CN115478364A - 一种自支撑电纺碳纳米纤维复合膜的制备方法及应用 - Google Patents
一种自支撑电纺碳纳米纤维复合膜的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种自支撑电纺碳纳米纤维复合膜的制备方法及应用,将MOF材料与PAN纺丝液,通过静电纺丝、预氧化和碳化过程,原位制备得到复合膜,其具备丰富的孔隙结构、高催化活性以及微生物相容性,能有效促进MFC产电和污水处理效能。
Description
技术领域
本发明属于复合膜材料制备技术领域,特别涉及一种自支撑电纺碳纳米纤维复合膜的制备方法及应用。
背景技术
微生物燃料电池(MFC)是一种经济有效的污水处理及能源回收的体系,它可以通过微生物代谢作用将废水中化学能转化为电能。然而,MFC产电效能仍不尽如人意,其中反应器的结构、电极材料和电解质等因素都会影响MFC产电性能。MFC阳极作为产电菌附着以及汇集电流的重要场所,其性能极大影响了电极电催化以及细菌胞外电子传递(EET)速率,是决定MFC整体效能的关键因素之一。因此,开发具有高比面积、多孔结构、良好导电性和生物相容性的高性能阳极对于提高MFC的产电性能势在必行。
如今,研究人员已经探索了具有高导电性、多孔性和生物亲和性的先进阳极材料,以提高MFC的产电效能。金属基材料(如不锈钢网)经常用于MFC阳极,具有高电导率和电化学性能。然而,腐蚀和低耐久性在很大程度上限制了它们的应用。碳基材料,如碳布、碳刷、碳纸等,具有良好的机械性能、耐久性和生物亲和性,但其导电性和电化学催化性能并不理想。纳米材料(如碳纳米管、石墨烯、纳米金属复合材料等)修饰电极通常获得优异的电子转移和电催化能力,与传统电极相比,细菌粘附更多,电子转移阻力更低,EET速率更高。然而,它们往往需要借助导电介质(如炭黑)以及导电粘结剂(如Nafion)才能修饰到电极表面,这往往导致催化剂导电性能降低,同时还面临着纳米材料聚集导致的阳极孔隙率降低等问题。此外,导电粘结剂价格昂贵,进一步影响了材料的进一步应用。因此,开发具备自支撑、经济、多孔性、高催化和稳定性的阳极材料至关重要。
静电纺丝碳纳米纤维(CNF)具有许多独特的特性,如高比面积和分级孔隙率。CNF可以很容易地加工成3D结构并在电极上进行装饰,而无需像炭黑这样的导电填料。聚丙烯腈(PAN)是最广泛使用的CNF前体,因为它具有高碳含量、易于形成均匀的纳米纤维和良好的商业可行性。先前的一项研究表明,3D CNFs吸引了MFC阳极上的电活性生物膜形成,并实现了21A/m2的高电流密度。此外,蔡等人制造了一种用CNF和碳纳米管改性的高性能MFC阳极(最高功率密度1.7W/m3)。然而,目前这些研究都需要借助粘结剂将纳米材料修饰到电极表面,影响了纳米纤维本身的孔隙结构。这些稳定的孔隙结构对于阳极表面微生物和电极之间电子和底物传输效能十分关键,是保证阳极生物膜稳定性的关键。因此,制备无粘结剂自支撑PAN碳纳米纤维电极对于形成良好机械性能、稳定性以及丰富的内部孔隙结果十分重要。
金属有机骨架(MOF)主要是由过渡金属离子与有机配体通过自组装方式形成具备周期性网络结构的晶体多孔材料,近些年来在环境修复、催化和储能等方面的应用受到大量关注。与传统的多孔材料相比,MOFs的主要优点是通过调节金属种类和有机连接剂可以轻松实现催化性能、结构和孔隙度调控。常规的MOFs由有机连接基和金属中心构成,由于较差的载流子迁移率和低电导率严重地限制了它们的应用。将MOFs经过热转化合成碳或金属碳材料是提高其导电性的一种常用方法。MOFs碳化后获得多孔碳材料能有效提高材料活性位点和电荷传输路径。然而散乱的MOFs碳化颗粒间相互作用力和电导率弱,无法满足应用需求,将MOFs引入到一维碳纳米纤维表面,是提高其电子传输和催化效能的有效方式。同时,通过原位混纺或原位生长的方式将MOFs引入电纺纳米纤维中,无需添加额外粘合剂,保证了MOFs高效稳定的催化性能不受非活性粘合剂影响。MOFs的引入不仅可以进一步提高CNFs比表面积和催化性能,还能复合多种利于提高细菌EET效能的元素(例如Fe、N、S等),可用于制备基于CNFs的高性能MFC阳极材料。基于此,本专利通过调控PAN碳纳米纤维复合MOF材料制备条件,获得自支撑电纺碳纳米纤维复合电极,以期强化MFC产电和污水处理效能。
