技术领域technical field
本发明涉及Nafion/氨基酸修饰空心介孔硅杂化膜及制备和应用，属于有机－无机杂化膜技术领域。The invention relates to a Nafion/amino acid modified hollow mesoporous silicon hybrid membrane and its preparation and application, and belongs to the technical field of organic-inorganic hybrid membranes.
背景技术Background technique
面对我国日益枯竭的能源及严重污染的环境，寻找可再生的清洁能源已经成为重要任务。燃料电池是一种利用可再生燃料(氢气、醇、碳氢类化合物等)与氧化剂(空气、氧气)发生氧化还原反应，将燃料的化学能直接转化为电能而不经过热机过程的电化学器件，具有燃料利用率高、绿色等优点，适应了人类社会的可持续发展。其中直接甲醇燃料电池(Direct methanol fuel cell，简称DMFC)以甲醇为燃料，因其结构简单、能量密度高、启动快速、运行可靠以及燃料补充方便等优点，被认为是最具潜力的新一代便携式电源。Facing our country's increasingly depleted energy and seriously polluted environment, it has become an important task to find renewable clean energy. A fuel cell is an electrochemical device that uses a redox reaction between a renewable fuel (hydrogen, alcohol, hydrocarbons, etc.) and an oxidant (air, oxygen) to convert the chemical energy of the fuel directly into electrical energy without going through a thermal process. , has the advantages of high fuel utilization rate and greenness, and adapts to the sustainable development of human society. Among them, direct methanol fuel cell (DMFC) uses methanol as fuel, and is considered to be the most promising new generation of portable fuel cells due to its simple structure, high energy density, fast start-up, reliable operation, and convenient fuel replenishment. power supply.
质子交换膜是DMFC的核心部件，目前使用的以Nafion膜为代表的全氟磺酸膜阻醇性能差，严重制约了DMFC的发展。因此，开发新型高性能质子交换膜已成为DMFC研究的重要挑战。有机-无机杂化膜由于同时具备有机膜(柔韧性好、易加工)和无机膜(热稳定性好、机械强度高、耐腐蚀)的优点，近年来得到了广泛关注。向有机高分子中引入无机组分，可以有效增强膜的阻醇性能、提高膜的机械性能和热稳定性，但是由于无机组分的导质子能力较弱，容易导致杂化膜的质子传导率有所下降。通过一定的物理化学方法将导质子官能团负载到无机组分上并将其填充到有机高分子中，可以有效地提高有机-无机杂化膜的质子传导率。The proton exchange membrane is the core component of DMFC. The currently used perfluorosulfonic acid membrane represented by Nafion membrane has poor alcohol resistance, which seriously restricts the development of DMFC. Therefore, developing new high-performance proton exchange membranes has become an important challenge in DMFC research. Organic-inorganic hybrid membranes have attracted extensive attention in recent years due to the advantages of both organic membranes (good flexibility, easy processing) and inorganic membranes (good thermal stability, high mechanical strength, and corrosion resistance). The introduction of inorganic components into organic polymers can effectively enhance the alcohol resistance of the membrane, improve the mechanical properties and thermal stability of the membrane, but due to the weak proton conductivity of the inorganic components, it is easy to cause the proton conductivity of the hybrid membrane to decrease. has declined. The proton conductivity of organic-inorganic hybrid membranes can be effectively improved by loading proton-conducting functional groups on inorganic components and filling them into organic polymers by certain physical and chemical methods.
将生物体高效、智能的结构及代谢原理进行研究并应用到科学技术中是一种快捷、高效的方法。研究生物体的结构可以发现，大部分生物体通过氨基酸进行离子传导，植物根部则通过毛细作用储存吸收水分。受这两种生物原型的启发，可以将生物内具有质子传递功能的特殊分子及空心保水结构引入到膜材料的制备中，得到性能优异的新型质子交换膜。到目前为止，Nafion/氨基酸修饰空心介孔硅杂化膜用于燃料电池未见文献报道。It is a fast and efficient method to study the efficient and intelligent structure and metabolism principles of organisms and apply them to science and technology. Studying the structure of organisms shows that most organisms conduct ion conduction through amino acids, and plant roots store and absorb water through capillary action. Inspired by these two biological prototypes, special molecules with proton transfer function and hollow water-retaining structures in organisms can be introduced into the preparation of membrane materials to obtain new proton exchange membranes with excellent performance. So far, there has been no literature report on the use of Nafion/amino acid modified hollow mesoporous silicon hybrid membranes in fuel cells.
发明内容Contents of the invention
针对上述现有技术，本发明提供一种Nafion(全氟磺酸-聚四氟乙烯共聚物)/氨基酸修饰空心介孔硅杂化膜及制备方法和应用，本发明提供的制备方法可控性强，所制备的杂化膜可以用于直接甲醇燃料电池，具有较高的质子传导能力和良好的阻醇性能。In view of the above prior art, the present invention provides a Nafion (perfluorosulfonic acid-polytetrafluoroethylene copolymer)/amino acid modified hollow mesoporous silicon hybrid membrane and its preparation method and application. The preparation method provided by the present invention is controllable Strong, the prepared hybrid membrane can be used in direct methanol fuel cells, with high proton conductivity and good alcohol resistance performance.
本发明提提出的一种Nafion/氨基酸修饰空心介孔硅杂化膜，该Nafion/氨基酸修饰空心介孔硅厚度为50～80微米，由Nafion与氨基酸修饰的空心介孔硅构成，其中，氨基酸修饰的空心介孔硅与Nafion质量比为0.02～0.04：1。The present invention proposes a Nafion/amino acid modified hollow mesoporous silicon hybrid membrane, the Nafion/amino acid modified hollow mesoporous silicon has a thickness of 50-80 microns, and is composed of Nafion and amino acid modified hollow mesoporous silicon, wherein the amino acid The mass ratio of the modified hollow mesoporous silicon to Nafion is 0.02-0.04:1.
