CN106744838A - The method that one step hydro thermal method prepares N doping porous graphene - Google Patents
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Abstract
Description
技术领域technical field
本发明属于碳材料与有机催化技术领域，具体涉及一种通过一步水热法制备氮掺杂多孔石墨烯的方法。The invention belongs to the technical field of carbon materials and organic catalysis, and specifically relates to a method for preparing nitrogen-doped porous graphene through a one-step hydrothermal method.
背景技术Background technique
石墨烯具有优异的电学、光学、热学和力学性能，以及高比表面积(理论值为2630m2/g)，是一种非常有潜力的新型碳材料。石墨烯中的碳原子皆为sp2杂化，具有完美的六角形蜂巢二维晶体结构。然而，也正是由于它规则和均匀的电子结构弱化了其催化活性，限制了其应用范围[Nat.Mater.2007,6,183-191]。Graphene has excellent electrical, optical, thermal and mechanical properties, as well as a high specific surface area (theoretical value is 2630m 2 /g), and is a very promising new carbon material. The carbon atoms in graphene are all sp 2 hybridized, with a perfect hexagonal honeycomb two-dimensional crystal structure. However, it is precisely because of its regular and uniform electronic structure that it weakens its catalytic activity and limits its application [Nat.Mater.2007,6,183-191].
向石墨烯原子结构中引入杂原子则可以调控其物理和化学性质，拓宽其应用范围。研究发现，采用杂原子对石墨烯进行掺杂时，可以改变与之相邻碳原子的电荷分布，产生催化活性位点[Science，2016，351,361-365]。向石墨烯中掺杂氮原子可以在石墨烯表面诱导形成高的局域电荷/自旋密度，提高其化学活性；掺杂磷原子可以增强碳原子的电荷离域，并造成更多边缘活性位点[ACS Nano，2012,6,7084-7091]。因此，研制高性能掺杂石墨烯材料的工作重点是选择合理原子尺寸和电负性的原子，并有效地将其掺杂入石墨烯结构中。此外，催化剂的催化活性与其比表面积、表面活性中心数量密切相关。然而，石墨烯片层之间有较强的π-π作用力，容易导致堆叠，降低其比表面积而影响催化性能[Angew.Chem.Int.Ed.2013,126,254-258]，而利用活化造孔的方法来提高其比表面积并加强传质[Nat.Commun.2014,5,4554]，可以有效增强催化活性。因此，通过在石墨烯上构建多孔结构是提高石墨烯基催化活性的有效手段之一。The introduction of heteroatoms into the atomic structure of graphene can regulate its physical and chemical properties and broaden its application range. Studies have found that when graphene is doped with heteroatoms, the charge distribution of adjacent carbon atoms can be changed to generate catalytic active sites [Science, 2016, 351, 361-365]. Doping nitrogen atoms into graphene can induce high local charge/spin density on the surface of graphene and improve its chemical activity; doping phosphorus atoms can enhance the charge delocalization of carbon atoms and create more edge active sites Point [ACS Nano, 2012, 6, 7084-7091]. Therefore, the focus of the development of high-performance doped graphene materials is to select atoms with reasonable atomic size and electronegativity and effectively dope them into the graphene structure. In addition, the catalytic activity of the catalyst is closely related to its specific surface area and the number of surface active centers. However, there is a strong π-π interaction between graphene sheets, which can easily lead to stacking, reduce its specific surface area and affect its catalytic performance [Angew.Chem.Int.Ed.2013,126,254-258]. The method of pores to increase its specific surface area and enhance mass transfer [Nat.Commun.2014,5,4554] can effectively enhance the catalytic activity. Therefore, building a porous structure on graphene is one of the effective means to improve the catalytic activity of graphene-based catalysts.
