技术领域Technical Field
本发明涉及PPS中空纤维制备领域，具体是一种壁厚可控的聚苯硫醚基中空纤维及其制备方法和应用。The invention relates to the field of PPS hollow fiber preparation, in particular to a polyphenylene sulfide-based hollow fiber with controllable wall thickness and a preparation method and application thereof.
背景技术Background technique
由于化石燃料的过度使用导致了地球环境的恶化和能源枯竭问题，开发绿色可持续发展的新能源是21世纪人类面临的最大挑战之一。具有极高理论能量密度的金属空气电池引发研究人员的广泛关注，然而目前驱动金属空气电池阴极的催化剂主要是贵金属Pt和Ru，其储量低、成本高、稳定性差等缺点限制了金属空气电池的大规模使用。因此，开发高效、低成本的功能化碳基催化剂来替代贵金属催化剂是实现金属空气电池大规模使用的重点。As the overuse of fossil fuels has led to the deterioration of the earth's environment and the depletion of energy, the development of green and sustainable new energy is one of the biggest challenges facing mankind in the 21st century. Metal-air batteries with extremely high theoretical energy density have attracted widespread attention from researchers. However, the catalysts driving the cathode of metal-air batteries are currently mainly precious metals Pt and Ru, which have low reserves, high costs, and poor stability, which limit the large-scale use of metal-air batteries. Therefore, the development of efficient and low-cost functionalized carbon-based catalysts to replace precious metal catalysts is the key to achieving large-scale use of metal-air batteries.
聚苯硫醚(PPS)是一种高含硫量的工程塑料材料，其理论含S量高达30％，因此将PPS材料热解后所形成的多孔碳用作金属空气电池的阴极的氧还原催化剂具有重大研究价值。然而，PPS材料在受热之后会发生融滴，严重影响了所制备碳材料孔道结构而无法起到优异的催化效果。申请号为201510631820.5的专利公开了一种具有自熄性和无融滴的聚苯硫醚纤维，这种新型PPS材料克服了受热融滴的缺点，可以在热解过程中保持形貌结构不变。基于此技术，文献《M.Wang,K.Su,M.Zhang,X.Du,Z.Li,Advanced TrifunctionalElectrocatalysis with Cu-,N-,S-Doped Defect-Rich Porous Carbon forRechargeable Zn-Air Batteries and Self-Driven Water Splitting,ACS SustainableChem.Eng.9(2021)13324-13336》利用PPS材料成功构筑了多孔的N、S共掺杂碳基氧还原催化剂，但是受限于PPS本身较大的微米级尺寸，所制备的催化剂比表面积较小，催化性能还有待进一步提升。Polyphenylene sulfide (PPS) is an engineering plastic material with a high sulfur content. Its theoretical sulfur content is as high as 30%. Therefore, the porous carbon formed by the pyrolysis of PPS material is used as an oxygen reduction catalyst for the cathode of metal-air batteries, which has great research value. However, the PPS material will produce droplets after heating, which seriously affects the pore structure of the prepared carbon material and cannot play an excellent catalytic effect. Patent application number 201510631820.5 discloses a polyphenylene sulfide fiber with self-extinguishing properties and no droplets. This new PPS material overcomes the disadvantages of heated droplets and can maintain the morphology and structure unchanged during the pyrolysis process. Based on this technology, the document "M. Wang, K. Su, M. Zhang, X. Du, Z. Li, Advanced Trifunctional Electrocatalysis with Cu-, N-, S-Doped Defect-Rich Porous Carbon for Rechargeable Zn-Air Batteries and Self-Driven Water Splitting, ACS Sustainable Chem. Eng. 9 (2021) 13324-13336" successfully constructed a porous N, S co-doped carbon-based oxygen reduction catalyst using PPS material. However, due to the large micron-sized size of PPS itself, the prepared catalyst has a small specific surface area and the catalytic performance needs to be further improved.
发明内容Summary of the invention
针对现有技术的不足，本发明拟解决的技术问题是，提供一种壁厚可控的聚苯硫醚基中空纤维及其制备方法和应用。In view of the deficiencies in the prior art, the technical problem to be solved by the present invention is to provide a polyphenylene sulfide-based hollow fiber with controllable wall thickness and a preparation method and application thereof.
本发明解决所述方法技术问题的技术方案是，提供一种壁厚可控的聚苯硫醚基中空纤维的制备方法，其特征在于，该方法包括以下步骤：The technical solution of the present invention to solve the technical problem of the method is to provide a method for preparing polyphenylene sulfide-based hollow fibers with controllable wall thickness, characterized in that the method comprises the following steps:
步骤1、将去离子水、氧化剂与酸共混形成氧化处理溶液；Step 1, mixing deionized water, an oxidant and an acid to form an oxidation treatment solution;
步骤2、将PPS纤维均匀分散在氧化处理溶液中，然后在20～100℃下氧化反应0.01～48h；取出后，冲洗至中性；干燥后，得到氧化程度可控的氧化PPS纤维；Step 2, uniformly dispersing the PPS fiber in the oxidation treatment solution, and then performing an oxidation reaction at 20 to 100° C. for 0.01 to 48 hours; after taking out, rinsing to neutrality; and after drying, obtaining oxidized PPS fiber with a controllable oxidation degree;
步骤3、将步骤2得到的氧化PPS纤维放入氧化性酸溶液中进行反应，直至不再产生棕红色气体并且在溶液中不再产生白色乳状物质；取出后，冲洗至中性；干燥后，得到壁厚可控的PPS基中空纤维。Step 3, placing the oxidized PPS fiber obtained in step 2 into an oxidizing acid solution for reaction until no brown-red gas is produced and no white milky substance is produced in the solution; after taking out, rinse to neutral; after drying, obtain a PPS-based hollow fiber with controllable wall thickness.
本发明解决所述中空纤维技术问题的技术方案是，提供一种所述方法制备得到的壁厚可控的聚苯硫醚基中空纤维。The technical solution of the present invention to solve the above-mentioned hollow fiber technical problem is to provide a polyphenylene sulfide-based hollow fiber with controllable wall thickness prepared by the above-mentioned method.
