CN115215328B - 一种竹林状石墨烯管阵列及其制备方法和应用 - Google Patents
一种竹林状石墨烯管阵列及其制备方法和应用 Download PDFInfo
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- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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Abstract
本发明提供了一种竹林状石墨烯管阵列的制备方法，包括如下步骤：首先通过水热方法合成了第一前驱体A2Ti3O7(A＝Li、Na、K，Rb)；其次第一前驱体通过离子交换合成第二前驱体Ma+ xA1+ yTi3O7(M＝Fe、Co、Ni，Cu)；再通过化学气相层积的方法将具有催化活性的金属M原子被合成成纳米颗粒，进行下一步的石墨烯管生长。本发明还提供由如上所述的制备方法制备的竹林状石墨烯管阵列及其在柔性可穿戴电子装置中的应用。本发明通过简单的方法可以实现很好的具有催化活性的金属纳米颗粒的铆定，而且具有催化活性的金属纳米颗粒元素的选择具有多元性，具有很好的实用性，并且可以实现大批量的石墨烯生长，具备良好的潜力可以应用在大规模的商业生产中。
Description
技术领域
本发明属于碳材料技术领域，尤其涉及一种竹林状石墨烯管阵列及其制备方法和在柔性可穿戴电子装置中的应用。
背景技术
柔性可穿戴电子设备在人们日常生活中越来越重要，特别是利用可穿戴设备对于人体生理信号、体征参数等采集以进一步提高人体健康水平与运动状态识别。其中，碳纳米管作为一种典型的碳基材料，具有良好的导电性和稳定性，因此在可穿戴电子中得到了广泛的应用。然而，碳纳米管与石墨烯材料类似，碳原子间为pi-pi共轭连接，因而使得碳纳米管具有一定的刚性，受压弯曲状态下结构易于破坏，难以表现足够的弹性特征与结构稳定性。而通常杂原子的掺入能够部分改善成键状态，从而在一定程度上提高碳基材料的弹性特征。如，在石墨烯中掺杂一定的的氮原子，可以使得石墨烯材料能够成承受更多的应力和弯曲。此外，通过碳基单元的二次结构组装亦能显著改善力学性能。如石墨烯组装形成的石墨烯气凝胶结构能够承受近乎180°的反转而保持回弹性能，可以很好的优化长久疲劳测试给整个结构带来不可逆破坏的问题。
包括石墨烯、碳纳米管等碳基材料最主要的制备方法是以气体碳源为前驱体，通过化学气相层积表面离子还原以及进行生长。其中，催化剂的结构与及载体分散形式对碳基材料的形貌和力学特性具有重要影响作用。通过离子交换进行分散催化剂是一种容易实现且能耗较低的方式，寻找到合适的交换基底是关键。众所周知，钛酸钠(Na2Ti3O7)作为一类典型类层状材料，层间钠离子易脱出交换成其它金属离子，包括具有催化活性的铁、铜、镍、钴等元素均可与其进行离子交换，因此作为一种载体广泛应用于电催化、储能等领域。然而，其作为催化剂载体用于碳基材料的研发还尚未得到应用。
发明内容
针对上述问题，本发明的目的在于提供一种具有超弹特性的竹林状石墨烯管阵列及其制备方法，采用钛酸钠纳米线作为前驱体进行离子交换，交换的离子在还原性气氛以及受热的情况下能够实现均匀的析出，获得具有原子级别分散的催化剂，在气体碳源的条件下能够很好的实现石墨烯管的生长。
为实现上述目的，本发明采用如下技术方案：
第一个方面，本发明提供了一种竹林状石墨烯管阵列的制备方法，包括如下步骤：
