CN109985656A - Synthesis method and application of a defect-rich carbon nitride catalyst - Google Patents
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Abstract
Description
技术领域technical field
本发明涉及一种富含缺陷的氮化碳催化剂的合成方法和应用，具体涉及一种以废弃尿不湿为原材料的非金属碳催化剂的合成方法，属于非金属碳催化剂制备和应用技术领域。The invention relates to a synthesis method and application of a defect-rich carbon nitride catalyst, in particular to a synthesis method of a non-metallic carbon catalyst using waste diapers as raw materials, and belongs to the technical field of non-metallic carbon catalyst preparation and application.
背景技术Background technique
近年来，基于硫酸根自由基的新型高级氧化技术由于在降解农药、全氟羧酸及药物及个人护理用品(PPCP)等新兴污染物上表现出突出的优势引了越来越多科研人员的研究兴趣。硫酸根自由基具有高的氧化还原电位(2.5-3.1V)，并且能与大多数有机物反应以近扩散控制速率的速度发氧化反应。同时，过硫酸盐多为固态，易于储存和运输，在环境中相对较稳定，水溶性较好，因此在实际应用中，其相对于其他的氧化剂具有明显的优势。单过硫酸过二硫酸盐等常用于产生硫酸根自由基。由于过硫酸盐的显著优点，在地下水和土壤的原位化学修复及去除难降解有机物的应用上，过硫酸盐新型活化高级氧化技术受到更多重视对此问题，其作为一种高效处理工艺得到了广泛的关注和应用。In recent years, new advanced oxidation technologies based on sulfate radicals have attracted more and more researchers' attention due to their outstanding advantages in degrading pesticides, perfluorocarboxylic acids, and emerging pollutants such as pharmaceuticals and personal care products (PPCPs). research interests. Sulfate radicals have high redox potentials (2.5-3.1 V) and can react with most organics to oxidatively react at nearly diffusion-controlled rates. At the same time, persulfate is mostly solid, easy to store and transport, relatively stable in the environment, and has good water solubility, so it has obvious advantages over other oxidants in practical applications. Monopersulfate peroxodisulfate and the like are often used to generate sulfate radicals. Due to the significant advantages of persulfate, in the application of in-situ chemical remediation of groundwater and soil and the removal of refractory organic matter, the new activated advanced oxidation technology of persulfate has received more attention to this problem. wide attention and application.
目前，过硫酸盐新型高级氧化技术使用的催化剂分为两大类：一类是传统的金属氧化物(Fe3O4、CuO、Co3O4、MnO2)催化剂，另一类是以碳纳米管、碳纤维、富勒烯、氧化石墨烯为代表的新型碳材料。研究表明新型碳材料因其独特的结构和化学特性，在环境污染物治理领域展示了良好的性能。近年来对石墨烯及类石墨烯材料的环境应用研究也越来越多，比如：研究了氧化石墨烯复合材料光催化降解有机物的效果；使用改性氧化石墨烯作为吸附剂，用于环境污染物的去除和痕量污染物的富集分析也被多次报道。氧化石墨烯优异的电子传递能力，丰富的功能基团和表面及边缘的缺陷结构使其在光催化、化学催化氧化中的应用前景广阔。而通过对其进行化学修饰，如非金属元素氮、磷、硫的掺杂，和金属氧化物形成复合材料更是拓宽了该材料的应用。氮掺杂氧化石墨烯后，其对BPA的吸附容量与其活化过硫酸盐降解BPA的反应速率常数较于普通氧化石墨烯有很大的提高，降解效率显著提高。但是石墨烯材料由于其繁琐制备过程带来生产成本的提高尚未得到解决，难以在环境治理方面广泛应用。At present, the catalysts used in the new advanced oxidation technology of persulfate are divided into two categories: one is traditional metal oxide (Fe 3 O 4 , CuO, Co 3 O 4 , MnO 2 ) catalysts, and the other is carbon-based catalysts New carbon materials represented by nanotubes, carbon fibers, fullerenes, and graphene oxide. Studies have shown that new carbon materials have demonstrated good performance in the field of environmental pollution control due to their unique structural and chemical properties. In recent years, there have been more and more researches on the environmental application of graphene and graphene-like materials. For example, the photocatalytic degradation of organic compounds by graphene oxide composite materials has been studied; modified graphene oxide is used as an adsorbent for environmental pollution. The removal of pollutants and the enrichment analysis of trace pollutants have also been reported many times. Graphene oxide's excellent electron transfer ability, abundant functional groups and defect structure on the surface and edge make it have broad application prospects in photocatalysis and chemical catalytic oxidation. By chemical modification, such as doping of non-metallic elements nitrogen, phosphorus and sulfur, and forming composite materials with metal oxides, the application of this material is broadened. After nitrogen-doped graphene oxide, its adsorption capacity for BPA and its reaction rate constant for activating persulfate to degrade BPA are greatly improved compared with ordinary graphene oxide, and the degradation efficiency is significantly improved. However, the increase in production cost of graphene materials due to its cumbersome preparation process has not been solved, and it is difficult to be widely used in environmental management.
