技术领域Technical field
本发明涉及材料制备技术领域，具体而言，涉及一种多孔空心碳纳米球的制备方法。The present invention relates to the technical field of material preparation, and specifically, to a preparation method of porous hollow carbon nanospheres.
背景技术Background technique
多孔空心碳微球是一种中空的，球壁上具有丰富空隙的规则球形形貌的碳材料，按照孔径大小将其分为微孔碳微球(孔径<2nm)、介孔碳微球(2nm<孔径<50nm)和大孔碳微球(孔径>50nm)，这种形态给碳纳米球带来丰富的结构性能。与碳纳米球相比，多孔空心碳微球的中空内部结构提供了更高的装载空间；多孔球壁增大了碳纳米球的空隙率和比表面积，增强了对预载物镶嵌、吸附和固定能力；同时，孔道的出现为预载物渗透到碳球内部提供了便捷的通道，提高了渗透性。除此之外，多孔空心碳纳米球还具有高导电性、低密度、化学稳定性好、生物相容性好、可设计性好等优点，特别是可设计性——改变制备方法可得到具有不同孔结构、微球粒径的多孔碳微球。因此，多孔空心碳纳米球在催化、吸附、能源储存、生物医药等领域有着良好的应用前景。Porous hollow carbon microspheres are a hollow carbon material with a regular spherical shape and abundant voids on the spherical wall. According to the pore size, they are divided into microporous carbon microspheres (pore diameter <2nm) and mesoporous carbon microspheres (pore diameter <2nm). 2nm<pore diameter<50nm) and macroporous carbon microspheres (pore diameter>50nm), this form brings rich structural properties to carbon nanospheres. Compared with carbon nanospheres, the hollow internal structure of porous hollow carbon microspheres provides a higher loading space; the porous spherical walls increase the porosity and specific surface area of carbon nanospheres, enhancing the inlay, adsorption and absorption of preloaded materials. Fixing ability; at the same time, the emergence of pores provides a convenient channel for the preloaded material to penetrate into the interior of the carbon balls, improving the permeability. In addition, porous hollow carbon nanospheres also have the advantages of high conductivity, low density, good chemical stability, good biocompatibility, and good designability. Especially the designability-changing the preparation method can obtain Porous carbon microspheres with different pore structures and microsphere particle sizes. Therefore, porous hollow carbon nanospheres have good application prospects in the fields of catalysis, adsorption, energy storage, biomedicine and other fields.
现阶段的多孔空心碳纳米球的制备方法通常采用模板法，该制备方法具有工艺简单、重复性好等优点。然而，模板法制备多孔空心碳纳米球时，需要加入交联剂和诱发剂，使碳纳米球的制备成本增高，还易引入其他的元素，影响碳纳米球的结构，且不利于碳纳米球的工业化推广。The current preparation method of porous hollow carbon nanospheres usually adopts the template method, which has the advantages of simple process and good repeatability. However, when preparing porous hollow carbon nanospheres by the template method, it is necessary to add cross-linking agents and inducers, which increases the preparation cost of carbon nanospheres. It is also easy to introduce other elements, which affects the structure of carbon nanospheres and is not conducive to carbon nanospheres. industrial promotion.
发明内容Contents of the invention
本发明解决的问题是模板法制备多孔空心碳纳米球时需加入交联剂和诱发剂使制备成本增高的问题。The problem solved by the present invention is that when preparing porous hollow carbon nanospheres by template method, cross-linking agents and inducers need to be added, which increases the preparation cost.
为解决上述问题，本发明提供一种多孔空心碳纳米球的制备方法，包括如下步骤：In order to solve the above problems, the present invention provides a preparation method of porous hollow carbon nanospheres, which includes the following steps:
步骤S1：将二氧化硅加入壳聚糖的醋酸溶液中并搅拌，再滴加三聚磷酸钠水溶液，密封反应并磁力搅拌后，得到壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体水相体系；Step S1: Add silica to the acetic acid solution of chitosan and stir, then add sodium tripolyphosphate aqueous solution dropwise, seal the reaction and stir magnetically to obtain chitosan/sodium tripolyphosphate/silica polymer colloid Aqueous phase system;
步骤S2：将棕榈酸异辛酯、霍霍巴油、十六-十八醇和乳化剂混合后，加热并搅拌至溶解后得到油相，将所述油相加入到所述壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体水相体系中并搅拌，得到油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂；Step S2: Mix isooctyl palmitate, jojoba oil, cetearyl alcohol and emulsifier, heat and stir until dissolved to obtain an oil phase, add the oil phase to the chitosan/tripolymer Sodium phosphate/silica polymer colloid aqueous phase system and stirred to obtain an oil-in-water emulsion of chitosan/sodium tripolyphosphate/silica core material wrapped in oil;
步骤S3：所述油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂经冷冻干燥、高温煅烧后，得到二氧化硅为核心的多孔碳纳米球；Step S3: After the oil-in-water emulsion of the oil-coated chitosan/sodium tripolyphosphate/silica core material is freeze-dried and calcined at high temperature, porous carbon nanospheres with silica as the core are obtained;
步骤S4：将所述二氧化硅为核心的多孔碳纳米球置于氢氟酸溶液中，经搅拌、离心、洗涤至中性后，得到多孔空心碳纳米球。Step S4: Place the silica-core porous carbon nanospheres in a hydrofluoric acid solution, stir, centrifuge, and wash until neutral to obtain porous hollow carbon nanospheres.
