CN110624558B - 一种四氧化三钴与氧化锡复合物纳米线的制备方法及用途 - Google Patents
一种四氧化三钴与氧化锡复合物纳米线的制备方法及用途 Download PDFInfo
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Abstract
本发明公开了一种四氧化三钴与氧化锡复合物纳米线的制备方法及用途，本发明以乙酸钴四水合物和四氯化锡五水合物为主要原料，加入适量的高分子(PVP)为粘合剂，在高电压条件下利用静电纺丝技术，制备静电纺丝产品，然后在马弗炉中，在空气氛围下，进行程序控制阶梯升温和高温烧结，得到一种Co3O4·SnO2复合物纳米线材料，该复合物纳米线作为催化氧化安息香的催化剂具有良好的催化性能，因而具有广阔的应用前景。在整个制备过程中，操作简单，绿色环保，设备投资少，适合批量生产。
Description
技术领域
本发明属于材料化学领域，具体涉及到一种四氧化三钴与氧化锡复合物纳米线的制备方法及用途。
背景技术
随着科学技术的不断发展，人类社会在信息、环境、能源、生物技术等领域的发展日新月异，对材料的性能要求也越来越高，单一的材料已经无法满足当前的需要，复合材料往往具有单一组分所不具有的特性，因此，发展性能好、科技含量高的新型复合材料有着重要的作用和意义。纳米材料由于具有小尺寸效应、量子效应、表面效应和宏观量子轨道效应等特殊效应引起了人们的广泛关注，纳米材料是指在三维空间中至少有一维处于纳米尺度范围或以纳米结构作为基本单元构成的材料，由于具有这些特性，纳米材料具有普通材料所不具备的特性，纳米材料可作为光学材料、电子材料、磁性材料以及高强度、高密度材料，在催化、生物医学、环保、工程材料等领域得到了广泛的应用。一维纳米材料合成方法主要包括相转移法、水热法、静电纺丝法、化学气相沉积法、气相蒸发法等方法，其中静电纺丝技术是制备连续纳米纤维最简单有效的方法，D.Li等人(Advance Materials,2004,16:1151-1170)综述了静电纺丝法的工作原理及各个因素对纳米纤维形貌的影响。静电纺丝装置主要包括纺丝前驱液，纺丝针头，高压电源，纺丝收集装置等部分。静电纺丝纤维形貌主要受以下几个因素的影响：系统参数(如聚合物的分子量，前驱体溶液的电导率、黏度、介电常数等)，操作参数(如针头的规格、电压、流速、喷丝头与纺丝收集装置之间的距离等)，环境参数(如湿度、温度等)，此外，纺丝纤维退火过程中的参数(如煅烧温度、氛围、升温速率等)对纳米纤维材料的结构、形貌和性能都有很大的影响。
过渡金属氧化物Co3O4是一种重要的磁性p型半导体，在锂离子电池、超级电容器、气体传感器和作为催化氧化剂等领域有广泛的应用，其制备方法有热分解法、化学喷雾热分解法、化学气相沉积法、静电纺丝法、溶胶-凝胶法等方法，由于Co3O4制备方法不同，形貌也大不相同，有纳米球、纳米立方体、纳米棒、纳米片、纳米纤维等形貌， Y,Ding等人(Materials Letters,2008,62:3410-3412)报道了Co3O4纳米纤维作为锂离子负极材料，经过40圈充放电循环后保持604mA h-1的容量。金属氧化物SnO2是一种n 型宽带隙半导体材料，其在催化、气敏器件、锂离子电池等方面具有广阔的应用，L,Li 等人(Electrochemistry Communications,2010,12:1383-1386)报道了SnO2纳米管作为锂离子电池负极材料，在180mA g-1电流密度下50圈充放电循环后容量还保持807mA h-1。然而单一组分材料在电池充放电过程中存在体积膨胀或循环性能差，催化氧化性能不够高稳定性不好等问题。
发明内容
本发明所要解决的技术问题是针对现有技术，利用静电纺丝技术与高温烧结技术相结合，提供一种四氧化三钴与氧化锡复合物纳米线的制备方法及用途。