本发明提出的一种Nafion/氨基酸修饰空心介孔硅杂化膜的制备方法，包括以下步骤：The preparation method of a kind of Nafion/amino acid modified hollow mesoporous silicon hybrid membrane proposed by the present invention comprises the following steps:
步骤一、空心介孔硅的制备：将乙醇、水、氨水按体积比为200:20:7混合均匀，剧烈搅拌下加入正硅酸乙酯，正硅酸乙酯与氨水的体积比为0.5～1.5:1，室温下搅拌12h，得到二氧化硅微球，离心洗涤干燥；将二氧化硅微球加入到水、乙醇、氨水和十六烷基三甲基溴化铵的混合液中，其中水、乙醇、氨水的体积比为1:(1～2)：(0.01～0.05)，十六烷基三甲基溴化铵的浓度为0.001～0.02g/mL，二氧化硅微球和十六烷基三甲基溴化铵的质量比为1:1～6，室温下搅拌30min，加入正硅酸乙酯，正硅酸乙酯与氨水的体积比为1:1～3，搅拌6h，得到双层硅球，离心洗涤；将双层硅球分散在0.2mol/L Na2CO3溶液中，在50℃下搅拌19h，得到空心硅球，离心洗涤；将空心硅球加入甲醇和浓盐酸混合液中，其中甲醇和浓盐酸体积比为10～20:1，在65℃下回流加热搅拌48h，得到空心介孔硅，离心洗涤干燥；Step 1. Preparation of hollow mesoporous silicon: Mix ethanol, water, and ammonia water evenly in a volume ratio of 200:20:7, and add ethyl orthosilicate under vigorous stirring. The volume ratio of ethyl orthosilicate to ammonia water is 0.5 ～1.5:1, stirred at room temperature for 12 hours to obtain silica microspheres, centrifuged, washed and dried; silica microspheres were added to the mixed solution of water, ethanol, ammonia and cetyltrimethylammonium bromide, The volume ratio of water, ethanol, and ammonia water is 1:(1~2):(0.01~0.05), the concentration of cetyltrimethylammonium bromide is 0.001~0.02g/mL, silica microspheres and The mass ratio of cetyltrimethylammonium bromide is 1:1~6, stir at room temperature for 30 minutes, add tetraethyl orthosilicate, the volume ratio of tetraethyl orthosilicate and ammonia water is 1:1~3, stir 6h, get double-layered silicon spheres, wash by centrifugation; disperse double-layered silicon spheres in 0.2mol/L Na2 CO3 solution, stir at 50°C for 19h, get hollow silicon spheres, wash by centrifugation; add hollow silicon spheres to methanol mixed with concentrated hydrochloric acid, wherein the volume ratio of methanol to concentrated hydrochloric acid is 10-20:1, heated and stirred under reflux at 65°C for 48 hours to obtain hollow mesoporous silicon, which was washed and dried by centrifugation;
步骤二、氨基酸修饰空心介孔硅：将步骤一得到的空心介孔硅分散于无水甲苯中，加入3-氨丙基三乙氧基硅烷，其中无水甲苯和3-氨丙基三乙氧基硅烷的体积比为40～60:1，充入氮气密封，105℃下回流反应24h得到氨基修饰的空心介孔硅；将氨基修饰的空心介孔硅分散在MES缓冲溶液中得到悬浮有氨基修饰空心介孔硅的悬浮液，其中，所述MES缓冲溶液制备方法为：2.66g 2-(N-吗啡啉)乙磺酸加入50mL水中溶解，用2mol/L NaOH溶液调节pH至6.5，再用水定容至250mL；将天门冬氨酸、磷酸丝氨酸和半胱氨酸中的任一种氨基酸加入悬浮液中得到氨基酸浓度为0.01～0.05g/mL的溶液A，然后向溶液A中加入1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和N-羟基琥珀酰亚胺，其中所述1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和N-羟基琥珀酰亚胺为活化剂，1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐，N-羟基琥珀酰亚胺和溶液A中氨基酸的质量比均为(1～2):(1～2):1，室温下搅拌1h进行活化；将上述活化的溶液A加入到悬浮液中，室温下搅拌反应1～3h，离心洗涤干燥，从而得到天门冬氨酸修饰的空心介孔硅或磷酸丝氨酸修饰的空心介孔硅或半胱氨酸修饰的空心介孔硅；将半胱氨酸修饰的空心介孔硅加入到体积分数为30％的双氧水溶液中搅拌氧化24h，离心洗涤干燥，得到氧化半胱氨酸修饰的空心介孔硅；Step 2, amino acid modified hollow mesoporous silicon: disperse the hollow mesoporous silicon obtained in step 1 in anhydrous toluene, add 3-aminopropyltriethoxysilane, wherein anhydrous toluene and 3-aminopropyltriethyl The volume ratio of oxysilane is 40-60:1, filled with nitrogen gas to seal, reflux reaction at 105°C for 24 hours to obtain amino-modified hollow mesoporous silicon; disperse amino-modified hollow mesoporous silicon in MES buffer solution to obtain suspended A suspension of amino-modified hollow mesoporous silicon, wherein the preparation method of the MES buffer solution is: 2.66g of 2-(N-morpholine)ethanesulfonic acid is dissolved in 50mL of water, and the pH is adjusted to 6.5 with 2mol/L NaOH solution, Then dilute to 250mL with water; add any amino acid of aspartic acid, phosphoserine and cysteine to the suspension to obtain a solution A with an amino acid concentration of 0.01-0.05g/mL, and then add 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, wherein the 1-(3-dimethylaminopropyl)-3-ethane Carbodiimide hydrochloride and N-hydroxysuccinimide as activators, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide The mass ratio of the amine to the amino acid in solution A is (1~2):(1~2):1, and it is activated by stirring for 1 hour at room temperature; 3h, centrifuged, washed and dried to obtain aspartic acid-modified hollow mesoporous silicon or phosphoserine-modified hollow mesoporous silicon or cysteine-modified hollow mesoporous silicon; cysteine-modified hollow mesoporous silicon Add it into a hydrogen peroxide solution with a volume fraction of 30%, stir and oxidize for 24 hours, centrifuge, wash and dry, and obtain hollow mesoporous silicon modified with oxidized cysteine;
步骤三、杂化膜制备与成膜：室温搅拌下，将Nafion加入到N,N-二甲基甲酰胺溶剂中配制成浓度为0.05～0.2g/mL的Nafion溶液；将步骤二得到的天门冬氨酸修饰的空心介孔硅或磷酸丝氨酸修饰的空心介孔硅或氧化半胱氨酸修饰的空心介孔硅加入到Nafion溶液中，天门冬氨酸修饰的空心介孔硅或磷酸丝氨酸修饰的空心介孔硅或氧化半胱氨酸修饰的空心介孔硅与Nafion质量比为0.02～0.04：1，搅拌24h，得到铸膜液；将铸膜液静置1～3h脱泡后在玻璃板上流延，80℃下干燥12h，120℃下处理12h，将膜揭下，依次置于体积分数为3％的双氧水溶液、1mol/L的硫酸水溶液、去离子水中均分别在80℃下浸泡1h，最终得到Nafion/氨基酸修饰空心介孔硅杂化膜。Step 3. Hybrid film preparation and film formation: under stirring at room temperature, add Nafion to N,N-dimethylformamide solvent to prepare a Nafion solution with a concentration of 0.05-0.2 g/mL; Hollow mesoporous silicon modified by aspartic acid or modified by phosphoserine or hollow mesoporous silicon modified by oxidized cysteine is added to the Nafion solution, hollow mesoporous silicon modified by aspartic acid or modified by phosphoserine The mass ratio of hollow mesoporous silicon or hollow mesoporous silicon modified by oxidized cysteine to Nafion is 0.02-0.04:1, and stirred for 24 hours to obtain the casting solution; the casting solution is left to stand for 1-3 hours to defoam and then put it on the glass Cast on a board, dry at 80°C for 12 hours, treat at 120°C for 12 hours, peel off the film, and place it in 3% hydrogen peroxide solution, 1mol/L sulfuric acid solution, and deionized water, respectively, at 80°C. After 1 h, the Nafion/amino acid modified hollow mesoporous silicon hybrid membrane was finally obtained.
本发明Nafion/氨基酸修饰空心介孔硅杂化膜用作直接甲醇燃料电池的质子交换膜，在温度25℃、饱和湿度下，质子传导率为0.084～0.112S/cm，甲醇渗透率为2.34×10-6～1.77×10-6cm2/s。The Nafion/amino acid modified hollow mesoporous silicon hybrid membrane of the present invention is used as a proton exchange membrane of a direct methanol fuel cell. At a temperature of 25°C and a saturated humidity, the proton conductivity is 0.084-0.112S/cm, and the methanol permeability is 2.34× 10-6 ~ 1.77×10-6 cm2 /s.
与现有技术相比，本发明的优点在于：Compared with the prior art, the present invention has the advantages of:
本发明制备过程绿色环保、可控性强，不仅利用空心介孔结构增强了膜的保水性能，还通过接枝氨基酸的方式，利用氨基酸的酸性基团与碱性基团相互作用，为杂化膜构建出了新的连续质子传递通道，促进质子的传递，该方法所制得的杂化膜表现出较高的质子传导率，与纯Nafion膜相比提高了53～104％。用作直接甲醇燃料电池质子交换膜，甲醇渗透率与纯Nafion膜相比也有明显降低。The preparation process of the present invention is environmentally friendly and highly controllable. It not only enhances the water retention performance of the membrane by using the hollow mesoporous structure, but also uses the interaction between the acidic group and the basic group of the amino acid to form a hybrid The membrane constructs a new continuous proton transfer channel to promote the transfer of protons. The hybrid membrane prepared by this method shows a higher proton conductivity, which is 53-104% higher than that of the pure Nafion membrane. When used as a proton exchange membrane for direct methanol fuel cells, the methanol permeability is also significantly lower than that of pure Nafion membranes.