进一步地，步骤S1中，所述磁力搅拌包括：在温度为45-55℃条件下进行水域磁力搅拌；所述密封反应的时间为10h。Further, in step S1, the magnetic stirring includes: performing magnetic stirring in the water area at a temperature of 45-55°C; the sealing reaction time is 10 hours.
进一步地，步骤S2中，所述将棕榈酸异辛酯、霍霍巴油、十六-十八醇和乳化剂混合后，加热并搅拌至溶解后得到油相，包括：Further, in step S2, after mixing isooctyl palmitate, jojoba oil, cetearyl alcohol and emulsifier, heat and stir until dissolved to obtain an oil phase, including:
将所述棕榈酸异辛酯、所述霍霍巴油和所述十六-十八醇混合后加热到80℃的过程中进行搅拌至溶解均匀，加入乳化剂，在温度为80℃的条件下继续搅拌至溶解均匀，得到油相。After mixing the isooctyl palmitate, the jojoba oil and the cetearyl alcohol and heating to 80°C, stir until uniformly dissolved, add an emulsifier, and stir at a temperature of 80°C. Continue stirring until evenly dissolved and an oil phase is obtained.
进一步地，步骤S2中，所述乳化剂为鲸蜡基葡萄糖苷。Further, in step S2, the emulsifier is cetyl glucoside.
进一步地，步骤S2中，所述将所述油相加入到所述壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体水相体系中并搅拌，得到油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂，包括：Further, in step S2, the oil phase is added to the chitosan/sodium tripolyphosphate/silica polymer colloid aqueous phase system and stirred to obtain oil-coated chitosan/tripolyphosphate. Oil-in-water emulsions of sodium phosphate/silica core materials, including:
在水域温度为80℃的条件下，在搅拌的同时将油相快速加到所述壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体水相体系中，搅拌并均质，降温至室温，得到油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂。Under the condition that the water temperature is 80°C, quickly add the oil phase to the chitosan/sodium tripolyphosphate/silica polymer colloid water phase system while stirring, stir and homogenize, and cool to room temperature. , an oil-in-water emulsion of chitosan/sodium tripolyphosphate/silica core material coated with oil was obtained.
进一步地，步骤S2中，所述搅拌时间为10min，所述均质的时间为3-5min。Further, in step S2, the stirring time is 10 min, and the homogenizing time is 3-5 min.
进一步地，步骤S3中，所述高温煅烧包括：在氮气保护氛围下，以2-5℃/min的速率升温至400-500℃，并保温1-2h；再以5-10℃的速率升温至950-1050℃，并保温3-4h。Further, in step S3, the high-temperature calcination includes: heating to 400-500°C at a rate of 2-5°C/min under a nitrogen protective atmosphere, and maintaining the temperature for 1-2 hours; and then raising the temperature at a rate of 5-10°C. to 950-1050℃ and keep warm for 3-4 hours.
进一步地，步骤S3中，还包括在高温煅烧前，将冷冻干燥后的所述油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂加入到低温无水乙醇中分散均匀，抽滤并真空干燥。Further, step S3 also includes adding the freeze-dried oil-in-water emulsion of the oil-coated chitosan/sodium tripolyphosphate/silica core material to low-temperature anhydrous ethanol before high-temperature calcination. Disperse evenly, filter and dry under vacuum.
进一步地，步骤S3中，所述无水乙醇的温度为-10℃。Further, in step S3, the temperature of the absolute ethanol is -10°C.
进一步地，步骤S4中，所述搅拌时间为10-12h。Further, in step S4, the stirring time is 10-12h.
