CN113322668A - 一种负载氮化碳的中间相沥青基碳纤维的制备方法和应用 - Google Patents
一种负载氮化碳的中间相沥青基碳纤维的制备方法和应用 Download PDFInfo
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Abstract
一种负载氮化碳的中间相沥青基碳纤维的制备方法和应用,属于新能源与环境工程技术领域。本发明通过自组装法聚合制备氮化碳将其负载于中间相沥青基碳纤维,该方法显著增加了MFC阳极的氮负载量,在兼顾碳刷阳极导电性能的前提下,制得了具有较好的生物相容性的且导电性能优异的氮化碳‑碳纤维阳极。使用氮化碳修饰阳极的MFC能显著提升输出电压及最大功率密度,MFC表观内阻降低,全方位提升了MFC电性能。本发明操作方法简单,效果明显,实现了绿色能源的回收利用。
Description
技术领域
本发明涉及一种负载氮化碳的中间相沥青基碳纤维生物电极的制备方法,具体地说是一种以三聚氰酸和三聚氰胺为原料,以中间相沥青基碳纤维为基体,通过自组装法聚合制备氮化碳将其负载于中间相沥青基碳纤维的方法,产品作为微生物燃料电池(MFC)阳极应用,属于新能源与环境工程技术领域。
背景技术
微生物燃料电池(Microbial fuel cell,MFC)是利用电化学活性微生物的胞外电子转移能力,实现能量转化的生物电化学装置。以常见的MFC为例,在阳极室,微生物(尤其是附着在电极表面上的微生物)对有机物进行厌氧氧化并降解,产生H+、电子和CO2;微生物细胞内的电子通过一系列的呼吸酶传递给细胞外的某些蛋白质(如C型胞外细胞色素),在通过不同的胞外电子传递方式传递到阳极表面;电子由外电路传递到阴极,H+跨过质子交换膜传递到阴极;在阴极表面,电子、H+和O2发生还原反应,完成整个氧化还原过程。
对MFC的阳极进行氮掺杂处理可以提高电池的电荷转移效率,提高生物相容性,因此阳极的氮掺杂改性一直被广泛关注。目前,氮掺杂碳的主要已知方式有三种:1)在合成氮掺杂碳的过程中,以含氮前驱体为氮源和碳源来获得氮掺杂碳。2)用含氮物质对碳材料进行表面化学改性,以达到氮掺杂的目的;3)用氮气或氨气加热碳源材料,得到含氮碳材料。改性碳材料的表面富含羧基和铵官能团,可促进细菌粘附和生物膜形成。
公开号为CN106207239A的中国专利提供了一种氮掺杂多孔碳的合成方法及其在微生物燃料电池阳极方面的应用,具体制备方法是以三聚氰胺为氮源,以柠檬酸钠为碳源,三聚氰胺和柠檬酸钠按一定比例混合研磨,在惰性气体Ar中800℃条件下锻烧5h,制备得到阳极材料以提高微生物燃料电池的电功率密度。该方法中材料制备工艺复杂,对设备要求较高,且三聚氰胺作为氮源制备的阳极氮含量并不理想。公开号为CN109244479B的中国专利提供了一种网状氮掺杂碳包覆二氧化锰碳布电极的制备方法及应用,以碳布为基体,采用三电极体系电化学沉积方法在碳布表面生长MnO2纳米网线,接着用三电极体系电化学沉积方法在MnO2纳米网线表面电沉积制备聚合吡咯,最后高温碳化,得到网状氮掺杂碳包覆二氧化锰修饰的碳布电极。该方法以碳布作为基体,碳布比表面积较小,不利于物生物大量附着,且材料制备工艺复杂,对设备要求高。
在含氮化合物中,g-C3N4具有密度低,化学稳定性高,生物相容性好和耐磨性强的优点。
发明内容
本发明的目的是提供一种负载氮化碳的中间相沥青基碳纤维生物电极的制备方法,该方法显著增加了MFC阳极的氮负载量,在兼顾碳刷阳极导电性能的前提下,制得了具有较好的生物相容性的且导电性能优异的氮化碳-碳纤维阳极。
本发明所提供的制备负载氮化碳的中间相沥青基碳纤维的方法,主要包括下述步骤:
步骤(1),将中间相沥青基碳纤维放置于硫酸与盐酸的混酸中酸洗24h;
步骤(2),各将三聚氰酸和三聚氰胺按照质量比1:1制备成混合溶液,将步骤(1)的碳纤维浸没在混合溶液中,75-90℃水浴加热1-5h,烘干;混合溶液中三聚氰酸的浓度为0.1-0.5g/L。
步骤(3),将步骤(2)中的碳纤维放入管式炉,在N2气氛下500-600℃烧制3-5h,制得负载氮化碳的中间相沥青基碳纤维。
根据上述方法将碳纤维制备成碳刷,将得到的碳刷作为生物电池的阳极。
得到的碳刷作为阳极,单室MFC,涂覆Pt/C的碳布作为MFC的阴极,反应室的阴极曝空气,提供O2作为电子受体,电池底物由污水和营养液按体积比1:1组成;外接电阻,电池运行室温控制在30±2℃。
具体的,本发明方法得到的碳刷作为阳极,单室MFC电池内容积为28mL,涂覆0.4mg/cm2的Pt/C碳布作为MFC的阴极(工作面积7cm2),反应室的阴极曝空气,提供O2作为电子受体,电池底物由污水和营养液按体积比1:1组成;外接电阻为1000Ω。
其中,所述营养液按每升去离子水计,包含如下组分:NaH2PO4·2H2O 3.32g、Na2HPO4·12H2O 10.36g、KCl 0.13g、NH4Cl 0.31g、CuSO4 0.125mg、ZnSO4 1.875mg、CaCl21.25mg、FeSO4·7H2O 1.25mg、NaCl 12.5mg、MgSO4·7H20 76.75mg、MnSO4 7mg、对氨基苯甲酸2.5mg、维生素B1 2.5mg、叶酸1mg、烟酸2.5mg、葡萄糖1g。
本发明进一步提出了上述方法制备得到的阳极再制备微生物燃料电池上的应用。
本发明具有以下优点:
(1)原料使用三聚氰酸、三聚氰胺,来源广,成本低;
(2)本方法工艺较为简单,不添加任何催化剂,无腐蚀性,对设备要求较低,适用于工业化生产;
(3)通过此方法制得的MFC阳极,具有含氮量高,生物亲和性强,导电性能优异的特点;
(4)生物电极可有效促进污染物去除和电子传递,达到产电及环境修复功能的可靠运行,即充分利用资源又环境友好。
附图说明
图1为本发明实施例1和对比例的SEM照片,空白中间相沥青基碳纤维碳刷电极(a1),负载生物膜后的空白中间相沥青基碳纤维碳刷电极(a2),本发明电极(b1),负载生物膜后的本发明电极(b2。
具体实施方式
下面结合附图和具体实施例的方式说明本发明,但不构成对本发明的限制。
实施例1:
本实施例使用单室构型的MFC反应器(28mL),阳极室的负载氮化碳中间相沥青基碳纤维碳刷阳极和碳布阴极(工作面积7cm2)外接有1000Ω电阻。电池底物由污水和营养液1:1构成,其中:
(1)MFC反应器的营养液包含(每升去离子水):NaH2PO4·2H2O 3.32g、Na2HPO4·12H2O 10.36g、KCl 0.13g、NH4Cl 0.31g、CuSO4 0.125mg、ZnSO4 1.875mg、CaCl2 1.25mg、FeSO4·7H2O 1.25mg、NaCl 12.5mg、MgSO4·7H20 76.75mg、MnSO4 7mg、对氨基苯甲酸2.5mg、维生素B1 2.5mg、叶酸1mg、烟酸2.5mg、葡萄糖1g。
(2)修饰中间相沥青基碳纤维碳刷阳极的方法为:步骤(1)将中间相沥青基碳纤维放置于硫酸与盐酸的混酸中酸洗24h,称取500mg纤维制成碳刷;步骤(2)各取50ml三聚氰酸(0.2g/L)和三聚氰胺(0.2g/L)溶液混合,将碳刷浸没在溶液中,80℃水浴加热4h,取出碳刷在80℃条件下烘干;步骤(3)将步骤(2)中的碳刷放入管式炉,在N2气氛下550℃烧制4h,制得负载氮化碳的中间相沥青基碳纤维阳极。
