultrasonic wave, ultrasonic for 3h, to obtain two-dimensional mica plate suspension;
S2：用盐酸将云母片悬浮液pH调节至1.0，加热至80℃，加入10g SnCl 4·5H 2O和0.6g SbCl 3，搅拌至完全溶解，将混合溶液逐步滴加入云母悬浮液中，用氨水溶液将混合溶液pH调至1.0，搅拌4h，粉体离心、洗涤、干燥，然后将粉体置于马弗炉中，升温至800℃，保温2h，获得掺锑二氧化锡包覆的云母片； S2: adjust the pH of the mica flake suspension to 1.0 with hydrochloric acid, heat to 80 ° C, add 10 g of SnCl 4 ·5H 2 O and 0.6 g of SbCl 3 , stir until completely dissolved, and gradually add the mixed solution to the mica suspension. Ammonia solution adjust the pH of the mixed solution to 1.0, stir for 4 hours, centrifuge the powder, wash and dry, then place the powder in a muffle furnace, heat up to 800 ° C, and keep it for 2 h to obtain mica doped with antimony-doped tin dioxide. sheet;
S3：称取0.4g二维云母和20g双氰胺均匀混合；将混合物置于100mL坩埚中，再将此坩埚放入300mL的坩埚中，两坩埚中填入一定量CuO，两坩埚之间CuO的堆积高度略高于小坩埚内混合物的堆积高度，在300mL坩埚外部包裹一层纤维毡子/二氧化硅气凝胶保温材料。将300mL坩埚置于微波装置中，在550w功率下微波15min后350w微波10min，冷却至室温得到二维云母负载氮化碳光催化材料。S3: Weigh 0.4 g of two-dimensional mica and 20 g of dicyandiamide uniformly; place the mixture in 100 mL of mash, place the mash in 300 mL of mash, fill a certain amount of CuO in the two mashes, and CuO between the two mashes. The stacking height is slightly higher than the stacking height of the mixture in the small crucible, and a layer of fiber felt/silica aerogel insulation material is wrapped outside the 300 mL crucible. 300 mL of cesium was placed in a microwave device, microwaved at 550 W for 15 min, then microwaved at 350 W for 10 min, and cooled to room temperature to obtain a two-dimensional mica-supported carbon nitride photocatalytic material.
图4为制备的云母负载氮化碳材料的降解罗丹明B性能图，说明了所制备的云母负载氮化碳材料具有较好的降解罗丹明B的性能，2小时降解率达98％。Figure 4 is a graph showing the degradation of rhodamine B in the prepared mica-loaded carbon nitride material, indicating that the prepared mica-loaded carbon nitride material has better degradation properties of rhodamine B, and the degradation rate is 98% in 2 hours.
实施例4Example 4
本实施案例所述的微波快速制备二维云母负载类石墨氮化碳的制备方法，包括以下步骤：The method for preparing a two-dimensional mica-loaded graphite carbon nitride by microwave in the present embodiment includes the following steps:
S1：将5g云母粉置于200mL乙醇，云母粉的质量百分含量为3％，搅拌至均匀，置于400W超声波中，超声2h，得到二维云母片悬浮液；S1: 5g of mica powder is placed in 200mL of ethanol, the mass percentage of mica powder is 3%, stirred until uniform, placed in 400W ultrasonic wave, ultrasonic 2h, to obtain a two-dimensional mica suspension;
S2：用盐酸将云母片悬浮液pH调节至1.5，加热至70℃，加入一定量5g SnCl 4·5H 2O和1g SbCl 3，用NaOH溶液将混合溶液pH调至1.5，搅拌2h，抽滤、洗涤、干燥，然后将粉体置于马弗炉中，升温至600℃，保温3h，获得掺锑二氧化锡包覆的云母片； S2: adjust the pH of the mica flake suspension to 1.5 with hydrochloric acid, heat to 70 ° C, add a certain amount of 5 g of SnCl 4 ·5H 2 O and 1 g of SbCl 3 , adjust the pH of the mixed solution to 1.5 with NaOH solution, stir for 2 h, and filter. Washing, drying, and then placing the powder in a muffle furnace, heating to 600 ° C, and holding for 3 h to obtain a mica plate coated with antimony-doped tin dioxide;
S3：称取1.2g二维云母和10g尿素均匀混合；将混合物置于100mL坩埚中，将100mL坩埚置于300mL坩埚中，两坩埚之间填入一定量CuO，两坩埚之间CuO的堆积高度小于小坩埚内混合物的堆积高度，在300mL坩埚外部一层纤维毡子/二氧化硅气凝胶保温材料。将300mL坩埚置于微波装置中，在700w功率下微波10min，冷却至室温得到二维云母负载氮化碳光催化材料。S3: Weigh 1.2g two-dimensional mica and 10g urea uniformly; put the mixture in 100mL mash, place 100mL 坩埚 in 300mL ,, fill a certain amount of CuO between the two ,, and stack height of CuO between two 坩埚Less than the stacking height of the mixture in the small crucible, a layer of fiber felt/silica aerogel insulation material is placed outside the 300 mL crucible. A 300 mL crucible was placed in a microwave device, microwaved at 700 W for 10 min, and cooled to room temperature to obtain a two-dimensional mica-supported carbon nitride photocatalytic material.
图5为制备的云母负载氮化碳材料的降解罗丹明B性能图，说明了所制备的云母负载氮化碳材料具有较好的降解罗丹明B的性能，1小时降解率达60％以上。Figure 5 is a graph showing the degradation of rhodamine B in the prepared mica-loaded carbon nitride material, indicating that the prepared mica-loaded carbon nitride material has better degradation performance of rhodamine B, and the degradation rate of more than 60% in one hour.