发明内容SUMMARY OF THE INVENTION
本发明所要解决的技术问题是：现有用于处理有机废水的石墨烯材料的制备过程繁琐，生产成本高的技术问题。The technical problem to be solved by the present invention is: the existing graphene material used for treating organic waste water has a complicated preparation process and high production cost.
为了解决上述问题，本发明提供了一种富含缺陷的氮化碳催化剂的合成方法，其特征在于，采用g-C3N4为前体，将g-C3N4与镁粉按比例混合，并研磨均匀后，在氩气氛围中煅烧后得到g-C3Nx活性材料，酸洗、干燥后，即得富含缺陷的氮化碳催化剂。In order to solve the above problems, the present invention provides a method for synthesizing a defect-rich carbon nitride catalyst, characterized in that gC 3 N 4 is used as a precursor, gC 3 N 4 is mixed with magnesium powder in proportion, and ground After homogenization, gC 3 N x active material is obtained after calcination in an argon atmosphere, and after pickling and drying, a carbon nitride catalyst rich in defects is obtained.
优选地，所述g-C3N4以尿素为原料合成制得。Preferably, the gC 3 N 4 is synthesized from urea as a raw material.
优选地，所述g-C3N4与镁粉的质量比为(1～5):1。Preferably, the mass ratio of the gC 3 N 4 to the magnesium powder is (1-5):1.
优选地，所述煅烧的温度为550℃～900℃，煅烧时间为1～5h。Preferably, the calcination temperature is 550°C to 900°C, and the calcination time is 1 to 5 hours.
优选地，所述酸洗具体为：采用质量浓度10％的稀醋酸酸洗两次，离心收集沉淀物，再用去离子水水洗两次，离心收集沉淀物。Preferably, the pickling is specifically: pickling twice with dilute acetic acid with a mass concentration of 10%, collecting the precipitate by centrifugation, washing twice with deionized water, and collecting the precipitate by centrifugation.
优选地，所述干燥条件为：60℃真空干燥。Preferably, the drying conditions are: vacuum drying at 60°C.
本发明还提供了上述富含缺陷的氮化碳催化剂的合成方法制得的富含缺陷的氮化碳催化剂在通过过硫酸盐活化高级氧化技术处理有机废水中的应用。The invention also provides the application of the defect-rich carbon nitride catalyst prepared by the above-mentioned synthesis method of the defect-rich carbon nitride catalyst in the treatment of organic wastewater by persulfate-activated advanced oxidation technology.
优选地，在处理有机废水时，先调节有机废水的pH值为7，然后，依次加入所述富含缺陷的氮化碳催化剂和过硫酸盐，震荡反应，即实现对有机废水的降解处理。Preferably, when the organic wastewater is treated, the pH value of the organic wastewater is first adjusted to 7, and then the defect-rich carbon nitride catalyst and persulfate are sequentially added, and the reaction is oscillated, that is, the degradation treatment of the organic wastewater is realized.
优选地，所述有机废水中的目标有机污染物为罗丹明B、卡马西平和对邻苯基苯酚中的至少一种。Preferably, the target organic pollutant in the organic wastewater is at least one of Rhodamine B, carbamazepine and p-o-phenylphenol.
更优选地，所述有机废水中的目标有机污染物的浓度为10-50mg/L，富含缺陷的氮化碳催化剂的加入量为0.1-0.5g/L有机废水，过硫酸盐的加入量为0.5-2.0mmol/L有机废水。More preferably, the concentration of the target organic pollutants in the organic waste water is 10-50mg/L, the addition of the defect-rich carbon nitride catalyst is 0.1-0.5g/L organic waste water, the addition of persulfate is 0.1-0.5g/L. It is 0.5-2.0mmol/L organic wastewater.
