技术领域technical field
本发明涉及一种以β-环糊精为基质材料合成介孔碳材料的方法。The invention relates to a method for synthesizing a mesoporous carbon material by using β-cyclodextrin as a matrix material.
背景技术Background technique
随着我国社会经济的蓬勃发展，工业产业发展迅速，包括石化、印染、制药等企业排放的各类污染物通常难以被传统生物法处理，会穿透市政污水处理设施，通过管网排入河流，对水体造成严重污染，危害人及生物链条的生长健康。通常一些企业为有效防范和降低此类污染物的排放，一般会在污染物排放源头做二次深度处理，通过一些物化强化手段来去除这部分污染物，例如活性炭吸附技术。而传统的活性炭材料由于生产工艺和材料本身性质的局限性造成其吸附能力有限，往往很快会被吸附饱和，尤其在应急处置中更需要具有吸附能力强，吸附速率快的吸附材料，另外高品质的活性炭一般需要大量的活化剂，一方面增加了活性炭的生产成本，另一方面延长了生产工艺也极易造成设备的腐蚀及二次污染。With the vigorous development of my country's social economy and the rapid development of industrial industries, various pollutants discharged by petrochemical, printing and dyeing, pharmaceutical and other enterprises are usually difficult to be treated by traditional biological methods, and will penetrate municipal sewage treatment facilities and be discharged into rivers through pipe networks , causing serious pollution to water bodies and endangering the growth and health of human beings and biological chains. Usually, in order to effectively prevent and reduce the discharge of such pollutants, some enterprises generally conduct secondary advanced treatment at the source of pollutant discharge, and remove this part of pollutants through some physical and chemical strengthening means, such as activated carbon adsorption technology. However, due to the limitations of the production process and the nature of the material itself, the traditional activated carbon material has limited adsorption capacity and will soon be saturated by adsorption. Especially in emergency disposal, it is more necessary to have adsorption materials with strong adsorption capacity and fast adsorption rate. In addition, high High-quality activated carbon generally requires a large amount of activator, which increases the production cost of activated carbon on the one hand, and prolongs the production process on the other hand, which can easily cause corrosion of equipment and secondary pollution.
介孔碳材料的性质不仅取决于前驱体本身的性质及表面和孔道结构，杂原子的掺杂也将影响介孔碳材料的性能。例如，氧原子的掺杂可以提高材料表面的亲水性能，提供催化和选择性吸附的催化位点；氮原子的掺杂可以提供材料表面的碱性基团、提高催化活性及阴离子交换能力；硼原子的掺杂可以提高材料的氧原子含量，提高材料的催化及电储能性能。因此，介孔碳材料的杂化过程不仅需要引入大量的杂原子功能基团，还需要准备调整杂原子功能基团的种类及密度以适应特殊的材料应用。The properties of mesoporous carbon materials not only depend on the properties of the precursor itself and the surface and pore structure, but also the doping of heteroatoms will affect the performance of mesoporous carbon materials. For example, the doping of oxygen atoms can improve the hydrophilicity of the surface of the material and provide catalytic sites for catalysis and selective adsorption; the doping of nitrogen atoms can provide basic groups on the surface of the material, improve catalytic activity and anion exchange capacity; The doping of boron atoms can increase the oxygen atom content of the material and improve the catalytic and electrical energy storage performance of the material. Therefore, the hybridization process of mesoporous carbon materials not only needs to introduce a large number of heteroatom functional groups, but also needs to adjust the type and density of heteroatom functional groups to adapt to special material applications.
