CN114527179A - 一种花状核壳结构的多元复合硫化物纳米粉体及制备方法 - Google Patents
一种花状核壳结构的多元复合硫化物纳米粉体及制备方法 Download PDFInfo
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Abstract
本发明公开了一种花状核壳结构的多元复合硫化物纳米粉体，由硫化物MeS和硫化物CuS复合而成，其结构式为(1‑x)MeS@xCuS，x的范围是0.3＜x＜0.9；本发明还公开了该纳米粉体的制备方法，首先，将Me的可溶性盐溶解于去离子水中，加入硫源和混合醇溶液，进行水热反应，将MeS反应溶液进行超声处理，加入Cu的可溶性盐、硫源和混合液，进行水热反应，洗涤干燥，即可。本发明合成的多元复合硫化物纳米粉体，具有低密度高比表面积的优点，使其表面的活性位点更多提高其催化活性，另外，多元复合结构的硫化物，会在界面处形成异质结构，有效提升材料的电子转移效率，使其在葡萄糖检测领域有宽阔的发展前景。
Description
技术领域
本发明属于电极材料制备技术领域，具体涉及一种花状核壳结构的多元复合硫化物纳米粉体，还涉及该多元复合硫化物纳米粉体的制备方法。
背景技术
糖尿病是一种以血液中葡萄糖浓度升高为特征的严重疾病。世界卫生组织(WHO)指出，糖尿病影响着全世界数百万人，尤其是来自中等或低收入国家的人群。如果治疗不当，还可能会导致严重的并发症，例如肾功能衰竭、失明、心脏病发作、中风和截肢。除此之外，其他葡萄糖代谢异常，如低血糖、糖耐量受损和空腹血糖受损，也可能预示着严重的疾病和致命的并发症。
因此，市场对廉价、快速和准确的血糖水平的测量方法的需求巨大，这导致业界对制造新的葡萄糖传感设备的兴趣不断提高。由于其原理不同，葡萄糖传感器可以通过其不同研究的方法进行分类，例如热、光、电化学、声和磁等。其中，研究最广泛的是电化学平台，而根据用于识别葡萄糖分子的材料不同，葡萄糖电化学传感器大致可分为酶葡萄糖电化学传感器和无酶葡萄糖电化学传感器两大类。有酶葡萄糖传感器的电化学检测是用酶作为传感元件，对葡萄糖进行氧化催化，产生电子流，测量该电子流以量化葡萄糖量。而无酶葡萄糖电化学传感器是以贵金属、过渡金属、金属氧化物等作为传感元件来检测葡萄糖。酶传感器经历了三代技术演进，成为当今葡萄糖生物传感器的主流产品。但在实际应用中，酶传感器的稳定性和重现性较差，使用环境也相对有限，技术复杂，成本较高。因此，无酶葡萄糖传感系统的开发是当前研究工作的重点。
近年来，贵金属因其催化活性和良好的导电性而被广泛应用于非酶葡萄糖传感的开发和应用。然而，贵金属电极中间体的积累会导致催化剂活性丧失和表面堵塞，其高成本也制约了其进一步发展。所以，过渡金属及其化合物，如氧化物、氢氧化物、硝酸盐、硫化物等，由于其成本低廉、制备工艺简单、电化学性能好等优点而备受关注。
发明内容
本发明的目的是提供一种花状核壳结构的多元复合硫化物纳米粉体，由于其表面的活性位点较多，进而能提高其催化活性。
本发明的另一目的是提供花状核壳结构的多元复合硫化物纳米粉体的制备方法。
本发明所采用的技术方案是，一种花状核壳结构的多元复合硫化物纳米粉体，由硫化物MeS和硫化物CuS复合而成，其结构式为(1-x)MeS@xCuS，其中，x的范围是0.3＜x＜0.9；硫化物MeS为核心纳米球，硫化物CuS作为花状外壳，核心纳米球被花状外壳包裹；Me为锌、铁、钴、镍中的一种或多种金属元素。