目前，掺杂多孔石墨烯的制备方法一般分为两步：首先构建石墨烯多孔结构，再采用氮源对多孔石墨烯进行掺杂(先造孔后掺杂)，如蒋仲杰[CN201510379585.7]利用浓硝酸对氧化石墨烯造孔，再利用含杂原子化合物在等离子体高温管式反应器中处理得到相应的氮掺杂多孔石墨烯。也可以先采用氮源对多孔石墨烯进行掺杂，再构建石墨烯多孔结构(先掺杂后造孔)，如马建民等[CN201410361326.7]将氮源与有机盐或与有机酸和盐类的混合物在非氧化性气氛下高温处理，再去除混合物中的金属氧化物，得到氮参杂多孔石墨烯。这些方法需要特殊设备，过程繁琐，能耗较高，生产效率较低。At present, the preparation method of doped porous graphene is generally divided into two steps: first construct the graphene porous structure, and then use nitrogen source to dope the porous graphene (pore creation first and then doping), such as Jiang Zhongjie [CN201510379585.7] Concentrated nitric acid is used to make holes in graphene oxide, and then treated with heteroatom-containing compounds in a plasma high-temperature tubular reactor to obtain the corresponding nitrogen-doped porous graphene. It is also possible to use a nitrogen source to dope porous graphene first, and then construct a graphene porous structure (doping first and then forming pores), such as Ma Jianmin et al [CN201410361326.7] combine nitrogen source with organic salt or with organic acid and salt The mixture is treated at high temperature in a non-oxidizing atmosphere, and then the metal oxide in the mixture is removed to obtain nitrogen-doped porous graphene. These methods require special equipment, the process is loaded down with trivial details, energy consumption is higher, and production efficiency is lower.
发明内容Contents of the invention
为克服现有技术存在的上述不足，本发明的首要目的在于提供一种仅通过一步水热法制备氮掺杂多孔石墨烯的方法，该方法在构建石墨烯多孔结构的同时实现了氮掺杂，工艺简单，对设备要求低。为实现上述目的，本发明的技术方案如下：In order to overcome the above-mentioned deficiencies in the prior art, the primary purpose of the present invention is to provide a method for preparing nitrogen-doped porous graphene only by a one-step hydrothermal method, which realizes nitrogen doping while constructing a graphene porous structure. , the process is simple, and the requirements for equipment are low. To achieve the above object, the technical scheme of the present invention is as follows:
一步水热法制备氮掺杂多孔石墨烯的方法，包括以下步骤：配制氧化石墨烯水溶液，分别向其中加入致孔剂和氮源，将溶液混合均匀，水热反应后得氮掺杂多孔石墨烯。A method for preparing nitrogen-doped porous graphene by a one-step hydrothermal method, comprising the following steps: preparing an aqueous solution of graphene oxide, adding a porogen and a nitrogen source to it respectively, mixing the solutions uniformly, and obtaining nitrogen-doped porous graphite after hydrothermal reaction alkene.
上述方案中，所述氧化石墨烯水溶液的浓度为3-10mg/mL。In the above scheme, the concentration of the graphene oxide aqueous solution is 3-10 mg/mL.
上述方案中，所述致孔剂为过氧化氢，其水溶液质量分数为0.3-30％。In the above scheme, the porogen is hydrogen peroxide, and the mass fraction of its aqueous solution is 0.3-30%.
上述方案中，所述氮源为氨，其水溶液质量分数为28-30％。In the above scheme, the nitrogen source is ammonia, and the mass fraction of its aqueous solution is 28-30%.
上述方案中，混合时氧化石墨烯与致孔剂、氮源的质量比为1：0.05-5：0.05-30。In the above scheme, the mass ratio of graphene oxide, porogen, and nitrogen source during mixing is 1:0.05-5:0.05-30.
上述方案中，所述水热反应温度为100-220℃，反应时间为5-24h。In the above scheme, the hydrothermal reaction temperature is 100-220°C, and the reaction time is 5-24h.
与现有技术相比，本发明具有以下有益效果：(1)首先将原有的两步法合并成一步水热法，工艺上更加简单，生产效率更高；(2)反应条件温和，所需原料简单易得，无需特殊或复杂反应设备，成本更低；(3)制备出的氮掺杂多孔石墨烯具有比表面积大、催化性能优异等特点，可用于电催化、超级电容器、锂离子电池和有机催化等领域。Compared with the prior art, the present invention has the following beneficial effects: (1) firstly, the original two-step method is combined into a one-step hydrothermal method, which is simpler in technology and higher in production efficiency; (2) the reaction conditions are mild, so The required raw materials are simple and easy to obtain, no special or complex reaction equipment is required, and the cost is lower; (3) The prepared nitrogen-doped porous graphene has the characteristics of large specific surface area and excellent catalytic performance, and can be used in electrocatalysis, supercapacitors, lithium-ion Batteries and organic catalysis and other fields.
附图说明Description of drawings
图1为本发明实施例1制备的氮掺杂多孔石墨烯不同条件下的图片，1-A为实物照片，1-B为扫描电镜图，1-C为高分辨扫描电镜图。Figure 1 is pictures of nitrogen-doped porous graphene prepared in Example 1 of the present invention under different conditions, 1-A is a physical photo, 1-B is a scanning electron microscope image, and 1-C is a high-resolution scanning electron microscope image.