Claims (9)

  1. 微波快速制备云母负载氮化碳光催化材料的方法，其具体步骤如下：A method for rapidly preparing a mica-loaded carbon nitride photocatalytic material by microwave, the specific steps of which are as follows:
    S1：将云母粉置于溶剂中，其中云母粉的质量百分含量占1％～20％，搅拌至均匀，置于超声波中超声分散，得到二维云母片悬浮液；S1: the mica powder is placed in a solvent, wherein the mass percentage of the mica powder is 1% to 20%, stirred until uniform, and ultrasonically dispersed in an ultrasonic wave to obtain a two-dimensional mica suspension;
    S2：用盐酸将云母片悬浮液pH调节至1～2，加热至70～80℃，加入一定量SnCl 4·5H 2O和SbCl 3，其中，SnCl 4·5H 2O与云母的质量比为0.5～2，SbCl 3与SnCl 4·5H 2O质量比为0.05～0.2，用碱性溶液将混合悬浮液溶液pH调至1～2，搅拌2～4h，将粉体离心、洗涤、烘干，然后将粉体置于高温炉中，升温至600～800℃，保温2～3h，获得掺锑二氧化锡包覆的二维片状云母； S2: adjusting the pH of the mica flake suspension to 1-2 with hydrochloric acid, heating to 70-80 ° C, adding a certain amount of SnCl 4 ·5H 2 O and SbCl 3 , wherein the mass ratio of SnCl 4 ·5H 2 O to mica is 0.5～2, the mass ratio of SbCl 3 to SnCl 4 ·5H 2 O is 0.05～0.2, adjust the pH of the mixed suspension solution to 1-2 with alkaline solution, stir for 2~4h, centrifuge, wash and dry the powder. Then, the powder is placed in a high temperature furnace, heated to 600-800 ° C, and kept for 2 to 3 hours to obtain a two-dimensional sheet mica coated with antimony-doped tin dioxide;
    S3：将二维云母和胺基化合物均匀混合，其中二维云母和胺基化合物的质量比为0.01～0.12:1；将放有二维云母和胺基化合物的坩埚置于更大的坩埚内，两坩埚之间填入微波吸收物质，在坩埚外部包裹一层气凝胶保温材料，将大坩埚放入微波装置中，在一定微波功率下，加热一段时间后，冷却得到云母负载氮化碳光催化材料。S3: uniformly mixing two-dimensional mica and an amine compound, wherein the mass ratio of the two-dimensional mica to the amine compound is 0.01 to 0.12:1; and the ruthenium containing the two-dimensional mica and the amine compound is placed in a larger crucible The microwave absorbing material is filled between the two crucibles, and a layer of aerogel insulation material is wrapped outside the crucible, and the big crucible is placed in a microwave device, and after heating for a certain period of time under microwave power, the mica-loaded carbon nitride is cooled. Photocatalytic material.
  2. 根据权利要求1所述的方法，其特征在于步骤S1中的超声分散的超声频率为100W-500W，超声时间为2～4h。The method of claim 1 wherein the ultrasonically dispersed ultrasonic frequency in step S1 is from 100 W to 500 W and the ultrasonic time is from 2 to 4 h.
  3. 根据权利要求1所述的方法，其特征在于步骤S1中的溶剂为去离子水或乙醇中的一种或两种混合液。The method according to claim 1, wherein the solvent in the step S1 is one or a mixture of deionized water or ethanol.
  4. 根据权利要求1所述的方法，其特征在于步骤S2中所述的碱性溶液为氢氧化钠溶液或氨水。The method according to claim 1, wherein the alkaline solution in the step S2 is a sodium hydroxide solution or ammonia water.
  5. 根据权利要求1所述的方法，其特征在于步骤S3中所述的胺基化合物为尿素、三聚氰胺或双氰胺中的一种或多种。The method of claim 1 wherein the amine compound in step S3 is one or more of urea, melamine or dicyandiamide.
  6. 根据权利要求1所述的方法，其特征在于步骤S3中所述的气凝胶保温材料为二氧化硅气凝胶、纤维毡气凝胶或二氧化硅-纤维毡复合气凝胶。The method according to claim 1, wherein the aerogel insulation material in the step S3 is a silica aerogel, a fiber felt aerogel or a silica-fiber mat composite aerogel.
  7. 根据权利要求1所述的方法，其特征在于步骤S3中所述的微波功率350W-700W。The method of claim 1 wherein said microwave power in said step S3 is 350W-700W.
  8. 根据权利要求1所述的方法，其特征在于步骤S3中所述的微波时间10min-30min。The method of claim 1 wherein said microwave time in step S3 is between 10 min and 30 min.
  9. 根据权利要求1所述的方法，其特征在于步骤S3中所述的微波吸收物质为无定型炭、CuO、Fe 3O 4、MnO 2、SnO 2或WO 3。 The method according to claim 1, wherein the microwave absorbing material in step S3 is amorphous carbon, CuO, Fe 3 O 4 , MnO 2 , SnO 2 or WO 3 .
PCT/CN2018/081339 2017-07-18 2018-03-30 Method for rapidly preparing mica-supported carbon nitride photocatalytic material by means of microwaves WO2019015356A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710585266.0A CN107456986A (en) 2017-07-18 2017-07-18 The method that microwave quickly prepares mica load carbonitride catalysis material
CN201710585266.0 2017-07-18