附图说明Description of drawings
图1是对比例1制得的纯Nafion膜的断面SEM图；Fig. 1 is the cross-sectional SEM figure of the pure Nafion film that comparative example 1 makes;
图2是对比例2制得的Nafion/空心介孔硅-2％杂化膜的断面SEM图；Fig. 2 is the cross-section SEM figure of the Nafion/hollow mesoporous silicon-2% hybrid membrane that comparative example 2 makes;
图3是实施例1制得的Nafion/天门冬氨酸修饰空心介孔硅-2％杂化膜的断面SEM图；Fig. 3 is the cross-sectional SEM figure of Nafion/aspartic acid modified hollow mesoporous silicon-2% hybrid membrane that embodiment 1 makes;
图4是实施例2制得的Nafion/磷酸丝氨酸修饰空心介孔硅-2％杂化膜的断面SEM图；Fig. 4 is the cross-sectional SEM figure of the Nafion/phosphoserine modified hollow mesoporous silicon-2% hybrid membrane prepared in Example 2;
图5是实施例3制得的Nafion/氧化半胱氨酸修饰空心介孔硅-2％杂化膜的断面SEM图；Fig. 5 is the cross-sectional SEM figure of the Nafion/oxidized cysteine modified hollow mesoporous silicon-2% hybrid membrane prepared in Example 3;
具体实施方式detailed description
以下通过实施例讲述本发明的详细过程，提供实施例是为了理解的方便，绝不是限制本发明。The following describes the detailed process of the present invention through the examples, and the examples are provided for the convenience of understanding, and are by no means limiting the present invention.
对比例1：制备纯Nafion膜。Comparative Example 1: Preparation of pure Nafion membrane.
室温搅拌下，称取0.5g Nafion加入到4mL N,N-二甲基甲酰胺溶剂中溶解完全，得到Nafion溶液；静置3h脱泡后在玻璃板(4×4cm)上流延，80℃下干燥12h，120℃下处理12h，将得到的膜依次置于体积分数为3％的双氧水溶液、1mol/L的硫酸水溶液、去离子水中，均在80℃分别各加热1h，得到厚度为60μm的纯Nafion膜。将该膜在温度25℃、饱和湿度下进行质子传导测试，质子传导率为0.0549S/cm，质子传导测试测试条件及计算方法为：使用电化学工作站(美国Princeton allpled reserch，型号Parstat 2273)在振荡电压为20mV、频率10-106Hz条件下得到膜的阻抗R，使用公式σ＝l/AR得到膜的质子传导率，其中l为膜的长度，A为膜的横截面积。在温度25℃下进行甲醇渗透测试，甲醇渗透率为2.42×10-6cm2/s。Under stirring at room temperature, weigh 0.5g Nafion and add it into 4mL N,N-dimethylformamide solvent to dissolve completely to obtain a Nafion solution; after standing for 3 hours to defoam, cast it on a glass plate (4×4cm), at 80°C Dry for 12 hours, treat at 120°C for 12 hours, place the obtained film in turn in 3% hydrogen peroxide solution, 1mol/L sulfuric acid solution, and deionized water, and heat each at 80°C for 1 hour to obtain a film with a thickness of 60 μm. Pure Nafion membrane. The membrane was subjected to a proton conduction test at a temperature of 25° C. and saturated humidity. The proton conductivity was 0.0549 S/cm. The impedance R of the membrane is obtained under the conditions of oscillating voltage of 20mV and frequency of 10-106 Hz, and the proton conductivity of the membrane is obtained by using the formula σ=l/AR, where l is the length of the membrane and A is the cross-sectional area of the membrane. The methanol permeation test was carried out at a temperature of 25°C, and the methanol permeability was 2.42×10-6 cm2 /s.
对比例2：制备Nafion/空心介孔硅-2％杂化膜。Comparative Example 2: Preparation of Nafion/hollow mesoporous silicon-2% hybrid membrane.
空心介孔硅的制备：量取200mL乙醇，20mL水，7mL氨水，混合均匀，剧烈搅拌下加入10.5mL正硅酸乙酯，室温下搅拌12h，得到二氧化硅微球，离心洗涤干燥。取1g二氧化硅微球加入到240mL水、480mL乙醇、12mL氨水、3.66g十六烷基三甲基溴化铵的混合液中，室温下搅拌30min，然后迅速加入5.0mL正硅酸乙酯，搅拌6h，得到双层硅球，离心洗涤。将双层硅球分散在250mL 0.2mol/L Na2CO3溶液中，在50℃下搅拌19h，得到空心硅球，离心洗涤。将空心硅球加入到300mL甲醇和20mL浓盐酸混合液中，65℃下回流加热搅拌48h，得到空心介孔硅，离心洗涤干燥。Preparation of hollow mesoporous silicon: Measure 200mL of ethanol, 20mL of water, and 7mL of ammonia water, mix well, add 10.5mL of ethyl orthosilicate under vigorous stirring, and stir at room temperature for 12h to obtain silica microspheres, which are washed and dried by centrifugation. Add 1g of silica microspheres to a mixture of 240mL of water, 480mL of ethanol, 12mL of ammonia water, and 3.66g of cetyltrimethylammonium bromide, stir at room temperature for 30min, then quickly add 5.0mL of ethyl orthosilicate , and stirred for 6h to obtain double-layer silicon spheres, which were washed by centrifugation. Disperse the double-layer silicon spheres in 250mL 0.2mol/L Na2 CO3 solution, stir at 50°C for 19h to obtain hollow silicon spheres, and wash them by centrifugation. Add hollow silicon spheres to 300mL methanol and 20mL concentrated hydrochloric acid mixture, heat and stir under reflux at 65°C for 48h to obtain hollow mesoporous silicon, which is washed and dried by centrifugation.
杂化膜制备与成膜：室温搅拌下，称取0.5g Nafion加入到4mL N,N-二甲基甲酰胺溶剂中溶解完全，得到Nafion溶液；称取0.01g空心介孔硅加入Nafion溶液中，搅拌24h，静置2h脱泡后在玻璃板(4×4cm)上流延，80℃下干燥12h，120℃下处理12h，将得到的膜依次置于体积分数为3％的双氧水溶液、1mol/L的硫酸水溶液、去离子水中，均在80℃分别各加热1h，得到厚度为65μm的Nafion/空心介孔硅-2％杂化膜。将该杂化膜在温度25℃、饱和湿度下进行质子传导测试，质子传导率为0.0594S/cm，在温度25℃下进行甲醇渗透测试，甲醇渗透率为2.34×10-6cm2/s。Hybrid film preparation and film formation: under stirring at room temperature, weigh 0.5g Nafion and add it to 4mL N,N-dimethylformamide solvent to dissolve completely to obtain Nafion solution; weigh 0.01g hollow mesoporous silicon and add it to Nafion solution , stirred for 24 hours, left to stand for 2 hours to defoam, and cast on a glass plate (4×4cm), dried at 80°C for 12 hours, and treated at 120°C for 12 hours, and the obtained film was placed in a volume fraction of 3% hydrogen peroxide solution, 1mol /L of sulfuric acid aqueous solution and deionized water were heated at 80°C for 1 h respectively to obtain a Nafion/hollow mesoporous silicon-2% hybrid membrane with a thickness of 65 μm. The hybrid membrane was subjected to a proton conduction test at a temperature of 25°C and saturated humidity, and the proton conductivity was 0.0594S/cm, and a methanol permeation test was performed at a temperature of 25°C, and the methanol permeability was 2.34×10-6 cm2 /s .
