CN113292733A - 一种导电金属有机框架纳米棒阵列复合材料及制备和应用 - Google Patents
一种导电金属有机框架纳米棒阵列复合材料及制备和应用 Download PDFInfo
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Abstract
本发明属于纳米材料技术领域,具体涉及一种导电金属有机框架纳米棒阵列复合材料及制备和应用。本发明制备方法包括以下步骤:(s1)将氢氧化物纳米棒阵列与导电有机配体通过水热反应自组装获得核壳结构纳米棒阵列;(s2)将核壳结构纳米棒阵列进行原位电化学还原,即可得到所述导电金属有机框架纳米棒阵列复合材料。本发明通过刻蚀、外延生长以及原位电还原方法合成导电金属有机框架纳米棒阵列复合材料,完成了导电金属有机框架的定向生长,金属氧化物的生成以及与金属有机框架的有效复合,由原位电化学还原法完成了导电金属有机框架与金属氧化物的复合,作为检测传感平台,具有广阔的应用前景。
Description
技术领域
本发明属于纳米材料技术领域,具体涉及一种导电金属有机框架纳米棒阵列复合材料及制备和应用。
背景技术
金属有机骨架(MOFs)是一种由金属离子和有机配体组成的晶体材料,具有大的表面积、可定制的成分和多孔结构,因而具有高的表面化学活性、大的化学吸附能力和高的表面-体积比,在分子识别、能源、气体分离等方面显示出巨大的潜力。尤其作为催化剂,金属有机框架材料具备一定的选择性和较好的催化活性。然而,绝大多数金属有机框架材料导电性较差,这严重限制了其在电化学传感上的应用。因此,一种十分可取的策略是开发导电金属有机框框架复合金属氧化物材料,提升材料导电性,将其作为高效的过氧化氢检测传感元。
近年来,类石墨烯的二维导电金属有机框架引起了科研人员的关注。这类二维金属有机框架材料是由三苯基配体分子和金属离子(如Cu2+、Ni2+、Co2+、Pt2+)配位形成的,具有类似石墨烯的六边形拓扑结构层,其导电性优异。尤其是该类晶体材料具备高孔隙率和均匀分布的金属活性位点,可以直接用作电催化剂,但难点是目前常规方法无法可控合成导电金属有机框架/金属氧化物的复合材料。
CN112300402A公开了一种二维导电金属有机框架电磁波吸收剂的制备方法,具体公开了以氧化亚铜和4-羟基苯硫酚为原料通过溶剂热回流法制备二维导电金属有机杂化层状配合物Cu(SPhOH),将制备的Cu(SPhOH)粉末与切片石蜡在超声加热分散,通过模压得到结构件。该技术方案提供了一种导电金属有机框架/金属氧化物,制备得到的产品能够作为电磁波吸收剂,但不具有催化能力。
CN112376080A公开了一种基于三环喹唑啉的二维导电金属有机框架材料及制备方法,具体公开了将2,3,7,8,12,13-六羟基三环喹唑啉与二价金属离子M2+溶于溶剂中,反应得到一种基于三环喹唑啉的二维导电金属有机框架材料M3(HHTQ)2(M=Cu,Ni,Co,Mn,Fe),具有式II所示结构。该技术方案合成步骤简单,所需条件温和,获得的是具有蜂窝状孔道的二维片层结构,具有高电导率,高结晶性,高稳定性等优势,但是导电金属有机框架材料和金属离子的结合力不够强,导电金属有机框架材料上的催化位点也不够多,催化能力还存在改进空间。
综上所述,现有技术仍缺乏一种催化效率高催化能力强的金属有机框架复合材料。
发明内容
针对现有技术的以上缺陷,本发明提供了一种导电金属有机框架纳米棒阵列复合材料的制备方法,通过刻蚀、外延生长以及原位电还原方法合成导电金属有机框架纳米棒阵列复合材料,由原位电化学还原法完成了导电金属有机框架与金属氧化物的复合,由此解决了金属有机框架材料导电性差,难以与金属氧化物复合,电催化性能不理想等问题。本发明的详细技术方案如下所述。