本发明解决所述应用技术问题的技术方案是，提供一种所述的壁厚可控的聚苯硫醚基中空纤维的应用，其特征在于，将所述PPS基中空纤维浸渍在金属盐溶液中来吸附金属离子，取出后蒸干水分；再置于密闭加热环境中在500℃～1200℃的氨气氛围中碳化0.5h～5h，得到金属、N、S共掺杂的中空纤维状碳基氧还原催化剂，用于锌-空气电池或氢燃料电池的氧还原催化剂。The technical solution of the present invention to solve the application technical problem is to provide an application of the polyphenylene sulfide-based hollow fiber with controllable wall thickness, characterized in that the PPS-based hollow fiber is immersed in a metal salt solution to adsorb metal ions, and the water is evaporated after being taken out; then it is placed in a closed heating environment and carbonized in an ammonia atmosphere at 500°C to 1200°C for 0.5h to 5h to obtain a metal, N, and S co-doped hollow fiber-shaped carbon-based oxygen reduction catalyst, which is used as an oxygen reduction catalyst for zinc-air batteries or hydrogen fuel cells.
与现有技术相比，本发明的有益效果在于：Compared with the prior art, the present invention has the following beneficial effects:
(1)本发明以PPS纤维为基体，通过纤维皮层可控氧化和芯层可控氧化溶出法相结合的工艺制备了一种壁厚可控的PPS基中空纤维。(1) The present invention uses PPS fiber as a matrix and prepares a PPS-based hollow fiber with controllable wall thickness by combining a process of controlled oxidation of the fiber skin layer and a controlled oxidation dissolution method of the core layer.
(2)本发明通过纤维皮层可控氧化法靶向调控PPS纤维的皮层性质，氧化进程是由外向内的，进而使纤维形成芯层仍为PPS成分而皮层为抗氧化性酸成分的皮芯结构复合纤维，同时，通过调控PPS纤维皮层的氧化处理深度，能够得到不同氧化深度的皮芯结构复合纤维，随后再使用芯层可控氧化溶出法去除纤维芯层的未氧化的PPS成分，从而形成中空结构，得到一系列不同壁厚的PPS基中空纤维。(2) The present invention targets and regulates the cortex properties of PPS fibers through a controlled oxidation method for the fiber cortex. The oxidation process proceeds from the outside to the inside, thereby allowing the fiber to form a core-skin structure composite fiber in which the core layer is still a PPS component and the cortex is an antioxidant acid component. At the same time, by regulating the oxidation treatment depth of the PPS fiber cortex, core-skin structure composite fibers with different oxidation depths can be obtained. Subsequently, a core layer controlled oxidation dissolution method is used to remove the unoxidized PPS component of the fiber core layer, thereby forming a hollow structure, and obtaining a series of PPS-based hollow fibers with different wall thicknesses.
(3)本发明所制备的中空纤维具有极强的耐酸性，可以在浓盐酸、浓硝酸甚至王水中长期稳定使用，是一种理想的过滤和分离材料，可以用于极端环境下的有机溶剂回收(强溶解性)和高浓污水处理(强腐蚀性)等。同时，其具有优异的耐高温稳定性，并且内部的孔腔结构大幅提高了与反应物的接触面积，未来可以广泛用于高温废气(含腐蚀性)处理以及细颗粒型工业危险废物高效分离、过滤及回收等领域。(3) The hollow fiber prepared by the present invention has extremely strong acid resistance and can be used stably for a long time in concentrated hydrochloric acid, concentrated nitric acid and even aqua regia. It is an ideal filtering and separation material and can be used for organic solvent recovery (strong solubility) and high-concentration sewage treatment (strong corrosiveness) in extreme environments. At the same time, it has excellent high-temperature stability, and the internal pore structure greatly increases the contact area with the reactants. In the future, it can be widely used in the fields of high-temperature waste gas (including corrosive) treatment and efficient separation, filtration and recovery of fine-particle industrial hazardous waste.
(4)本发明所制备的中空纤维作为前驱体所制备的碳材料，具有独特的中空结构，可以暴露出大量的活性位点，具有更高比表面积和孔隙率，在热解过程中将极大的提高气体与前驱体的接触面积。其可以作为催化剂用于能源存储和转换领域(例如：锂硫电池、金属空气电池和超级电容器)。特别是将其作为金属空气电池阴极的氧还原催化剂，表现出了极其优异的催化活性和稳定性，能够推动金属空气电池的商业化发展。(4) The hollow fiber prepared by the present invention is used as a carbon material prepared by the precursor, which has a unique hollow structure, can expose a large number of active sites, has a higher specific surface area and porosity, and will greatly increase the contact area between the gas and the precursor during the pyrolysis process. It can be used as a catalyst in the field of energy storage and conversion (for example: lithium-sulfur batteries, metal-air batteries and supercapacitors). In particular, it is used as an oxygen reduction catalyst for the cathode of a metal-air battery, showing extremely excellent catalytic activity and stability, which can promote the commercial development of metal-air batteries.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为本发明实施例1-6中使用的PPS纤维的扫描电镜图；FIG1 is a scanning electron microscope image of the PPS fiber used in Examples 1-6 of the present invention;
图2为本发明实施例1中制得的HOPPS-1的扫描电镜图；FIG2 is a scanning electron microscope image of HOPPS-1 prepared in Example 1 of the present invention;
图3为本发明实施例1中的PPS、OPPS-1和HOPPS-1的傅里叶红外图谱；FIG3 is a Fourier transform infrared spectrum of PPS, OPPS-1 and HOPPS-1 in Example 1 of the present invention;
图4为本发明实施例1中制得的Ni@NS-HCF的扫描电镜图(a为600倍，b为5000倍)；FIG4 is a scanning electron microscope image of Ni@NS-HCF prepared in Example 1 of the present invention (a is 600 times, b is 5000 times);