实施例1：制备Nafion/天门冬氨酸修饰空心介孔硅-2％杂化膜。Example 1: Preparation of Nafion/aspartic acid modified hollow mesoporous silicon-2% hybrid membrane.
空心介孔硅的制备：量取200mL乙醇，20mL水,7mL氨水，混合均匀，剧烈搅拌下加入7mL正硅酸乙酯，室温下搅拌12h，得到二氧化硅微球，离心洗涤干燥。取1g二氧化硅微球加入到240mL水、480mL乙醇、12mL氨水、3.66g十六烷基三甲基溴化铵的混合液中，室温下搅拌30min，然后迅速加入5.0mL正硅酸乙酯，搅拌6h，得到双层硅球，离心洗涤。将双层硅球分散在250mL 0.2mol/L Na2CO3溶液中，在50℃下搅拌19h，得到空心硅球，离心洗涤。将空心硅球加入到300mL甲醇和20mL浓盐酸混合液中，65℃下回流加热搅拌48h，得到空心介孔硅，离心洗涤干燥。Preparation of hollow mesoporous silicon: Measure 200mL of ethanol, 20mL of water, and 7mL of ammonia water, mix well, add 7mL of ethyl orthosilicate under vigorous stirring, and stir at room temperature for 12 hours to obtain silica microspheres, which are washed and dried by centrifugation. Add 1g of silica microspheres to a mixture of 240mL of water, 480mL of ethanol, 12mL of ammonia water, and 3.66g of cetyltrimethylammonium bromide, stir at room temperature for 30min, then quickly add 5.0mL of ethyl orthosilicate , and stirred for 6h to obtain double-layer silicon spheres, which were washed by centrifugation. Disperse the double-layer silicon spheres in 250mL 0.2mol/L Na2 CO3 solution, stir at 50°C for 19h to obtain hollow silicon spheres, and wash them by centrifugation. Add hollow silicon spheres to 300mL methanol and 20mL concentrated hydrochloric acid mixture, heat and stir under reflux at 65°C for 48h to obtain hollow mesoporous silicon, which is washed and dried by centrifugation.
天门冬氨酸修饰空心介孔硅：将1g上述空心介孔硅分散于120mL无水甲苯中，与2.4mL3-氨丙基三乙氧基硅烷混合后，充入氮气密封，105℃下回流反应24h，得到的氨基修饰空心介孔硅，将其分散于150mL MES缓冲溶液中，得到悬浮有氨基修饰空心介孔硅的悬浮液，其中，所述MES缓冲溶液制备方法为：2.66g 2-(N-吗啡啉)乙磺酸加入50mL水中溶解，用2mol/L NaOH溶液调节pH至6.5，再用水定容至250mL。将1.0g天门冬氨酸加入100mLMES缓冲液中，然后分别加入1g 1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和1gN-羟基琥珀酰亚胺，室温下剧烈搅拌1h进行活化。将上述活化的天门冬氨酸溶液加入到悬浮液中，室温下反应2h，离心洗涤干燥，得到天门冬氨酸修饰的空心介孔硅。Aspartic acid modified hollow mesoporous silicon: Disperse 1g of the above hollow mesoporous silicon in 120mL of anhydrous toluene, mix it with 2.4mL of 3-aminopropyltriethoxysilane, fill it with nitrogen and seal it, and reflux at 105°C 24h, the obtained amino-modified hollow mesoporous silicon was dispersed in 150mL MES buffer solution to obtain a suspension suspended with amino-modified hollow mesoporous silicon, wherein the preparation method of the MES buffer solution was: 2.66g 2-( N-morpholine) ethanesulfonic acid was dissolved in 50 mL of water, the pH was adjusted to 6.5 with 2 mol/L NaOH solution, and then the volume was adjusted to 250 mL with water. Add 1.0 g of aspartic acid to 100 mL of MES buffer, then add 1 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 1 g of N-hydroxysuccinimide, respectively, at room temperature Under vigorous stirring for 1 h to activate. The activated aspartic acid solution was added to the suspension, reacted at room temperature for 2 hours, centrifuged, washed and dried to obtain aspartic acid-modified hollow mesoporous silicon.
杂化膜制备与成膜：室温搅拌下，称取0.5g Nafion加入到4mL N,N-二甲基甲酰胺溶剂中溶解完全，得到Nafion溶液；称取0.01g天门冬氨酸修饰的空心介孔硅加入Nafion溶液中，搅拌24h，得到铸膜液；将铸膜液静置1h脱泡后在玻璃板(4×4cm)上流延，80℃下干燥12h，120℃下处理12h，将膜揭下，依次置于体积分数为3％的双氧水溶液、1mol/L的硫酸水溶液、去离子水中，均在80℃下分别各加热1h，得到厚度为70μm的Nafion/天门冬氨酸修饰空心介孔硅-2％杂化膜。将该杂化膜在温度25℃、饱和湿度下进行质子传导测试，质子传导率为0.094S/cm，在温度25℃下进行甲醇渗透测试，甲醇渗透率为2.34×10-6cm2/s。Hybrid film preparation and film formation: under stirring at room temperature, weigh 0.5g Nafion and add it to 4mL N,N-dimethylformamide solvent to dissolve completely to obtain Nafion solution; weigh 0.01g aspartic acid-modified hollow medium Add the porous silicon into the Nafion solution, stir for 24 hours to obtain the casting solution; let the casting solution stand for 1 hour to defoam, cast it on a glass plate (4×4cm), dry it at 80°C for 12 hours, and treat it at 120°C for 12 hours. Take it off, put it in 3% hydrogen peroxide solution, 1mol/L sulfuric acid solution, and deionized water in sequence, and heat it at 80°C for 1 hour to obtain a Nafion/aspartic acid-modified hollow medium with a thickness of 70 μm. Porous silicon-2% hybrid membrane. The hybrid membrane was subjected to a proton conduction test at a temperature of 25°C and saturated humidity, and the proton conductivity was 0.094S/cm, and a methanol permeation test was performed at a temperature of 25°C, and the methanol permeability was 2.34×10-6 cm2 /s .
图1示出了对比例1制备得到的纯Nafion膜的断面SEM图，图2示出了对比例2制得的Nafion/空心介孔硅-2％杂化膜的断面SEM图，图3示出了实施例1制得的Nafion/天门冬氨酸修饰空心介孔硅-2％杂化膜的断面SEM图。从图1，图2和图3可以看出，与对比例1的纯Nafion膜相比，填充无机颗粒后的杂化膜(对比例2和实施例1)的界面形态结构发生明显的变化，由较为平整变为凹凸不平的结构，且实施例1中填充天门冬氨酸修饰空心介孔硅的杂化膜与对比例2中填充空心介孔硅的杂化膜相比，无机颗粒(即天门冬氨酸修饰空心介孔硅)在膜中的分散性得到提高，断面形貌变得平滑，说明通过天门冬氨酸修饰，一定程度上提高了无机粒子与有机高分子的相容性。通过对比例2和实施例1的质子传递与甲醇渗透性能，与填充未修饰空心介孔硅的杂化膜相比，填充天门冬氨酸修饰空心介孔硅的杂化膜的质子传导与阻醇能力均得到提高。Fig. 1 shows the cross-sectional SEM figure of the pure Nafion membrane that comparative example 1 prepares, and Fig. 2 shows the cross-sectional SEM figure of the Nafion/hollow mesoporous silicon-2% hybrid membrane that comparative example 2 makes, and Fig. 3 shows A cross-sectional SEM image of the Nafion/aspartic acid modified hollow mesoporous silicon-2% hybrid membrane prepared in Example 1 is shown. As can be seen from Fig. 1, Fig. 2 and Fig. 3, compared with the pure Nafion film of comparative example 1, the interfacial morphology structure of the hybrid film (comparative example 2 and embodiment 1) after filling the inorganic particles changes significantly, From relatively flat to uneven structure, and the hybrid membrane filled with aspartic acid modified hollow mesoporous silicon in Example 1 is compared with the hybrid membrane filled with hollow mesoporous silicon in Comparative Example 2, the inorganic particles (i.e. The dispersion of aspartic acid modified hollow mesoporous silicon) in the membrane is improved, and the cross-sectional morphology becomes smoother, indicating that the aspartic acid modification improves the compatibility of inorganic particles and organic polymers to a certain extent. Compared with the hybrid membrane filled with unmodified hollow mesoporous silicon, the proton conduction and barrier properties of the hybrid membrane filled with aspartic acid-modified hollow mesoporous silicon were compared with those of comparative example 2 and example 1. Alcohol capacity was improved.