更优选地，所述的过硫酸盐为过硫酸氢钾复合盐。More preferably, the persulfate is potassium hydrogen persulfate complex salt.
更优选地，所述震荡反应的条件为：温度25℃，反应时间30min。More preferably, the conditions of the shaking reaction are as follows: the temperature is 25° C. and the reaction time is 30 minutes.
本发明以氮化碳为催化剂，过硫酸盐为氧化剂，活化过硫酸盐使其形成高活性的含氧物种,从而进一步氧化水体中毒性大难生物降解的有机污染物，达到净化水质的目的。The invention uses carbon nitride as a catalyst and persulfate as an oxidant to activate the persulfate to form highly active oxygen-containing species, thereby further oxidizing the highly toxic and biodegradable organic pollutants in the water body to achieve the purpose of purifying water.
本发明合成的非金属碳催化剂在处理有机废水时，运用的是非自由基氧化原理，其主要活性物质单线态氧(1O2)较其它自由基类氧化活性物种(O2 -·、OH·、SO4 2-·)相比在水溶液中具有最长的存活时间(10-6～10-3秒)，克服了自由基在实际水体中易被猝灭的缺点，可有效的抵抗水中背景有机物及无机物的干扰高效的氧化和矿化有机污染物。与经典的自由基氧化体系相比，1O2介导的氧化体系在有机物污染的实际水体物的修复技术具有突出的优势。The non-metallic carbon catalyst synthesized in the present invention adopts the principle of non-radical oxidation when treating organic wastewater, and its main active material singlet oxygen ( 1 O 2 ) is more active than other free radical oxidation active species (O 2 - ·, OH · , SO 4 2- ·) has the longest survival time (10 -6 ~ 10 -3 seconds) in aqueous solution, overcomes the disadvantage that free radicals are easily quenched in actual water, and can effectively resist the background in water Interference with organic and inorganic substances Efficient oxidation and mineralization of organic pollutants. Compared with the classical free radical oxidation system, the 1 O 2 mediated oxidation system has outstanding advantages in the remediation technology of actual water bodies polluted by organic matter.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1)通过镁热脱氮技术合成的高氮缺陷氮化碳材料既克服了石墨烯材料制备复杂带来的高成本问题，又克服了氮化碳导电性差催化效率低的问题，在活化过硫酸盐降解有机污染物体系中展现出优异的性能，且制备过程简单易行且绿色无污染；(1) The high nitrogen defect carbon nitride material synthesized by magnesium thermal denitrification technology not only overcomes the high cost problem caused by the complex preparation of graphene materials, but also overcomes the problem of poor conductivity and low catalytic efficiency of carbon nitride. The sulfate-degrading organic pollutant system exhibits excellent performance, and the preparation process is simple and easy to operate, and it is green and pollution-free;
(2)材料以价格低廉的尿素为原料，镁热脱氮工艺后所得催化剂为非金属催化剂绿色无污染且，极具实用价值和经济效益。(2) The material uses low-cost urea as the raw material, and the catalyst obtained after the magnesium thermal denitrification process is a non-metallic catalyst that is green and pollution-free, and has great practical value and economic benefit.
(3)在有机物降解的过程中运用的是非自由基氧化的机理，降解效果不易受本底污染物和水中其它阴离子的干扰，与传统的自由基氧化体系相比，1O2介导的氧化体系在有机物污染的实际水体物的修复技术具有突出的优势；(3) The mechanism of non-radical oxidation is used in the process of organic matter degradation, and the degradation effect is not easily disturbed by background pollutants and other anions in water. Compared with the traditional free radical oxidation system, 1 O 2 mediated oxidation The system has outstanding advantages in the restoration technology of actual water bodies polluted by organic matter;
(4)该催化剂应用于基于过硫酸盐活化高级氧化技术，对罗丹明B、卡马西平、邻苯基苯酚有良好的降解效果，尤其对邻苯基苯酚废水具有良好的矿化效果，出水水质澄清透明。(4) The catalyst is applied to the advanced oxidation technology based on persulfate activation, and has a good degradation effect on rhodamine B, carbamazepine and o-phenylphenol, especially has a good mineralization effect on the o-phenylphenol wastewater. The water is clear and transparent.