步骤(1)，制备第一前驱体A2Ti3O7纳米线，其中A选自Li、Na、K和Rb中的至
少一种；
步骤(2)，通过离子交换方法将步骤(1)得到的第一前驱体A2Ti3O7纳米线中部分的A交换成具有催化活性的金属离子M，获得第二前驱体Ma+ xA1+ yTi3O7纳米线，其中，M选自Fe、Co、Ni和Cu中的至少一种，A选自Li、Na、K和Rb中的至少一种，ax+y＝2，a为2～4的整数；
步骤(3)，通过化学气相沉积的方法，将步骤(2)得到的第二前驱体Ma+ xA1+ yTi3O7纳米线中的金属原子M析出，形成金属纳米颗粒，然后通入气体碳源和辅助气氛，在一定温度下，所述金属纳米颗粒作为催化剂在作为载体的所述第二前驱体纳米线的表面上生长成石墨烯，获得竹林状石墨烯管阵列。
较佳地，步骤(1)的制备步骤包括：将钛基前驱体氧化钛与结构导向剂分散于金属氢氧化物溶液中，置于在耐高温高压密闭容器中，在150～200℃下反应1d～7d，静置，水和乙醇分别洗涤3次，烘箱干燥，得到所述第一前驱体A2Ti3O7纳米线。
较佳地，所述钛基前驱体氧化钛选自P25、锐钛矿氧化钛、金红石氧化钛、S掺杂TiO2粉末、TiO颗粒和Ti3O5颗粒中的至少一种，所述钛基前驱体氧化钛的粒径优选为50nm-500μm；所述结构导向剂选自乙二胺四乙酸EDTA、聚乙烯吡咯烷酮PVP和聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物PEO-PPO-PEO中的至少一种；所述金属氢氧化物选自Li、Na、K、Rb的氢氧化物中的至少一种，优选为NaOH；得到的所述第一前驱体A2Ti3O7纳米线的直径为10-500nm。
较佳地，步骤(2)中的制备步骤包括：将步骤(1)得到的所述第一前驱体A2Ti3O7纳米线置于盐水溶液中，进行搅拌处理，通过离子交换得到所述的第二前驱体Ma+ xA1+ yTi3O7纳米线。
较佳地，所述盐水溶液包括Fe、Co、Ni、Cu的硝酸盐、氯化盐、硫酸盐、乙酸盐、乙酰丙酮盐中的至少一种，盐离子摩尔比为M：A＝1：1～10：1。
较佳地，步骤(3)中的制备步骤包括：将步骤(2)得到的所述第二前驱体MxAyTi3O7纳米线置于坩埚内，放入气氛炉中升温，并通入气体碳源进行生长，得到长度为20-100μm的竹林状石墨烯管阵列。
较佳地，所述气体碳源选自甲烷、乙烯和乙炔中的至少一种，所述辅助气氛选自氨气、氢气、氩气和氮气中的至少一种；优选地，当所述气体碳源为乙烯气体时，气氛炉中升温后的的保温温度为800～850℃，升温速率为1-30℃，通入气流量比值为：乙烯：氢气：氨气：氩气/氮气＝(20-30)：15：10：200；当所述气体碳源为甲烷气体时，气氛炉中升温后的的保温温度为1000～1100℃，升温速率为1-10℃，通入气流量比值为：甲烷：氢气：氨气：氩气/氮气＝(40-50)：15：10：200。
第二个方面，本发明还提供一种由如上所述的制备方法制备的竹林状石墨烯管阵列。
第三个方面，本发明还提供一种如上所述的竹林状石墨烯管阵列在柔性可穿戴电子装置中的应用。