图2为本发明实施例1制备的氮掺杂多孔石墨烯在透射电镜图(2-A)和高分辨投射电镜图(2-B)。Fig. 2 is a transmission electron microscope image (2-A) and a high-resolution transmission electron microscope image (2-B) of the nitrogen-doped porous graphene prepared in Example 1 of the present invention.
图3为本发明实施例1制备的氮掺杂多孔石墨烯的X-射线光电子能谱测试结果图，3-A为全谱图，3-B为高分辨C 1s峰，3-C为高分辨N 1s峰。Fig. 3 is the X-ray photoelectron spectrum test result figure of the nitrogen-doped porous graphene prepared in Example 1 of the present invention, 3-A is full spectrum figure, 3-B is high resolution C 1s peak, 3-C is high Resolve N 1s peaks.
图4为本发明实施例1制备的氮掺杂多孔石墨烯的N2吸附脱附曲线图(A)和孔径分布图(B)。Fig. 4 is the N2 adsorption-desorption curve (A) and pore size distribution diagram (B) of the nitrogen-doped porous graphene prepared in Example 1 of the present invention.
具体实施方式detailed description
为使本领域普通技术人员充分理解本发明的技术方案和有益效果，以下结合具体实施例进行进一步充分说明。In order to enable those skilled in the art to fully understand the technical solutions and beneficial effects of the present invention, further detailed description will be given below in conjunction with specific examples.
一步水热法制备氮掺杂多孔石墨烯的方法，首先配制氧化石墨烯水溶液，向其中加入浓度为0.3-30wt％的过氧化氢溶液和浓度为28-30wt％的氨水溶液并混合均匀，将混合溶液加热至100-220℃进行水热反应5-24h，最终得到氮掺杂多孔石墨烯。其中，氧化石墨烯与过氧化氢、氨三者纯物质的质量比为1:0.05-5:0.05-30。A method for preparing nitrogen-doped porous graphene by a one-step hydrothermal method, first preparing an aqueous solution of graphene oxide, adding a hydrogen peroxide solution with a concentration of 0.3-30wt% and an ammonia solution with a concentration of 28-30wt% and mixing uniformly, and The mixed solution is heated to 100-220° C. for hydrothermal reaction for 5-24 hours, and nitrogen-doped porous graphene is finally obtained. Wherein, the mass ratio of graphene oxide to pure substances of hydrogen peroxide and ammonia is 1:0.05-5:0.05-30.
实施例1Example 1
按照氧化石墨烯与过氧化氢、氨1:0.1:30的质量比投料。取40mL浓度为7.5mg/mL的氧化石墨烯水溶液，将其装入100mL聚四氟乙烯反应釜内胆中，在搅拌条件下加入10mL质量分数为0.3％的过氧化氢溶液和30mL质量分数为28-30％的氨水溶液。将混合均匀的反应物，装入水热反应釜中，在180℃烘箱中水热反应6h，得氮掺杂多孔石墨烯。Feed according to the mass ratio of graphene oxide to hydrogen peroxide and ammonia 1:0.1:30. Get 40mL concentration and be the graphene oxide aqueous solution of 7.5mg/mL, put it into 100mL polytetrafluoroethylene reactor liner, add 10mL mass fraction as 0.3% hydrogen peroxide solution and 30mL mass fraction as 28-30% ammonia solution. The uniformly mixed reactants were put into a hydrothermal reaction kettle, and subjected to a hydrothermal reaction in an oven at 180° C. for 6 hours to obtain nitrogen-doped porous graphene.
为更充分的了解本实施例制得的氮掺杂多孔石墨烯的结构特征及其性能，分别对其进行了SEM、TEM、XPS、吸附脱附以及孔径分布测试。如图1-A所示，氧化石墨烯纳米片在水热反应后组装成为圆柱形水凝胶，扫描电镜图则证实制备的氮掺杂多孔石墨烯具有蓬松的三维网状结构。图2所示的透射电镜照片表明，制备的氮掺杂多孔石墨烯被刻蚀成为多孔结构，石墨烯片上分布有有大量介孔。图3所示的XPS分析表明，制备的氮掺杂多孔石墨烯中掺杂有78.7wt.％的碳元素、10.80wt.％的氧元素和10.47wt.％的氮元素。比表面分析结果则表明，制备的氮掺杂多孔石墨烯比表面积为322.1m2/g，孔径分布在微孔和介孔范围。In order to fully understand the structural characteristics and properties of the nitrogen-doped porous graphene prepared in this example, SEM, TEM, XPS, adsorption-desorption, and pore size distribution tests were carried out on it. As shown in Figure 1-A, graphene oxide nanosheets were assembled into cylindrical hydrogels after hydrothermal reaction, and scanning electron microscopy confirmed that the prepared nitrogen-doped porous graphene had a fluffy three-dimensional network structure. The transmission electron microscope photos shown in Figure 2 show that the prepared nitrogen-doped porous graphene is etched into a porous structure, and there are a large number of mesopores distributed on the graphene sheet. The XPS analysis shown in Figure 3 shows that the prepared nitrogen-doped porous graphene is doped with 78.7wt.% of carbon elements, 10.80wt.% of oxygen elements and 10.47wt.% of nitrogen elements. The results of specific surface analysis show that the specific surface area of the prepared nitrogen-doped porous graphene is 322.1m 2 /g, and the pore size distribution is in the micropore and mesopore range.