β-环糊精作为一种常见的碳水化合物，由于其独特的双亲性及包埋能力，已广泛用于制药、化工、材料、环保等领域，另外其表面富含的大量羟基成为化学改性及负载的绝佳切入点。在吸附材料的制备方面，以往β-环糊精主要利用其羟基基团进行化学改性或接枝共聚反应，以提高其吸附性能，主要是增强其化学吸附能力，但这种改性的效率往往不高，且吸附的对象有限；另外在介孔碳材料合成方面，利用β-环糊精及其衍生物为基质材料也有相关的报道，但一般都是采用硬模板法来合成介孔碳材料，这是一种需要预制模板，碳化后还需要酸洗脱除模板的方法，工艺复杂且成本较高，不具备大规模工业化生产的条件。As a common carbohydrate, β-cyclodextrin has been widely used in pharmaceutical, chemical, material, environmental protection and other fields due to its unique amphiphilicity and embedding ability. An excellent entry point for loads. In the preparation of adsorption materials, in the past, β-cyclodextrin mainly used its hydroxyl groups for chemical modification or graft copolymerization to improve its adsorption performance, mainly to enhance its chemical adsorption capacity, but the efficiency of this modification Often not high, and the adsorption objects are limited; in addition, in the synthesis of mesoporous carbon materials, there are related reports using β-cyclodextrin and its derivatives as matrix materials, but the hard template method is generally used to synthesize mesoporous carbon Material, this is a method that requires prefabricated templates and pickling to remove the templates after carbonization. The process is complicated and the cost is high, and it does not meet the conditions for large-scale industrial production.
发明内容Contents of the invention
有鉴于此，为弥补传统活性炭材料吸附能力的不足，避免活化剂的使用，采用模板法合成的介孔碳材料无疑是传统碳吸附材料最有效的替代品。因此有必要开发一种工艺简单、能够合成出具有丰富介孔结构和广谱吸附能力的介孔碳材料的方法。In view of this, in order to make up for the lack of adsorption capacity of traditional activated carbon materials and avoid the use of activators, mesoporous carbon materials synthesized by template method are undoubtedly the most effective substitutes for traditional carbon adsorption materials. Therefore, it is necessary to develop a method with simple process and the ability to synthesize mesoporous carbon materials with rich mesoporous structure and broad-spectrum adsorption capacity.
本发明公开了一种以β-环糊精作为碳源前躯体、硼酸作为催化剂、三嵌段共聚物为模板剂的合成掺杂硼原子的介孔碳材料的软模板合成方法。该种方法主要包括下列几个步骤：The invention discloses a soft template synthesis method for synthesizing mesoporous carbon materials doped with boron atoms by using β-cyclodextrin as a carbon source precursor, boric acid as a catalyst and triblock copolymer as a template. This method mainly includes the following steps:
(1)三嵌段共聚物的溶解，在其中加入水，搅拌直至其完全溶解，得到无色透明溶液；(1) Dissolving of triblock copolymer, adding water therein, stirring until it dissolves completely, obtains colorless transparent solution;
(2)将硼酸和β-环糊精加入到步骤(1)所得到的的溶液当中，搅拌以形成乳白色混合液，完成硼酸催化β-环糊精网状络合物的生成及络合物与三嵌段共聚物的分子自组装过程；(2) Add boric acid and β-cyclodextrin to the solution obtained in step (1), stir to form a milky white mixture, and complete the formation of boric acid-catalyzed β-cyclodextrin network complex and complex Molecular self-assembly process with triblock copolymers;
(3)将步骤(2)得到的乳白色混合液倒入水热反应釜加热，生成白色粘稠状混合物；(3) Pour the milky white mixed solution obtained in step (2) into a hydrothermal reaction kettle for heating to generate a white viscous mixture;
(4)将步骤(3)得到的白色粘稠状混合物置于烘干装置内，在60℃条件下烘干，得到白色固体；(4) Place the white viscous mixture obtained in step (3) in a drying device, and dry it at 60° C. to obtain a white solid;
(5)将步骤(4)得到的白色固体碳化，经冷却后得到掺杂硼原子的介孔碳材料；(5) carbonizing the white solid obtained in step (4), and obtaining a mesoporous carbon material doped with boron atoms after cooling;
在步骤(1)中，三嵌段共聚物与水的重量份比例可以为：1-3∶25-35。In step (1), the weight ratio of tri-block copolymer to water can be: 1-3:25-35.