Publications (1)

Publication Number Publication Date
WO2019015356A1 true WO2019015356A1 (en) 2019-01-24

Family

ID=60544364

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/081339 WO2019015356A1 (en) 2017-07-18 2018-03-30 Method for rapidly preparing mica-supported carbon nitride photocatalytic material by means of microwaves

Country Status (2)

Country Link
CN (1) CN107456986A (en)
WO (1) WO2019015356A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113663717A (en) * 2021-09-29 2021-11-19 西安热工研究院有限公司 Method for preparing composite tin oxide graphite phase carbon nitride photocatalyst by one-step synthesis
CN115323766A (en) * 2022-08-24 2022-11-11 安徽理工大学环境友好材料与职业健康研究院(芜湖) Cobaltosic oxide/carbon cloth flexible wave-absorbing material and preparation method thereof
CN116037185A (en) * 2022-12-29 2023-05-02 聊城大学 Preparation method of ricepaper pith carbon/graphite-like phase carbon nitride photocatalyst
CN116809106A (en) * 2023-06-25 2023-09-29 重庆工商大学 Microwave-assisted oxygen-enriched vacancy Co@NC for efficiently degrading organic pollutants X A aerogel catalyst
CN116809100A (en) * 2023-03-07 2023-09-29 唐山学院 Preparation method of carbon nitride photocatalyst