实施例2：制备Nafion/磷酸丝氨酸修饰空心介孔硅-2％杂化膜。Example 2: Preparation of Nafion/phosphoserine-modified hollow mesoporous silicon-2% hybrid membrane.
采用与实施例1相同的方法制备空心介孔硅。Hollow mesoporous silicon was prepared by the same method as in Example 1.
磷酸丝氨酸修饰空心介孔硅：将1g上述空心介孔硅分散于120mL无水甲苯中，与2.4mL3-氨丙基三乙氧基硅烷混合后，充入氮气密封，105℃下回流反应24h，得到的氨基修饰空心介孔硅，将其分散于150mL MES缓冲溶液中，得到悬浮有氨基修饰空心介孔硅的悬浮液，其中，所述MES缓冲溶液制备方法为：2.66g 2-(N-吗啡啉)乙磺酸加入50mL水中溶解，用2mol/L NaOH溶液调节pH至6.5，再用水定容至250mL。将1.0g磷酸丝氨酸加入100mLMES缓冲液中，然后分别加入1g 1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和1gN-羟基琥珀酰亚胺，室温下剧烈搅拌1h进行活化。将上述活化的磷酸丝氨酸溶液加入到悬浮液中，室温下反应2h，离心洗涤干燥，得到磷酸丝氨酸修饰的空心介孔硅。Phosphoserine-modified hollow mesoporous silicon: Disperse 1 g of the above hollow mesoporous silicon in 120 mL of anhydrous toluene, mix it with 2.4 mL of 3-aminopropyltriethoxysilane, fill it with nitrogen and seal it, and reflux at 105°C for 24 hours. The obtained amino-modified hollow mesoporous silicon was dispersed in 150mL MES buffer solution to obtain a suspension having amino-modified hollow mesoporous silicon, wherein the preparation method of the MES buffer solution was: 2.66g 2-(N- Morpholine) ethanesulfonic acid was dissolved in 50 mL of water, adjusted to pH 6.5 with 2 mol/L NaOH solution, and then adjusted to 250 mL with water. Add 1.0 g of phosphoserine to 100 mL of MES buffer, then add 1 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 1 g of N-hydroxysuccinimide, and vigorously Stir for 1h to activate. The activated phosphoserine solution was added to the suspension, reacted at room temperature for 2 hours, centrifuged, washed and dried to obtain hollow mesoporous silicon modified with phosphoserine.
杂化膜制备与成膜：室温搅拌下，称取0.5g Nafion加入到4mL N,N-二甲基甲酰胺溶剂中溶解完全，得到Nafion溶液；称取0.01g磷酸丝氨酸修饰的空心介孔硅加入Nafion溶液中，搅拌24h，Hybrid film preparation and film formation: under stirring at room temperature, weigh 0.5g Nafion and add it to 4mL N,N-dimethylformamide solvent to dissolve completely to obtain Nafion solution; weigh 0.01g phosphoserine-modified hollow mesoporous silicon Added in Nafion solution, stirred for 24h,
静置1h脱泡后在玻璃板(4×4cm)上流延，80℃下干燥12h，120℃下处理12h，将得到的膜依次置于体积分数为3％的双氧水溶液、1mol/L的硫酸水溶液、去离子水中在80℃加热3h，得到厚度为50μm的Nafion/磷酸丝氨酸修饰空心介孔硅-2％杂化膜。将该杂化膜在温度25℃、饱和湿度下进行质子传导测试，质子传导率为0.084S/cm，在温度25℃下进行甲醇渗透测试，甲醇渗透率为1.99×10-6cm2/s。After standing for 1h to defoam, cast on a glass plate (4×4cm), dry at 80°C for 12h, and treat at 120°C for 12h. The aqueous solution and deionized water were heated at 80° C. for 3 hours to obtain a Nafion/phosphoserine-modified hollow mesoporous silicon-2% hybrid membrane with a thickness of 50 μm. The hybrid membrane was tested for proton conduction at a temperature of 25°C and saturated humidity, and the proton conductivity was 0.084S/cm, and the methanol permeation test was carried out at a temperature of 25°C, and the methanol permeability was 1.99×10-6 cm2 /s .
图4为实施例2制得的Nafion/磷酸丝氨酸修饰空心介孔硅-2％杂化膜的断面SEM图。与对比例2中填充空心介孔硅的杂化膜相比，无机颗粒(即磷酸丝氨酸修饰空心介孔硅)在膜中的分散性得到提高，断面形貌变得平滑，说明通过磷酸丝氨酸修饰，一定程度上提高了无机粒子与有机高分子的相容性。通过对比例2和实施例2的质子传递与甲醇渗透性能，与填充未修饰空心介孔硅的杂化膜相比，填充磷酸丝氨酸修饰空心介孔硅的杂化膜的质子传导与阻醇能力均得到提高。FIG. 4 is a cross-sectional SEM image of the Nafion/phosphoserine-modified hollow mesoporous silicon-2% hybrid membrane prepared in Example 2. FIG. Compared with the hybrid membrane filled with hollow mesoporous silicon in Comparative Example 2, the dispersion of inorganic particles (i.e., phosphoserine-modified hollow mesoporous silicon) in the membrane was improved, and the cross-sectional morphology became smoother, indicating that the phosphoserine modification , to some extent improve the compatibility of inorganic particles and organic polymers. Compared with the hybrid membrane filled with unmodified hollow mesoporous silicon, the proton conduction and alcohol resistance of the hybrid membrane filled with phosphoserine modified hollow mesoporous silicon through the proton transfer and methanol permeation performance of Comparative Example 2 and Example 2 have been improved.
实施例3：制备Nafion/氧化半胱氨酸修饰空心介孔硅-2％杂化膜。Example 3: Preparation of Nafion/oxidized cysteine modified hollow mesoporous silicon-2% hybrid membrane.
采用与实施例1相同的方法制备空心介孔硅。Hollow mesoporous silicon was prepared by the same method as in Example 1.
氧化半胱氨酸修饰空心介孔硅：将1g上述空心介孔硅分散于120mL无水甲苯中，与2.4mL 3-氨丙基三乙氧基硅烷混合后，充入氮气密封，105℃下回流反应24h，得到的氨基修饰空心介孔硅，将其分散于150mL MES缓冲溶液中，其中，所述MES缓冲溶液制备方法为：2.66g 2-(N-吗啡啉)乙磺酸加入50mL水中溶解，用2mol/L NaOH溶液调节pH至6.5，再用水定容至250mL。将1.0g半胱氨酸加入100mLMES缓冲液中，然后分别加入1g 1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐和1g N-羟基琥珀酰亚胺，室温下剧烈搅拌1h进行活化。将上述活化的半胱氨酸溶液加入到悬浮液中，室温下反应2h，得到半胱氨酸修饰的空心介孔硅。将上述制得的半胱氨酸修饰空心介孔硅加入100mL体积分数为30％的双氧水溶液中搅拌氧化24h，离心洗涤干燥，得到氧化半胱氨酸修饰的空心介孔硅。Modified hollow mesoporous silicon with oxidized cysteine: Disperse 1g of the above hollow mesoporous silicon in 120mL of anhydrous toluene, mix it with 2.4mL 3-aminopropyltriethoxysilane, fill it with nitrogen and seal it at 105°C Refluxing reaction for 24 hours, the obtained amino-modified hollow mesoporous silicon was dispersed in 150 mL of MES buffer solution, wherein, the preparation method of the MES buffer solution was: 2.66 g of 2-(N-morpholine) ethanesulfonic acid was added to 50 mL of water Dissolve, adjust the pH to 6.5 with 2mol/L NaOH solution, and then dilute to 250mL with water. Add 1.0 g of cysteine to 100 mL of MES buffer, then add 1 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 1 g of N-hydroxysuccinimide, respectively, Stir vigorously at room temperature for 1 h to activate. The above-mentioned activated cysteine solution was added to the suspension, and reacted at room temperature for 2 hours to obtain cysteine-modified hollow mesoporous silicon. The cysteine-modified hollow mesoporous silicon prepared above was added into 100 mL of 30% hydrogen peroxide solution, stirred and oxidized for 24 hours, centrifuged, washed and dried to obtain oxidized cysteine-modified hollow mesoporous silicon.