在步骤(2)中，硼酸与β-环糊精的重量份比例可以为：1.9∶3。In step (2), the weight ratio of boric acid to β-cyclodextrin may be 1.9:3.
在步骤(3)中，加热条件可以为在80℃-120℃下加热24h-36h。In step (3), the heating condition may be heating at 80°C-120°C for 24h-36h.
在步骤(5)中，碳化条件可以为，在氮气的保护下，以1℃/min的升温速率升至指定温度，碳化温度控制在500℃-900℃，碳化时间控制在1h-3h。In step (5), the carbonization conditions can be, under the protection of nitrogen, increase the temperature to a specified temperature at a rate of 1°C/min, control the carbonization temperature at 500°C-900°C, and control the carbonization time at 1h-3h.
进一步地，将步骤(5)得到的掺杂硼原子介孔碳材料按照1重量份的硼酸，浸泡于30重量份的10wt％的溶液中，24h后过滤，用大量水冲洗，直至上清液pH不再变化为止，将所得材料置于烘干装置内105℃下烘干12h后即可得到分层孔道结构的介孔碳材料。Further, the boron atom-doped mesoporous carbon material obtained in step (5) is soaked in 30 parts by weight of a 10wt% solution according to 1 part by weight of boric acid, filtered after 24 hours, and rinsed with a large amount of water until the supernatant Until the pH no longer changes, the obtained material is dried in a drying device at 105° C. for 12 hours to obtain a mesoporous carbon material with a layered pore structure.
具体地，碳源前躯体为β-环糊精或者其衍生物，三嵌段共聚物为P123、F127、F108或它们的混合物，进一步合成分层孔道结构的介孔碳材料过程中的浸泡溶液为氢氟酸溶液。Specifically, the carbon source precursor is β-cyclodextrin or its derivatives, and the tri-block copolymer is P123, F127, F108 or their mixture, and the soaking solution in the process of further synthesizing the mesoporous carbon material with layered pore structure For hydrofluoric acid solution.
本发明的方法主要利用环糊精表面的羟基基团和硼原子之间的络合作用，以及环糊精表面的羟基基团与三嵌段共聚物PEO段间的氢键作用，分别形成β-环糊精网状络合物和β-环糊精纳米复合物。合成的介孔碳材料既可以掺杂硼原子，也可以通过HF酸将硼原子去除，脱除的硼原子造成原子空穴，形成微孔结构，形成了最终具有分层孔道结构的介孔碳材料。The method of the present invention mainly utilizes the complexation between the hydroxyl group on the surface of the cyclodextrin and the boron atom, and the hydrogen bond between the hydroxyl group on the surface of the cyclodextrin and the PEO segment of the triblock copolymer to form β - Cyclodextrin network complexes and β-cyclodextrin nanocomplexes. The synthesized mesoporous carbon material can be doped with boron atoms, or boron atoms can be removed by HF acid. The removed boron atoms form atomic holes, forming microporous structures, and finally forming mesoporous carbon with a layered pore structure. Material.
利用本发明方法获得的掺硼介孔碳材料具有大的比表面积，较窄的孔径分布，高含量的硼原子掺杂，可用于水处理、氨气吸附、催化及电化学储能领域。并通过按照1重量份的硼酸，300重量份的10wt％的HF酸溶液对硼原子的剔除，可以形成分层孔道结构的介孔碳材料。所获得材料的结构及表征参见图2、图3、表1、表2。The boron-doped mesoporous carbon material obtained by the method of the invention has a large specific surface area, a narrow pore size distribution and a high content of boron atom doping, and can be used in the fields of water treatment, ammonia gas adsorption, catalysis and electrochemical energy storage. And by removing boron atoms according to 1 weight part of boric acid and 300 weight parts of 10 wt% HF acid solution, a mesoporous carbon material with layered pore structure can be formed. The structures and characterizations of the obtained materials are shown in Figure 2, Figure 3, Table 1, and Table 2.