实施例2Example 2
按照氧化石墨烯与过氧化氢、氨1：0.05：0.05的质量比投料。取75mL浓度为4mg/mL氧化石墨烯水溶液，装入100mL聚四氟乙烯反应釜内胆中，在搅拌条件下加入4.5mL质量分数为0.3％的过氧化氢溶液和0.05mL质量分数为28-30％的氨水溶液。将混合均匀的反应物，装入水热反应釜中，在130℃烘箱中水热反应24h，得氮掺杂多孔石墨烯。Feed according to the mass ratio of graphene oxide to hydrogen peroxide and ammonia 1:0.05:0.05. Take 75mL concentration of 4mg/mL graphene oxide aqueous solution, put it into a 100mL polytetrafluoroethylene reactor liner, add 4.5mL hydrogen peroxide solution with a mass fraction of 0.3% and 0.05mL with a mass fraction of 28- 30% ammonia solution. The uniformly mixed reactants were put into a hydrothermal reaction kettle, and subjected to a hydrothermal reaction in an oven at 130° C. for 24 hours to obtain nitrogen-doped porous graphene.
实施例3Example 3
按照氧化石墨烯与过氧化氢、氨1：0.4：20的质量比投料。取50mL浓度为3mg/mL氧化石墨烯水溶液，装入100mL聚四氟乙烯反应釜内胆中，在搅拌条件下加入20mL质量分数为0.3％的过氧化氢溶液和10mL质量分数为28-30％的氨水溶液。将混合均匀的反应物，装入水热反应釜中，在150℃烘箱中水热反应8h，得氮掺杂多孔石墨烯。Feed according to the mass ratio of graphene oxide to hydrogen peroxide and ammonia 1:0.4:20. Take 50mL of graphene oxide aqueous solution with a concentration of 3mg/mL, put it into a 100mL polytetrafluoroethylene reactor liner, add 20mL of hydrogen peroxide solution with a mass fraction of 0.3% and 10mL with a mass fraction of 28-30% of ammonia solution. The uniformly mixed reactants were put into a hydrothermal reaction kettle, and subjected to a hydrothermal reaction in an oven at 150° C. for 8 hours to obtain nitrogen-doped porous graphene.
实施例4Example 4
按照氧化石墨烯与过氧化氢、氨1：0.3：15的质量比投料。取50mL浓度为4mg/mL氧化石墨烯水溶液，装入100mL聚四氟乙烯反应釜内胆中，在搅拌条件下加入20mL质量分数为0.3％的过氧化氢溶液和10mL质量分数为28-30％的氨水溶液。将混合均匀的反应物，装入水热反应釜中，在100℃烘箱中水热反应24h，得氮掺杂多孔石墨烯。Feed according to the mass ratio of graphene oxide to hydrogen peroxide and ammonia 1:0.3:15. Take 50mL of graphene oxide aqueous solution with a concentration of 4mg/mL, put it into a 100mL polytetrafluoroethylene reactor liner, add 20mL of hydrogen peroxide solution with a mass fraction of 0.3% and 10mL with a mass fraction of 28-30% of ammonia solution. The uniformly mixed reactants were put into a hydrothermal reaction kettle, and subjected to a hydrothermal reaction in an oven at 100°C for 24 hours to obtain nitrogen-doped porous graphene.