图5为本发明实施例1中制得的Ni@NS-HCF的截面的透射电镜图(a为3000倍，b为100000倍，c为1000000倍)；FIG5 is a transmission electron microscope image of a cross section of Ni@NS-HCF prepared in Example 1 of the present invention (a is 3000 times, b is 100000 times, and c is 1000000 times);
图6为本发明实施例1中制得的Ni@NS-HCF的XRD图谱；FIG6 is an XRD pattern of Ni@NS-HCF prepared in Example 1 of the present invention;
图7为本发明实施例1中制得的Ni@NS-HCF的Raman图谱；FIG7 is a Raman spectrum of Ni@NS-HCF prepared in Example 1 of the present invention;
图8为本发明实施例1中制得的Ni@NS-HCF的XPS图谱；FIG8 is an XPS spectrum of Ni@NS-HCF prepared in Example 1 of the present invention;
图9为本发明实施例1中制得的Ni@NS-HCF的氮气-吸脱附曲线图；FIG9 is a nitrogen adsorption-desorption curve of Ni@NS-HCF prepared in Example 1 of the present invention;
图10为本发明实施例1中制得的Ni@NS-HCF的孔径分布曲线图；FIG10 is a pore size distribution curve of Ni@NS-HCF prepared in Example 1 of the present invention;
图11为本发明实施例1中制得的Ni@NS-HCF在O2饱和的0.1M的KOH中的循环伏安曲线图；FIG11 is a cyclic voltammogram of Ni@NS-HCF prepared in Example 1 of the present invention in O2 -saturated 0.1 M KOH;
图12为本发明实施例1中制得的Ni@NS-HCF在O2饱和的0.1M的KOH中的线性扫描伏安曲线图；FIG12 is a linear sweep voltammetry curve of Ni@NS-HCF prepared in Example 1 of the present invention in O2 -saturated 0.1 M KOH;
图13为本发明实施例1中制得的Ni@NS-HCF的I-t稳定性测试结果图；FIG13 is a graph showing the I-t stability test results of Ni@NS-HCF prepared in Example 1 of the present invention;
图14为本发明对比例1中制得的NS-HCF的扫描电镜图(a为600倍，b为5000倍)；FIG14 is a scanning electron microscope image of the NS-HCF prepared in Comparative Example 1 of the present invention (a is 600 times, b is 5000 times);
图15为本发明对比例1中制得的NS-HCF的XRD图谱；FIG15 is an XRD pattern of NS-HCF prepared in Comparative Example 1 of the present invention;
图16为本发明对比例1中制得的NS-HCF的Raman图谱；FIG16 is a Raman spectrum of NS-HCF prepared in Comparative Example 1 of the present invention;
图17为本发明对比例1中制得的NS-HCF的XPS图谱；FIG17 is an XPS spectrum of NS-HCF prepared in Comparative Example 1 of the present invention;
图18为本发明对比例1中制得的NS-HCF的氮气-吸脱附曲线图；FIG18 is a nitrogen-adsorption-desorption curve of NS-HCF prepared in Comparative Example 1 of the present invention;
图19为本发明对比例1中制得的NS-HCF的孔径分布曲线图；FIG19 is a pore size distribution curve of NS-HCF prepared in Comparative Example 1 of the present invention;
图20为本发明对比例1中制得的NS-HCF在O2饱和的0.1M的KOH中的循环伏安曲线图；FIG20 is a cyclic voltammogram of NS-HCF prepared in Comparative Example 1 of the present invention in O2 -saturated 0.1 M KOH;
图21为本发明对比例1中制得的NS-HCF在O2饱和的0.1M的KOH中的线性扫描伏安曲线图；FIG21 is a linear sweep voltammetry curve of NS-HCF prepared in Comparative Example 1 of the present invention in O2 -saturated 0.1 M KOH;
图22为本发明对比例1中制得的NS-HCF的I-t稳定性测试结果图；FIG22 is a graph showing the I-t stability test results of the NS-HCF prepared in Comparative Example 1 of the present invention;
图23为本发明实施例2中制得的HOPPS-2的扫描电镜图；FIG23 is a scanning electron microscope image of HOPPS-2 prepared in Example 2 of the present invention;
图24为本发明实施例3中制得的HOPPS-3的扫描电镜图；FIG24 is a scanning electron microscope image of HOPPS-3 prepared in Example 3 of the present invention;
图25为本发明实施例4中制得的HOPPS-4的扫描电镜图；FIG25 is a scanning electron microscope image of HOPPS-4 prepared in Example 4 of the present invention;
图26为本发明实施例5中制得的HOPPS-5的扫描电镜图；FIG26 is a scanning electron microscope image of HOPPS-5 prepared in Example 5 of the present invention;
图27为本发明实施例6中制得的HOPPS-6的扫描电镜图。FIG27 is a scanning electron microscope image of HOPPS-6 prepared in Example 6 of the present invention.
具体实施方式Detailed ways
下面给出本发明的具体实施例。具体实施例仅用于进一步详细说明本发明，不限制本申请权利要求的保护范围。The specific embodiments of the present invention are given below. The specific embodiments are only used to further illustrate the present invention in detail and do not limit the protection scope of the claims of this application.
本发明提供了一种壁厚可控的聚苯硫醚基中空纤维的制备方法(简称方法)，其特征在于，该方法包括以下步骤：The present invention provides a method for preparing a polyphenylene sulfide-based hollow fiber with controllable wall thickness (hereinafter referred to as the method), characterized in that the method comprises the following steps:
步骤1、将去离子水、氧化剂与酸共混形成氧化处理溶液；Step 1, mixing deionized water, an oxidant and an acid to form an oxidation treatment solution;
优选地，步骤1中，氧化剂为过氧乙酸、双氧水、过甲酸、HClO、NaClO、过硫酸钠或过氧化苯甲酸(优选双氧水)。Preferably, in step 1, the oxidant is peracetic acid, hydrogen peroxide, performic acid, HClO, NaClO, sodium persulfate or benzoic acid peroxide (preferably hydrogen peroxide).
优选地，步骤1中，酸为硫酸、盐酸、硝酸、磷酸、杂多酸、甲酸、乙酸、苯甲酸、苯磺酸、三氟乙酸、酸性分子筛、固体超强酸或醋酸(优选盐酸)。Preferably, in step 1, the acid is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, heteropoly acid, formic acid, acetic acid, benzoic acid, benzenesulfonic acid, trifluoroacetic acid, acidic molecular sieve, solid super acid or acetic acid (preferably hydrochloric acid).
优选地，步骤1中，氧化剂的质量分数为20～70wt％(优选30wt％)，酸的质量分数为5～20wt％(优选10wt％)。Preferably, in step 1, the mass fraction of the oxidant is 20-70 wt% (preferably 30 wt%), and the mass fraction of the acid is 5-20 wt% (preferably 10 wt%).