杂化膜制备与成膜：室温搅拌下，称取0.5g Nafion加入到4mL N,N-二甲基甲酰胺溶剂中溶解完全，得到Nafion溶液；称取0.01g氧化半胱氨酸修饰的空心介孔硅加入Nafion溶液中，搅拌24h，得到铸膜液；将铸膜液静置3h脱泡后在玻璃板(4×4cm)上流延，80℃下干燥12h，120℃下处理12h，将得到的膜依次置于体积分数为3％的双氧水溶液、1mol/L的硫酸水溶液、去离子水中均在80℃分别加热1h，得到厚度为,70μm的Nafion/氧化半胱氨酸修饰空心介孔硅-2％杂化膜。将该杂化膜在温度25℃、饱和湿度下进行质子传导测试，质子传导率为0.099S/cm，在温度25℃下进行甲醇渗透测试，甲醇渗透率为1.98×10-6cm2/s。Hybrid film preparation and film formation: under stirring at room temperature, weigh 0.5g Nafion and add it to 4mL N,N-dimethylformamide solvent to dissolve completely to obtain Nafion solution; weigh 0.01g oxidized cysteine-modified hollow Add mesoporous silicon into the Nafion solution, stir for 24 hours to obtain the casting solution; let the casting solution stand for 3 hours to defoam, cast it on a glass plate (4×4cm), dry it at 80°C for 12 hours, and treat it at 120°C for 12 hours. The obtained membrane was placed in 3% aqueous hydrogen peroxide solution, 1mol/L sulfuric acid aqueous solution, and deionized water, respectively, and heated at 80°C for 1 hour to obtain Nafion/oxidized cysteine-modified hollow mesopores with a thickness of 70 μm. Silicon-2% hybrid film. The hybrid membrane was tested for proton conduction at a temperature of 25°C and saturated humidity, and the proton conductivity was 0.099 S/cm, and the methanol permeation test was carried out at a temperature of 25°C, and the methanol permeability was 1.98×10-6 cm2 /s .
图5为实施例3制得的Nafion/氧化半胱氨酸修饰空心介孔硅-2％杂化膜的断面SEM图。与对比例2中填充空心介孔硅的杂化膜相比，无机颗粒(即氧化半胱氨酸修饰空心介孔硅)在膜中的分散性得到提高，断面形貌变得平滑，说明通过氧化半胱氨酸酸修饰，一定程度上提高了无机粒子与有机高分子的相容性。通过对比例2和实施例3的质子传递与甲醇渗透性能，与填充未修饰空心介孔硅的杂化膜相比，填充氧化半胱氨酸修饰空心介孔硅的杂化膜的质子传导与阻醇能力均得到提高。FIG. 5 is a cross-sectional SEM image of the Nafion/oxidized cysteine-modified hollow mesoporous silicon-2% hybrid membrane prepared in Example 3. FIG. Compared with the hybrid membrane filled with hollow mesoporous silicon in Comparative Example 2, the dispersion of inorganic particles (i.e. oxidized cysteine-modified hollow mesoporous silicon) in the membrane is improved, and the cross-sectional morphology becomes smoother, which shows that by Oxidation of cysteine acid modification improves the compatibility of inorganic particles and organic polymers to a certain extent. Through the proton transfer and methanol permeation performance of Comparative Example 2 and Example 3, compared with the hybrid membrane filled with unmodified hollow mesoporous silicon, the proton conduction and Alcohol inhibition ability has been improved.
对比例3：制备Nafion/空心介孔硅-4％杂化膜。Comparative Example 3: Preparation of Nafion/hollow mesoporous silicon-4% hybrid membrane.
采用与上述对比例2相同的方法制备空心介孔硅。Hollow mesoporous silicon was prepared by the same method as in Comparative Example 2 above.
杂化膜制备与成膜：室温搅拌下，称取0.5g Nafion加入到4mL N,N-二甲基甲酰胺溶剂中溶解完全，得到Nafion溶液；称取0.02g空心介孔硅加入Nafion溶液中，搅拌24h，静置2h脱泡后在玻璃板(4×4cm)上流延，80℃下干燥12h，120℃下处理12h，将得到的膜依次置于体积分数为3％的双氧水溶液、1mol/L的硫酸水溶液、去离子水中在80℃加热3h，得到厚度为75μm的Nafion/空心介孔硅-4％杂化膜。将该杂化膜在温度25℃、饱和湿度下进行质子传导测试，质子传导率为0.0798S/cm，在温度25℃下进行甲醇渗透测试，甲醇渗透率为2.15×10-6cm2/s。Hybrid film preparation and film formation: under stirring at room temperature, weigh 0.5g Nafion and add it to 4mL N,N-dimethylformamide solvent to dissolve completely to obtain Nafion solution; weigh 0.02g hollow mesoporous silicon and add it to Nafion solution , stirred for 24 hours, left to stand for 2 hours to defoam, and cast on a glass plate (4×4cm), dried at 80°C for 12 hours, and treated at 120°C for 12 hours, and the obtained film was placed in a volume fraction of 3% hydrogen peroxide solution, 1mol /L sulfuric acid aqueous solution and deionized water were heated at 80°C for 3 hours to obtain a Nafion/hollow mesoporous silicon-4% hybrid membrane with a thickness of 75 μm. The hybrid membrane was tested for proton conduction at a temperature of 25°C and saturated humidity, and the proton conductivity was 0.0798S/cm, and the methanol permeation test was carried out at a temperature of 25°C, and the methanol permeability was 2.15×10-6 cm2 /s .
实施例4：制备Nafion/天门冬氨酸修饰空心介孔硅-4％杂化膜。Example 4: Preparation of Nafion/aspartic acid modified hollow mesoporous silicon-4% hybrid membrane.
采用与实施例1相同的方法制备空心介孔硅。Hollow mesoporous silicon was prepared by the same method as in Example 1.
采用与实施例1相同的方法制备天门冬氨酸修饰空心介孔硅。The same method as in Example 1 was used to prepare aspartic acid-modified hollow mesoporous silicon.