本发明所采用的另一技术方案是，一种花状核壳结构的多元复合硫化物纳米粉体的制备方法，具体按照以下步骤实施：
步骤1，制备硫化物MeS核心纳米球：将金属元素Me的可溶性盐溶解于去离子水中，混合均匀后，依次加入硫源和混合醇溶液，之后置于水热釜中进行水热反应，得到MeS反应溶液；
步骤2，将MeS反应溶液进行超声分散处理30min，在分散过程中依次加入金属Cu的可溶性盐、硫源和混合液，在粘性沉淀未完全形成前迅速转移至水热釜中进行水热反应，将所得的沉淀抽滤后，使用无水乙醇和去离子水洗涤，干燥，即可得到花状核壳结构的多元复合硫化物纳米粉体。
本发明的特点还在于，
步骤1中，水热反应温度为80～220℃，水热反应时间为3.5～12h；混合醇溶液由体积比为1～2：1的乙醇和乙二醇混合而成；硫源与金属元素Me的可溶性盐的摩尔比为1.8～2：1。
步骤1和步骤2中，硫源为硫脲、硫代乙酰胺、硫代硫酸钠中的一种或多种。
步骤2中，水热反应温度为60～200℃，水热反应时间为4～15h；干燥温度为80℃，干燥时间为4h。
步骤2中，混合液由体积比为1～2：1的聚乙二醇与乙醇混合而成；MeS反应溶液、金属Cu的可溶性盐和硫源的摩尔比为3～5：7～10：18～20。
本发明的有益效果是：
本发明合成的具有花状核壳结构的多元复合硫化物纳米粉体，具有低密度高比表面积的优点，使其表面的活性位点更多提高其催化活性，另外，多元复合结构的硫化物，会在界面处形成异质结构，这将有效提升材料的电子转移效率，同时多元的协同作用也导致材料的催化作用得到改善，使得其在葡萄糖检测领域有宽阔的发展前景。
附图说明
图1为本发明制备得到的0.3NiS@0.7CuS纳米粉体的SEM图；
图2为本发明制备得到的0.3NiS@0.7CuS纳米粉体的TEM图(一)；
图3为本发明制备得到的0.3NiS@0.7CuS纳米粉体的TEM图(二)；
图4为本发明制备得到的0.5ZnS/NiS2@0.5CuS纳米粉体的SEM图；
图5为本发明制备得到的0.3NiS@0.7CuS纳米粉体在0.1mol/L的KOH溶液环境中是否加入1mM葡萄糖时的CV特性曲线图；
图6为本发明制备得到的0.3NiS@0.7CuS纳米粉体在0.1mol/L的KOH溶液环境中不同时间滴加葡萄糖浓度1-15mmol/L的I-t曲线图；
图7为本发明制备得到的具有花状核壳结构的0.3NiS@0.7CuS复合纳米粉体对连续滴加1mM葡萄糖、0,1mM尿酸(UA)、0.1mM抗坏血酸(AA)、0.1mM多巴胺(DA)和0.1mM尿素(Urea)的I-t关系图。
具体实施方式
下面结合具体实施方式和附图对本发明进行详细说明。
本发明一种花状核壳结构的多元复合硫化物纳米粉体，由硫化物MeS和硫化物CuS复合而成，其结构式为(1-x)MeS@xCuS，其中x的范围是0.3＜x＜0.9，硫化物MeS为核心纳米球，硫化物CuS作为花状外壳，其核心纳米球被花状外壳包裹；Me为锌、铁、钴、镍中的一种或多种金属元素；
本发明一种花状核壳结构的多元复合硫化物纳米粉体的制备方法，具体按照以下步骤实施：
步骤1，制备硫化物MeS核心纳米球：将金属元素Me的可溶性盐溶解于去离子水中，混合均匀后，依次加入硫源和混合醇溶液，之后置于水热釜中进行水热反应，得到MeS反应溶液；