本发明提供的一种竹林状石墨烯管阵列的制备方法，以具有层状结构的钛酸盐A2Ti3O7(A＝Li、Na、K，Rb)纳米线为载体，通过一步离子交换，获得具有催化活性的MxAyTi3O7(M＝Fe、Co、Ni，Cu)纳米线。经由交换得到的MxAyTi3O7的晶体构型不变，形貌不变，具有催化活性的M呈现原子级分散。分散的具有催化活性的M离子在加热还原气氛的状态下能够析出均匀的金属纳米颗粒，碳源在具有催化活性的金属纳米颗粒的表面形成二维石墨烯纳米片，并进行管状组装，形成竹林状的一维管状石墨烯结构，且管壁由石墨烯纳米片紧密堆叠组装，保留有丰富的孔道结构。管状内部丰富的孔道结构在受压弯曲过程中能够有效释放应力，避免应力集中对于结构的破坏性，赋予管状石墨烯材料超弹特性和弯曲稳定性。
与现有技术相比，本发明具有如下有益效果：
本发明提供了一种竹林状石墨烯管阵列的制备方法。首先通过水热方法合成了第一前驱体A2Ti3O7(A＝Li、Na、K，Rb)，其中金属A所对应的价态为正一价。其次第一前驱体通过离子交换合成第二前驱体Ma+ xA1+ yTi3O7(M＝Fe、Co、Ni，Cu)，其中金属M所对应的价态为正二价、正三价或正四价。再通过化学气相层积的方法将具有催化活性的金属M原子被合成纳米颗粒，进行下一步的石墨烯管生长。其中制备的第一前驱体具备良好的纳米线状，第二前驱体在交换过程中完美的保留了第一前驱体的纳米线状结构，并且在水中交换部分A离子。分散的具有催化活性的M离子在加热还原气氛的状态下能够析出均匀的金属纳米颗粒，这个纳米颗粒可以作为催化剂在气体碳源中形成石墨烯，通过定向的一维组装成石墨烯管。本发明通过简单的方法可以实现很好的具有催化活性的金属纳米颗粒的铆定，而且具有催化活性的金属纳米颗粒元素的选择具有多元性，具有很好的实用性，并且可以实现大批量的石墨烯管生长，具备良好的潜力可以应用在大规模的商业生产中。
附图说明
图1为本发明实施例1中钛酸钠纳米线的SEM图和元素分布图，其中a)为钛酸钠纳米线的SEM图，b)为钛酸钠纳米线元素分布测试采样图，c)为Na元素分布图，d)为氧元素分布图，e)为Ti元素分布图；
图2为本发明实施例1中镍交换钛酸钠纳米线的SEM图和元素分布图，其中a)为镍交换钛酸钠纳米线的SEM图，b)为镍交换钛酸钠纳米线元素分布测试采样图，c)为Na元素分布图，d)为氧元素分布图，e)为Ti元素分布图，f)为镍元素图，g)为元素分布比例；
图3为本发明实施例1中钛酸钠纳米线和镍交换钛酸钠纳米线的XRD图；
图4为本发明实施例1中超弹性竹林状石墨烯管阵列的SEM图和TEM图，其中a)为竹林状石墨烯管阵列的SEM图，b)石墨烯管的TEM图，c)石墨烯管的高倍率TEM图；
图5为本发明实施例1中竹林状石墨烯管阵列的XRD(a)和Raman光谱图(b)；
图6为本发明实施例1竹林状石墨烯管的原位压缩性能测试。
具体实施方式
以下通过下述实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。
以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。
实施例1
Ni基催化石墨烯管的生长。(1)前体一钛酸钠纳米线的合成：称取1g P25，48g氢氧化钠，溶于120ml的去离子水溶液中，搅拌、超声分散后，在180℃下反应24h；抽滤，按照乙醇-水-水-乙醇的顺序洗涤，共计洗涤4次，烘箱干燥，得到钛酸钠纳米线。(2)前体二镍交换钛酸钠纳米线的合成：将上述得到的钛酸钠纳米线前驱体分散于50ml水溶液中，加入硝酸镍水溶液(摩尔比Na：Ni＝1:10)，反应12h；抽滤，按照乙醇-水-水-乙醇的顺序洗涤，共计洗涤4次，烘箱干燥，得到镍钛氧前体二。(3)石墨烯管制备：将上述得到的镍钛氧前驱体放置在坩埚上，放入管式炉中以5°/min的速度升温至850℃，通入乙烯：氢气：氨气：氩气/氮气＝20-30：15：10：200(体积比)，热处理2h得到石墨烯管。