附图说明Description of drawings
图1为实施例1制得的氮化碳催化剂的扫描电镜图像；Fig. 1 is the scanning electron microscope image of the carbon nitride catalyst prepared in Example 1;
图2为实施例1制得的氮化碳催化剂的透射电镜图像；2 is a transmission electron microscope image of the carbon nitride catalyst prepared in Example 1;
图3为实施例2-4中分别对20ppm浓度的罗丹明B(RhB)、卡马西平(CBZ)、2-苯基苯酚(OPP)的降解曲线图；3 is a graph showing the degradation curves of Rhodamine B (RhB), carbamazepine (CBZ) and 2-phenylphenol (OPP) at a concentration of 20 ppm in Example 2-4;
图4为对比例1-2、实施例5中分别对卡马西平的降解曲线图。4 is a graph showing the degradation curves of carbamazepine in Comparative Examples 1-2 and Example 5, respectively.
具体实施方式Detailed ways
为使本发明更明显易懂，兹以优选实施例，并配合附图作详细说明如下。In order to make the present invention more obvious and comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
实施例1Example 1
以尿素为原料合成氮化碳后，结合镁热脱氮技术对在750℃下进行脱氮，酸洗，干燥，得到活性材料g-C3Nx，即为氮化碳催化剂。After synthesizing carbon nitride with urea as raw material, combined with magnesium thermal denitrification technology, denitrification, pickling and drying are carried out at 750°C to obtain the active material gC 3 N x , which is a carbon nitride catalyst.
图1和图2分别显示了实施例1制得的活性材料g-C3Nx的扫描电镜图像和投射电镜图像。从图中可以看出经过镁热反应后g-C3Nx保留了由薄片组成的纳米花结构，且更为疏松多孔。FIG. 1 and FIG. 2 show the scanning electron microscope image and the projection electron microscope image of the active material gC 3 N x prepared in Example 1, respectively. It can be seen from the figure that gC 3 N x retains the nanoflower structure composed of flakes after the magnesium thermal reaction, and is more loose and porous.
实施例2Example 2
取10mL配置好的20mg/L含RhB的废水标准溶液于锥形瓶中，加入90mL缓冲溶液，调节pH＝7，依次加入实施例1所制得的g-C3Nx 0.2g/L，Oxone 2mmol/L置于水浴恒温震荡箱中进行30min反应，按0、5、10、15、20、25、30min的时间节点取样后，样品随即用高效液相色谱进行浓度分析。30min染料被完全降解溶液澄清无色。Take 10 mL of prepared 20 mg/L RhB-containing wastewater standard solution in a conical flask, add 90 mL of buffer solution, adjust pH=7, and sequentially add gC 3 N x 0.2 g/L, Oxone 2 mmol prepared in Example 1 /L was placed in a water bath constant temperature shaking box for 30min reaction. After sampling at time points of 0, 5, 10, 15, 20, 25, and 30min, the samples were immediately analyzed for concentration by high performance liquid chromatography. After 30min, the dye was completely degraded and the solution was clear and colorless.
实施例3Example 3
取10mL配置好的20mg/L含卡马西平的废水标准溶液于锥形瓶中，加入90mL缓冲溶液，调节pH＝7，依依次加入实施例1所制得的g-C3Nx 0.2g/L，Oxone 2mmol/L，置于水浴恒温震荡箱中进行30min反应，按0、5、10、15、20、25、30min的时间节点取样后，样品随即用高效液相色谱进行浓度分析。30min卡马西平被降解90％以上。Take 10 mL of prepared 20 mg/L carbamazepine-containing wastewater standard solution in a conical flask, add 90 mL of buffer solution, adjust pH=7, and add gC 3 N x 0.2 g/L prepared in Example 1 in sequence. , Oxone 2mmol/L, placed in a water bath constant temperature shaking box for 30min reaction, after sampling at the time nodes of 0, 5, 10, 15, 20, 25, 30min, the sample was immediately analyzed by high performance liquid chromatography. 30min carbamazepine was degraded more than 90%.
实施例4Example 4
取10mL配置好的20mg/L含对苯基苯酚的废水标准溶液于锥形瓶中，加入90mL缓冲溶液，调节pH＝7，依次加入实施例1所制得的g-C3Nx 0.2g/L，Oxone 2mmol/L，置于水浴恒温震荡箱中进行30min反应，按0、5、10、15、20、25、30min的时间节点取样后，样品随即用高效液相色谱进行浓度分析。30min后对苯基苯酚被完全降解。Take 10 mL of prepared 20 mg/L wastewater standard solution containing p-phenylphenol in a conical flask, add 90 mL of buffer solution, adjust pH=7, and sequentially add gC 3 N x 0.2 g/L prepared in Example 1 , Oxone 2mmol/L, placed in a water bath constant temperature shaking box for 30min reaction, after sampling at the time nodes of 0, 5, 10, 15, 20, 25, 30min, the sample was immediately analyzed by high performance liquid chromatography. The p-phenylphenol was completely degraded after 30 min.