水热反应温度为80～220℃，水热反应时间为3.5～12h；
混合醇溶液由体积比为1～2：1的乙醇和乙二醇混合而成；
硫源与金属元素Me的可溶性盐的摩尔比为1.8～2：1；
硫源为硫脲、硫代乙酰胺、硫代硫酸钠中的任意一种或多种；
步骤2，将MeS反应溶液进行超声分散处理30min，在分散过程中依次加入金属Cu的可溶性盐、硫源和混合液，在粘性沉淀未完全形成前迅速转移至水热釜中进行水热反应，将所得的沉淀抽滤后，使用无水乙醇和去离子水洗涤，干燥，即可得到花状核壳结构的多元复合硫化物纳米粉体，呈黑色粉末状；
水热反应温度为60～200℃，水热反应时间为4～15h；干燥温度为80℃，干燥时间为4h；
混合液由体积比为1～2：1的聚乙二醇与乙醇混合而成；
MeS反应溶液、金属Cu的可溶性盐和硫源的摩尔比为3～5：7～10：18～20；
硫源为硫脲、硫代乙酰胺、硫代硫酸钠中的任意一种或多种；
实施例1
本发明一种花状核壳结构的多元复合硫化物纳米粉体的制备方法，具体按照以下步骤实施：
步骤1、制备硫化物核心纳米球(NiS)：将0.262g的NiSO4·6H2O溶解于15ml去离子水中，依次加入0.6mmol的硫代乙酰胺和15ml乙二醇及15ml无水乙醇，搅拌至乳白色溶液，然后转移至水热反应釜，在100℃下处理8h，待冷却后取出；
步骤2、制备具有花状核壳结构的多元复合硫化物(0.3NiS@0.7CuS)：将步骤1制备得到的反应溶液超声处理30min；在分散过程中依次加入0.489g CuSO4·5H2O，1.4mmol硫源和15ml聚乙二醇与15ml乙醇的混合溶液，在粘性沉淀未完全形成前迅速转移至聚四氟乙烯内衬中，放入水热釜进行在150℃下水热处理10h，将所得的沉淀抽滤后，使用无水乙醇和去离子水洗涤，在80℃下干燥4h，即得到具有花状核壳结构的二元复合硫化物，呈黑色粉末状。
通过扫描电子显微镜对所得产物的结构，形貌进行了表征，参照图1，图2，图3可知所得产物为具有花状核壳结构的0.3NiS@0.7CuS复合硫化物。
实施例2
本发明一种花状核壳结构的多元复合硫化物纳米粉体的制备方法，具体按照以下步骤实施：
步骤1、制备硫化物核心纳米球(ZnS/NiS2)：将0.219g的Zn(CH3COO)2·2H2O和0.257g的NiCl2·6H2O溶解于30ml去离子水中，依次加入4mmol的硫脲和20ml乙二醇及15ml无水乙醇，搅拌至乳白色溶液，然后转移至水热反应釜，在170℃下处理10h，待冷却后取出。
步骤2、制备具有花状核壳结构的多元复合硫化物(0.5ZnS/NiS2@0.5CuS)：将步骤1制备得到的反应溶液超声处理30min；在分散过程中依次加入0.355g CuCl2·2H2O，2mmol硫代硫酸钠和18ml聚乙二醇与10ml乙醇的混合溶液，在粘性沉淀未完全形成前迅速转移至聚四氟乙烯内衬中，放入水热釜进行在180℃下水热处理16h，将所得的沉淀抽滤后，使用无水乙醇和去离子水洗涤，在60℃下干燥4h，即得到具有花状核壳结构的复合硫化物，呈灰褐色粉末状。所得产物形貌不均一参照图4，由图可得，随着反应物的比例及有机溶剂的混合比例不同会导致材料表面形貌的变化。
图5所示为实施例1中反应产物修饰电极在0.1MKOH溶液中是否添加1mM葡萄糖时的电化学CV特性测试曲线，可以明显看出在滴加葡萄糖后曲线所显示的氧化还原峰移动，峰值有加大变化，以此反映出反应物修饰电极对葡萄糖的高催化活性。