通过对钛酸钠纳米线和镍交换钛酸钠纳米线的扫描电镜形貌观测可知，呈现出30-50nm的直径以及大约50μm长度的钛酸钠纳米线，并且经由交换得到的镍交换钛酸钠纳米线的形貌并未发生大的转变，如图1-2所示。对镍交换钛酸钠纳米线的元素分布图所示，镍元素遍布整个线上，具有良好的分散性。
粉末X射线衍射测试，证明镍钛酸钠纳米线结构具有类层状单斜结构P 21/m，离子交换完后的镍交换钛酸钠纳米线出现高角度偏移，证实了交换完后镍离子插入层间致使层间距减少，如图3所示。
通过对合成的石墨烯管进行扫描形貌以及透射电镜形貌的观测，得到的石墨烯管具有50-200nm的管径以及大约50μm的长度，如图4a-b所示。二维的石墨烯纳米片再进行二次3D管状组装，形成竹林状的一维管状石墨烯结构，如图4c所示(图4中，Outer Graphene为管外壁石墨烯层，Inner Graphene为管内壁石墨烯层，Bridging Graphene为连接内外壁的桥连石墨烯层)。
通过XRD和拉曼的峰，XRD出现大的碳峰，以及合成过程中得到的TiN的峰，可知得到了相应的石墨烯管结构，拉曼测试表明了很好的DG峰ID/IG＝0.74，具有大的2D峰证实其石墨化程度高，如图5所示。
原位力学测试：石墨烯管由一端固定住材料，另一端经由探针对石墨烯管进行力学测试。从扫描图中可知，石墨烯管可由探针进行弹性压缩实验。最大弯曲可以达到180°，近乎一半的压缩占比16μm(32μm总长)，如图6所示。说明本发明制备的竹林状石墨烯管阵列具有超弹特性。
实施例2
Fe基催化石墨烯管的生长。(1)前体一钠钛氧的合成：如上述例一所示。(2)前体二铁钛氧合成的合成：将上述得到的钠钛氧前驱体分散于50ml水溶液中，加入硝酸铁水溶液(摩尔比Na：Fe＝1:10)，反应12h；抽滤，按照乙醇-水-水-乙醇的顺序洗涤，共计洗涤4次，烘箱干燥，得到铁钛氧前体二。(3)石墨烯管制备：将上述得到的镍钛氧前驱体放置在坩埚上，放入管式炉中以5°/min的速度升温至850℃，通入乙烯：氢气：氨气：氩气/氮气＝20-30：15：10：200(体积比)，热处理2h得到石墨烯管。
实施例3
Co基催化石墨烯管的生长。((1)前体一钠钛氧的合成：如上述例一所示。(2)前体二钴钛氧合成的合成：将上述得到的钠钛氧前驱体分散于50ml水溶液中，加入硝酸钴水溶液(摩尔比Na：Co＝1:10)，反应12h；抽滤，按照乙醇-水-水-乙醇的顺序洗涤，共计洗涤4次，烘箱干燥，得到钴钛氧前体二。(3)石墨烯管制备：将上述得到的镍钛氧前驱体放置在坩埚上，放入管式炉中以5°/min的速度升温至850℃，通入乙烯：氢气：氨气：氩气/氮气＝20-30：15：10：200(体积比)，热处理2h得到石墨烯管。
实施例4
Cu基催化石墨烯管的生长。(1)前体一钠钛氧的合成：如上述例一所示。(2)前体二铜钛氧合成的合成：将上述得到的钠钛氧前驱体分散于50ml水溶液中，加入硝酸铜水溶液(摩尔比Na：Cu＝1:10)，反应12h；抽滤，按照乙醇-水-水-乙醇的顺序洗涤，共计洗涤4次，烘箱干燥，得到铜钛氧前体二。(3)石墨烯管制备：将上述得到的铜钛氧前驱体放置在坩埚上，放入管式炉中以5°/min的速度升温至850℃，通入乙烯：氢气：氨气：氩气/氮气＝20-30：15：10：200(体积比)，热处理2h得到石墨烯管。