为实现上述目的,按照本发明的一个方面,提供了一种导电金属有机框架纳米棒阵列复合材料的制备方法,其特征在于,包括以下步骤:
(s1)将氢氧化物纳米棒阵列与导电有机配体通过水热反应自组装获得核壳结构纳米棒阵列;
(s2)将核壳结构纳米棒阵列进行原位电化学还原,即可得到所述导电金属有机框架纳米棒阵列复合材料。
作为优选,步骤(s1)中所述导电有机配体包括2,3,6,7,10,11-六羟基三苯、六氨基三亚苯和六亚氨基苯中的任意一种。
作为优选,所述导电有机配体的浓度为0.006mol/L-0.01mol/L,所述导电有机配体的溶剂为甲醇或乙醇。
作为优选,所述水热反应的时间为12h-24h,温度为60℃-90℃。
作为优选,步骤(s2)中所述电化学还原的电还原电压为(-0.8)V-(-0.3)V,电还原时间为1h-3h,优选的,步骤(s2)中电解质为PBS溶液或KHCO3溶液。
作为优选,所述氢氧化物纳米棒阵列是将泡沫金属进行刻蚀制备而成,优选的,所述泡沫金属为金属铜。
作为优选,所述氢氧化物纳米棒阵列是将泡沫金属进行刻蚀,然后与第二金属盐进行离子交换;优选的,所述泡沫金属为金属铜,所述第二金属为镍、钴、锰和铁中的任意一种。
作为优选,将泡沫金属刻蚀前进行了预处理,所述预处理为使用醇和酸的混合溶液超声清洗,优选的,所述醇为乙醇、丙醇和异丙醇中的至少一种;所述酸为盐酸、硫酸和硝酸中的至少一种;所述超声清洗的时间为10-30min。
按照本发明的另一方面,提供了一种导电金属有机框架纳米棒阵列复合材料,根据前面所述的制备方法制备而成。
按照本发明的另一方面,提供了一种所述的导电金属有机框架纳米棒阵列复合材料在催化剂领域或传感器领域中的应用。
本发明的有益效果有:
(1)本发明通过刻蚀、外延生长以及原位电还原方法合成导电金属有机框架纳米棒阵列复合材料,创造性地完成了导电金属有机框架的定向生长,金属氧化物的生成以及与金属有机框架的有效复合,由原位电化学还原法完成了导电金属有机框架与金属氧化物的复合,由此解决了金属有机框架材料导电性差,难以与金属氧化物复合,电催化性能不理想等问题。
(2)本发明制备获得的纳米棒阵列复合材料,能拥有预先设计的三维分层定向结构,具有较大的比表面积,不仅能够暴露大量的活性位点,而且可以有效地阻止纳米粒子的聚集,其独特的组装结构为优化电极性能提供了新的视角。
(3)本发明制备获得的纳米棒阵列复合材料催化活性位点分散,能提高活性位点的利用率,具有优异的电催化H2O2传感性能,灵敏度极高(8150.6μA mM-1),线性范围宽(0.1μM-5mM),检出限低(0.05μM),选择性良好,可以作为检测传感平台,具有广阔的应用前景。
附图说明
图1是实施例1制备的产物扫描电镜(SEM)图,其中,图1中的A和图1中的B分别为放大5千倍和1万倍的表面沉积Cu(OH)2纳米棒阵列的泡沫铜的平面扫描电镜(SEM)图,图1中的C和图1中的D分别为放大1万倍和5万倍的Cu2O/CuHHTP核壳结构纳米棒阵列,图1中的E和图1中的F分别为放大1万倍和5万倍的Cu2O颗粒镶嵌的Cu2O/CuHHTP/Cu2O NP纳米棒阵列。
图2是实施例1中的Cu2O/CuHHTP/Cu2O NP纳米棒阵列复合材料的X射线衍射谱图(XRD),纵坐标为峰强度,横坐标为两倍衍射角。
图3是实施例1制备的Cu2O/CuHHTP/Cu2O NP纳米棒阵列复合材料作为电极在PBS(pH=7.4)缓冲溶液中对不同浓度的过氧化氢的计时电流响应曲线图。
图4是由实施例1制备的Cu2O/CuHHTP/Cu2O NP纳米棒阵列复合材料作为电极在PBS(pH=7.4)缓冲溶液中对不同浓度的过氧化氢的计时电流响应曲线图所得到的线性范围拟合图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1
