CN106944141B - 片状Co-MOF纳米材料的制备方法及其在电催化中的应用 - Google Patents
片状Co-MOF纳米材料的制备方法及其在电催化中的应用 Download PDFInfo
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
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Abstract
片状Co‑MOF纳米材料的制备方法及其在电催化中的应用,涉及电解水、燃料电池和金属‑空气电池等技术领域,本发明的片状Co‑MOF电极材料是由简单水热法制备而成,采用的原材料环保、成本低,工艺简单,易于操作控制,适于连续化大规模生产,制备过程绿色环保。经实验证实,这种Co‑MOF纳米材料具有片状结构,由于其高的比表面积、优良的电导率等优异性能,可用于电催化。
Description
技术领域
本发明涉及电解水、燃料电池和金属-空气电池等技术领域,特别是其电极材料的制备技术。
背景技术
化石燃料的过渡消耗及其所引起的环境污染问题,迫使着人们不断寻求清洁可再生新能源。因为通过电催化反应直接将化学能转换成电能,具有高转换效率、低噪声和低排放等优点。燃料电池和金属空气电池是目前很具有应用前景的新型能源装置。传统上使用金属氧化物(例如RuO2和IrO2)和贵金属(例如Pt)来加速析氧反应(OER)和氧还原反应(ORR),然而,这些贵金属基催化剂通常具有高成本,低选择性,差的稳定性以及对环境不利的影响。因此,开发廉价和高效的非贵重金属材料用于电催化,以代替昂贵的基于Ir和Ru的化合物,人们已经作出了巨大的努力。钴(Co)已经成为设计和制造坚固的最常见的非贵重元素之一和高效的OER催化剂。
金属有机骨架材料(Metal-organic frameworks, MOFs)是一种由金属离子和有机配体通过配位键组装的无机-有机杂化功能材料,是近十几年来发展最为迅速的一种新型多孔材料,具有三维的孔结构,一般以金属离子为连接点,有机配位体支撑构成空间3D延伸,系沸石和碳纳米管之外的又一类重要的新型多孔材料,在催化、储能和分离中都有广泛应用。相比与其他配体材料,因为大表面积,高孔隙率,低密度,可控结构,可调孔径,MOFs材料被认为是未来纳米领域中最有前景的材料之一。
近年来,MOFs及其衍生物因其独特结构和物理化学性质,在电化学能源转换中的应用备受关注。MOFs作为电催化剂具有以下几个显著特点:(i)具有高度有序多孔结构,孔径分布均一,比表面积大,有利于活性组分的分散,为电催化反应提供大量活性位点;(ii)孔径的可调控性,通过调整金属中心和有机配体可得到超微孔到介孔各种孔径的MOFs材料,有利于复杂多孔催化剂的制备;(iii)易功能化和修饰,有利于MOFs与其他功能性物质相结合,制备复合材料,改善MOFs本身的电催化性能;(iv)可采用几种不同金属制备MOFs,并保持原来的拓扑结构。
发明内容
针对以上现有技术和缺陷,本发明首先提出一种片状Co-MOF纳米材料的制备方法。
本发明包括以下步骤:
1)将二价钴盐溶于去离子水中,制得二价钴盐溶液;
将对苯二甲酸(C8H6O4)溶于二甲基甲酰胺(DMF)与乙醇(C2H5OH)的混合溶液中,制得对苯二甲酸的DMF/C2H5OH溶液;
2)将所述二价钴盐溶液与对苯二甲酸的DMF/C2H5OH溶液混合,再加入聚乙烯吡咯烷酮(PVP)进行水热反应,得到沉淀物;
3)将沉淀物以水和乙醇洗涤后干燥,即得片状Co-MOF纳米材料。
本发明的片状Co-MOF电极材料是由简单水热法制备而成,采用的原材料环保、成本低,工艺简单,易于操作控制,适于连续化大规模生产,制备过程绿色环保。
经实验证实,这种Co-MOF纳米材料具有片状结构,由于其高的比表面积、优良的电导率等优异性能,可用于电催化。
进一步地,本发明所述二价钴盐为Co(NO3)2•6H2O、CoSO4•H2O或Co(CH3COO)2•4H2O,经实验证明,由于这几种金属盐所带的酸根易脱去,更易得到所需的产物,因此优先采用这种金属盐。
为了取得产物形貌最佳且性能最优,所述二甲基甲酰胺(DMF)与乙醇(C2H5OH)的体积比为1∶1。
另外,本发明对苯二甲酸(C8H6O4)和二价钴盐的投料摩尔比为1∶2,此比例下Co-MOF的形貌和性能较好。
本发明所述水热反应的温度条件为110℃。经反复实验证明,在此水热温度下,能够合成生长良好、纯度较高的片状Co-MOF,是最佳的工艺条件。
进一步地,为了获得具有较好形貌的目标产物,聚乙烯吡咯烷酮(PVP)与二价钴盐的投料质量比为1∶1 。控制好PVP的量,PVP的量对Co-MOF的形貌有较大的影响。
本发明另一目的还提出采用以上方法制成的片状Co-MOF纳米材料在电催化中的应用。
超声条件下,把所述片状Co-MOF纳米材料溶解在Nafion水溶液中,然后修饰在玻碳电极上,得到修饰样品的玻碳电极。
该应用的特点及优点:
(1)Co-MOF纳米材料虽然其导电性较差,但其特殊的片状的纳米结构,大大提高了在氧析出反应(OER)等方面的电催化性能。
(2)利用电子传递,只需要通过很薄的膜层,电子就可以到达载体电极上。