目前,许多研究围绕电纺碳纳米纤维修饰电极的研究已经展开,但是大都是将制备好的碳纳米纤维碾碎后进行电极修饰,无法保证纳米纤维之间的孔隙度。同时额外添加的昂贵的导电粘结剂一方面降低了材料的催化和导电性能,影响了碳纳米纤维的整体催化效能。碳纳米纤维在尺度上十分具有优势,然而单纯的碳材料的催化效能仍然不足,进一步提高其效能就需要考虑到纳米金属材料的加入。MOF具备高比表面积、可控的结构和催化性能等优势,对于强化电极材料催化性能有先天的优势。单独将MOF修饰到电极表面必然导致严重的材料聚集等问题,同时传统的MOF导电性差,需要通过碳化的过程提高其导电效能。目前已有研究学者将MOF通过热压、混纺以及原位生长等方式与电纺纳米纤维结合,但是对于MOF复合电纺碳纳米纤维的性能优化以及在MFC阳极中的应用很少。此外,自支撑电纺碳纳米纤维复合电极在MFC阳极上的应用也鲜有报道。
发明内容
本发明目的在于获得一种自支撑碳纳米纤维复合膜电极材料,使其具备丰富的孔隙结构、高催化活性以及微生物相容性,促进MFC产电和污水处理效能。
为解决上述技术问题,本发明提供如下技术方案:
一种自支撑电纺碳纳米纤维复合膜的制备方法,其特征在于包括以下步骤:
步骤S1:将2-氨基对苯二甲酸、FeCl3˙6H2O溶解于DMF中,之后将混合溶液置于反应釜中反应一段时间,将反应产物清洗并烘干,获得MOF材料;
步骤S2:将聚丙烯腈(PAN)按一定比例与N,N-二甲基甲酰胺(DMF)充分搅拌制备成纺丝液,将以上制备好的MOF材料按一定掺杂比例与PAN纺丝液混合,将混合物进行静电纺丝、预氧化处理,之后在保护气氛下碳化,制备得到自支撑电纺碳纳米纤维复合膜。
进一步的,还包括步骤S3:为了快速获得电化学性能更加优异、机械强度更高的电极材料,通过叠加碳纳米纤维复合膜,得到不同层数的碳纳米纤维复合膜。
进一步的,步骤S2中PAN在纺丝液中的占比为5-16wt%。
进一步的,步骤S2中MOF材料掺杂比例为1-4wt%。
进一步的,步骤S2中搅拌转速为100-1750rpm。
进一步的,步骤S3中叠加至少一层自支撑电纺纳米纤维复合膜。
进一步的,步骤S2中预氧化是在200-300℃下保温1-3h。
进一步的,步骤S2中碳化是在800-1000℃下保温1-3h。
将自支撑电纺纳米纤维复合膜用于微生物燃料电池电极材料,特别是用于制作阳极材料。
将使用自支撑电纺纳米纤维复合膜为电极材料的微生物燃料电池用于污水处理。
与现有技术相比,本发明技术方案的有益效果是:通过电纺法原位获得高性能自支撑碳纳米纤维复合膜,很好的规避了粘接剂的使用以及催化剂的聚合效应。并且通过优化搅拌转速、PAN含量、MOF掺杂量及最终PAN碳化膜层数,复合膜获得了更优的导电性、多孔性以及高催化活性,能显著强化MFC产电及污染物降解效能,利于工业大规模生产和推广使用。
附图说明
为了更清楚地说明本发明实施例中的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明实施例1中不同轴转速下获得的电纺PAN碳纳米纤维膜电化学阻抗谱。
图2为本发明实施例1中不同PAN投加量条件下表面形貌(放大倍数20,000倍),其中图2(A)为PAN添加量5wt%;图2(B)为PAN添加量8wt%;图2(C)为PAN添加量10wt%;图2(D)为PAN添加量12wt%;图2(E)为PAN添加量14wt%;图2(F)为PAN添加量16wt%。