制备铜基有机框架纳米复合材料Cu2O/CuHHTP/Cu2O NP,包括以下步骤:
(1)使用乙醇、3mol/L的盐酸和去离子水超声清洗泡沫铜,超声时间为10min;
(2)将步骤(1)中得到的泡沫铜作为支撑衬底置于2.5mol/L NaOH和0.2mol/L(NH4)2S2O8的混合溶液中化学氧化30min得到泡沫铜支撑的Cu(OH)2纳米棒阵列,如图1中的A和图1中的B所示;
(3)再将步骤(2)中得到的的泡沫铜/氢氧化铜浸泡于HHTP的甲醇溶液(HHTP浓度为0.006mol/L)中水热12h,生成Cu2O/CuHHTP核壳结构纳米棒阵列,如图1中的C和图1中的D所示;
(4)将步骤(3)中生成的泡沫铜/Cu2O/CuHHTP核壳结构纳米棒阵列与0.1M PBS(ph=7.4)溶液中于-0.6V下电还原2h得到Cu2O颗粒镶嵌的Cu2O/CuHHTP/Cu2O NP纳米棒阵列,如图1中的E和图1中的F所示。
将步骤(2)、步骤(3)和步骤(4)制备的产物进行扫描电镜测试,得到图1所示的结果,其中,图1中的A和图1中的B分别为放大5千倍和1万倍的表面沉积Cu(OH)2纳米棒阵列的泡沫铜的平面扫描电镜(SEM)图,图1中的C和图1中的D分别为放大1万倍和5万倍的Cu2O/CuHHTP核壳结构纳米棒阵列,图1中的E和图1中的F分别为放大1万倍和5万倍的Cu2O颗粒镶嵌的Cu2O/CuHHTP/Cu2O NP纳米棒阵列。
由图1可知,泡沫铜表面经过化学刻蚀后生长出均匀、致密的氢氧化铜纳米棒阵列,并且氢氧化铜纳米棒表面光滑平整。在与配体反应生成后,其表面生成了粗糙多孔的MOF层,经过电化学还原以后,MOF表面的粗造度明显减小,并且生成了均匀分布的Cu2O纳米颗粒。
图2为本实施例制备得到的Cu2O/CuHHTP/Cu2O NP纳米棒阵列复合材料的XRD谱图,可以看出,各样品分别有明显的的特征峰。
实施例2
本实施例与实施例1不同之处在于,步骤(3所用的导电金属有机框架配体不同,具体如下所述。
(1)使用乙醇、3mol/L的盐酸和去离子水超声清洗泡沫铜,超声时间为10min;
(2)将步骤(1)中得到的泡沫铜作为支撑衬底置于2.5mol/L NaOH和0.2mol/L(NH4)2S2O8的混合溶液中化学氧化30min得到泡沫铜支撑的Cu(OH)2纳米棒阵列;
(3)再将步骤(2)中得到的的泡沫铜/氢氧化铜浸泡于HITP的甲醇溶液(HITP浓度为0.006mol/L)中水热12h,生成Cu2O/CuHITP核壳结构纳米棒阵列;
(4)将步骤(3)中生成的泡沫铜/Cu2O/CuHITP核壳结构纳米棒阵列与0.1M PBS(ph=7.4)溶液中于-0.6V下电还原2h得到Cu2O颗粒镶嵌的Cu2O/CuHITP/Cu2O NP纳米棒阵列。
实施例3
本实施例与实施例1不同之处在于,电化学还原的电还原电压和电还原时间不同,具体如下所述。
(1)使用乙醇、3mol/L的盐酸和去离子水超声清洗泡沫铜,超声时间为10min;
(2)将步骤(1)中得到的泡沫铜作为支撑衬底置于2.5mol/L NaOH和0.2mol/L(NH4)2S2O8的混合溶液中化学氧化30min得到泡沫铜支撑的Cu(OH)2纳米棒阵列;
(3)再将步骤(2)中得到的的泡沫铜/氢氧化铜浸泡于HHTP的甲醇溶液(HHTP浓度为0.006mol/L)中水热3h,生成Cu2O/CuHHTP核壳结构纳米棒阵列;
(4)将步骤(3)中生成的泡沫铜/Cu2O/CuHHTP核壳结构纳米棒阵列与0.1M PBS(ph=7.4)溶液中于-0.8V下电还原1h得到Cu2O颗粒镶嵌的Cu2O/CuHHTP/Cu2O NP纳米棒阵列。
实施例4
本实施例与实施例1不同之处在于,步骤(4)电化学还原电解质不同,具体如下所述。