本发明为解决上述技术问题所采取的技术方案为：一种四氧化三钴(Co3O4)与氧化锡(SnO2)复合物纳米线的制备方法，所述制备方法利用静电纺丝技术以乙酸钴·四水合物、四氯化锡·五水合物为主要原料，加入适量的高分子为粘合剂，磁力搅拌一段后得到澄清透明纺丝前驱液，利用静电纺丝技术在高电压条件下，制备静电纺丝产品，随后在马弗炉中空气氛围下进行烧结，得到一种Co3O4与SnO2复合物纳米线，具体包括以下步骤：
(1)在烧杯中加入一定量的乙酸钴四水合物(C4H6CoO4·4H2O)，加入适量的N,N-二甲基甲酰胺(DMF)搅拌1h，使乙酸钴四水合物完全溶解，再加入适量PVP(K-120，聚乙烯吡咯烷酮)、无水乙醇、冰醋酸和四氯化锡五水合物(SnCl4·5H2O)，搅拌12h，得到澄清透明的纺丝前驱液；
(2)将澄清透明的纺丝前驱液吸入注射器中，在13～18kV的电压，针头与接收器的距离为15～19cm，流率为0.8mL h-1，空气湿度为45％，温度为28～35℃条件下进行静电纺丝，得纺丝产品并在100℃空气氛围下干燥3h；
(3)将干燥后的静电纺丝产物转移到马弗炉中，在空气氛围下，程序控制阶梯升温，首先在200℃条件下保温200min，然后经过180min升温，在600℃～800℃温度下保温200min，自然冷却，得到一种Co3O4与SnO2复合物纳米线；
所述复合物的化学简式为Co3O4·SnO2。
进一步的，本发明还提供了上述制备得到的四氧化三钴与氧化锡(Co3O4·SnO2)复合物纳米线的用途，该复合物纳米线作为催化氧化安息香的催化剂，在空气氛围下，在DMF和水体积比为1：2的混合溶剂中，反应温度为50oC、反应40min，苯偶酰的收率达到80％以上；催化剂循环使用三次，苯偶酰的收率可达到68％以上。
与现有技术相比，本发明合成的复合物纳米线的特点如下：
(a)本发明采用静电纺丝合成技术；(b)本发明制得的Co3O4·SnO2复合物形貌为纳米线，平均直径为650nm；(c)本发明制得的复合物纳米线作为催化氧化安息香的催化剂，循环使用三次，在DMF和水混合溶剂中50℃、反应40min，苯偶酰的收率达到68％以上，该复合物纳米线在催化材料领域具有广阔的应用前景。
附图说明
图1为本发明制得的Co3O4·SnO2复合物纳米线的XRD图；
图2为本发明制得的Co3O4·SnO2复合物纳米线的SEM图；
具体实施方式
本发明技术方案不局限于以下所列举具体实施方式，还包括各具体实施方式间的任意组合。
实施例1：
在烧杯中加入3mmoL乙酸钴四水合物，加入5.0mL N,N-二甲基甲酰胺(简写为DMF)搅拌1h，使乙酸钴四水合物完全溶解，再加入1.5g PVP(K-120，聚乙烯吡咯烷酮)、10.0mL无水乙醇、2mL冰醋酸和3mmoL四氯化锡五水合物(SnCl4·5H2O)，搅拌12h，得到澄清透明的纺丝前驱液；将澄清透明的纺丝前驱液装入10mL注射器中，在13kV的电压，针头与铂丝网接收器的距离为15cm，流率为0.8mL h-1，温度为35℃，空气湿度为45％条件下进行静电纺丝；收集静电纺丝产物并在100℃空气氛围下干燥 3h，然后将其转移到坩埚中，将坩埚置于马弗炉中，然后设置加热程序，空气氛围下，从室温经过60min升温至200℃并保温200min，再经过180min升温至600℃并保温 200min后，自然冷却，得到复合物Co3O4·SnO2纳米线，将得到的复合物Co3O4·SnO2纳米线进行X射线粉末衍射分析(XRD)和扫描电子显微镜分析(SEM)。
实施例2：