本发明首次采用软模板法合成β-环糊精基介孔碳材料，可实现对材料孔道结构的方便调控，工艺简单。The present invention adopts the soft template method for the first time to synthesize the β-cyclodextrin-based mesoporous carbon material, which can realize the convenient regulation and control of the pore structure of the material, and the process is simple.
合成过程中，硼原子可有效的结合到β-环糊精的网状络合物中，经过水热反应和碳化固定后得以保留下来，增强了材料本身电化学方面的应用性能。During the synthesis process, boron atoms can be effectively combined into the network complex of β-cyclodextrin, and can be retained after hydrothermal reaction and carbonization fixation, which enhances the electrochemical performance of the material itself.
软模板法合成的掺杂硼原子介孔碳材料，经过HF酸的浸泡后可去除杂原子硼，脱除的硼原子形成原子空穴，在介孔碳材料内部及表面形成大量的微孔结构，一方面增加了材料的比表面积和孔容，另一方面打通了孔道间的连接，增强了其孔道间的传输能力，更有利于传质效应。The boron-doped mesoporous carbon material synthesized by the soft template method can remove heteroatom boron after soaking in HF acid, and the removed boron atoms form atomic holes, forming a large number of microporous structures inside and on the surface of the mesoporous carbon material On the one hand, it increases the specific surface area and pore volume of the material, on the other hand, it opens up the connection between the channels, enhances the transmission capacity between the channels, and is more conducive to the mass transfer effect.
本发明合成出的介孔碳材料具有良好的吸附性能，吸附能力优于市面的活性炭产品，可用于污水处置及水中毒害物的去除，也可以应用于氨气吸附、催化及电化学储能领域。The mesoporous carbon material synthesized by the present invention has good adsorption performance, and its adsorption capacity is superior to that of activated carbon products on the market. It can be used for sewage treatment and removal of toxic substances in water, and can also be used in the fields of ammonia adsorption, catalysis and electrochemical energy storage. .
附图说明Description of drawings
图1是本发明的软模板法制备β-环糊精基掺硼介孔碳材料的方法的一种实施方式的工艺流程图。Fig. 1 is a process flow chart of an embodiment of the method for preparing β-cyclodextrin-based boron-doped mesoporous carbon materials by the soft template method of the present invention.
图2是本发明的软模板法制备β-环糊精基掺硼介孔碳材料的方法的掺杂硼原子的介孔碳材料的氮气吸附脱附曲线图。Fig. 2 is a nitrogen adsorption-desorption curve of boron-doped mesoporous carbon materials prepared by the soft template method of the present invention.
图3是本发明的软模板法制备β-环糊精基掺硼介孔碳材料的方法的掺杂硼原子的介孔碳材料的孔径分布曲线图。Fig. 3 is a curve diagram of the pore size distribution of the boron-doped mesoporous carbon material prepared by the soft template method of the present invention.
图4是本发明的软模板法制备β-环糊精基掺硼介孔碳材料的方法的掺杂硼原子的介孔碳材料的吸附效果图。Fig. 4 is an adsorption effect diagram of the boron-doped mesoporous carbon material prepared by the soft template method of the present invention.
具体实施方式detailed description
下面结合具体合成步骤对本发明做更进一步的解释。凡采用等同替换或等效变换的方式所获得的技术方案，均处于本发明的保护范围之中。The present invention will be further explained below in conjunction with specific synthesis steps. All technical solutions obtained by means of equivalent replacement or equivalent transformation are within the protection scope of the present invention.