优选地，步骤1中，氧化处理溶液的pH控制在3～9，其中碱性环境优选pH＝8，酸性环境优选pH＝5。Preferably, in step 1, the pH of the oxidation treatment solution is controlled at 3-9, wherein the alkaline environment preferably has a pH of 8 and the acidic environment preferably has a pH of 5.
步骤2、PPS纤维皮层的可控氧化：将PPS纤维均匀分散在氧化处理溶液中，然后在20～100℃(优选70℃)下氧化反应0.01～48h(优选1min)；取出后，冲洗至中性；干燥后，得到氧化程度可控的氧化PPS纤维(简称氧化PPS纤维，命名为OPPS)；Step 2, controlled oxidation of the PPS fiber cortex: the PPS fiber is uniformly dispersed in an oxidation treatment solution, and then oxidized at 20 to 100° C. (preferably 70° C.) for 0.01 to 48 hours (preferably 1 minute); after being taken out, it is rinsed to neutrality; after drying, an oxidized PPS fiber with a controllable oxidation degree (abbreviated as oxidized PPS fiber, named OPPS) is obtained;
优选地，步骤2中，PPS纤维与氧化处理溶液的质量体积比为5～20g:100ml。Preferably, in step 2, the mass volume ratio of the PPS fiber to the oxidation treatment solution is 5-20 g:100 ml.
优选地，步骤2中，PPS纤维是PPS短纤维、PPS长纤维、熔喷PPS纤维、超细PPS纤维、PPS膈膜或PPS针刺毡(优选PPS短纤维)。Preferably, in step 2, the PPS fibers are PPS short fibers, PPS long fibers, melt-blown PPS fibers, ultrafine PPS fibers, PPS diaphragms or PPS needle-punched felt (preferably PPS short fibers).
优选地，步骤2中，20～100℃为水浴加热、烘箱加热、真空加热、微波炉加热、油浴加热或酒精灯加热。干燥温度为0～200℃。Preferably, in step 2, 20-100°C is water bath heating, oven heating, vacuum heating, microwave heating, oil bath heating or alcohol lamp heating. The drying temperature is 0-200°C.
步骤3、氧化PPS纤维芯层的可控氧化溶出：将步骤2得到的氧化PPS纤维放入氧化性酸溶液中进行反应，直至不再产生棕红色气体并且在溶液中不再产生白色乳状物质；取出后，冲洗至中性；干燥后，得到壁厚可控的PPS基中空纤维(简称PPS基中空纤维，命名为HOPPS)。Step 3, controllable oxidative dissolution of the oxidized PPS fiber core layer: the oxidized PPS fiber obtained in step 2 is placed in an oxidizing acid solution for reaction until no brown-red gas is generated and no white milky substance is generated in the solution; after taking out, rinse to neutrality; after drying, a PPS-based hollow fiber with controllable wall thickness (referred to as PPS-based hollow fiber, named HOPPS) is obtained.
优选地，步骤3中，氧化性酸溶液为NMP、浓硝酸、浓硫酸或王水中的至少一种(优选浓硝酸、浓硫酸或王水，更优选浓硝酸)。Preferably, in step 3, the oxidizing acid solution is at least one of NMP, concentrated nitric acid, concentrated sulfuric acid or aqua regia (preferably concentrated nitric acid, concentrated sulfuric acid or aqua regia, more preferably concentrated nitric acid).
优选地，步骤3中，氧化性酸溶液的质量分数为40～80wt％(优选65wt％的浓硝酸)。Preferably, in step 3, the mass fraction of the oxidizing acid solution is 40-80 wt % (preferably 65 wt % concentrated nitric acid).
优选地，步骤3中，反应温度为20℃～100℃(优选70℃)，反应时间为1～48h(优选24h)。Preferably, in step 3, the reaction temperature is 20°C to 100°C (preferably 70°C), and the reaction time is 1 to 48 hours (preferably 24 hours).
本发明同时提供了一种所述方法制备得到的壁厚可控的聚苯硫醚基中空纤维。The invention also provides a polyphenylene sulfide-based hollow fiber with controllable wall thickness prepared by the method.
本发明同时提供了一种所述壁厚可控的聚苯硫醚基中空纤维的应用，其特征在于，将所述PPS基中空纤维浸渍在金属盐溶液中1～4h来吸附金属离子，取出后蒸干水分；再置于密闭加热环境中在500℃～1200℃(优选800～1000℃，更优选950℃)的氨气氛围中碳化0.5h～5h(优选2.5h)，得到金属、N、S共掺杂的中空纤维状碳基氧还原催化剂，用于锌-空气电池或氢燃料电池的氧还原催化剂(命名为Ni@NS-HCF)。The present invention also provides an application of the polyphenylene sulfide-based hollow fiber with controllable wall thickness, characterized in that the PPS-based hollow fiber is immersed in a metal salt solution for 1 to 4 hours to adsorb metal ions, and the water is evaporated after being taken out; then the fiber is placed in a closed heating environment and carbonized in an ammonia atmosphere at 500°C to 1200°C (preferably 800 to 1000°C, more preferably 950°C) for 0.5h to 5h (preferably 2.5h) to obtain a metal, N, and S co-doped hollow fiber-shaped carbon-based oxygen reduction catalyst, which is used as an oxygen reduction catalyst for zinc-air batteries or hydrogen fuel cells (named Ni@NS-HCF).
优选地，金属盐溶液为硝酸镍溶液、乙酸镍溶液、硝酸铁溶液、硫酸铁溶液、硫酸钴溶液或硫酸铜溶液(优选硝酸镍溶液)。Preferably, the metal salt solution is a nickel nitrate solution, a nickel acetate solution, a ferric nitrate solution, a ferric sulfate solution, a cobalt sulfate solution or a copper sulfate solution (preferably a nickel nitrate solution).
优选地，蒸干溶液中的水分是放入20℃～200℃(优选120℃)的环境中蒸干。Preferably, the water in the evaporated solution is evaporated in an environment of 20°C to 200°C (preferably 120°C).