本发明制备的竹林状石墨烯管阵列可应用在柔性可穿戴电子装置，如柔性电阻式力学传感器，可应用于皮肤表面的压力信号的检测，包括脉搏、呼吸、运动姿态等力学信息的精准测试。
最后有必要在此说明的是：以上实施例只用于对本发明的技术方案作进一步详细地说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容做出的一些非本质的改进和调整均属于本发明的保护范围。
Claims (5)
1.一种竹林状石墨烯管阵列的制备方法，其特征在于，包括如下步骤：
步骤（1），制备第一前驱体A2Ti3O7纳米线，其中A选自 Li、Na、K和Rb中的至少一种；
步骤（2），将步骤（1）得到的所述第一前驱体A2Ti3O7纳米线置于盐水溶液中，进行搅拌处理，通过离子交换方法将步骤（1）得到的第一前驱体A2Ti3O7纳米线中部分的A交换成具有催化活性的金属离子M，获得第二前驱体Ma+ xA1+ yTi3O7纳米线，其中，M选自Fe、Co、Ni和Cu中的至少一种，ax+y=2，a为2~4的整数；所述盐水溶液包括Fe、Co、Ni、Cu的硝酸盐、氯化盐、硫酸盐、乙酸盐、乙酰丙酮盐中的至少一种，盐离子摩尔比为M：A=1：1~10：1；
步骤（3），将步骤（2）得到的第二前驱体Ma+ xA1+ yTi3O7纳米线置于坩埚内，放入气氛炉中升温以将其中的金属原子M析出，形成金属纳米颗粒，然后通入气体碳源和辅助气氛，通过化学气相沉积的方法，在一定温度下，以所述金属纳米颗粒作为催化剂在作为载体的第二前驱体Ma+ xA1+ yTi3O7纳米线的表面上生长成石墨烯，获得竹林状石墨烯管阵列；所述气体碳源为乙烯或者甲烷，所述辅助气氛选自氨气、氢气、氩气和氮气中的至少一种；当所述气体碳源为乙烯气体时，气氛炉中升温后的保温温度为800~850℃，升温速率为1-30℃，通入气体的体积比为：乙烯：氢气：氨气：氩气/氮气=（20-30）：15：10：200；当所述气体碳源为甲烷气体时，气氛炉中升温后的的保温温度为1000~1100℃，升温速率为1-10℃，通入气体的体积比为：甲烷：氢气：氨气：氩气/氮气=（40-50）：15：10：200。
2.根据权利要求1所述的制备方法，其特征在于，步骤（1）的制备步骤包括：将钛基前驱体氧化钛与结构导向剂分散于金属氢氧化物溶液中，置于在耐高温高压密闭容器中，在150~200℃下反应1d~7d，静置，水和乙醇分别洗涤3次，烘箱干燥，得到所述第一前驱体A2Ti3O7纳米线。
3.根据权利要求2所述的制备方法，其特征在于，所述钛基前驱体氧化钛选自P25、锐钛矿氧化钛、金红石氧化钛、S掺杂TiO2粉末、TiO颗粒和Ti3O5颗粒中的至少一种，所述钛基前驱体氧化钛的粒径为50nm-500μm；所述结构导向剂选自乙二胺四乙酸EDTA、聚乙烯吡咯烷酮PVP和聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物PEO-PPO-PEO中的至少一种；所述金属氢氧化物选自Li、Na、K、Rb的氢氧化物中的至少一种；得到的所述第一前驱体A2Ti3O7纳米线的直径为10-500nm。
4.一种由权利要求1-3中任一项所述的制备方法制备的竹林状石墨烯管阵列。
5.一种如权利要求4所述的竹林状石墨烯管阵列在柔性可穿戴电子装置中的应用。
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