图6所示为实施例1中反应产物修饰电极在0.1MKOH溶液中的安培阶梯曲线，反映出在加入葡萄糖浓度在0.001-15mmol内的变化情况，以此为基础可以计算出，反应产物的灵敏度为5800μA mM-1cm-2，检测范围宽广，明显优于相似种类的硫化物电极。
图7所示为实施例1中反应产物修饰电极在0.1MKOH溶液中的选择性曲线，可以看出在类人体血液环境下，该电极对葡萄糖的特异性选择，使得其在葡萄糖传感领域有着良好的应用前景。
本发明合成的具有花状核壳结构的多元复合硫化物纳米粉体形貌好，通过扫描可以明显的看出表面的花状结构，通过透射清晰表示出核壳结构。本发明的多元复合硫化物纳米粉体的制备方法，重复性好，且条件易于控制，后期不需要进行煅烧。
本发明具有花状核壳结构的多元复合硫化物纳米粉体，作为混合催化剂通过协同组合效应以增强电催化作用，具有更高的比表面积以缩短传输路径，暴露出的更多活性位点，同时在葡萄糖检测实验中表现出超灵敏度，低检测限和宽线性范围的优良性能，有望作为非酶葡萄糖检测的理想电催化材料。
Claims (7)
1.一种花状核壳结构的多元复合硫化物纳米粉体，其特征在于，由硫化物MeS和硫化物CuS复合而成，其结构式为(1-x)MeS@xCuS，其中，x的范围是0.3＜x＜0.9。
2.根据权利要求1所述的一种花状核壳结构的多元复合硫化物纳米粉体，其特征在于，所述硫化物MeS为核心纳米球，硫化物CuS作为花状外壳，核心纳米球被花状外壳包裹；Me为锌、铁、钴、镍中的一种或多种金属元素。
3.一种花状核壳结构的多元复合硫化物纳米粉体的制备方法，其特征在于，具体按照以下步骤实施：
步骤1，制备硫化物MeS核心纳米球：将金属元素Me的可溶性盐溶解于去离子水中，混合均匀后，依次加入硫源和混合醇溶液，之后置于水热釜中进行水热反应，得到MeS反应溶液；
步骤2，将MeS反应溶液进行超声分散处理30min，在分散过程中依次加入金属Cu的可溶性盐、硫源和混合液，在粘性沉淀未完全形成前迅速转移至水热釜中进行水热反应，将所得的沉淀抽滤后，使用无水乙醇和去离子水洗涤，干燥，即可得到花状核壳结构的多元复合硫化物纳米粉体。
4.根据权利要求3所述的一种花状核壳结构的多元复合硫化物纳米粉体的制备方法，其特征在于，所述步骤1中，水热反应温度为80～220℃，水热反应时间为3.5～12h；混合醇溶液由体积比为1～2：1的乙醇和乙二醇混合而成；硫源与金属元素Me的可溶性盐的摩尔比为1.8～2：1。
5.根据权利要求3所述的一种花状核壳结构的多元复合硫化物纳米粉体的制备方法，其特征在于，所述步骤1和步骤2中，硫源为硫脲、硫代乙酰胺、硫代硫酸钠中的任意一种或多种。
6.根据权利要求3所述的一种花状核壳结构的多元复合硫化物纳米粉体的制备方法，其特征在于，所述步骤2中，水热反应温度为60～200℃，水热反应时间为4～15h；干燥温度为80℃，干燥时间为4h。
7.根据权利要求3所述的一种花状核壳结构的多元复合硫化物纳米粉体的制备方法，其特征在于，所述步骤2中，混合液由体积比为1～2：1的聚乙二醇与乙醇混合而成；MeS反应溶液、金属Cu的可溶性盐和硫源的摩尔比为3～5：7～10：18～20。
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