图3为本发明实施例2中不同层数条件下不同MOF掺杂量碳纳米纤维复合电极循环伏安曲线图,其中图3(A)为纯PAN膜;图3(B)为掺杂0.1gMOF-PAN复合膜;图3(C)为掺杂0.2gMOF-PAN复合膜;图3(D)为掺杂0.3g MOF-PAN复合膜;图3(E)为掺杂0.4gMOF-PAN复合膜;图3(F)为两层PAN膜条件下不同MOF掺杂量碳纳米纤维复合电极驯化伏安曲线。
图4为制备完成的自支撑PAN碳纳米纤维复合电极。
图5为驯化完成后的不同阳极材料MFC功率密度曲线(A)以及COD去除率和库伦效率(B)。
图6为本发明制备流程图。
具体实施方式
为使本发明要解决的技术问题、技术方案和优点更加清楚,下面将结合附图及具体实施例进行详细描述。
实施例1
高强度取向纳米纤维的制备及PAN含量优化:
以12wt%PAN投加量为标准,将PAN与N,N-二甲基甲酰胺(DMF)充分混合制备成纺丝液(共10g),在常温条件下充分搅拌24h。将获得的纺丝液置于10mL纺丝注射器中,注射器与纺丝针头连接后安装在纺丝机中,针头距纺丝轴距离为10cm,纺丝过程中对针头施加-2.0kV的电压,纺丝轴电压为18kV,注射器推进速度设置为1mL/min,湿度保持在10%左右,温度保持在40℃。之后在不同轴转速条件下(100rpm、250rpm、500rpm、750rpm、1000rpm、1250rpm、1500rpm、1750rpm)进行静电纺丝,获得PAN纳米纤维膜后将膜切割成一定大小,在马弗炉中预氧化(升温速率1℃/min,250℃保持1h),最后在管式炉中碳化(Ar气氛围,升温速率2℃/min,900℃保持1h)获得相应的PAN碳纳米纤维。通过对比不同轴转速条件下碳纳米纤维的成膜状态和导电性能等参数,获得最优轴转速下的PAN碳纳米纤维膜。如图1所示,当轴转速达到1500rpm时电极的电阻最小,因此选定1500rpm为最优轴转速。
在1500rpm转速下,重复上述制备过程,对比不同PAN投加比例(5wt%、8wt%、10wt%、12wt%、14wt%、16wt%)条件下获得的PAN碳纳米纤维的直径、取向、机械强度以及导电性能等参数,获得最优的PAN投加比例。PAN纳米纤维形貌如图2所示,可以看出PAN纳米纤维在PAN投加量低于10wt%时纤维的直径不均匀,孔径分布差异较大,当PAN投加量大于10wt%时纤维呈现取向规律分布,但是投加量大于14wt%后纤维表面出现明显串珠。因此综合考虑形貌以及电化学性能,最终采用10wt%PAN的投加量为最优投加量。
实施例2
自支撑碳纳米纤维复合膜电极材料的制备:
首先将225mg 2-氨基对苯二甲酸、675mg FeCl3˙6H2O溶解于60mL DMF中,使其充分溶解。之后将混合溶液置于反应釜中110℃的条件下水热反应,反应时间设定为10小时、15小时、20小时和24小时,之后通过DMF、乙醇、水按顺序清洗之后,置于烘箱中烘干后获得MOF材料。经过扫描电子显微镜观察,发现当反应时间为20小时的时候,MOF的材料更加均匀,尺寸合适,杂质较少。
将以上制备好的MOF材料与10wt%PAN(10g)纺丝液混合,调节MOF的掺杂比例(MOF的掺杂量为0.1g(1wt%)、0.2g(2wt%)、0.3g(3wt%)和0.4g(4wt%)),之后进行以上最优条件下静电纺丝过程,然后在马弗炉中预氧化(升温速率1℃/min,250℃保持1h),最后在管式炉中碳化(Ar气氛围,升温速率2℃/min,900℃保持1h),获得不同MOF掺杂量的PAN纳米纤维。如图3F所示,PAN碳纳米纤维复合MOF后电化学性能显著提高,电化学性能呈现先升高后降低的整体趋势,其中当MOF掺杂量为0.3g(3wt%)时电化学性能最高。
通过叠加不同层数的碳纳米纤维复合膜(1层、2层和3层)条件下获得的多层PAN复合碳化膜。如图3中所示,不同MOF掺杂量PAN复合膜,在叠加不同层数时,电化学性能均呈现先升高后降低的整体趋势,其中层数为2层的时候,其电化学性能均为最优。图4展示了整体性能优化后的碳纳米纤维复合膜的形貌。
实施例3
MFC反应器构建与应用:
MFC阳极材料选用:根据以上几种优化策略后,考察双层PAN碳化膜,MOF掺杂比例为0.1g(1wt%)和0.3g(1wt%)的复合双层碳化膜在MFC阳极中的性能,探究不同MOF掺杂量对MFC产电及污水处理的影响。
MFC反应器的构建及驯化:采用双极室有机玻璃MFC反应器,阴极室和阳极室由质子交换膜分隔,单室反应器外尺寸为6×6×7cm,内部为圆柱形,单室有效容积为108mL。阴极采用2×2cm的碳布,以100mM的铁***与50mM的磷酸盐缓冲溶液(PBS,11.55g/LNa2HPO4·12H2O、2.77g/L NaH2PO4·2H2O)作为阴极液。阳极材料采用2×3cm的碳纳米纤维电极,阳极液成分为0.41g/L乙酸钠、50mM PBS、0.13g/L KCl、0.13g/L NH4Cl、维生素和矿质元素。MFC阳极液在驯化阶段换液的时候需要接种1mL污泥(污水处理厂二沉池污泥),驯化阶段以4天为一个周期,新的阳极液需要经过吹氮气除去溶液中的空气,保证阳极液厌氧状态。MFC外电路通过连接一个1kΩ的电阻,通过多通道数据采集***采集电阻两端电压,作为体系的输出电压。待MFC体系电压达到最高且稳定2个周期之后,说明MFC体系已经稳定。之后观察MFC输出电压变化,当电压低于0.05V时,更换阳极液和阴极液。
MFC产电及污水处理效能解析:在驯化完成后的稳定的MFC体系中,测体系中COD去除率,库伦效率等,检测MFC驯化完成后的电极及悬浮液电化学性能,借助电化学工作站测试循环伏安曲线、电化学阻抗谱和电流-时间曲线,评估电极表面和悬浮液中电子传递效能以及存在的电子传递中介体,比较不同体系EET速率,结合微生物蛋白测试、高通量测试以及宏基因组等微生物分子学手段,解析复合材料强化MFC产电效能的机制。如图5所示,当采用0.1gMOF复合的碳纳米纤维具有最优产电效能、COD去除效能和库伦效率,且产电量高达2286.9mW/m2,相较于传统的碳基电极(如碳布和碳毡)具有很大的提升,说明自支撑碳纳米纤维复合电极对于强化MFC产电及污水处理行之有效,并具有一定的应用前景。为清晰表示本发明整体过程,本发明制备流程如图6所示。
以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明所述原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种自支撑电纺碳纳米纤维复合膜的制备方法,其特征在于:包括以下步骤:
步骤S1:将2-氨基对苯二甲酸、FeCl3˙6H2O溶解于DMF中,之后将混合溶液置于反应釜中水热反应一段时间,将反应产物清洗并烘干,获得MOF材料;
步骤S2:将聚丙烯腈按一定比例与N,N-二甲基甲酰胺充分搅拌制备成纺丝液,将以上制备好的MOF材料按一定掺杂比例与所述纺丝液混合,将混合物进行静电纺丝、预氧化处理,之后在保护气氛下碳化,制备得到自支撑电纺碳纳米纤维复合膜。
2.根据权利要求1所述的方法,其特征在于:还包括步骤S3:叠加碳纳米纤维复合膜,得到不同层数的碳纳米纤维复合膜,优选叠加至少一层自支撑电纺纳米纤维复合膜。
3.根据权利要求1所述的方法,其特征在于:步骤S2中聚丙烯腈在纺丝液中的比例为5-16wt%。
4.根据权利要求1所述的方法,其特征在于:步骤S2中MOF材料掺杂比例为1-4wt%。
5.根据权利要求1所述的方法,其特征在于:步骤S2中搅拌转速为100-1750rpm。
6.根据权利要求1所述的方法,其特征在于:步骤S2中预氧化是在200-300℃下保温1-3h。
7.根据权利要求1所述的方法,其特征在于:步骤S2中碳化是在800-1000℃下保温1-3h。
8.权利要求1-8任一项所述方法制备得到的自支撑电纺纳米纤维复合膜。
9.权利要求8所述的自支撑电纺纳米纤维复合膜在制作微生物燃料电池阳极材料中的应用。
10.权利要求9所述的阳极材料在微生物燃料电池能源回收及处理污水中的应用。