(1)使用乙醇、3mol/L的盐酸和去离子水超声清洗泡沫铜,超声时间为10min;
(2)将步骤(1)中得到的泡沫铜作为支撑衬底置于2.5mol/L NaOH和0.2mol/L(NH4)2S2O8的混合溶液中化学氧化2min得到泡沫铜支撑的Cu(OH)2纳米棒阵列;
(3)再将步骤(2)中得到的的泡沫铜/氢氧化铜浸泡于HHTP的甲醇溶液(HHTP浓度为0.006mol/L)中水热3h,生成Cu2O/CuHHTP核壳结构纳米棒阵列;
(4)将步骤(3)中生成的泡沫铜/Cu2O/CuHHTP核壳结构纳米棒阵列与0.1M KHCO3(ph=8)溶液中于-0.4V下电还原3h得到Cu2O颗粒镶嵌的Cu2O/CuHHTP/Cu2O NP纳米棒阵列。
实施例5
本实施例与实施例1不同之处在于,步骤(2)刻蚀反应时间不同,具体如下所述。
(1)使用乙醇、3mol/L的盐酸和去离子水超声清洗泡沫铜,超声时间为10min;
(2)将步骤(1)中得到的泡沫铜作为支撑衬底置于2.5mol/L NaOH和0.2mol/L(NH4)2S2O8的混合溶液中化学氧化2min得到泡沫铜支撑的Cu(OH)2纳米棒阵列;
(3)再将步骤(2)中得到的的泡沫铜/氢氧化铜浸泡于HHTP的甲醇溶液(HHTP浓度为0.006mol/L)中水热3h,生成Cu2O/CuHHTP核壳结构纳米棒阵列;
(4)将步骤(3)中生成的泡沫铜/Cu2O/CuHHTP核壳结构纳米棒阵列与0.1M PBS(ph=7.4)溶液中于-0.4V下电还原3h得到Cu2O颗粒镶嵌的Cu2O/CuHHTP/Cu2O NP纳米棒阵列。
实施例6
本实施例与实施例1不同之处在于,通过离子交换的方法使氢氧化铜纳米棒阵列转化为氢氧化钴纳米棒阵列,氢氧化钴纳米棒阵列再与配体反应生成CoO/CoHHTP纳米棒阵列,最后电还原生成CoO/CoHHTP/Co NP纳米棒阵列。
(1)使用乙醇、3mol/L的盐酸和去离子水超声清洗泡沫铜,超声时间为10min;
(2)将步骤(1)中得到的泡沫铜作为支撑衬底置于2.5mol/L NaOH和0.2mol/L(NH4)2S2O8的混合溶液中化学氧化30min得到泡沫铜支撑的Cu(OH)2纳米棒阵列;
(3)将1.36mg CoCl2·6H2O加入70毫升乙醇/水(3:4,v/v)混合溶剂形成悬浮液,然后加入40ml的Na2S2O3·5H2O(1.5M)溶液,连续搅拌20min后,将生长了氢氧化铜纳米棒阵列的泡沫铜浸入上述悬浮液中,室温浸泡1h。然后取出泡沫铜,用去离子水和乙醇反复洗涤,在80℃的真空中烘干,得到泡沫铜支撑的Co(OH)2纳米棒阵列;
(4)再将步骤(3)中得到的的泡沫铜/氢氧化钴浸泡于HHTP的甲醇溶液(HHTP浓度为0.006mol/L)中水热12h,生成CoO/CoHHTP核壳结构纳米棒阵列;
(5)将步骤(3)中生成的泡沫铜/CoO/CoHHTP核壳结构纳米棒阵列与0.1M PBS(ph=7.4)溶液中于-0.6V下电还原2h得到CoO颗粒镶嵌的CoO/CoHHTP/CoO NP纳米棒阵列。
实施例7
本实施例与实施例1不同之处在于,通过离子交换的方法使氢氧化铜纳米棒阵列转化为氢氧化镍纳米棒阵列,氢氧化镍纳米棒阵列再与配体反应生成NiO/NiHHTP纳米棒阵列,最后电还原生成NiO/NiHHTP/NiO NP纳米棒阵列。
(1)使用乙醇、3mol/L的盐酸和去离子水超声清洗泡沫铜,超声时间为10min;
(2)将步骤(1)中得到的泡沫铜作为支撑衬底置于2.5mol/L NaOH和0.2mol/L(NH4)2S2O8的混合溶液中化学氧化30min得到泡沫铜支撑的Cu(OH)2纳米棒阵列;