实施例1Example 1
(1)将50ml去离子水、50ml双氧水与10ml盐酸共混形成氧化处理溶液；(1) 50 ml of deionized water, 50 ml of hydrogen peroxide and 10 ml of hydrochloric acid were mixed to form an oxidation treatment solution;
(2)将5g的PPS短纤维分散在氧化处理溶液中，然后在70℃反应1min；然后取出纤维，用去离子水冲洗至中性，再在70℃干燥2h，得到氧化PPS纤维(命名为OPPS-1)；(2) 5 g of PPS short fibers were dispersed in the oxidation treatment solution and then reacted at 70 °C for 1 min. The fibers were then taken out, rinsed with deionized water until neutral, and dried at 70 °C for 2 h to obtain oxidized PPS fibers (named OPPS-1).
(3)将步骤2得到的OPPS-1放入浓硝酸溶液中，在70℃下反应24h至不再产生棕红色气体并且在溶液中不再产生白色乳状物质；取出后，冲洗至中性；干燥后，得到壁厚可控的PPS基中空纤维(命名为HOPPS-1)。(3) The OPPS-1 obtained in step 2 is placed in a concentrated nitric acid solution and reacted at 70° C. for 24 h until no brown-red gas is generated and no white milky substance is generated in the solution; after being taken out, it is rinsed to neutrality; after drying, a PPS-based hollow fiber with controllable wall thickness (named HOPPS-1) is obtained.
由图1可以看出，PPS纤维是一种实心纤维，表面光滑平整，直径约为15μm。As can be seen from Figure 1, PPS fiber is a solid fiber with a smooth surface and a diameter of about 15 μm.
由图2可以看出，实施例1成功制备了具有中空结构的纤维，该中空纤维表面粗糙，直径约为15μm，壁厚约1μm，其直径与PPS纤维相一致。这说明OPPS-1纤维芯层的PPS成分被浓硝酸所溶解；而经过氧化处理的皮层结构可以在浓硝酸中保持结构不变，具有极强的耐酸性。As can be seen from Figure 2, Example 1 successfully prepared a fiber with a hollow structure, which has a rough surface, a diameter of about 15 μm, and a wall thickness of about 1 μm, and its diameter is consistent with that of the PPS fiber. This shows that the PPS component of the core layer of the OPPS-1 fiber is dissolved by concentrated nitric acid; while the oxidized cortical structure can maintain its structure unchanged in concentrated nitric acid and has extremely strong acid resistance.
表1为实施例1中PPS、OPPS-1和HOPPS-1纤维的元素分析结果。由表1可以看出，相对于PPS，经过氧化处理的OPPS-1中O元素的含量(16.66wt％)大幅提升，尤其是在溶解PPS芯层后得到的HOPPS-1中O元素的含量高达23.36wt％。同时，由图3可以看出，OPPS-1的皮层与HOPPS-1的表面成分高度一致，并且相对于PPS额外增加了S＝O与O＝S＝O的含O官能团，对应了表1的元素分析结果。Table 1 shows the elemental analysis results of PPS, OPPS-1 and HOPPS-1 fibers in Example 1. As can be seen from Table 1, the content of O element (16.66wt%) in OPPS-1 after oxidation treatment is greatly increased compared with PPS, especially the content of O element in HOPPS-1 obtained after dissolving the PPS core layer is as high as 23.36wt%. At the same time, it can be seen from Figure 3 that the surface composition of the skin of OPPS-1 is highly consistent with that of HOPPS-1, and the O-containing functional groups S=O and O=S=O are additionally added compared with PPS, which corresponds to the elemental analysis results in Table 1.
表1Table 1
应用：将步骤3得到的HOPPS-1浸渍在硝酸镍溶液中1h，取出后放入120℃烘箱中蒸干水分；再置于密闭加热环境(管式炉)中在氨气氛围下950℃碳化2.5h，得到Ni、N、S共掺杂的中空纤维状碳基氧还原催化剂(命名为Ni@NS-HCF)。Application: The HOPPS-1 obtained in step 3 was immersed in a nickel nitrate solution for 1 hour, taken out and placed in a 120°C oven to evaporate the water; then placed in a closed heating environment (tube furnace) and carbonized at 950°C for 2.5 hours under an ammonia atmosphere to obtain a Ni, N, and S co-doped hollow fiber carbon-based oxygen reduction catalyst (named Ni@NS-HCF).
由图4可以看出，实施例1所制备的Ni@NS-HCF与HOPPS-1的形貌高度相似，没有明显变化。As can be seen from Figure 4, the morphologies of Ni@NS-HCF prepared in Example 1 are highly similar to those of HOPPS-1, with no obvious changes.
由图5可以看出，在Ni@NS-HCF中空纤维的内外表面以及碳基体中弥散分布了金属纳米粒子，在图5c的高倍透射电镜下观察到金属颗粒上存在晶面间距为0.20nm的晶格条纹，与Ni的(111)晶面相一致。同时，在图6的XRD图谱中进一步证实了Ni的存在，这些弥散分布Ni金属纳米粒子将作为高效活性中心来提高催化剂的催化活性。As can be seen from Figure 5, metal nanoparticles are dispersed on the inner and outer surfaces of the Ni@NS-HCF hollow fiber and in the carbon matrix. Under the high-power transmission electron microscope in Figure 5c, lattice fringes with a crystal plane spacing of 0.20nm were observed on the metal particles, which is consistent with the (111) crystal plane of Ni. At the same time, the XRD spectrum in Figure 6 further confirms the existence of Ni. These dispersed Ni metal nanoparticles will serve as efficient active centers to improve the catalytic activity of the catalyst.
由图7可以看出，在1330cm-1和1580cm-1处显示了碳材料的典型D峰和G峰，其ID/IG值为1.12，证实了催化剂中存在大量的缺陷位点。As can be seen from Figure 7, the typical D peak and G peak of carbon materials are shown at 1330 cm-1 and 1580 cm-1 , and theID /IG value is 1.12, confirming the existence of a large number of defect sites in the catalyst.
由图8可以看出，C、N、O、S及Ni元素的存在，证实了Ni、N、S元素成功掺杂到了碳基体中。As can be seen from Figure 8, the presence of C, N, O, S and Ni elements confirms that Ni, N and S elements are successfully doped into the carbon matrix.