表1本发明合成出掺杂硼原子介孔碳材料的结构数据Table 1 The structural data of boron-doped mesoporous carbon materials synthesized by the present invention
表2本发明合成出掺杂硼原子介孔碳材料的原子组成数据(XPS数据)Table 2 The atomic composition data (XPS data) of boron-doped mesoporous carbon materials synthesized by the present invention
实施例1：Example 1:
本发明公开了一种以β-环糊精作为碳源前躯体、硼酸作为催化剂、三嵌段共聚物为模板剂的合成掺杂硼原子的介孔碳材料的软模板合成方法。该种方法包括如下步骤：The invention discloses a soft template synthesis method for synthesizing mesoporous carbon materials doped with boron atoms by using β-cyclodextrin as a carbon source precursor, boric acid as a catalyst and triblock copolymer as a template. This method includes the following steps:
(1)三嵌段共聚物P123的溶解，按照1重量份的P123加入35重量份的水，室温下搅拌直至其完全溶解，得到无色透明溶液；(1) Dissolution of the triblock copolymer P123, add 35 parts by weight of water according to 1 part by weight of P123, stir at room temperature until it is completely dissolved, and obtain a colorless and transparent solution;
(2)按照1.9重量份的硼酸和3重量份的β-环糊精加入到步骤(1)所得到的的溶液当中，在室温下搅拌6h以上，形成乳白色混合液，完成硼酸催化β-环糊精网状络合物的生成及络合物与P123的分子自组装过程；(2) Add 1.9 parts by weight of boric acid and 3 parts by weight of β-cyclodextrin to the solution obtained in step (1), and stir at room temperature for more than 6 hours to form a milky white mixture, completing the boric acid catalyzed β-cyclodextrin Formation of dextrin network complexes and molecular self-assembly process of the complexes and P123;
(3)将步骤(2)得到的乳白色混合液加入到反应釜中，在80℃-120℃条件下加热24h-36h，生成白色粘稠状混合物；(3) Add the milky white mixture obtained in step (2) into the reaction kettle, and heat at 80°C-120°C for 24h-36h to form a white viscous mixture;
(4)将步骤(3)得到的白色粘稠状混合物放入烘干装置内，在60℃条件下烘干，得到白色固体；(4) Put the white viscous mixture obtained in step (3) into a drying device, and dry it at 60° C. to obtain a white solid;
(5)将步骤(4)得到的白色固体放入碳化炉内，在氮气的保护下，以1℃/min的升温速率升至指定温度，碳化温度控制在500℃-900℃，碳化时间控制在1h-3h，经冷却后得到掺杂硼原子的介孔碳材料；(5) Put the white solid obtained in step (4) into a carbonization furnace, and under the protection of nitrogen, raise the temperature to the specified temperature at a rate of 1°C/min. The carbonization temperature is controlled at 500°C-900°C, and the carbonization time is controlled. In 1h-3h, a mesoporous carbon material doped with boron atoms is obtained after cooling;
(6)将步骤(5)得到的掺杂硼原子介孔碳材料按照1重量份的硼酸，浸泡于30重量份的10％wt的HF酸溶液中，24h后过滤，用大量的水冲洗，直至上清液pH不再变化为止，将所得材料置于烘干装置内105℃下烘干12h后即可得到分层孔道结构的介孔碳材料。(6) The boron atom-doped mesoporous carbon material obtained in step (5) is soaked in 30 parts by weight of 10%wt HF acid solution according to 1 part by weight of boric acid, filtered after 24h, and rinsed with a large amount of water. Until the pH of the supernatant does not change any more, the obtained material is dried in a drying device at 105° C. for 12 hours to obtain a mesoporous carbon material with a layered pore structure.