(3)将1.36mg NiCl2·6H2O加入70毫升乙醇/水(3:4,v/v)混合溶剂形成悬浮液,然后加入40ml的Na2S2O3·5H2O(1.5M)溶液,连续搅拌20min后,将生长了氢氧化铜纳米棒阵列的泡沫铜浸入上述悬浮液中,室温浸泡1h。然后取出泡沫铜,用去离子水和乙醇反复洗涤,在80℃的真空中烘干,得到泡沫铜支撑的Ni(OH)2纳米棒阵列。
(4)再将步骤(3)中得到的的泡沫铜/氢氧化镍浸泡于HHTP的甲醇溶液(HHTP浓度为0.006mol/L)中水热12h,生成NiO/NiHHTP核壳结构纳米棒阵列;
(5)将步骤(3)中生成的泡沫铜/NiO/NiHHTP核壳结构纳米棒阵列与0.1M PBS(ph=7.4)溶液中于-0.6V下电还原2h得到NiO颗粒镶嵌的NiO/NiHHTP/NiO NP纳米棒阵列。
应用实施例
实施例1制备的将泡沫铜支撑Cu2O/CuHHTP/Cu2O NP纳米棒阵列复合材料电极应用于过氧化氢电化学传感器,检测灵敏度和检测限。
构建三电极体系,工作电极为泡沫铜支撑Cu2O/CuHHTP/Cu2O NP纳米棒阵列复合材料电极,辅助电极为铂电极,参比银/氯化银电极,测试溶液为PBS缓冲溶液,测量其计时电流曲线。如图3所示,随着过氧化氢浓度的增加,电流逐渐增加,呈现阶梯上升;如图4所示,线性范围良好。
由图3和图4可以看出,以上结果表明看出泡沫铜支撑分Cu2O/CuHHTP/Cu2O NP纳米棒阵列复合材料电极应用于过氧化氢电化学传感器,电化学传感性能良好,电化学传感性能良好,线性范围为0.1μM-6.661mM,检测限为0.05μM。
本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种导电金属有机框架纳米棒阵列复合材料的制备方法,其特征在于,包括以下步骤:
(s1)将氢氧化物纳米棒阵列与导电有机配体通过水热反应自组装获得核壳结构纳米棒阵列;
(s2)将核壳结构纳米棒阵列进行原位电化学还原,即可得到所述导电金属有机框架纳米棒阵列复合材料。
2.根据权利要求1所述的制备方法,其特征在于,步骤(s1)中所述导电有机配体包括2,3,6,7,10,11-六羟基三苯、六氨基三亚苯和六亚氨基苯中的任意一种。
3.根据权利要求2所述的制备方法,其特征在于,所述导电有机配体的浓度为0.006mol/L-0.01mol/L,所述导电有机配体的溶剂为甲醇或乙醇。
4.根据权利要求2或3所述的制备方法,其特征在于,所述水热反应的时间为12h-24h,温度为60℃-90℃。
5.根据权利要求1或2或3所述的制备方法,其特征在于,步骤(s2)中所述电化学还原的电还原电压为(-0.8)V-(-0.3)V,电还原时间为1h-3h,优选的,步骤(s2)中电解质为PBS溶液或KHCO3溶液。
6.根据权利要求1所述的制备方法,其特征在于,所述氢氧化物纳米棒阵列是将泡沫金属进行刻蚀制备而成,优选的,所述泡沫金属为金属铜。
7.根据权利要求1所述的制备方法,其特征在于,所述氢氧化物纳米棒阵列是将泡沫金属进行刻蚀,然后与第二金属盐进行离子交换;优选的,所述泡沫金属为金属铜,所述第二金属为镍、钴、锰和铁中的任意一种。
8.根据权利要求6或7所述的制备方法,其特征在于,将泡沫金属刻蚀前进行了预处理,所述预处理为使用醇和酸的混合溶液超声清洗,优选的,所述醇为乙醇、丙醇和异丙醇中的至少一种;所述酸为盐酸、硫酸和硝酸中的至少一种;所述超声清洗的时间为10-30min。
9.一种导电金属有机框架纳米棒阵列复合材料,其特征在于,根据权利要求1-8任一项所述的制备方法制备而成。
10.根据权利要求9所述的导电金属有机框架纳米棒阵列复合材料在催化剂领域或传感器领域中的应用。
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