(3)将修饰电极置于电池室阳极,确保反应室内充满电池底液,气泡被排出,电池运行室温控制在30±2℃,使用蓝电电池测试系统监测外电阻两端的电压,记录为电池的输出电压,电池启动阶段,每隔24h更换接种液,连续数次监测到相同最大输出电压时,视为MFC启动完成。
经过氮化碳修饰的阳极电池反应器各个参数性能如表1所示。由表1可知,经过阳极修饰的最大稳定输出电压为610mV,相较于未经修饰的试验组,电压有所提升。经过过阳极修饰的MFC最大功率密度为800.8mW/m2,相较于试验组提升了19%,电化学性能有了明显改善。图1(b2)是经过氮化碳修饰的碳刷阳极SEM图,由图可知,经过氮化碳修饰的中间相沥青基碳纤维生物膜密集,相比于未经修饰的试验组富集了更多的产电菌,强化了电池性能。
对比例:
构建一套未经氮化碳修饰的MFC控制试验组。使用单室构型的MFC反应器(28mL),阳极室的负载氮化碳中间相沥青基碳纤维碳刷阳极和碳布阴极(工作面积7cm2)外接有1000Ω电阻。电池底物由污水和营养液1:1构成,其中:
(1)MFC反应器的营养液包含(每升去离子水):NaH2PO4·2H2O 3.32g、Na2HPO4·12H2O 10.36g、KCl 0.13g、NH4Cl 0.31g、CuSO4 0.125mg、ZnSO4 1.875mg、CaCl2 1.25mg、FeSO4·7H2O 1.25mg、NaCl 12.5mg、MgSO4·7H20 76.75mg、MnSO4 7mg、对氨基苯甲酸2.5mg、维生素B1 2.5mg、叶酸1mg、烟酸2.5mg、葡萄糖1g。
(2)制备酸处理中间相沥青基碳纤维碳刷阳极的方法为:将中间相沥青基碳纤维放置于硫酸与盐酸的混酸中酸洗24h,取出后水洗至Ph=7,在80℃条件下烘干。称取500mg纤维制成碳刷,制得酸处理的中间相沥青基碳纤维阳极。
(3)将酸处理碳刷电极置于电池室阳极,确保反应室内充满电池底液,气泡被排出,电池运行室温控制在30±2℃,使用蓝电电池测试系统监测外电阻两端的电压,记录为电池的输出电压,电池启动阶段,每隔24h更换接种液,连续数次监测到相同最大输出电压时,视为MFC启动完成。
由表1可知,酸处理阳极的最大稳定输出电压为460mV,最大功率密度为674mW/m2。图1(a2)是经过酸处理的碳刷阳极SEM图,由图可知,未经过氮化碳修饰的中间相沥青基碳纤维生物膜较为松散,产电菌数量较少,电池综合性能较低。
表1为微生物燃料电池系统的电性能数据。
以上已对本发明的较佳实施例进行了具体说明,但本发明并不限于所述实施例,熟悉本领域的技术人员在不违背本发明精神的前提下还可作出种种的等同的变型或替换,这些等同的变型或替换均包含在本申请权利要求所限定的范围内。
Claims (6)
1.一种负载氮化碳的中间相沥青基碳纤维的制备方法,其特征在于,主要包括下述步骤:
步骤(1),将中间相沥青基碳纤维放置于硫酸与盐酸的混酸中酸洗24h;
步骤(2),各将三聚氰酸和三聚氰胺按照质量比1:1制备成混合溶液,将步骤(1)的碳纤维浸没在混合溶液中,75-90℃水浴加热1-5h,烘干;
步骤(3),将步骤(2)中的碳纤维放入管式炉,在N2气氛下500-600℃烧制3-5h,制得负载氮化碳的中间相沥青基碳纤维。
2.按照权利要求1所述的一种负载氮化碳的中间相沥青基碳纤维的制备方法,其特征在于,步骤(2)混合溶液中三聚氰酸的浓度为0.1-0.5g/L。
3.按照权利要求1或2所述的方法制备得到的一种负载氮化碳的中间相沥青基碳纤维。
4.权利要求1或2所述的一种负载氮化碳的中间相沥青基碳纤维的制备方法的应用,根据上述方法将碳纤维制备成碳刷,将得到的碳刷作为生物电池的阳极。