实施例2-4的数据结果如图3所示。The data results of Examples 2-4 are shown in FIG. 3 .
对比例1Comparative Example 1
取10mL配置好的20mg/L含卡马西平的医药类废水标准溶液于锥形瓶中，加入90mL缓冲溶液，调节pH＝7，只加入g-C3N4置于水浴恒温震荡箱中进行30min反应，按0、5、10、15、20、25、30min的时间节点取样后，样品随即用高效液相色谱进行浓度分析。30min后对苯基苯酚基本不被降解。Take 10mL of the prepared 20mg/L standard solution of pharmaceutical wastewater containing carbamazepine in a conical flask, add 90mL buffer solution, adjust pH= 7 , only add gC3N4 and place it in a water bath constant temperature shaking box for 30min reaction , after sampling at time points of 0, 5, 10, 15, 20, 25, and 30 min, the samples were then analyzed for concentration by high performance liquid chromatography. After 30min, p-phenylphenol was basically not degraded.
对比例2Comparative Example 2
取10mL配置好的20mg/L含卡马西平的医药类废水标准溶液于锥形瓶中，加入90mL缓冲溶液，调节pH＝7，只加入Oxone 2mmol/L置于水浴恒温震荡箱中进行30min反应，按0、5、10、15、20、25、30min的时间节点取样后，样品随即用高效液相色谱进行浓度分析。30min后对苯基苯酚基本不被降解。Take 10mL of the prepared 20mg/L standard solution of pharmaceutical wastewater containing carbamazepine in a conical flask, add 90mL buffer solution, adjust pH=7, only add Oxone 2mmol/L and place it in a water bath constant temperature shaking box for 30min reaction , after sampling at time points of 0, 5, 10, 15, 20, 25, and 30 min, the samples were then analyzed for concentration by high performance liquid chromatography. After 30min, p-phenylphenol was basically not degraded.
对比例5Comparative Example 5
取10mL配置好的20mg/L含卡马西平的医药类废水标准溶液于锥形瓶中，加入90mL缓冲溶液，调节pH＝7，依次加所制得的g-C3N4 0.2g/L，Oxone 2mmol/L，置于水浴恒温震荡箱中进行30min反应，按0、5、10、15、20、25、30min的时间节点取样后，样品随即用高效液相色谱进行浓度分析。30min后对苯基苯酚基本不被降解。Take 10 mL of the prepared 20 mg/L standard solution of pharmaceutical wastewater containing carbamazepine in a conical flask, add 90 mL of buffer solution, adjust pH=7, and sequentially add the prepared gC 3 N 4 0.2 g/L, Oxone 2mmol/L, placed in a water bath constant temperature shaking box for 30min reaction, after sampling at the time points of 0, 5, 10, 15, 20, 25, 30min, the samples were immediately analyzed by high performance liquid chromatography. After 30min, p-phenylphenol was basically not degraded.
对比例1-2、实施例5的数据结果如图4所示。The data results of Comparative Examples 1-2 and Example 5 are shown in FIG. 4 .