由图9可以看出，经计算，Ni@NS-HCF比表面积高达1321.439m2·g-1。并且通过图10的孔径分布曲线可以得知，Ni@NS-HCF主要以微孔形式存在，其孔体积为0.609cm3·g-1。As can be seen from Figure 9, the calculated specific surface area of Ni@NS-HCF is as high as 1321.439 m2 ·g-1 . And from the pore size distribution curve in Figure 10 , it can be seen that Ni@NS-HCF mainly exists in the form of micropores, and its pore volume is 0.609 cm3 ·g-1 .
由图11可以看出，在0.9V处出现一个明显的还原峰，证实了催化剂的催化活性。由图12可以看出，Ni@NS-HCF可以在1600的转速下达到0.86V的半波电位和5.5mA·cm-2的极限电流密度。循环伏安曲线及线性扫描伏安曲线结果充分说明Ni@NS-HCF表现了优异的氧还原催化性能。As can be seen from Figure 11, an obvious reduction peak appears at 0.9V, confirming the catalytic activity of the catalyst. As can be seen from Figure 12, Ni@NS-HCF can reach a half-wave potential of 0.86V and a limiting current density of 5.5mA·cm-2 at a rotation speed of 1600. The results of the cyclic voltammetry curve and the linear sweep voltammetry curve fully demonstrate that Ni@NS-HCF exhibits excellent oxygen reduction catalytic performance.
由图13可以看出，在经过30个小时的测试后，Ni@NS-HCF的电流密度仅仅衰减了15.28％，证明了其良好的稳定性。As can be seen from Figure 13, after 30 hours of testing, the current density of Ni@NS-HCF only decayed by 15.28%, demonstrating its good stability.
对比例1Comparative Example 1
应用：将实施例1得到的HOPPS-1置于密闭加热环境(管式炉)中在氨气氛围下950℃碳化2.5h，得到N、S共掺杂的中空纤维状碳基氧还原催化剂(命名为NS-HCF)。Application: The HOPPS-1 obtained in Example 1 was placed in a closed heating environment (tube furnace) and carbonized at 950° C. for 2.5 h under an ammonia atmosphere to obtain a N and S co-doped hollow fiber carbon-based oxygen reduction catalyst (named NS-HCF).
由图14可以看出，NS-CHF与HOPPS-1是一致的中空纤维形貌，碳化并不对其结构产生影响。As can be seen from Figure 14, NS-CHF and HOPPS-1 have consistent hollow fiber morphology, and carbonization does not affect their structure.
由图15可以看出，在23°和44°附近显示出2个宽峰，对应了典型石墨碳的(002)和(100)晶面。As can be seen from FIG15 , two broad peaks are shown near 23° and 44°, corresponding to the (002) and (100) crystal planes of typical graphitic carbon.
由图16可以看出，其ID/IG值为1.21，说明了催化剂存在缺陷的特征。As can be seen from Figure 16, itsID /IG value is 1.21, which shows that the catalyst has defects.
由图17可以看出，催化剂中存在C、N、O和S元素，说明N和S元素成功引入到了碳基体中。As can be seen from Figure 17, C, N, O and S elements exist in the catalyst, indicating that N and S elements are successfully introduced into the carbon matrix.
由图18可以看出，经计算，NS-HCF比表面积高达1642.382m2·g-1。由图19可以看出，催化剂中同时存在微孔和介孔结构，其孔体积高达0.952cm3·g-1。对比例1的比表面积和孔体积均大于实施例1的Ni@NS-HCF。As shown in Figure 18, the calculated specific surface area of NS-HCF is as high as 1642.382m2 ·g-1 . As shown in Figure 19, the catalyst has both micropores and mesopores, and its pore volume is as high as 0.952cm3 ·g-1 . The specific surface area and pore volume of Comparative Example 1 are greater than those of Ni@NS-HCF of Example 1.
由图20可以看出，在0.89V处观察到了一个微弱的还原峰，同时在图21的线性扫描伏安曲线中观察到0.82V的半波电位及3.6mA·cm-2的极限电流密度，这显示出NS-HCF的氧还原催化活性。此外，由图22证实了NS-HCF催化剂优异的稳定性。As can be seen from Figure 20, a weak reduction peak was observed at 0.89 V, and a half-wave potential of 0.82 V and a limiting current density of 3.6 mA cm-2 were observed in the linear sweep voltammetry curve of Figure 21, which shows the oxygen reduction catalytic activity of NS-HCF. In addition, Figure 22 confirms the excellent stability of the NS-HCF catalyst.
因此，与对比例1所制备的NS-HCF相比，实施例1所制备的Ni@NS-HCF在碱性电解液中表现出优异的氧还原催化性能，说明Ni的引入大幅提高了催化剂的氧还原性能。Therefore, compared with the NS-HCF prepared in Comparative Example 1, the Ni@NS-HCF prepared in Example 1 exhibits excellent oxygen reduction catalytic performance in alkaline electrolyte, indicating that the introduction of Ni greatly improves the oxygen reduction performance of the catalyst.
实施例2Example 2
(1)将50ml去离子水、50ml双氧水与10ml盐酸共混形成氧化处理溶液；(1) 50 ml of deionized water, 50 ml of hydrogen peroxide and 10 ml of hydrochloric acid were mixed to form an oxidation treatment solution;
(2)将5g的PPS短纤维分散在氧化处理溶液中，然后在70℃反应5min；然后取出纤维，用去离子水冲洗至中性，再在70℃干燥2h，得到氧化PPS纤维(命名为OPPS-2)；(2) 5 g of PPS short fibers were dispersed in the oxidation treatment solution and then reacted at 70 °C for 5 min. The fibers were then taken out, rinsed with deionized water until neutral, and dried at 70 °C for 2 h to obtain oxidized PPS fibers (named OPPS-2).
(3)将步骤2得到的OPPS-2放入浓硝酸溶液中，在70℃下反应24h至不再产生棕红色气体并且在溶液中不再产生白色乳状物质；取出后，冲洗至中性；干燥后，得到壁厚可控的PPS基中空纤维(命名为HOPPS-2)。(3) The OPPS-2 obtained in step 2 is placed in a concentrated nitric acid solution and reacted at 70° C. for 24 h until no brown-red gas is generated and no white milky substance is generated in the solution; after being taken out, it is rinsed to neutrality; after drying, a PPS-based hollow fiber with controllable wall thickness (named HOPPS-2) is obtained.