本发明所述的一种多孔空心碳纳米球的制备方法相对于现有技术的优势在于：The advantages of the preparation method of porous hollow carbon nanospheres compared with the existing technology are:
(1)本发明通过将二氧化硅加入壳聚糖的醋酸溶液中并搅拌，再缓慢滴加三聚磷酸钠水溶液，密封反应并磁力搅拌，使壳聚糖的醋酸溶液与三聚磷酸钠水溶液通过聚电解质复合机制形成聚合物胶体水相体系，且二氧化硅可以均匀悬浮在凝胶体系中，可有效地形成二氧化硅为核心、壳聚糖/三聚磷酸钠凝胶为壁材的微观囊球结构，为碳纳米球形成提供球心模板；(1) In the present invention, silica is added to the acetic acid solution of chitosan and stirred, and then the sodium tripolyphosphate aqueous solution is slowly added dropwise, the reaction is sealed and magnetically stirred, so that the acetic acid solution of chitosan and the sodium tripolyphosphate aqueous solution are The polymer colloid aqueous phase system is formed through the polyelectrolyte composite mechanism, and the silica can be evenly suspended in the gel system, which can effectively form a silica core and chitosan/sodium tripolyphosphate gel as the wall material. The microscopic capsule structure provides a core template for the formation of carbon nanospheres;
(2)本发明以棕榈酸异辛酯、霍霍巴油、十六-十八醇和乳化剂为油相与水相的壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体体系在高速剪切力作用下形成的乳剂体系中，油相通过H-O配位与壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体水相体系交联，在乳化剂作用下形成最外层为乳化剂、内层依次为二氧化硅为核心、壳聚糖/三聚磷酸钠层、油脂层组成的复合纳米微球分散相，乳化剂的亲油基与微球内层的油相结合，亲水基与连续相水结合，将纳米微球均匀地分散在水相中而不相连，形成了分散均匀而独立的碳纳米球；(2) The chitosan/sodium tripolyphosphate/silica polymer colloid system of the present invention, which uses isooctyl palmitate, jojoba oil, cetearyl alcohol and emulsifier as oil phase and water phase, is sheared at high speed. In the emulsion system formed under the action of shear force, the oil phase is cross-linked with the chitosan/sodium tripolyphosphate/silica polymer colloid water phase system through H-O coordination, and the outermost layer is formed under the action of the emulsifier. , the inner layer is composed of silica as the core, chitosan/sodium tripolyphosphate layer, and grease layer as the composite nano-microsphere dispersed phase. The lipophilic group of the emulsifier is combined with the oil phase in the inner layer of the microsphere to make it hydrophilic. The base is combined with the continuous phase water to evenly disperse the nanospheres in the water phase without being connected, forming uniformly dispersed and independent carbon nanospheres;
(3)本发明的壳聚糖与油相含有大量的含氧官能团，高温煅烧过程中，大部分含氧官能团发生C-O键断裂而逃逸，使碳纳米球石墨化壁层出现空洞，完成碳纳米球造孔，造孔方法简单，无需添加造孔剂，制备方法简单，成本低，条件温和，易于控制。(3) The chitosan and oil phase of the present invention contain a large number of oxygen-containing functional groups. During the high-temperature calcination process, most of the oxygen-containing functional groups break the C-O bonds and escape, causing holes to appear in the graphitized wall layer of the carbon nanospheres, completing the carbon nanospheres. The ball hole making method is simple, no need to add a hole forming agent, the preparation method is simple, the cost is low, the conditions are mild, and it is easy to control.
附图说明Description of the drawings
图1为本发明实施例中的多孔空心碳纳米球的制备方法流程图。Figure 1 is a flow chart of a method for preparing porous hollow carbon nanospheres in an embodiment of the present invention.
具体实施方式Detailed ways
为使本发明的上述目的、特征和优点能够更为明显易懂，下面结合附图对本发明的具体实施例做详细的说明。In order to make the above objects, features and advantages of the present invention more obvious and understandable, specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
需要说明的是，在本申请实施例的描述中，术语“一些具体的实施例”的描述意指结合该实施例或示例描述的具体特征、结构、材料或特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不一定指的是相同的实施或实例。而且，描述的具体特征、结构、材料或特点可以在任何的一个或多个实施例或示例中以合适的方式结合。It should be noted that in the description of the embodiments of this application, the term "some specific embodiments" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one implementation of the present invention. example or examples. In this specification, schematic representations of the above terms do not necessarily refer to the same implementation or example. Furthermore, the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
如图1所示，本发明提供一种多孔空心碳纳米球的制备方法，包括如下步骤：As shown in Figure 1, the present invention provides a method for preparing porous hollow carbon nanospheres, which includes the following steps:
步骤S1：将二氧化硅加入壳聚糖的醋酸溶液中并搅拌，再滴加三聚磷酸钠水溶液，密封反应并磁力搅拌后，得到壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体水相体系；Step S1: Add silica to the acetic acid solution of chitosan and stir, then add sodium tripolyphosphate aqueous solution dropwise, seal the reaction and stir magnetically to obtain chitosan/sodium tripolyphosphate/silica polymer colloid Aqueous phase system;
步骤S2：将棕榈酸异辛酯、霍霍巴油、十六-十八醇和乳化剂混合后，加热并搅拌至溶解后得到油相，将油相加入到壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体水相体系中并搅拌，得到油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂；Step S2: Mix isooctyl palmitate, jojoba oil, cetearyl alcohol and emulsifier, heat and stir until dissolved to obtain an oil phase, add the oil phase to chitosan/sodium tripolyphosphate/bis Put it into the silica polymer colloid aqueous phase system and stir to obtain an oil-in-water emulsion of chitosan/sodium tripolyphosphate/silica core material wrapped in oil;
步骤S3：油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂经冷冻干燥、高温煅烧后，得到二氧化硅为核心的多孔碳纳米球；Step S3: After freeze-drying and high-temperature calcination of the oil-in-water emulsion of the oil-coated chitosan/sodium tripolyphosphate/silica core material, porous carbon nanospheres with silica as the core are obtained;
步骤S4：将二氧化硅为核心的多孔碳纳米球置于氢氟酸溶液中，经搅拌、离心、洗涤至中性后，得到多孔空心碳纳米球。Step S4: Place the silica-core porous carbon nanospheres in a hydrofluoric acid solution, stir, centrifuge, and wash until neutral to obtain porous hollow carbon nanospheres.