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107456986A (en) * 2017-07-18 2017-12-12 南京工业大学 The method that microwave quickly prepares mica load carbonitride catalysis material
CN114100658B (en) * 2021-11-23 2023-09-12 湖南农业大学 Carbon nitride/tungsten trioxide/sulfur doped antimony oxychloride double-Z-type composite photocatalyst, and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105772056A (en) * 2016-04-28 2016-07-20 成都理工大学 Preparation method and application of graphite-phase carbon nitride photocatalysis material
US20160240851A1 (en) * 2015-02-12 2016-08-18 Yang Zhang Method of producing triazine-based graphitic carbon nitride films
CN106268907A (en) * 2016-08-15 2017-01-04 南京工业大学 A kind of two dimension Conductive mica load carbonitride catalysis material and preparation method thereof
CN107456986A (en) * 2017-07-18 2017-12-12 南京工业大学 The method that microwave quickly prepares mica load carbonitride catalysis material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006044076A1 (en) * 2006-09-20 2008-03-27 Merck Patent Gmbh Photocatalytically active coating
CN103285920B (en) * 2013-05-27 2015-04-08 东华大学 Three-dimensional fiber-based aerogel catalyst carrier and preparation method thereof
CN104415786A (en) * 2013-09-04 2015-03-18 安徽大学 Method for quickly preparing quasi-graphite-structure carbon nitride material by adopting microwave heating
CN105536844B (en) * 2015-12-15 2018-07-17 南京工业大学 A kind of agraphitic carbon composite nitride carbon catalysis material and preparation method thereof
CN106582768B (en) * 2016-12-29 2019-01-15 南京工业大学 A kind of two-dimentional, three-dimensional carrier enhancing carbonitride catalysis material preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160240851A1 (en) * 2015-02-12 2016-08-18 Yang Zhang Method of producing triazine-based graphitic carbon nitride films
CN105772056A (en) * 2016-04-28 2016-07-20 成都理工大学 Preparation method and application of graphite-phase carbon nitride photocatalysis material
CN106268907A (en) * 2016-08-15 2017-01-04 南京工业大学 A kind of two dimension Conductive mica load carbonitride catalysis material and preparation method thereof
CN107456986A (en) * 2017-07-18 2017-12-12 南京工业大学 The method that microwave quickly prepares mica load carbonitride catalysis material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WANG, GUIQING: "Preparation of Sb Doped Sn02 Powder by Wet Chemical Coprecipitation and Conductive Mechanism", YUNNAN CHEMICAL TECHNOLOGY, vol. 38, no. 3, 30 June 2011 (2011-06-30) *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113663717A (en) * 2021-09-29 2021-11-19 西安热工研究院有限公司 Method for preparing composite tin oxide graphite phase carbon nitride photocatalyst by one-step synthesis
CN115323766A (en) * 2022-08-24 2022-11-11 安徽理工大学环境友好材料与职业健康研究院(芜湖) Cobaltosic oxide/carbon cloth flexible wave-absorbing material and preparation method thereof
CN116037185A (en) * 2022-12-29 2023-05-02 聊城大学 Preparation method of ricepaper pith carbon/graphite-like phase carbon nitride photocatalyst
CN116809100A (en) * 2023-03-07 2023-09-29 唐山学院 Preparation method of carbon nitride photocatalyst
CN116809106A (en) * 2023-06-25 2023-09-29 重庆工商大学 Microwave-assisted oxygen-enriched vacancy Co@NC for efficiently degrading organic pollutants X A aerogel catalyst

Also Published As

Publication number Publication date
CN107456986A (en) 2017-12-12

Similar Documents

Publication Publication Date Title
WO2019015356A1 (en) Method for rapidly preparing mica-supported carbon nitride photocatalytic material by means of microwaves
CN105350113B (en) A kind of preparation method and products obtained therefrom of azotized carbon nano fiber
CN105217676B (en) Titania aerogel with nanometer sheet and nano-porous structure and preparation method thereof
CN109502987A (en) A method of high rigidity antireflective film is prepared based on hollow silica
CN110227532B (en) Preparation method of lead cesium bromide quantum dot/carbon nitride nanosheet photocatalyst
CN104973615B (en) Microwave burning preparation method of nano gadolinium oxide powder
CN109395762A (en) A kind of stannic oxide with core-shell structure/N doping graphite/zinc sulphide composite material and preparation method
CN105762283A (en) Perovskite solar cell light-absorbing layer nano sol film-coating solution and preparation method
CN103146387B (en) Process for preparing porous rare-earth luminescent material by freeze-drying method
CN100594976C (en) Preparation method of purificant in nano titanic oxide photochemical catalyst chamber
CN110606736A (en) Solvent-free synthesized ceramic microsphere and preparation method and application thereof
Liu et al. Preparation and characterization of novel CuS/SiO2@ n‐octadecane phase‐change nanocapsules enhanced photothermal conversion for solar energy utilization
CN100486895C (en) Preparation method for nanometer magnesium oxide
CN112062573B (en) Sheet SiC-SiO2 composite material and preparation method thereof
CN109569687A (en) A kind of stannic oxide with core-shell structure/N doping graphite/cadmium sulfide composite material and preparation method thereof
CN106957065B (en) A kind of supper-fast preparation method of N, Ti3+ codope porous TiO2 nanometer sheet
CN108927197A (en) A kind of g-C of high catalytic performance3N4Preparation method and purposes
CN107500672A (en) The integrated high heat conduction bend resistance cement-based material and preparation method thereof of floor heating
CN109482191B (en) Foamed nickel loaded zinc titanate/tourmaline photocatalytic material and preparation method thereof
CN101531502B (en) Preparation method for barium ferrite magnetic powder
CN101597160A (en) A kind of carbon-containing wall surface decoration materials and preparation method thereof
CN103332870A (en) Preparation method of nanometer titanium dioxide film
CN105498776A (en) Nickel ferrite composite photocatalytic material and preparation method thereof
CN102952419A (en) Preparation method of modified titanium oxide coating applied to metal matrix corrosive protection
CN103187180B (en) Preparation method for nanometre silicon carbide-ruthenium oxide composite material

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18835373

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18835373

Country of ref document: EP

Kind code of ref document: A1