(3)氧析出反应(OER)被认为是对环境友好和可再生的能源系统。
附图说明
附图1为本发明制备的片状Co-MOF电极材料的扫描电镜图(SEM)。
附图2为本发明制备的片状Co-MOF电极材料的透射电镜图(TEM)。
附图3为本发明制备的片状Co-MOF电极材料的X射线衍射图(XRD)。
附图4为本发明制备的片状Co-MOF电极材料的热重分析图(TG)。
附图5为本发明制备的片状Co-MOF电极材料的OER的循环伏安曲线图。
附图6为本发明制备的片状Co-MOF电极材料的OER的线性扫描曲线图。
具体实施方式
下面结合附图和具体实施方式用实例对本发明作进一步说明,但不限于此。
一、制备片状Co-MOF纳米材料:
将0.250 g钴盐{Co(NO3)2•6H2O、CoSO4•H2O或Co(CH3COO)2•4H2O}溶于20 mL去离子水中,得到混合溶液I。
将0.0714 g对苯二甲酸溶于由20mL二甲基甲酰胺(DMF)和20mL乙醇(C2H5OH)组成的混合液中,得混合溶液II。
将溶液I和II混合,再加入0.25 g聚乙烯吡咯烷酮(PVP)用于Co-MOF的垂直生长,在110℃条件下水热反应60小时,得到的橙色沉淀用去离子水和乙醇分别洗涤3次后干燥,即得到片状Co-MOF纳米材料。
二、片状Co-MOF纳米材料的特征:
对片状Co-MOF纳米材料进行SEM测试:图1为Co-MOF放大10000倍下的扫描电子显微镜照片,其显示典型的分层结晶结构,可以为扩散和储存电解质离子提供空腔。
对片状Co-MOF纳米材料进行TEM测试:图2为Co-MOF的透射电镜图,其表明样品为无明显孔隙的片状结构。
对片状Co-MOF纳米材料进行XRD测试:图3为Co-MOF的X射线衍射图,其峰可以和标准峰对上,从而表明所合成的样品为所需要的样品。
对片状Co-MOF纳米材料进行TG测试:图4为Co-MOF的热重分析图,Co-MOF的TG曲线显示在150-350℃范围内的轻微重量损失,对应于吸附在内表面上的痕量H2O分子,以及吸附在内表面的孔内的那些Co-MOF。C8H4O4 2-配体大约在410℃开始气化,C8H4O4 2-配体在540℃完全分解,然后将残余物质转化为Co3O4。
三、电催化电极的制备:
1、将直径为3 mm的玻碳电极分别用吸附了1 μm氧化铝悬浮液的砂纸和吸附了0.3μm氧化铝悬浮液的砂纸打磨抛光。
2、将打磨抛光好的玻碳电极依次放在去离子水中超声清洗1分钟后,在0.5M KCl+K3[Fe(CN)6]溶液中扫描循环伏安曲线,以测试电极是否磨好,最后取得洁净的玻碳电极,晾干以待用。
3、取6 mg步骤制备的片状Co-MOF纳米材料加入由800 mL H2O和200 mL Nafion混合组成的Nafion水溶液中,超声混合,制成混合溶液,随后将5 μL混合溶液采用涂覆的方法修饰在直径为3 mm的洁净的玻碳电极表面,自然晾干后即得片状Co-MOF电催化电极。
4、配置电解液:
以氢氧化钾作为电解液,其中,氢氧化钾浓度为1 mol/L。
5、检测电极的电催化性能:
将片状Co-MOF电催化电极放置在1 mol/L的KOH溶液中进行测定。
利用电化学工作站,将制备的待测电极在事先通入大约半小时氮气的电解质溶液中,在-0.9~0.4 V之间的电位下,扫描速率控制为0.1 V/s,先进行循环伏安扫描,然后在0.2~1.5 V之间的电位下,扫描速率控制为5 mV/s,进行线性伏安扫描,测试样品的电化学性能。
图5显示了样品Co-MOF修饰的电极在电位(相对于标准氢电极)为-0.4 V—1.4 V范围内显示无明显的氧化还原峰。
图6显示了样品Co-MOF修饰的电极在电位(相对于标准氢电极)为1.2 V—1.75 V在1 mol/L氢氧化钾电解质溶液中显示出良好的OER电催化性能,在电流密度为10 mA cm-2时对应的电压为1.5V。
Claims (4)
1.片状Co-MOF纳米材料的制备方法,其特征在于包括以下步骤:
1)将二价钴盐溶于去离子水中,制得二价钴盐溶液;
将对苯二甲酸溶于二甲基甲酰胺与乙醇的混合溶液中,制得对苯二甲酸的DMF/C2H5OH溶液;
2)将所述二价钴盐溶液与对苯二甲酸的DMF/C2H5OH溶液混合,所述对苯二甲酸和二价钴盐的投料摩尔比为1∶2,再加入聚乙烯吡咯烷酮进行水热反应,所述聚乙烯吡咯烷酮与二价钴盐的投料质量比为1∶1,所述水热反应的温度条件为110℃,得到沉淀物;
3)将沉淀物以水和乙醇洗涤后干燥,即得片状Co-MOF纳米材料。
2.根据权利要求1所述的制备方法,其特征在于所述二价钴盐为Co(NO3)2•6H2O、CoSO4•H2O或Co(CH3COO)2•4H2O。
3.根据权利要求1所述的制备方法,其特征在于所述二甲基甲酰胺和乙醇的混合体积比为1∶1。
4.如权利要求1所述制备方法制得的片状Co-MOF纳米材料在电催化中的应用,其特征在于:超声条件下,把所述片状Co-MOF纳米材料溶解在Nafion水溶液中,然后修饰在玻碳电极之上,得到修饰样品的玻碳电极。
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