本发明实施例通过将二氧化硅加入壳聚糖的醋酸溶液中并搅拌，再缓慢滴加三聚磷酸钠水溶液，密封反应并磁力搅拌，使壳聚糖的醋酸溶液与三聚磷酸钠水溶液通过聚电解质复合机制形成聚合物胶体水相体系，且二氧化硅可以均匀悬浮在凝胶体系中，可有效地形成二氧化硅为核心、壳聚糖/三聚磷酸钠凝胶为壁材的微观囊球结构，为碳纳米球形成提供球心模板。In the embodiment of the present invention, silicon dioxide is added to the acetic acid solution of chitosan and stirred, and then the sodium tripolyphosphate aqueous solution is slowly added dropwise, the reaction is sealed and magnetically stirred, so that the acetic acid solution of chitosan and the sodium tripolyphosphate aqueous solution pass through The polyelectrolyte composite mechanism forms a polymer colloid aqueous phase system, and silica can be evenly suspended in the gel system, effectively forming a microstructure with silica as the core and chitosan/sodium tripolyphosphate gel as the wall material. The capsule structure provides a core template for the formation of carbon nanospheres.
本发明实施例以棕榈酸异辛酯、霍霍巴油、十六-十八醇和乳化剂为油相与水相的壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体体系在高速剪切力作用下形成的乳剂体系中，油相通过H-O配位与壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体水相体系交联，在乳化剂作用下形成最外层为乳化剂、内层依次为二氧化硅为核心、壳聚糖/三聚磷酸钠层、油脂层组成的复合纳米微球分散相，乳化剂的亲油基与微球内层的油相结合，亲水基与连续相水结合，将纳米微球均匀地分散在水相中而不相连，形成了分散均匀而独立的碳纳米球，提高了碳纳米球的分散性。In the embodiment of the present invention, the chitosan/sodium tripolyphosphate/silica polymer colloid system using isooctyl palmitate, jojoba oil, cetearyl alcohol and emulsifier as oil phase and water phase is sheared at high speed. In the emulsion system formed under the action of force, the oil phase is cross-linked with the chitosan/sodium tripolyphosphate/silica polymer colloid water phase system through H-O coordination, and the outermost layer is formed under the action of the emulsifier. The inner layer is composed of silica as the core, chitosan/sodium tripolyphosphate layer, and grease layer as the composite nanosphere dispersed phase. The lipophilic group of the emulsifier is combined with the oil phase in the inner layer of the microsphere, and the hydrophilic group Combined with the continuous phase water, the nanometer microspheres are evenly dispersed in the water phase without being connected, forming uniformly dispersed and independent carbon nanospheres, which improves the dispersion of the carbon nanospheres.
本发明实施例的壳聚糖与油相含有大量的含氧官能团，高温煅烧过程中，大部分含氧官能团发生C-O键断裂而逃逸，使碳纳米球石墨化壁层出现空洞，完成碳纳米球造孔，造孔方法简单，无需添加造孔剂，制备方法简单，条件温和，易于控制。The chitosan and oil phase in the embodiments of the present invention contain a large amount of oxygen-containing functional groups. During the high-temperature calcination process, most of the oxygen-containing functional groups break the C-O bonds and escape, causing holes to appear in the graphitized wall layer of the carbon nanospheres, completing the carbon nanospheres. The pore-making method is simple, no pore-forming agent is needed, the preparation method is simple, the conditions are mild, and it is easy to control.
具体地，本发明实施例采用的是硬模板法，通常的硬模板法是将硬模板剂二氧化硅浸入液相状态的碳前体中发生聚合和交联，在惰性气氛中碳化，再用溶液刻蚀硬模板剂，以获得空心碳纳米球。通常需要加入交联剂和诱发剂，使碳纳米球的制备成本增高，还易引入其他的元素。本发明实施例的多孔空心碳纳米球的制备过程中，对制备工艺进行了优化，无需加入交联剂和诱发剂及造孔剂等添加剂，降低了制造成本。Specifically, the embodiments of the present invention adopt a hard template method. The usual hard template method is to immerse the hard template agent silica into a carbon precursor in a liquid phase to polymerize and cross-link, carbonize in an inert atmosphere, and then use The hard template agent is solution etched to obtain hollow carbon nanospheres. It is usually necessary to add cross-linking agents and inducers, which increases the cost of preparing carbon nanospheres and makes it easy to introduce other elements. In the preparation process of the porous hollow carbon nanospheres in the embodiments of the present invention, the preparation process is optimized, and there is no need to add additives such as cross-linking agents, inducers, and pore-forming agents, thereby reducing manufacturing costs.
在一些具体的实施例中，步骤S1中，磁力搅拌包括：在温度为45-55℃条件下进行水域磁力搅拌；密封反应的时间为10h。由此，在密封条件下，通过磁力搅拌加速形成以二氧化硅为核心、壳聚糖/三聚磷酸钠凝胶为壁材的微观囊球结构，为碳纳米球形成提供球心模板。In some specific embodiments, in step S1, magnetic stirring includes: performing magnetic stirring in water at a temperature of 45-55°C; the sealing reaction time is 10 hours. As a result, under sealed conditions, magnetic stirring accelerates the formation of a microscopic capsule structure with silica as the core and chitosan/sodium tripolyphosphate gel as the wall material, providing a core template for the formation of carbon nanospheres.