5.按照权利要求4的应用,得到的碳刷作为阳极,单室MFC,涂覆Pt/C的碳布作为MFC的阴极,反应室的阴极曝空气,提供O2作为电子受体,电池底物由污水和营养液按体积比1:1组成;外接电阻,电池运行室温控制在30±2℃。
6.按照权利要求5的应用,所述营养液按每升去离子水计,包含如下组分:NaH2PO4·2H2O 3.32g、Na2HPO4·12H2O 10.36g、KCl 0.13g、NH4Cl 0.31g、CuSO40.125mg、ZnSO41.875mg、CaCl2 1.25mg、FeSO4·7H2O 1.25mg、NaCl 12.5mg、MgSO4·7H20 76.75mg、MnSO47mg、对氨基苯甲酸2.5mg、维生素B1 2.5mg、叶酸1mg、烟酸2.5mg、葡萄糖1g。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004218144A (ja) * | 2003-01-15 | 2004-08-05 | Hitachi Chem Co Ltd | 絶縁被覆カーボンファイバー、その製造方法及びそれを用いたコンポジット |
CN103165931A (zh) * | 2013-02-28 | 2013-06-19 | 哈尔滨工业大学 | 空气阴极微生物燃料电池处理餐厨垃圾回收电能的方法 |
CN106087116A (zh) * | 2016-06-26 | 2016-11-09 | 吴迪 | 一种木屑液化液改性中间相沥青基碳纤维的制备方法 |
CN106629655A (zh) * | 2017-01-05 | 2017-05-10 | 中国科学院新疆理化技术研究所 | 一种生物质基氮掺杂多孔碳的制备方法及应用 |
CN110255697A (zh) * | 2019-06-26 | 2019-09-20 | 合肥工业大学 | 一种氮掺杂碳材阳极的制备及其在催化湿式空气氧化中的应用 |
CN111744523A (zh) * | 2020-07-06 | 2020-10-09 | 中国石油大学(华东) | 一种氮掺杂碳纳米片、其制备方法及其应用 |
-
2021
- 2021-04-21 CN CN202110433805.5A patent/CN113322668A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004218144A (ja) * | 2003-01-15 | 2004-08-05 | Hitachi Chem Co Ltd | 絶縁被覆カーボンファイバー、その製造方法及びそれを用いたコンポジット |
CN103165931A (zh) * | 2013-02-28 | 2013-06-19 | 哈尔滨工业大学 | 空气阴极微生物燃料电池处理餐厨垃圾回收电能的方法 |
CN106087116A (zh) * | 2016-06-26 | 2016-11-09 | 吴迪 | 一种木屑液化液改性中间相沥青基碳纤维的制备方法 |
CN106629655A (zh) * | 2017-01-05 | 2017-05-10 | 中国科学院新疆理化技术研究所 | 一种生物质基氮掺杂多孔碳的制备方法及应用 |
CN110255697A (zh) * | 2019-06-26 | 2019-09-20 | 合肥工业大学 | 一种氮掺杂碳材阳极的制备及其在催化湿式空气氧化中的应用 |
CN111744523A (zh) * | 2020-07-06 | 2020-10-09 | 中国石油大学(华东) | 一种氮掺杂碳纳米片、其制备方法及其应用 |
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