实施例5Example 5
按照氧化石墨烯与过氧化氢、氨1：0.375：20.8的质量比投料。取24mL浓度为10mg/mL氧化石墨烯水溶液，装入100mL聚四氟乙烯反应釜内胆中，在搅拌条件下加入30mL质量分数为0.3％的过氧化氢溶液和15mL质量分数为28-30％的氨水溶液。将混合均匀的反应物，装入水热反应釜中，在150℃烘箱中水热反应8h，得氮掺杂多孔石墨烯。Feed according to the mass ratio of graphene oxide to hydrogen peroxide and ammonia 1:0.375:20.8. Take 24mL of graphene oxide aqueous solution with a concentration of 10mg/mL, put it into a 100mL polytetrafluoroethylene reactor liner, add 30mL of hydrogen peroxide solution with a mass fraction of 0.3% and 15mL with a mass fraction of 28-30% of ammonia solution. The uniformly mixed reactants were put into a hydrothermal reaction kettle, and subjected to a hydrothermal reaction in an oven at 150° C. for 8 hours to obtain nitrogen-doped porous graphene.
实施例6Example 6
按照氧化石墨烯与过氧化氢、氨水1：0.83：18.5的质量比投料。取45mL浓度6mg/mL氧化石墨烯水溶液，装入100mL聚四氟乙烯反应釜内胆中，在搅拌条件下加入25mL质量分数为0.9％的过氧化氢溶液和15mL质量分数为28-30％的氨水溶液。将混合均匀的反应物，装入水热反应釜中，在220℃烘箱中水热反应5h，得氮掺杂多孔石墨烯。Feed according to the mass ratio of graphene oxide to hydrogen peroxide and ammonia water 1:0.83:18.5. Take 45 mL of graphene oxide aqueous solution with a concentration of 6 mg/mL, put it into a 100 mL polytetrafluoroethylene reactor liner, add 25 mL of hydrogen peroxide solution with a mass fraction of 0.9% and 15 mL of hydrogen peroxide solution with a mass fraction of 28-30% under stirring conditions Ammonia solution. The uniformly mixed reactants were put into a hydrothermal reaction kettle, and subjected to a hydrothermal reaction in an oven at 220° C. for 5 hours to obtain nitrogen-doped porous graphene.
实施例7Example 7
按照氧化石墨烯与过氧化氢、氨1：1：20的质量比为投料。取50mL浓度为6mg/mL氧化石墨烯水溶液，装入100mL聚四氟乙烯反应釜内胆中，在搅拌条件下加入10mL质量分数为3％的过氧化氢溶液和20mL质量分数为28-30％的氨水溶液。将混合均匀的反应物，装入水热反应釜中，在120℃烘箱中水热反应10h，得氮掺杂多孔石墨烯。The mass ratio of graphene oxide to hydrogen peroxide and ammonia is 1:1:20. Take 50mL graphene oxide aqueous solution with a concentration of 6mg/mL, put it into a 100mL polytetrafluoroethylene reactor liner, add 10mL hydrogen peroxide solution with a mass fraction of 3% and 20mL with a mass fraction of 28-30% of ammonia solution. The uniformly mixed reactants were put into a hydrothermal reaction kettle, and subjected to a hydrothermal reaction in an oven at 120°C for 10 hours to obtain nitrogen-doped porous graphene.
实施例8Example 8
按照氧化石墨烯与过氧化氢、氨1：5：30的质量比为投料。取50mL浓度为6mg/mL氧化石墨烯水溶液，装入100mL聚四氟乙烯反应釜内胆中，在搅拌条件下加入4.5mL质量分数为30％的过氧化氢溶液和30mL质量分数为28-30％的氨水溶液。将混合均匀的反应物，装入水热反应釜中，在120℃烘箱中水热反应10h，得氮掺杂多孔石墨烯。The mass ratio of graphene oxide to hydrogen peroxide and ammonia is 1:5:30. Take 50 mL of graphene oxide aqueous solution with a concentration of 6 mg/mL, put it into a 100 mL polytetrafluoroethylene reactor liner, add 4.5 mL of hydrogen peroxide solution with a mass fraction of 30% and 30 mL with a mass fraction of 28-30 % ammonia solution. The uniformly mixed reactants were put into a hydrothermal reaction kettle, and subjected to a hydrothermal reaction in an oven at 120°C for 10 hours to obtain nitrogen-doped porous graphene.
以上所述仅为本发明的部分实施例，并非限制本发明的保护范围。凡是利用本发明技术方案所进行的修改，或者对其中部分或全部技术特征进行等同替换，均应落入本发明的保护范围之内。The above descriptions are only some embodiments of the present invention, and do not limit the protection scope of the present invention. Any modification made by using the technical solution of the present invention, or an equivalent replacement of some or all of the technical features shall fall within the protection scope of the present invention.
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