在一些具体的实施例中，步骤S2中，将棕榈酸异辛酯、霍霍巴油、十六-十八醇和乳化剂混合后，加热并搅拌至溶解后得到油相，包括：In some specific embodiments, in step S2, isooctyl palmitate, jojoba oil, cetadecanol and emulsifier are mixed, heated and stirred until dissolved to obtain an oil phase, including:
将棕榈酸异辛酯、霍霍巴油和十六-十八醇混合后加热到80℃的过程中进行搅拌至溶解均匀，加入乳化剂，在温度为80℃的条件下继续搅拌至溶解均匀，得到油相。Mix isooctyl palmitate, jojoba oil and cetearyl alcohol and stir until uniformly dissolved when heated to 80℃. Add emulsifier and continue stirring at 80℃ until uniformly dissolved. An oil phase is obtained.
本实施例的加热搅拌过程中保持搅拌温度在80℃，有利于相互之间的均匀溶解。During the heating and stirring process of this embodiment, the stirring temperature is maintained at 80°C, which is beneficial to uniform dissolution of each other.
在一些具体的实施例中，步骤S2中，乳化剂为鲸蜡基葡萄糖苷。由此，原料易得，且乳化效果好。In some specific embodiments, in step S2, the emulsifier is cetyl glucoside. As a result, the raw materials are easily available and the emulsification effect is good.
在一些具体的实施例中，步骤S2中，将油相加入到壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体水相体系中并搅拌，得到油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂，包括：In some specific embodiments, in step S2, the oil phase is added to the chitosan/sodium tripolyphosphate/silica polymer colloid aqueous phase system and stirred to obtain oil-coated chitosan/tripolyphosphate. Oil-in-water emulsions of sodium/silica core materials, including:
在水域温度为80℃的条件下，在搅拌的同时将油相快速加到壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体水相体系中，搅拌并均质，降温至室温，得到油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂。Under the condition that the water temperature is 80°C, quickly add the oil phase to the chitosan/sodium tripolyphosphate/silica polymer colloid water phase system while stirring, stir and homogenize, and cool to room temperature to obtain Oil-in-water emulsion with oil-coated chitosan/sodium tripolyphosphate/silica core.
本实施例中，为了保证乳化效果，防止离析或分层，需保持对油相的搅拌，因此将油相加入到壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体水相体系中时，时刻保持搅拌状态并保持温度为80℃，同时通过均质将油相充分打散成小液滴，这样有助于乳化剂对油相或水相充分包裹形成较为细小的乳化颗粒，有助于产品的稳定性，最终完成乳化得到油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂。In this embodiment, in order to ensure the emulsification effect and prevent segregation or stratification, the oil phase needs to be kept stirred. Therefore, when the oil phase is added to the chitosan/sodium tripolyphosphate/silica polymer colloid aqueous phase system , keep stirring at all times and keep the temperature at 80°C, and at the same time fully disperse the oil phase into small droplets through homogenization, which will help the emulsifier to fully wrap the oil phase or water phase to form relatively fine emulsified particles, which will help Due to the stability of the product, the emulsification is finally completed to obtain an oil-in-water emulsion of chitosan/sodium tripolyphosphate/silica core material wrapped in oil.
在一些具体的实施例中，步骤S2中，搅拌时间为10min，均质的时间为3-5min。由此，实现充分乳化，使油脂包裹壳聚糖/三聚磷酸钠/二氧化硅芯材。In some specific embodiments, in step S2, the stirring time is 10 min, and the homogenizing time is 3-5 min. Thus, sufficient emulsification is achieved, allowing the chitosan/sodium tripolyphosphate/silica core material to be coated with oil.
在一些具体的实施例中，步骤S3中，高温煅烧包括：在氮气保护氛围下，以2-5℃/min的速率升温至400-500℃，并保温1-2h；再以5-10℃的速率升温至950-1050℃，并保温3-4h。In some specific embodiments, in step S3, high-temperature calcination includes: heating to 400-500°C at a rate of 2-5°C/min under a nitrogen protective atmosphere, and maintaining the temperature for 1-2 hours; and then heating at 5-10°C Raise the temperature to 950-1050℃ at a certain rate and keep it warm for 3-4h.
由此，经过高温煅烧实现壳聚糖与油相中的大量含氧官能团发生C-O键断裂而逃逸，使碳纳米球石墨化壁层出现空洞，完成碳纳米球造孔。造孔方法简单，无需添加造孔剂，制备方法简单，条件温和，易于控制。As a result, after high-temperature calcination, a large number of oxygen-containing functional groups in the chitosan and oil phase break and escape, causing holes to appear in the graphitized wall layer of the carbon nanospheres, completing the pore creation of the carbon nanospheres. The pore-making method is simple, no pore-forming agent is needed, the preparation method is simple, the conditions are mild, and it is easy to control.