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110311119A (en) * | 2019-07-10 | 2019-10-08 | 陕西科技大学 | A preparation method of lithium-ion battery negative electrode material SnS/ND-CN |
| CN111185220A (en) * | 2020-03-20 | 2020-05-22 | 中国科学院长春应用化学研究所 | A kind of Pd-based catalyst supported by carbon nitride, its preparation method and application |
| CN113617375A (en) * | 2021-08-09 | 2021-11-09 | 东莞理工学院 | Graphite phase carbon nitride photocatalytic material and preparation method thereof |
| CN113617350A (en) * | 2021-08-11 | 2021-11-09 | 北京林业大学 | Defective carbon material and preparation method and application thereof |
| CN113929197A (en) * | 2021-09-23 | 2022-01-14 | 重庆大学 | A method for visible light-assisted activation of peroxymonosulfate for treating organic wastewater |
| CN113964325A (en) * | 2021-12-20 | 2022-01-21 | 北京航空航天大学 | Nitrogen-deficient g-C3N4Loaded with Mg3N2Application of composite material as negative electrode material and lithium-based battery |
| CN115337952A (en) * | 2022-09-16 | 2022-11-15 | 东莞理工学院 | Method for one-step synthesis of iron-manganese bimetallic oxide loaded carbon nitride containing nitrogen vacancies |
| CN115845902A (en) * | 2022-12-08 | 2023-03-28 | 上海交通大学深圳研究院 | Graphite phase carbon nitride photocatalytic material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903485A (en) * | 2016-07-15 | 2016-08-31 | 河海大学 | Synthesis method of porous carbon nitride/hydroxy iron nanorod composite photo-Fenton material with visible light response |
| CN107983391A (en) * | 2017-12-14 | 2018-05-04 | 河南师范大学 | Insoluble magnetic cobalt/defective g-C3N4 composite catalysts and its application in Oxone degrading waste waters are catalyzed |
| CN109158123A (en) * | 2018-09-19 | 2019-01-08 | 上海电力学院 | Using discarded diaper as the method for raw material synthetic non-metallic C catalyst |
| CN109248704A (en) * | 2018-09-29 | 2019-01-22 | 广州大学 | Carbon, the preparation of oxygen codope graphite phase carbon nitride and its application in catalytic activation persulfate degradation water pollutant |
-
2019
- 2019-04-28 CN CN201910349264.0A patent/CN109985656A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903485A (en) * | 2016-07-15 | 2016-08-31 | 河海大学 | Synthesis method of porous carbon nitride/hydroxy iron nanorod composite photo-Fenton material with visible light response |
| CN107983391A (en) * | 2017-12-14 | 2018-05-04 | 河南师范大学 | Insoluble magnetic cobalt/defective g-C3N4 composite catalysts and its application in Oxone degrading waste waters are catalyzed |
| CN109158123A (en) * | 2018-09-19 | 2019-01-08 | 上海电力学院 | Using discarded diaper as the method for raw material synthetic non-metallic C catalyst |
| CN109248704A (en) * | 2018-09-29 | 2019-01-22 | 广州大学 | Carbon, the preparation of oxygen codope graphite phase carbon nitride and its application in catalytic activation persulfate degradation water pollutant |
Non-Patent Citations (3)
| Title |
|---|
| CHEN JINGJING ET AL.: "Nitrogen-Deficient Graphitic Carbon Nitride with Enhanced Performance for Lithium Ion Battery Anodes", 《ACS NANO》 * |
| WEI MINGYU ET AL.: "Activation of peroxymonosulfate by graphitic carbon nitride loaded on activated carbon for organic pollutants degradation", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| XIAOGUANG DUAN ETAL.: ""Nitrogen-Doped Graphene for Generation and Evolution of Reactive Radicals by Metal-Free Catalysis"", 《APPLIED MATERIALS & INTERFACES》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110311119A (en) * | 2019-07-10 | 2019-10-08 | 陕西科技大学 | A preparation method of lithium-ion battery negative electrode material SnS/ND-CN |
| CN111185220A (en) * | 2020-03-20 | 2020-05-22 | 中国科学院长春应用化学研究所 | A kind of Pd-based catalyst supported by carbon nitride, its preparation method and application |
| CN113617375A (en) * | 2021-08-09 | 2021-11-09 | 东莞理工学院 | Graphite phase carbon nitride photocatalytic material and preparation method thereof |
| CN113617375B (en) * | 2021-08-09 | 2023-06-30 | 东莞理工学院 | Graphite-phase carbon nitride photocatalytic material and preparation method thereof |
| CN113617350A (en) * | 2021-08-11 | 2021-11-09 | 北京林业大学 | Defective carbon material and preparation method and application thereof |
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| CN113964325B (en) * | 2021-12-20 | 2022-03-18 | 北京航空航天大学 | Nitrogen-depleted g-C3N4-supported Mg3N2 composites as anode materials and lithium-based batteries |
| CN115337952A (en) * | 2022-09-16 | 2022-11-15 | 东莞理工学院 | Method for one-step synthesis of iron-manganese bimetallic oxide loaded carbon nitride containing nitrogen vacancies |
| CN115845902A (en) * | 2022-12-08 | 2023-03-28 | 上海交通大学深圳研究院 | Graphite phase carbon nitride photocatalytic material and preparation method thereof |
| CN115845902B (en) * | 2022-12-08 | 2024-04-19 | 上海交通大学深圳研究院 | Graphite-phase carbon nitride photocatalytic material and preparation method thereof |
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