杂化膜制备与成膜：室温搅拌下，称取0.5g Nafion加入到4mL N,N-二甲基甲酰胺溶剂中溶解完全，得到Nafion溶液；称取0.02g天门冬氨酸修饰的空心介孔硅加入Nafion溶液中，搅拌24h，得到铸膜液；将铸膜液静置2h脱泡后在玻璃板(4×4cm)上流延，80℃下干燥12h，120℃下处理12h，将得到的膜依次置于体积分数为3％的双氧水溶液、1mol/L的硫酸水溶液、去离子水中均在80℃分别各加热1h，得到厚度为80μm的Nafion/天门冬氨酸修饰空心介孔硅-4％杂化膜。将该杂化膜在温度25℃、饱和湿度下进行质子传导测试，质子传导率为0.102S/cm，在温度25℃下进行甲醇渗透测试，甲醇渗透率为2.05×10-6cm2/s。Hybrid film preparation and film formation: under stirring at room temperature, weigh 0.5g Nafion and add it to 4mL N,N-dimethylformamide solvent to dissolve completely to obtain Nafion solution; weigh 0.02g aspartic acid-modified hollow medium Porous silicon was added to the Nafion solution, stirred for 24 hours to obtain a casting solution; the casting solution was left to stand for 2 hours to defoam and cast on a glass plate (4×4cm), dried at 80°C for 12 hours, and treated at 120°C for 12 hours to obtain The membrane was placed in 3% aqueous hydrogen peroxide solution, 1mol/L sulfuric acid aqueous solution, and deionized water and heated at 80°C for 1 hour respectively to obtain a Nafion/aspartic acid-modified hollow mesoporous silicon- 4% hybrid film. The hybrid membrane was subjected to a proton conduction test at a temperature of 25°C and saturated humidity, and the proton conductivity was 0.102S/cm, and a methanol permeation test was performed at a temperature of 25°C, and the methanol permeability was 2.05×10-6 cm2 /s .
通过对比例3和实施例4的质子传递与甲醇渗透性能，与填充未修饰空心介孔硅的杂化膜相比，填充天门冬氨酸修饰空心介孔硅的杂化膜的质子传导与阻醇能力均得到提高。通过实施例1和实施例4的质子传递与甲醇渗透性能，可以看出提高天门冬氨酸修饰空心介孔硅的填充量也使得杂化膜的质子传导与阻醇能力得以提高。Through the proton transfer and methanol permeation performance of Comparative Example 3 and Example 4, compared with the hybrid membrane filled with unmodified hollow mesoporous silicon, the proton conduction and barrier properties of the hybrid membrane filled with aspartic acid modified hollow mesoporous silicon Alcohol capacity was improved. From the proton transfer and methanol permeation properties of Examples 1 and 4, it can be seen that increasing the filling amount of aspartic acid-modified hollow mesoporous silicon also improves the proton conduction and alcohol resistance capabilities of the hybrid membrane.
实施例5：制备Nafion/磷酸丝氨酸修饰空心介孔硅-4％杂化膜。Example 5: Preparation of Nafion/phosphoserine-modified hollow mesoporous silicon-4% hybrid membrane.
采用与实施例2相同的方法制备空心介孔硅。Hollow mesoporous silicon was prepared by the same method as in Example 2.
采用与实施例2相同的方法制备磷酸丝氨酸修饰空心介孔硅。The same method as in Example 2 was used to prepare phosphoserine-modified hollow mesoporous silicon.
杂化膜制备与成膜：室温搅拌下，称取0.5g Nafion加入到4mL N,N-二甲基甲酰胺溶剂中溶解完全，得到Nafion溶液；称取0.02g磷酸丝氨酸修饰的空心介孔硅加入Nafion溶液中，搅拌24h，得到铸膜液；将铸膜液静置1h脱泡后在玻璃板(4×4cm)上流延，80℃下干燥12h，120℃下处理12h，将得到的膜依次置于体积分数为3％的双氧水溶液、1mol/L的硫酸水溶液、去离子水中均在80℃下分别各加热1h，得到厚度为75μm的Nafion/磷酸丝氨酸修饰空心介孔硅-4％杂化膜。将该杂化膜在温度25℃、饱和湿度下进行质子传导测试，质子传导率为0.091S/cm，在温度25℃下进行甲醇渗透测试，甲醇渗透率为1.77×10-6cm2/s。Hybrid film preparation and film formation: under stirring at room temperature, weigh 0.5g Nafion and add it to 4mL N,N-dimethylformamide solvent to dissolve completely to obtain Nafion solution; weigh 0.02g phosphoserine-modified hollow mesoporous silicon Add the Nafion solution, stir for 24 hours to obtain the casting solution; let the casting solution stand for 1 hour to defoam, cast it on a glass plate (4×4cm), dry it at 80°C for 12 hours, and treat it at 120°C for 12 hours. Place in 3% aqueous hydrogen peroxide solution, 1mol/L sulfuric acid aqueous solution, and deionized water in sequence and heat at 80°C for 1 hour respectively to obtain a Nafion/phosphoserine-modified hollow mesoporous silicon-4% heterostructure with a thickness of 75 μm. film. The hybrid membrane was tested for proton conduction at a temperature of 25°C and saturated humidity, and the proton conductivity was 0.091S/cm, and the methanol permeation test was carried out at a temperature of 25°C, and the methanol permeability was 1.77×10-6 cm2 /s .
通过对比例3和实施例5的质子传递与甲醇渗透性能，与填充未修饰空心介孔硅的杂化膜相比，填充磷酸丝氨酸修饰空心介孔硅的杂化膜的质子传导与阻醇能力均得到提高。通过实施例2和实施例5的质子传递与甲醇渗透性能，可以看出提高磷酸丝氨酸修饰空心介孔硅的填充量也使得杂化膜的质子传导与阻醇能力得以提高。Compared with the hybrid membrane filled with unmodified hollow mesoporous silicon, the proton conduction and alcohol inhibition ability of the hybrid membrane filled with phosphoserine modified hollow mesoporous silicon compared with the proton transfer and methanol permeation performance of Comparative Example 3 and Example 5 have been improved. From the proton transfer and methanol permeation properties of Examples 2 and 5, it can be seen that increasing the filling amount of phosphoserine-modified hollow mesoporous silicon also improves the proton conduction and alcohol resistance of the hybrid membrane.
实施例6：制备Nafion/氧化半胱氨酸修饰空心介孔硅-4％杂化膜。Example 6: Preparation of Nafion/oxidized cysteine modified hollow mesoporous silicon-4% hybrid membrane.
采用与实施例3相同的方法制备空心介孔硅。Hollow mesoporous silicon was prepared by the same method as in Example 3.
采用与实施例3相同的方法制备氧化半胱氨酸修饰空心介孔硅。The same method as in Example 3 was used to prepare oxidized cysteine-modified hollow mesoporous silicon.
杂化膜制备与成膜：室温搅拌下，称取0.5g Nafion加入到4mL N,N-二甲基甲酰胺溶剂中溶解完全，得到Nafion溶液；称取0.02g氧化半胱氨酸修饰的空心介孔硅加入Nafion溶液中，搅拌24h，得到铸膜液；将铸膜液静置3h脱泡后在玻璃板(4×4cm)上流延，80℃下干燥12h，120℃下处理12h，将得到的膜依次置于体积分数为3％的双氧水溶液、1mol/L的硫酸水溶液、去离子水中，均在80℃下分别各加热1h，得到厚度为75μm的Nafion/氧化半胱氨酸修饰空心介孔硅-4％杂化膜。将该杂化膜在温度25℃、饱和湿度下进行质子传导测试，质子传导率为0.112S/cm，在温度25℃下进行甲醇渗透测试，甲醇渗透率为1.79×10-6cm2/s。Hybrid film preparation and film formation: under stirring at room temperature, weigh 0.5g Nafion and add it to 4mL N,N-dimethylformamide solvent to dissolve completely to obtain Nafion solution; weigh 0.02g oxidized cysteine-modified hollow Add mesoporous silicon into the Nafion solution, stir for 24 hours to obtain the casting solution; let the casting solution stand for 3 hours to defoam, cast it on a glass plate (4×4cm), dry it at 80°C for 12 hours, and treat it at 120°C for 12 hours. The obtained membranes were placed in 3% hydrogen peroxide solution, 1mol/L sulfuric acid solution, and deionized water in sequence, and were heated at 80°C for 1 hour respectively to obtain Nafion/oxidized cysteine-modified hollow membranes with a thickness of 75 μm. Mesoporous silicon-4% hybrid membrane. The hybrid membrane was tested for proton conduction at a temperature of 25°C and saturated humidity, and the proton conductivity was 0.112 S/cm, and the methanol permeation test was carried out at a temperature of 25°C, and the methanol permeability was 1.79×10-6 cm2 /s .