在一些具体的实施例中，步骤S3中，还包括在高温煅烧前，将冷冻干燥后的油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂加入到低温无水乙醇中分散均匀，抽滤并真空干燥。In some specific embodiments, step S3 also includes adding the freeze-dried grease-coated oil-in-water emulsion of chitosan/sodium tripolyphosphate/silica core material to the low-temperature calcination Disperse evenly in absolute ethanol, filter and dry under vacuum.
本实施例中的乙醇为极性分子，低温下乙醇对油脂类溶解度极低，以低温乙醇为分散剂对乳剂进行分散，在不破坏乳剂微球情况下，与水相相溶增大连续相体积，更有利于乳剂微球独立分散及后续碳化造孔。The ethanol in this embodiment is a polar molecule. The solubility of ethanol to oils and fats is extremely low at low temperatures. Low-temperature ethanol is used as a dispersant to disperse the emulsion. It is compatible with the water phase and increases the size of the continuous phase without destroying the emulsion microspheres. The volume is more conducive to the independent dispersion of emulsion microspheres and subsequent carbonization to create pores.
在一些具体的实施例中，步骤S3中，无水乙醇的温度为-10℃。In some specific embodiments, in step S3, the temperature of absolute ethanol is -10°C.
本实施例将乙醇降温至-10以下对制备的乳剂进行分散，不会破坏乳剂微球，而与水相相溶更有利于乳剂微球独立分散及后续碳化造孔。In this embodiment, the temperature of ethanol is lowered to below -10 to disperse the prepared emulsion without destroying the emulsion microspheres. The miscibility with the water phase is more conducive to the independent dispersion of the emulsion microspheres and subsequent carbonization to create pores.
在一些具体的实施例中，步骤S4中，搅拌时间为10-12h。由此实现对二氧化硅模板剂的充分刻蚀。In some specific embodiments, in step S4, the stirring time is 10-12 hours. This achieves sufficient etching of the silica template.
实施例1Example 1
本实施例通过多孔空心碳纳米球的制备方法制备多孔空心碳纳米球，包括如下步骤：In this embodiment, porous hollow carbon nanospheres are prepared through a method for preparing porous hollow carbon nanospheres, which includes the following steps:
步骤S1：将0.25g壳聚糖加入到50mL1％的醋酸溶液中放入圆底烧瓶中磁力搅拌溶解，将0.1g二氧化硅加入到壳聚糖的醋酸溶液中磁力搅拌分散均匀；另称取三聚磷酸钠0.05g用10mL蒸馏水溶解，置于恒压漏斗中，缓慢滴加到壳聚糖/二氧化硅溶液中，30min滴完，再在50℃的水域磁力搅拌下密闭反应10h，制得壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体水相体系。Step S1: Add 0.25g of chitosan to 50mL of 1% acetic acid solution, put it into a round-bottomed flask and stir with magnetic stirring to dissolve, add 0.1g of silica to the acetic acid solution of chitosan and stir with magnetic stirring to disperse evenly; weigh another Dissolve 0.05g of sodium tripolyphosphate in 10mL of distilled water, place it in a constant-pressure funnel, slowly add it dropwise to the chitosan/silica solution, complete the dripping in 30 minutes, and then react in a closed state for 10h under magnetic stirring in waters of 50°C to prepare A chitosan/sodium tripolyphosphate/silica polymer colloid aqueous phase system was obtained.
步骤S2：将3.4g棕榈酸异辛酯、3.4g霍霍巴油、3.4g十六-十八醇混合，搅拌升温至80℃，溶解均匀后，加入乳化剂鲸蜡基葡萄糖苷，再在80℃下搅拌溶解均匀，得到油相；将S1中的水相体系转至烧杯中，放入水域中升温至80℃，搅拌下将油相快速加到水相体系中，搅拌10min后，均质3min，降温至室温，得到油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂；Step S2: Mix 3.4g isooctyl palmitate, 3.4g jojoba oil, and 3.4g cetearyl alcohol, stir and raise the temperature to 80°C, after dissolving evenly, add the emulsifier cetyl glucoside, and then heat at 80 Stir and dissolve evenly at ℃ to obtain the oil phase; transfer the water phase system in S1 to a beaker, put it into the water and heat it to 80 ℃, quickly add the oil phase to the water phase system while stirring, stir for 10 minutes, and homogenize After 3 minutes, cool down to room temperature to obtain an oil-in-water emulsion of chitosan/sodium tripolyphosphate/silica core material wrapped in oil;
步骤S3：将油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂置入冷冻干燥机中冷冻干燥，获得冻干粉；将冻干粉加入到-10℃的无水乙醇中分散均匀，抽滤，真空干燥，得干燥粉末；将干燥粉末放置在石英舟内，氮气保护下，以2℃/min的速率升温至450℃，在该温度下保温1h；再以5℃的速率升温至1000℃，在该温度下保温3.5h；在氮气保护下冷却至室温，得到二氧化硅为核心的多孔碳纳米球；Step S3: Put the oil-in-water emulsion of the oil-coated chitosan/sodium tripolyphosphate/silica core material into a freeze dryer and freeze-dry it to obtain a freeze-dried powder; add the freeze-dried powder to -10°C Disperse evenly in anhydrous ethanol, filter, and vacuum dry to obtain dry powder; place the dry powder in a quartz boat, under nitrogen protection, raise the temperature to 450°C at a rate of 2°C/min, and keep it at this temperature for 1 hour; Then raise the temperature to 1000°C at a rate of 5°C and keep it at this temperature for 3.5 hours; cool to room temperature under nitrogen protection to obtain porous carbon nanospheres with silica as the core;
步骤S4：将二氧化硅为核心的多孔碳纳米球置于氢氟酸溶液中，室温搅拌反应11h，离心分离、洗涤至中性，得到多孔空心碳纳米球。Step S4: Place the silica-core porous carbon nanospheres in a hydrofluoric acid solution, stir and react at room temperature for 11 hours, centrifuge, and wash until neutral to obtain porous hollow carbon nanospheres.