由图23可以看出，实施例2同样成功制备了具有中空结构的HOPPS纤维，HOPPS-2的壁厚约为2μm，说明随着步骤2的氧化处理时间的延长，氧化处理深度逐渐增加，同时在溶解芯层PPS后得到中空纤维的壁厚也在逐渐增加。而该中空纤维外壁的直径保持不变，约为15μm，说明本发明仅仅是调控了PPS纤维的皮层结构，不影响纤维直径。As can be seen from Figure 23, Example 2 also successfully prepared a HOPPS fiber with a hollow structure, and the wall thickness of HOPPS-2 was about 2 μm, indicating that as the oxidation treatment time in step 2 was extended, the oxidation treatment depth gradually increased, and the wall thickness of the hollow fiber obtained after dissolving the core layer PPS also gradually increased. The diameter of the outer wall of the hollow fiber remained unchanged, about 15 μm, indicating that the present invention only regulates the cortical structure of the PPS fiber and does not affect the fiber diameter.
实施例3Example 3
(1)将50ml去离子水、50ml双氧水与10ml盐酸共混形成氧化处理溶液；(1) 50 ml of deionized water, 50 ml of hydrogen peroxide and 10 ml of hydrochloric acid were mixed to form an oxidation treatment solution;
(2)将5g的PPS短纤维分散在氧化处理溶液中，然后在70℃反应20min；然后取出纤维，用去离子水冲洗至中性，再在70℃干燥2h，得到皮芯结构复合纤维(命名为OPPS-3)；(2) 5 g of PPS short fibers were dispersed in an oxidative treatment solution and then reacted at 70 °C for 20 min. The fibers were then taken out, rinsed with deionized water until neutral, and dried at 70 °C for 2 h to obtain a core-skin composite fiber (named OPPS-3).
(3)将步骤2得到的OPPS-3纤维放入浓硝酸溶液中，在70℃下反应24h至不再产生棕红色气体并且在溶液中不再产生白色乳状物质；取出后，冲洗至中性；干燥后，得到壁厚可控的PPS基中空纤维(命名为HOPPS-3)。(3) The OPPS-3 fiber obtained in step 2 is placed in a concentrated nitric acid solution and reacted at 70° C. for 24 h until no brown-red gas is generated and no white milky substance is generated in the solution; after being taken out, it is rinsed to neutrality; after drying, a PPS-based hollow fiber with controllable wall thickness (named HOPPS-3) is obtained.
由图24可以看出，实施例3所制备的HOPPS-3纤维的壁厚约为3.5μm，随着氧化处理时间的延长，氧化处理深度进一步增加，在溶解芯层PPS后得到中空纤维的壁厚也逐渐增加。As can be seen from Figure 24, the wall thickness of the HOPPS-3 fiber prepared in Example 3 is about 3.5 μm. As the oxidation treatment time increases, the oxidation treatment depth further increases, and the wall thickness of the hollow fiber obtained after dissolving the core layer PPS also gradually increases.
实施例4Example 4
(1)将50ml去离子水、50ml双氧水与10ml盐酸共混形成氧化处理溶液；(1) 50 ml of deionized water, 50 ml of hydrogen peroxide and 10 ml of hydrochloric acid were mixed to form an oxidation treatment solution;
(2)将5g的PPS短纤维分散在氧化处理溶液中，然后在70℃反应1h；然后取出纤维，用去离子水冲洗至中性，再在70℃干燥2h，得到皮芯结构复合纤维(命名为OPPS-4)；(2) 5 g of PPS short fibers were dispersed in an oxidative treatment solution and then reacted at 70 °C for 1 h. The fibers were then taken out, rinsed with deionized water until neutral, and dried at 70 °C for 2 h to obtain a core-skin composite fiber (named OPPS-4).
(3)将步骤2得到的OPPS-4纤维放入浓硝酸溶液中，在70℃下反应24h至不再产生棕红色气体并且在溶液中不再产生白色乳状物质；取出后，冲洗至中性；干燥后，得到壁厚可控的PPS基中空纤维(命名为HOPPS-4)。(3) The OPPS-4 fiber obtained in step 2 is placed in a concentrated nitric acid solution and reacted at 70° C. for 24 h until no brown-red gas is generated and no white milky substance is generated in the solution; after being taken out, it is rinsed to neutrality; after drying, a PPS-based hollow fiber with controllable wall thickness (named HOPPS-4) is obtained.
由图25可以看出，实施例4所制备的HOPPS-4纤维的壁厚约为4.7μm，随着氧化处理时间的延长，氧化处理深度进一步增加，在溶解芯层PPS后得到中空纤维的壁厚也逐渐增加，纤维壁厚明显大于HOPPS-1、HOPPS-2和HOPPS-3。As can be seen from Figure 25, the wall thickness of the HOPPS-4 fiber prepared in Example 4 is about 4.7 μm. As the oxidation treatment time increases, the oxidation treatment depth further increases, and the wall thickness of the hollow fiber obtained after dissolving the core layer PPS also gradually increases. The fiber wall thickness is significantly greater than that of HOPPS-1, HOPPS-2 and HOPPS-3.
实施例5Example 5
(1)将50ml去离子水、50ml双氧水与10ml盐酸共混形成氧化处理溶液；(1) 50 ml of deionized water, 50 ml of hydrogen peroxide and 10 ml of hydrochloric acid were mixed to form an oxidation treatment solution;
(2)将5g的PPS短纤维分散在氧化处理溶液中，然后在70℃反应4h；然后取出纤维，用去离子水冲洗至中性，再在70℃干燥2h，得到皮芯结构复合纤维(命名为OPPS-5)；(2) 5 g of PPS short fibers were dispersed in an oxidative treatment solution and then reacted at 70 °C for 4 h. The fibers were then taken out, rinsed with deionized water until neutral, and dried at 70 °C for 2 h to obtain a core-skin composite fiber (named OPPS-5).
(3)将步骤2得到的OPPS-5纤维放入浓硝酸溶液中，在70℃下反应24h至不再产生棕红色气体并且在溶液中不再产生白色乳状物质；取出后，冲洗至中性；干燥后，得到壁厚可控的PPS基中空纤维(命名为HOPPS-5)。(3) The OPPS-5 fiber obtained in step 2 is placed in a concentrated nitric acid solution and reacted at 70° C. for 24 h until no brown-red gas is generated and no white milky substance is generated in the solution; after being taken out, it is rinsed to neutrality; after drying, a PPS-based hollow fiber with controllable wall thickness (named HOPPS-5) is obtained.