通过对比例3和实施例6的质子传递与甲醇渗透性能，与填充未修饰空心介孔硅的杂化膜相比，填充氧化半胱氨酸修饰空心介孔硅的杂化膜的质子传导与阻醇能力均得到提高。通过实施例3和实施例6的质子传递与甲醇渗透性能，可以看出提高氧化半胱氨酸修饰空心介孔硅的填充量也使得杂化膜的质子传导与阻醇能力得以提高。According to the proton transfer and methanol permeation properties of Comparative Example 3 and Example 6, compared with the hybrid membrane filled with unmodified hollow mesoporous silicon, the proton conduction and Alcohol inhibition ability has been improved. From the proton transfer and methanol permeation properties of Examples 3 and 6, it can be seen that increasing the filling amount of oxidized cysteine-modified hollow mesoporous silicon also improves the proton conduction and alcohol resistance of the hybrid membrane.
尽管上面结合图对本发明进行了描述，但是本发明并不局限于上述的具体实施方式，上述的具体实施方式仅仅是示意性的，而不是限制性的，本领域的普通技术人员在本发明的启示下，在不脱离本发明宗旨的情况下，还可以作出很多变形，这些均属于本发明的保护之内。Although the present invention has been described above in conjunction with the drawings, the present invention is not limited to the above-mentioned specific embodiments, and the above-mentioned specific embodiments are only illustrative, rather than restrictive. Under the inspiration, many modifications can be made without departing from the gist of the present invention, and these all belong to the protection of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410721070.6ACN104448638B (en) | 2014-12-02 | 2014-12-02 | The amino acid modified hollow mesoporous silicon hybridized film of Nafion/ and preparation and application |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410721070.6ACN104448638B (en) | 2014-12-02 | 2014-12-02 | The amino acid modified hollow mesoporous silicon hybridized film of Nafion/ and preparation and application |
| Publication Number | Publication Date |
|---|---|
| CN104448638A CN104448638A (en) | 2015-03-25 |
| CN104448638Btrue CN104448638B (en) | 2016-12-07 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410721070.6AExpired - Fee RelatedCN104448638B (en) | 2014-12-02 | 2014-12-02 | The amino acid modified hollow mesoporous silicon hybridized film of Nafion/ and preparation and application |
| Country | Link |
|---|---|
| CN (1) | CN104448638B (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175960B (en)* | 2015-10-08 | 2017-10-24 | 天津大学 | Nafion/ phytic acid modifies hollow dopamine composite membrane and preparation and application |
| CN110571392B (en)* | 2018-06-29 | 2020-12-08 | 华中科技大学 | Functional interlayer material for lithium-sulfur battery and preparation method thereof |
| CN115558169A (en)* | 2022-09-27 | 2023-01-03 | 南开大学 | Preparation method of bell-type zwitterionic microsphere chitosan hybrid membrane with high proton conductivity |
| CN116544428B (en)* | 2023-04-18 | 2024-12-24 | 东风汽车集团股份有限公司 | A composite material and its preparation method and application |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101320815A (en)* | 2008-07-21 | 2008-12-10 | 中国科学院长春应用化学研究所 | Preparation method of Nafion/mesoporous silica composite proton exchange membrane |
| CN103433005A (en)* | 2013-08-26 | 2013-12-11 | 江苏大学 | Preparation method for triglycine functionalized mesoporous material surface imprinting adsorbent |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101320815A (en)* | 2008-07-21 | 2008-12-10 | 中国科学院长春应用化学研究所 | Preparation method of Nafion/mesoporous silica composite proton exchange membrane |
| CN103433005A (en)* | 2013-08-26 | 2013-12-11 | 江苏大学 | Preparation method for triglycine functionalized mesoporous material surface imprinting adsorbent |
| Title |
|---|
| Advanced Mesostructured Hybrid Silica-Nafion Membranes for High-Performance PEM Fuel Cell;Franck Pereira,etc;《Chemistry of Materials》;20080216;第20卷(第5期);第1710-1718页* |
| Nove Nafion composite membranes with mesoporous silica nanospheres as inorganic fillers;Yonggang Jin,etc;《Journal of Power Sources》;20080909;第185卷(第2期);第664-669页* |
| 介孔二氧化硅/Nafion复合材料的制备及其酸催化性能的研究;郑净植等;《化学与生物工程》;20120920;第29卷(第6期);第59-61页* |
| Publication number | Publication date |
|---|---|
| CN104448638A (en) | 2015-03-25 |
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Ethylenediamine-functionalized graphene oxide incorporated acid-base ion exchange membranes for vanadium redox flow battery | |
| CN103296297B (en) | Preparation method of organic-inorganic composite proton exchange membrane for fuel cell | |
| CN103337649B (en) | A kind of modified graphene/sulfonated poly (phenylene oxide) PEM and preparation method thereof | |
| CN103304979B (en) | Phosphorylation titanium dioxide hollow sphere-filled sulfonated polyether ether ketone film as well as preparation and application | |
| CN102516531B (en) | Imidazole-ionic-liquid-grafted SPEEK proton exchange membrane material and preparation method thereof | |
| CN103351576B (en) | Imidazole-microcapsule-supported heteropoly acid-sulfonated polyether ether ketone composite membrane, preparation and application thereof | |
| CN104183859A (en) | Proton exchange membrane and preparation method thereof | |
| CN104448638B (en) | The amino acid modified hollow mesoporous silicon hybridized film of Nafion/ and preparation and application | |
| CN106432766A (en) | Nafion/orthophosphoric loaded covalent organic framework material composite film, preparation and application | |
| CN103715438A (en) | Nano-composite proton exchange membrane as well as preparation method and application thereof | |
| CN102299353B (en) | Application of Organic-Inorganic Composite Membranes in Acidic Electrolyte Flow Energy Storage Batteries | |
| CN105390721B (en) | A kind of preparation method of boron phosphate enveloped carbon nanometer tube compound proton exchange membrane | |
| CN105175960B (en) | Nafion/ phytic acid modifies hollow dopamine composite membrane and preparation and application | |
| CN101624449A (en) | Organic phosphorylated titanium dioxide micrballon-filled chitosan hybrid membrane as well as preparation and application | |
| CN103611575B (en) | Containing the preparation method of the catalyst of imidazole and its derivants | |
| CN102881853A (en) | Blending membrane for all-vanadium redox flow battery and preparation method for blending membrane | |
| CN105070933A (en) | Composite proton-exchange membrane for fuel cell and preparation method of composite proton-exchange membrane | |
| CN103855408B (en) | A Membrane Electrode for Improved Anode Water Management in Proton Exchange Membrane Fuel Cells | |
| CN107195937A (en) | Compound alkalescence polyelectrolyte film and preparation method thereof and alkaline polyelectrolyte fuel cell | |
| CN109400905A (en) | A kind of metal organic framework Mn-BTC and preparation method and application | |
| CN105597568B (en) | Chloromethylation polyether-ether-ketone/imidazoles carbon nano tube hybridized film and preparation and application | |
| CN116826124A (en) | Composite perfluorosulfonic acid proton exchange membrane and preparation method and application thereof | |
| CN114373971B (en) | A kind of preparation method of proton exchange membrane blended with perfluorosulfonic acid resin and Ce-MOF | |
| CN108878933A (en) | A kind of preparation method of Nafion/lignin compound proton exchange membrane | |
| CN102389823B (en) | Preparation method of fuel-cell catalyst with high utilization rate |
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee | Granted publication date:20161207 Termination date:20211202 |