实施例2：Example 2:
本发明公开了一种以β-环糊精作为碳源前躯体、硼酸作为催化剂、三嵌段共聚物为模板剂的合成掺杂硼原子的介孔碳材料的软模板合成方法。该种方法包括如下步骤：The invention discloses a soft template synthesis method for synthesizing mesoporous carbon materials doped with boron atoms by using β-cyclodextrin as a carbon source precursor, boric acid as a catalyst and triblock copolymer as a template. This method includes the following steps:
(1)三嵌段共聚物P123的溶解，按照2重量份的P123加入35重量份的水，室温下搅拌直至其完全溶解，得到无色透明溶液；(1) Dissolution of the triblock copolymer P123, add 35 parts by weight of water according to 2 parts by weight of P123, stir at room temperature until it is completely dissolved, and obtain a colorless transparent solution;
(2)按照1.9重量份的硼酸和3重量份的β-环糊精加入到步骤(1)所得到的的溶液当中，在室温下搅拌6h以上，形成乳白色混合液，完成硼酸催化β-环糊精网状络合物的生成及络合物与P123的分子自组装过程；(2) Add 1.9 parts by weight of boric acid and 3 parts by weight of β-cyclodextrin to the solution obtained in step (1), and stir at room temperature for more than 6 hours to form a milky white mixture, completing the boric acid catalyzed β-cyclodextrin Formation of dextrin network complexes and molecular self-assembly process of the complexes and P123;
(3)将步骤(2)得到的乳白色混合液加入到反应釜中，在80℃-120℃条件下加热24h-36h，生成白色粘稠状混合物；(3) Add the milky white mixture obtained in step (2) into the reaction kettle, and heat at 80°C-120°C for 24h-36h to form a white viscous mixture;
(4)将步骤(3)得到的白色粘稠状混合物放入烘干装置内，在60℃条件下烘干，得到白色固体；(4) Put the white viscous mixture obtained in step (3) into a drying device, and dry it at 60° C. to obtain a white solid;
(5)将步骤(4)得到的白色固体放入碳化炉内，在氮气的保护下，以1℃/min的升温速率升至指定温度，碳化温度控制在500℃-900℃，碳化时间控制在1h-3h，经冷却后得到掺杂硼原子的介孔碳材料；(5) Put the white solid obtained in step (4) into a carbonization furnace, and under the protection of nitrogen, raise the temperature to the specified temperature at a rate of 1°C/min. The carbonization temperature is controlled at 500°C-900°C, and the carbonization time is controlled. In 1h-3h, a mesoporous carbon material doped with boron atoms is obtained after cooling;
(6)将步骤(5)得到的掺杂硼原子介孔碳材料按照1重量份的硼酸，浸泡于30重量份的10％wt的HF酸溶液中，24h后过滤，用大量的水冲洗，直至上清液pH不在变化为止，将所得材料置于烘干装置内105℃下烘干12h后即可得到分层孔道结构的介孔碳材料。(6) The boron atom-doped mesoporous carbon material obtained in step (5) is soaked in 30 parts by weight of 10%wt HF acid solution according to 1 part by weight of boric acid, filtered after 24h, and rinsed with a large amount of water. Until the pH of the supernatant does not change, the obtained material is dried in a drying device at 105° C. for 12 hours to obtain a mesoporous carbon material with a layered pore structure.