由图26可以看出，实施例5所制备的HOPPS-5纤维的壁厚约为6μm，其壁厚明显大于HOPPS-1、HOPPS-2、HOPPS-3和HOPPS-4。As can be seen from FIG. 26 , the wall thickness of the HOPPS-5 fiber prepared in Example 5 is about 6 μm, which is significantly greater than that of HOPPS-1, HOPPS-2, HOPPS-3 and HOPPS-4.
实施例6Example 6
(1)将50ml去离子水、50ml双氧水与10ml盐酸共混形成氧化处理溶液；(1) 50 ml of deionized water, 50 ml of hydrogen peroxide and 10 ml of hydrochloric acid were mixed to form an oxidation treatment solution;
(2)将5g的PPS短纤维分散在氧化处理溶液中，然后在70℃反应10h；然后取出纤维，用去离子水冲洗至中性，再在70℃干燥2h，得到皮芯结构复合纤维(命名为OPPS-6)；(2) 5 g of PPS short fibers were dispersed in an oxidative treatment solution and then reacted at 70 °C for 10 h. The fibers were then taken out, rinsed with deionized water until neutral, and dried at 70 °C for 2 h to obtain a core-skin composite fiber (named OPPS-6).
(3)将步骤2得到的OPPS-5纤维放入浓硝酸溶液中，在70℃下反应24h至不再产生棕红色气体并且在溶液中不再产生白色乳状物质；取出后，冲洗至中性；干燥后，得到壁厚可控的PPS基中空纤维(命名为HOPPS-6)。(3) The OPPS-5 fiber obtained in step 2 is placed in a concentrated nitric acid solution and reacted at 70° C. for 24 h until no brown-red gas is generated and no white milky substance is generated in the solution; after being taken out, it is rinsed to neutrality; after drying, a PPS-based hollow fiber with controllable wall thickness (named HOPPS-6) is obtained.
由图27可以看出，实施例6所制备HOPPS-6纤维的壁厚约为7.2μm，纤维壁厚明显大于HOPPS-1、HOPPS-2、HOPPS-3、HOPPS-4和HOPPS-5。随着氧化处理时间的延长，氧化处理深度不断增加，而芯层的PPS比例越来越少，在溶解芯层PPS后得到中空纤维的直径只有一个很小的孔，孔直径约200nm。这说明随着步骤2的氧化处理时间的延长，PPS纤维由外向内逐渐被完全氧化。As can be seen from Figure 27, the wall thickness of the HOPPS-6 fiber prepared in Example 6 is about 7.2 μm, which is significantly greater than that of HOPPS-1, HOPPS-2, HOPPS-3, HOPPS-4 and HOPPS-5. As the oxidation treatment time increases, the oxidation treatment depth increases, while the proportion of PPS in the core layer decreases. After dissolving the core layer PPS, the diameter of the hollow fiber obtained has only a very small hole with a hole diameter of about 200 nm. This shows that as the oxidation treatment time of step 2 increases, the PPS fiber is gradually completely oxidized from the outside to the inside.
本发明未述及之处适用于现有技术。Any matters not described in the present invention are applicable to the prior art.
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| CN202211204278.1ACN115513473B (en) | 2022-09-29 | 2022-09-29 | A polyphenylene sulfide-based hollow fiber with controllable wall thickness and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103572398A (en)* | 2012-07-24 | 2014-02-12 | 上海杜为化纤有限公司 | Preparation method of microporous hollow polyphenylene sulfide monofilament for filtration |
| CN108905655A (en)* | 2018-07-06 | 2018-11-30 | 天津工业大学 | A kind of preparation method of micropore polyphenylene sulfide hollow-fibre membrane |
| CN113058618A (en)* | 2021-03-25 | 2021-07-02 | 福州大学 | In situ supported sulfur-doped graphene denitration and sulfur-resistant catalyst polyphenylene sulfide composite material and preparation method thereof |
| KR20210113780A (en)* | 2020-03-09 | 2021-09-17 | 도레이첨단소재 주식회사 | Spinning solution for flexible PPS porous hollow fiber having hydrophilicity, flexible PPS porous hollow fiber membrane having hydrophilicity and Manufacturing method thereof |
| CN113481626A (en)* | 2021-07-14 | 2021-10-08 | 天津工业大学 | Preparation method of polyphenylene sulfide sulfone ketone fiber |
| CN113818246A (en)* | 2021-09-08 | 2021-12-21 | 安徽元琛环保科技股份有限公司 | Preparation method of antioxidant PPS fiber |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5246647A (en)* | 1989-03-28 | 1993-09-21 | The Dow Chemical Company | Process of making microporous hollow fiber or film membrane of poly(phenylene sulfide) (PPS) |
| CN103572398A (en)* | 2012-07-24 | 2014-02-12 | 上海杜为化纤有限公司 | Preparation method of microporous hollow polyphenylene sulfide monofilament for filtration |
| CN108905655A (en)* | 2018-07-06 | 2018-11-30 | 天津工业大学 | A kind of preparation method of micropore polyphenylene sulfide hollow-fibre membrane |
| KR20210113780A (en)* | 2020-03-09 | 2021-09-17 | 도레이첨단소재 주식회사 | Spinning solution for flexible PPS porous hollow fiber having hydrophilicity, flexible PPS porous hollow fiber membrane having hydrophilicity and Manufacturing method thereof |
| CN113058618A (en)* | 2021-03-25 | 2021-07-02 | 福州大学 | In situ supported sulfur-doped graphene denitration and sulfur-resistant catalyst polyphenylene sulfide composite material and preparation method thereof |
| CN113481626A (en)* | 2021-07-14 | 2021-10-08 | 天津工业大学 | Preparation method of polyphenylene sulfide sulfone ketone fiber |
| CN113818246A (en)* | 2021-09-08 | 2021-12-21 | 安徽元琛环保科技股份有限公司 | Preparation method of antioxidant PPS fiber |
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| CN115513473A (en) | 2022-12-23 |
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