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Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007050460A2 (en) * | 2005-10-25 | 2007-05-03 | Inorganic Specialists, Inc. | Carbon nanofiber paper and applications |
CN102576877A (zh) * | 2009-08-10 | 2012-07-11 | ***纪念研究院 | 石墨烯和金属氧化物材料的自组装多层纳米复合材料 |
US20130122391A1 (en) * | 2010-07-29 | 2013-05-16 | National University Corporation Gunma University | Electrode for use in a fuel cell |
KR20160083321A (ko) * | 2014-12-30 | 2016-07-12 | 현대자동차주식회사 | 다층구조형 고분자 전해질막 연료전지용 전극 및 이의 제조방법 |
CN105829593A (zh) * | 2013-12-27 | 2016-08-03 | 东丽株式会社 | 碳纤维无纺布、碳纤维无纺布的制造方法和碳纤维前体纤维无纺布 |
KR20190091615A (ko) * | 2018-01-29 | 2019-08-07 | 한국세라믹기술원 | Mfc용 압전세라믹 소자 |
EP3539644A1 (en) * | 2018-03-13 | 2019-09-18 | Gaznat SA | Graphene membrane filter for gas separation |
CN111081995A (zh) * | 2019-11-07 | 2020-04-28 | 东北大学 | 一种基于MOFs衍生金属氧化物碳纳米纤维电极材料的制备方法 |
CN111354929A (zh) * | 2019-12-30 | 2020-06-30 | 中国计量大学 | 一种多层核壳结构的碳纤维-二硫化锡电极材料的制备 |
CN113005568A (zh) * | 2021-02-24 | 2021-06-22 | 北京科技大学 | 一种PVP辅助ZIF生长制备多孔Co/C纳米纤维的方法 |
CN113054207A (zh) * | 2021-03-02 | 2021-06-29 | 北京科技大学 | 金属盐辅助快速生长金属有机骨架衍生物的制备方法 |
CN113178606A (zh) * | 2021-04-19 | 2021-07-27 | 中山大学 | 一种柔性可穿戴复合式能量收集器件及其制作方法与应用 |
CN114447291A (zh) * | 2021-12-22 | 2022-05-06 | 西安理工大学 | 自支撑三氟化铁-碳纳米纤维正极材料及其制备方法 |
US20220158157A1 (en) * | 2020-11-18 | 2022-05-19 | Hyundai Motor Company | Carbon-metal organic framework composite, manufacturing method thereof, and lithium air battery including the same |
CN115000343A (zh) * | 2022-05-30 | 2022-09-02 | 三峡大学 | 一种柔性双层自支撑电极的制备方法 |
-
2022
- 2022-09-26 CN CN202211173442.7A patent/CN115478364B/zh active Active