实施例3：Example 3:
本发明公开了一种以β-环糊精作为碳源前躯体、硼酸作为催化剂、三嵌段共聚物为模板剂的合成掺杂硼原子的介孔碳材料的软模板合成方法。该种方法包括如下步骤：The invention discloses a soft template synthesis method for synthesizing mesoporous carbon materials doped with boron atoms by using β-cyclodextrin as a carbon source precursor, boric acid as a catalyst and triblock copolymer as a template. This method includes the following steps:
(1)三嵌段共聚物P123的溶解，按照3重量份的P123加入35重量份的水，室温下搅拌直至其完全溶解，得到无色透明溶液；(1) For the dissolution of the triblock copolymer P123, add 35 parts by weight of water according to 3 parts by weight of P123, stir at room temperature until it is completely dissolved, and obtain a colorless and transparent solution;
(2)按照1.9重量份的硼酸和3重量份的β-环糊精加入到步骤(1)所得到的的溶液当中，在室温下搅拌6h以上，形成乳白色混合液，完成硼酸催化β-环糊精网状络合物的生成及络合物与P123的分子自组装过程；(2) Add 1.9 parts by weight of boric acid and 3 parts by weight of β-cyclodextrin to the solution obtained in step (1), and stir at room temperature for more than 6 hours to form a milky white mixture, completing the boric acid catalyzed β-cyclodextrin Formation of dextrin network complexes and molecular self-assembly process of the complexes and P123;
(3)将步骤(2)得到的乳白色混合液加入到反应釜中，在100℃-140℃条件下加热24h-36h，生成白色粘稠状混合物；(3) Add the milky white mixture obtained in step (2) into the reaction kettle, and heat it at 100°C-140°C for 24h-36h to form a white viscous mixture;
(4)将步骤(3)得到的白色粘稠状混合物放入烘干装置内，在60℃条件下烘干，得到白色固体；(4) Put the white viscous mixture obtained in step (3) into a drying device, and dry it at 60° C. to obtain a white solid;
(5)将步骤(4)得到的白色固体放入碳化炉内，在氮气的保护下，以1℃/min的升温速率升至指定定温度，碳化温度控制在500℃-900℃，碳化时间控制在1h-3h，经冷却后得到掺杂硼原子的介孔碳材料；(5) Put the white solid obtained in step (4) into a carbonization furnace, and under the protection of nitrogen, raise the temperature to a specified temperature at a rate of 1°C/min. The carbonization temperature is controlled at 500°C-900°C, and the carbonization time is Controlled at 1h-3h, after cooling, a mesoporous carbon material doped with boron atoms is obtained;
(6)将步骤(5)得到的掺杂硼原子介孔碳材料按照1重量份的硼酸，浸泡于30重量份的10％wt的HF酸溶液中，24h后过滤，用大量的水冲洗，直至上清液pH不在变化为止，将所得材料置于烘干装置内105℃下烘干12h后即可得到分层孔道结构的介孔碳材料。(6) The boron atom-doped mesoporous carbon material obtained in step (5) is soaked in 30 parts by weight of 10%wt HF acid solution according to 1 part by weight of boric acid, filtered after 24h, and rinsed with a large amount of water. Until the pH of the supernatant does not change, the obtained material is dried in a drying device at 105° C. for 12 hours to obtain a mesoporous carbon material with a layered pore structure.
在本发明的方法中，主要利用环糊精表面的羟基基团和硼原子之间的络合作用，以及环糊精表面的羟基基团与三嵌段共聚物PEO段间的氢键作用，分别形成β-环糊精网状络合物和β-环糊精纳米复合物。合成介孔碳材料既可以掺杂硼原子，也可以通过HF酸将硼原子去除，脱除的硼原子造成原子空穴，形成微孔结构，形成了最终具有分层孔道结构的介孔碳材料。合成的碳源前躯体为β-环糊精或者其衍生物(例：甲基-β-环糊精、β-环糊精聚合物)所替代，所涉及到的表面活性剂P123，也可用其他三嵌段共聚物(如：F127、F108或者它们的混合物)替代。所得到的掺硼介孔碳材料，具有大的比表面积，较窄的孔径分布，具有较高的硼掺杂量，适用于水处理，氨气吸附、催化及电化学储能领域。In the method of the present invention, the complexation between the hydroxyl group on the surface of the cyclodextrin and the boron atom, and the hydrogen bond between the hydroxyl group on the surface of the cyclodextrin and the PEO segment of the three-block copolymer are mainly used, Formation of β-cyclodextrin network complexes and β-cyclodextrin nanocomplexes, respectively. The synthesized mesoporous carbon material can be doped with boron atoms, or boron atoms can be removed by HF acid. The removed boron atoms form atomic holes, forming microporous structures, and finally forming mesoporous carbon materials with a layered pore structure. . The synthetic carbon source precursor is replaced by β-cyclodextrin or its derivatives (for example: methyl-β-cyclodextrin, β-cyclodextrin polymer), and the surfactant P123 involved can also be used Other tri-block copolymers (such as: F127, F108 or their mixture) instead. The obtained boron-doped mesoporous carbon material has large specific surface area, narrow pore size distribution and high boron doping content, and is suitable for water treatment, ammonia gas adsorption, catalysis and electrochemical energy storage fields.