在烧杯中加入3mmoL乙酸钴四水合物(C4H6CoO4·4H2O)，加入5.0mL N,N-二甲基甲酰胺(DMF)搅拌1h，使乙酸钴四水合物完全溶解，再加入1.5g PVP、10.0mL 无水乙醇、2mL冰醋酸和3mmoL四氯化锡五水合物(SnCl4·5H2O)，搅拌12h，得到澄清透明的纺丝前驱液；将澄清透明的纺丝前驱液装入10mL注射器中，在18kV的电压，针头与铂丝网接收器的距离为19cm，流率为0.8mL h-1，温度为28℃，空气湿度为45％条件下进行静电纺丝；收集静电纺丝产物并在100℃空气氛围下干燥3h，然后将其转移到坩埚中，将坩埚置于马弗炉中，然后设置加热程序，空气氛围下，从室温经过60min升温至200℃并保温200min，再经过180min升温至700℃并保温200min后，自然冷却，得到复合物Co3O4·SnO2纳米线，将得到的复合物Co3O4·SnO2纳米线进行X 射线粉末衍射分析，扫描电子显微镜分析。
实施例3：
在烧杯中加入3mmoL乙酸钴四水合物(C4H6CoO4·4H2O)，加入5.0mL N,N-二甲基甲酰胺(DMF)搅拌1h，使乙酸钴四水合物完全溶解，再加入1.5g PVP、10.0mL无水乙醇、2mL冰醋酸和3mmoL四氯化锡五水合物(SnCl4·5H2O)，搅拌12h，得到澄清透明的纺丝前驱液；将澄清透明的纺丝前驱溶液装入10mL注射器中，在15kV的电压，针头与铂丝网接收器的距离为17cm，流率为0.8mL h-1，温度为32℃，空气湿度为45％条件下进行静电纺丝；收集静电纺丝产物并在100℃空气氛围下干燥3h，然后将其转移到坩埚中，将坩埚置于马弗炉中，然后设置加热程序，空气氛围下，从室温经过60min升温至200℃并保温200min，再经过180min升温至800℃并保温200min后，自然冷却，得到复合物Co3O4·SnO2纳米线，将得到的复合物Co3O4·SnO2纳米线进行X 射线粉末衍射分析(XRD)，扫描电子显微镜分析(SEM)。
由图1可以看出，实施例1-3成功合成出复合物Co3O4·SnO2纳米线；由图2可以看出，实施例1-3制得的Co3O4·SnO2复合物形貌为纳米线，平均直径为650nm。
将上述实施例中所制得的Co3O4·SnO2复合物纳米线作为催化氧化安息香的催化剂，在DMF和水体积比为1：2的混合溶剂中，反应温度50oC、反应40min，苯偶酰的收率达到80％以上；反应结束后对上述反应的催化剂进行回收循环使用，结果显示催化剂循环使用三次，苯偶酰的收率可达到68％以上，反应简式如下式所示：
Claims (1)
1.一种四氧化三钴与氧化锡复合物纳米线的用途，其特征在于，所述复合物纳米线的制备方法包括以下步骤：
(1)在烧杯中加入乙酸钴四水合物，加入DMF，搅拌1h，使乙酸钴四水合物完全溶解，再加入K-120型聚乙烯吡咯烷酮、无水乙醇、冰醋酸和四氯化锡五水合物，搅拌12h，得到澄清透明的纺丝前驱液；
(2)将澄清透明的纺丝前驱液吸入注射器中，在13～18kV的电压，针头与接收器的距离为15～19cm，流率为0.8mL h-1，空气湿度为45％，温度为28～35℃条件下进行静电纺丝，得纺丝产品并在100℃空气氛围下干燥3h；
(3)将干燥后的静电纺丝产物转移到马弗炉中，在空气氛围下，程序控制阶梯升温，首先在200℃条件下保温200min，然后经过180min升温，在600℃～800℃温度下保温200min，自然冷却，得到一种Co3O4与SnO2复合物纳米线；
所述DMF为N,N-二甲基甲酰胺的简写；
所述复合物纳米线的化学简式为Co3O4·SnO2；
所述复合物纳米线作为催化氧化安息香的催化剂，在空气氛围下，在DMF和水的体积比为1：2的混合溶液中，反应温度为50℃、反应40min，苯偶酰的收率达到80％以上；催化剂循环使用三次，苯偶酰的收率达到68％以上。
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|---|
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