实施例2Example 2
本实施例通过多孔空心碳纳米球的制备方法制备多孔空心碳纳米球，包括如下步骤：In this embodiment, porous hollow carbon nanospheres are prepared through a method for preparing porous hollow carbon nanospheres, which includes the following steps:
步骤S1：将0.25g壳聚糖加入到50mL1％的醋酸溶液中放入圆底烧瓶中磁力搅拌溶解，将0.1g二氧化硅加入到壳聚糖的醋酸溶液中磁力搅拌分散均匀；另称取三聚磷酸钠0.05g用10mL蒸馏水溶解，置于恒压漏斗中，缓慢滴加到壳聚糖/二氧化硅溶液中，30min滴完，再在55℃的水域磁力搅拌下密闭反应10h，制得壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体水相体系。Step S1: Add 0.25g of chitosan to 50mL of 1% acetic acid solution, put it into a round-bottomed flask and stir with magnetic stirring to dissolve, add 0.1g of silica to the acetic acid solution of chitosan and stir with magnetic stirring to disperse evenly; weigh another Dissolve 0.05g of sodium tripolyphosphate in 10mL of distilled water, place it in a constant pressure funnel, slowly add it dropwise to the chitosan/silica solution, complete the dripping in 30 minutes, and then react in a closed state for 10h under magnetic stirring in waters of 55°C to prepare A chitosan/sodium tripolyphosphate/silica polymer colloid aqueous phase system was obtained.
步骤S2：将3.4g棕榈酸异辛酯、3.4g霍霍巴油、3.4g十六-十八醇混合，搅拌升温至80℃，溶解均匀后，加入乳化剂鲸蜡基葡萄糖苷，再在80℃下搅拌溶解均匀，得到油相；将S1中的水相体系转至烧杯中，放入水域中升温至80℃，搅拌下将油相快速加到水相体系中，搅拌10min后，均质5min，降温至室温，得到油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂；Step S2: Mix 3.4g isooctyl palmitate, 3.4g jojoba oil, and 3.4g cetearyl alcohol, stir and raise the temperature to 80°C, after dissolving evenly, add the emulsifier cetyl glucoside, and then heat at 80 Stir and dissolve evenly at ℃ to obtain the oil phase; transfer the water phase system in S1 to a beaker, put it into the water and heat it to 80 ℃, quickly add the oil phase to the water phase system while stirring, stir for 10 minutes, and homogenize Cool to room temperature for 5 minutes to obtain an oil-in-water emulsion of chitosan/sodium tripolyphosphate/silica core material wrapped in oil;
步骤S3：将油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂置入冷冻干燥机中冷冻干燥，获得冻干粉；将冻干粉加入到-10℃的无水乙醇中分散均匀，抽滤，真空干燥，得干燥粉末；将干燥粉末放置在石英舟内，氮气保护下，以5℃/min的速率升温至400℃，在该温度下保温2h；再以10℃的速率升温至1050℃，在该温度下保温3h；在氮气保护下冷却至室温，得到二氧化硅为核心的多孔碳纳米球；Step S3: Put the oil-in-water emulsion of the oil-coated chitosan/sodium tripolyphosphate/silica core material into a freeze dryer and freeze-dry it to obtain a freeze-dried powder; add the freeze-dried powder to -10°C Disperse evenly in anhydrous ethanol, filter, and vacuum dry to obtain dry powder; place the dry powder in a quartz boat, under nitrogen protection, raise the temperature to 400°C at a rate of 5°C/min, and keep it at this temperature for 2 hours; Then raise the temperature to 1050°C at a rate of 10°C, and keep it at this temperature for 3 hours; cool to room temperature under nitrogen protection to obtain porous carbon nanospheres with silica as the core;
步骤S4：将二氧化硅为核心的多孔碳纳米球置于氢氟酸溶液中，室温搅拌反应12h，离心分离、洗涤至中性，得到多孔空心碳纳米球。Step S4: Place the silica-core porous carbon nanospheres in a hydrofluoric acid solution, stir and react at room temperature for 12 hours, centrifuge, and wash until neutral to obtain porous hollow carbon nanospheres.