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007050460A2 (en) * | 2005-10-25 | 2007-05-03 | Inorganic Specialists, Inc. | Carbon nanofiber paper and applications |
CN102576877A (zh) * | 2009-08-10 | 2012-07-11 | ***纪念研究院 | 石墨烯和金属氧化物材料的自组装多层纳米复合材料 |
US20130122391A1 (en) * | 2010-07-29 | 2013-05-16 | National University Corporation Gunma University | Electrode for use in a fuel cell |
CN105829593A (zh) * | 2013-12-27 | 2016-08-03 | 东丽株式会社 | 碳纤维无纺布、碳纤维无纺布的制造方法和碳纤维前体纤维无纺布 |
KR20160083321A (ko) * | 2014-12-30 | 2016-07-12 | 현대자동차주식회사 | 다층구조형 고분자 전해질막 연료전지용 전극 및 이의 제조방법 |
KR20190091615A (ko) * | 2018-01-29 | 2019-08-07 | 한국세라믹기술원 | Mfc용 압전세라믹 소자 |
EP3539644A1 (en) * | 2018-03-13 | 2019-09-18 | Gaznat SA | Graphene membrane filter for gas separation |
CN111081995A (zh) * | 2019-11-07 | 2020-04-28 | 东北大学 | 一种基于MOFs衍生金属氧化物碳纳米纤维电极材料的制备方法 |
CN111354929A (zh) * | 2019-12-30 | 2020-06-30 | 中国计量大学 | 一种多层核壳结构的碳纤维-二硫化锡电极材料的制备 |
US20220158157A1 (en) * | 2020-11-18 | 2022-05-19 | Hyundai Motor Company | Carbon-metal organic framework composite, manufacturing method thereof, and lithium air battery including the same |
CN113005568A (zh) * | 2021-02-24 | 2021-06-22 | 北京科技大学 | 一种PVP辅助ZIF生长制备多孔Co/C纳米纤维的方法 |
CN113054207A (zh) * | 2021-03-02 | 2021-06-29 | 北京科技大学 | 金属盐辅助快速生长金属有机骨架衍生物的制备方法 |
CN113178606A (zh) * | 2021-04-19 | 2021-07-27 | 中山大学 | 一种柔性可穿戴复合式能量收集器件及其制作方法与应用 |
CN114447291A (zh) * | 2021-12-22 | 2022-05-06 | 西安理工大学 | 自支撑三氟化铁-碳纳米纤维正极材料及其制备方法 |
CN115000343A (zh) * | 2022-05-30 | 2022-09-02 | 三峡大学 | 一种柔性双层自支撑电极的制备方法 |
Non-Patent Citations (1)
Title |
---|
钟丽萍等: "阳极碳纸叠加层数对微生物燃料电池产电性能的影响", 化工新型材料, vol. 43, no. 3, pages 126 - 129 * |
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