参见图1，将水、表活剂(P123)、硼酸和β-环糊精依次按照配比加入到搅拌装置1中，进行搅拌后，倒入反应釜2中，在反应釜2中进行水热反应，将得到的活化液置于烘干装置3中，进行干燥，干燥后得到的白色固体放入碳化炉4，碳化炉4的尾气与吸附塔5连接，碳化过程中排出的气体导入吸附塔5，进行安全排放。碳化炉4碳化后得到的黑色固体即是掺杂硼原子介孔碳材料，对这种材料进一步进行HF酸的酸洗，再经过过滤实现固液分离，过滤得到的固体进行水洗，然后放入烘干装置3进行干燥处理，最后筛分得到分层孔道结构的介孔碳材料。Referring to Figure 1, water, surfactant (P123), boric acid and β-cyclodextrin are added to the stirring device 1 in sequence according to the proportion, after stirring, pour into the reactor 2, and the water Thermal reaction, put the obtained activation solution in the drying device 3 for drying, the white solid obtained after drying is put into the carbonization furnace 4, the tail gas of the carbonization furnace 4 is connected to the adsorption tower 5, and the gas discharged during the carbonization process is introduced into the adsorption Tower 5 for safe discharge. The black solid obtained after carbonization in the carbonization furnace 4 is the mesoporous carbon material doped with boron atoms. This material is further pickled with HF acid, and then filtered to achieve solid-liquid separation. The filtered solid is washed with water, and then put into The drying device 3 performs drying treatment, and finally sieves to obtain a mesoporous carbon material with a layered pore structure.
吸附实验：在250mL三角瓶中，分别装入100mL一定浓度的双酚A和黄连素溶液，分别加入0.02gβ-环糊精基介孔碳材料及其它3种市面上的活性炭1、2、3，室温条件下160rpm震荡，隔夜后过滤吸附质，所得溶液进行双酚A和黄连素浓度的测量，计算其吸附量，具体吸附效果参见图4。Adsorption experiment: In a 250mL Erlenmeyer flask, 100mL of a certain concentration of bisphenol A and berberine solution were respectively added, and 0.02g of β-cyclodextrin-based mesoporous carbon material and other three kinds of activated carbon 1, 2 and 3 on the market were added respectively. , shake at 160 rpm at room temperature, filter the adsorbate after overnight, measure the concentration of bisphenol A and berberine in the obtained solution, and calculate the adsorption amount, see Figure 4 for the specific adsorption effect.
表2本发明与传统β-环糊精吸附材料的不同点Table 2 Differences between the present invention and traditional β-cyclodextrin adsorption materials
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610009440.2ACN105692583A (en) | 2016-01-08 | 2016-01-08 | Method for preparing beta-cyclodextrin-based boron-doped mesoporous carbon material through soft template method |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610009440.2ACN105692583A (en) | 2016-01-08 | 2016-01-08 | Method for preparing beta-cyclodextrin-based boron-doped mesoporous carbon material through soft template method |
| Publication Number | Publication Date |
|---|---|
| CN105692583Atrue CN105692583A (en) | 2016-06-22 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610009440.2APendingCN105692583A (en) | 2016-01-08 | 2016-01-08 | Method for preparing beta-cyclodextrin-based boron-doped mesoporous carbon material through soft template method |
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