实施例3Example 3
本实施例通过多孔空心碳纳米球的制备方法制备多孔空心碳纳米球，包括如下步骤：In this embodiment, porous hollow carbon nanospheres are prepared through a method for preparing porous hollow carbon nanospheres, which includes the following steps:
步骤S1：将0.25g壳聚糖加入到50mL1％的醋酸溶液中放入圆底烧瓶中磁力搅拌溶解，将0.1g二氧化硅加入到壳聚糖的醋酸溶液中磁力搅拌分散均匀；另称取三聚磷酸钠0.05g用10mL蒸馏水溶解，置于恒压漏斗中，缓慢滴加到壳聚糖/二氧化硅溶液中，30min滴完，再在45℃的水域磁力搅拌下密闭反应10h，制得壳聚糖/三聚磷酸钠/二氧化硅聚合物胶体水相体系。Step S1: Add 0.25g of chitosan to 50mL of 1% acetic acid solution, put it into a round-bottomed flask and stir with magnetic stirring to dissolve, add 0.1g of silica to the acetic acid solution of chitosan and stir with magnetic stirring to disperse evenly; weigh another Dissolve 0.05g of sodium tripolyphosphate in 10mL of distilled water, place it in a constant pressure funnel, slowly add it dropwise to the chitosan/silica solution, complete the dripping in 30 minutes, and then react in a closed state for 10h under magnetic stirring in waters of 45°C to prepare A chitosan/sodium tripolyphosphate/silica polymer colloid aqueous phase system was obtained.
步骤S2：将3.4g棕榈酸异辛酯、3.4g霍霍巴油、3.4g十六-十八醇混合，搅拌升温至80℃，溶解均匀后，加入乳化剂鲸蜡基葡萄糖苷，再在80℃下搅拌溶解均匀，得到油相；将S1中的水相体系转至烧杯中，放入水域中升温至80℃，搅拌下将油相快速加到水相体系中，搅拌10min后，均质4min，降温至室温，得到油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂；Step S2: Mix 3.4g isooctyl palmitate, 3.4g jojoba oil, and 3.4g cetearyl alcohol, stir and raise the temperature to 80°C, after dissolving evenly, add the emulsifier cetyl glucoside, and then heat at 80 Stir and dissolve evenly at ℃ to obtain the oil phase; transfer the water phase system in S1 to a beaker, put it into the water and heat it to 80 ℃, quickly add the oil phase to the water phase system while stirring, stir for 10 minutes, and homogenize After 4 minutes, cool down to room temperature to obtain an oil-in-water emulsion of chitosan/sodium tripolyphosphate/silica core material wrapped in oil;
步骤S3：将油脂包裹的壳聚糖/三聚磷酸钠/二氧化硅芯材的水包油型乳剂置入冷冻干燥机中冷冻干燥，获得冻干粉；将冻干粉加入到-10℃的无水乙醇中分散均匀，抽滤，真空干燥，得干燥粉末；将干燥粉末放置在石英舟内，氮气保护下，以4℃/min的速率升温至500℃，在该温度下保温1.5h；再以8℃的速率升温至950℃，在该温度下保温4h；在氮气保护下冷却至室温，得到二氧化硅为核心的多孔碳纳米球；Step S3: Put the oil-in-water emulsion of the oil-coated chitosan/sodium tripolyphosphate/silica core material into a freeze dryer and freeze-dry it to obtain a freeze-dried powder; add the freeze-dried powder to -10°C Disperse evenly in absolute ethanol, filter, and vacuum dry to obtain dry powder; place the dry powder in a quartz boat, under nitrogen protection, raise the temperature to 500°C at a rate of 4°C/min, and keep it at this temperature for 1.5h ; Then raise the temperature to 950°C at a rate of 8°C, and keep it at this temperature for 4 hours; cool to room temperature under nitrogen protection, and obtain porous carbon nanospheres with silica as the core;
步骤S4：将二氧化硅为核心的多孔碳纳米球置于氢氟酸溶液中，室温搅拌反应10h，离心分离、洗涤至中性，得到多孔空心碳纳米球。Step S4: Place the silica-core porous carbon nanospheres in a hydrofluoric acid solution, stir and react at room temperature for 10 hours, centrifuge, and wash until neutral to obtain porous hollow carbon nanospheres.
虽然本发明公开披露如上，但本发明公开的保护范围并非仅限于此。本领域技术人员在不脱离本发明公开的精神和范围的前提下，可进行各种变更与修改，这些变更与修改均将落入本发明的保护范围。Although the present invention is disclosed as above, the protection scope of the present invention is not limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the disclosure of the present invention, and these changes and modifications will fall within the protection scope of the present invention.
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| CN202210683075.9ACN115193349B (en) | 2022-06-17 | 2022-06-17 | A method for preparing porous hollow carbon nanospheres |
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| CN202210683075.9ACN115193349B (en) | 2022-06-17 | 2022-06-17 | A method for preparing porous hollow carbon nanospheres |
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| CN202210683075.9AActiveCN115193349B (en) | 2022-06-17 | 2022-06-17 | A method for preparing porous hollow carbon nanospheres |
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