CN111450850B - 一种四元铋基硫族壳-核纳米球及其制备方法和应用 - Google Patents
一种四元铋基硫族壳-核纳米球及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于半导体合成技术领域，公开了一种四元铋基硫族壳‑核纳米球及其制备方法和应用，本发明通过控制原料配比、反应时间以及油胺的加入，形成四元铋基硫族壳‑核纳米球，该纳米球可以制备成薄膜，替代用于光物理和光化学应用的传统半导体，如：光催化，光伏，光电二极管传感器，潜在的还包括LED，集成电路，晶体管及半导体激光器。特别的，该纳米球能够在光催化降解染料的前提下，还可以保证其光催化降解的稳定性(使用制备得到的四元铋基硫族壳‑核纳米球对罗丹明B进行三次降解，都能够保证其降解率在60％左右)，说明其降解稳定性很好。可应用在稳定性光催化降解染料领域。
Description
技术领域
本发明涉及半导体合成技术领域，更具体的，涉及一种四元铋基硫族壳-核纳米球及其制备方法和应用。
背景技术
当前的功能纳米材料的性能需要符合人们多种多样需求，而单个化合物、通过真空沉积以及通过半导体纳米晶体沉积烧结等方法制备的半导体薄膜很难全部实现这些性能。因此，异质纳米结构的纳米材料以及非传统的多元材料得以被广泛应用。由于其独特的性能，过去几十年里人们对胶体半导体纳米晶体的研究日益增加。溶液法能在大气压下进行，产量高，材料利用率高，因此具有大面积卷对卷兼容沉积来大幅度降低薄膜光伏电池制造成本的潜力。已经报道了利用这些纳米晶体的离散或聚合特性的光催化和光伏等应用。目前在光伏薄膜中广泛应用的CdTe和CuIn1-xGaxSe2材料中的Te，Ga和In这些稀有元素限制了其成本和广泛,因此用地球上含量比较丰富的元素替代这些元素合成新的材料成为了趋势。CuInS2(CIS)，CuInxGa1-xSe2(CIGS)和Cu2ZnSnS4(CZTS)等三元、四元铜基化合物是由地球上含量丰富的元素组成的具有高吸收系数，低毒性并且具有合适带隙的可用于太阳能转化和光降解环境污染物的材料。
尽管已经在CIS,CIGS和CZTS等胶体的合成及尺寸控制上已经有许多进展，但对于四元BiS3/Cu2ZnS3胶体而言这仍是一大难题。Bi在6s轨道中良好的分散性已被证实能有效的提升光生载流子的迁移率并能有效减小带隙。并且，已被证实二元硫属铋化物能对光催化性能有所提升。因此可以预测四元硫属化合物CZBS能在光催化应用中起到很好的增强效果。CZBS胶体纳米晶体可以通过旋转浇铸，喷涂，或者印刷等方式制备成薄膜吸收层，这与真空制备方法相比成本大大降低。虽然已有文献报道使用溶液法合成了含有Cu(铜)，Zn(锌)，In(铟)，Ga(镓)或Sn(锡)的四元硫族半导体化合物，但具有壳-核结构的含有Bi(铋)的四元硫族半导体至今还没被报道过。
发明内容
本发明的目的在于克服现有技术存在的上述缺陷，提供一种四元铋基硫族壳-核纳米球。
本发明的另一个目的是提供上述四元铋基硫族壳-核纳米球的制备方法。
本发明的第三个目的是提供上述四元铋基硫族壳-核纳米球的应用。
本发明的目的是通过以下技术方案予以实现：
一种四元铋基硫族壳-核纳米球，所述纳米球以Cu2ZnS3为核，以BiS3为壳，所述纳米球的直径为50～55nm。
本发明还提供所述的四元铋基硫族壳-核纳米球的制备方法，是在惰性气氛下，以乙酰丙酮铜，醋酸锌，硝酸铋为反应原料，同时加入油胺反应形成金属油胺络合物，冷却后加入硫前体反应1～3h，分离后即得；所述乙酰丙酮铜，醋酸锌，硝酸铋的摩尔比为2：1：1。
发明人经前期实验发现，要获得壳-核结构的四元铋基硫族纳米球，需要控制以下几个因素：(1)严格控制乙酰丙酮铜，醋酸锌，硝酸铋的摩尔比，如此才能成功制备得到四元铋基硫族半导体，(2)控制反应时间，发明人对通过不同反应时间得到的物质进行了EDX分析，并绘制了物质中的各原子的占比随时间变化的曲线，可以发现，反应过程中是先生成铜锌硫元素组成的中间体，后续再反应生成硫铋元素组成的产物；(3)油胺的加入，在控制了反应时间的前提下，由于油胺的加入，形成了金属油胺络合物，金属油胺络合物的热解阻止了硫铋元素组成的产物在铜锌硫元素组成的中间体上的扩散，从而使得硫铋元素组成的产物在铜锌硫元素组成的中间体上形成壳，即最终得到壳-核结构的纳米球。
优选的，在上述四元铋基硫族壳-核纳米球的制备方法中，加入油胺的同时，还加入1-十八碳烯。
优选的，在上述四元铋基硫族壳-核纳米球的制备方法中，所述硫前体为十二烷硫醇和叔十二烷基硫醇，所述十二烷硫醇和叔十二烷基硫醇的质量比为1：2。
优选的，在上述四元铋基硫族壳-核纳米球的制备方法中，形成金属油胺络合物的反应温度为150～200℃。
优选的，在上述四元铋基硫族壳-核纳米球的制备方法中，冷却后的的温度为125～140℃，然后再加入硫前体进行下一步反应。
优选的，在上述四元铋基硫族壳-核纳米球的制备方法中，所述惰性气氛选自氮气、氩气。
本发明制备得到的四元铋基硫族壳-核纳米球可以制备成薄膜，替代用于光物理和光化学应用的传统半导体，如：光催化，光伏，光电二极管传感器，潜在的还包括LED，集成电路，晶体管及半导体激光器。
发明人通过后期研究制备得到的四元铋基硫族壳-核纳米球的应用，发现其能够在光催化降解染料的前提下，还可以保证其光催化降解的稳定性(使用制备得到的四元铋基硫族壳-核纳米球对罗丹明B进行三次降解，都能够保证其降解率在60％左右)，说明其降解稳定性很好。
因此，本发明还提供上述四元铋基硫族壳-核纳米球在制备光催化降解材料中的应用。
本发明还提供四元铋基硫族壳-核纳米球在在光催化降解染料中的应用。优选的，所述染料为罗丹明B。
与现有技术相比，本发明具有以下有益效果：
本发明通过控制原料配比、反应时间以及油胺的加入，形成四元铋基硫族壳-核纳米球，该纳米球可以制备成薄膜，替代用于光物理和光化学应用的传统半导体，如：光催化，光伏，光电二极管传感器，潜在的还包括LED，集成电路，晶体管及半导体激光器。特别的，该纳米球能够在光催化降解染料的前提下，还可以保证其光催化降解的稳定性(使用制备得到的四元铋基硫族壳-核纳米球对罗丹明B进行三次降解，都能够保证其降解率在60％左右)，说明其降解稳定性很好。可应用在稳定性光催化降解染料领域。
附图说明
图1为四元铋基硫族壳-核纳米球合成示意图；
图2为通过EDX分析原子占比绘制的四元铋基硫族壳-核纳米球的合成随时间变化曲线图；
图3为四元铋基硫族壳-核纳米球的TEM图像(左上和右上)、电子衍射图像(左下)、和Tauc曲线(右下)；其中，右上是左上放大5倍呈现的图像；
图4为四元铋基硫族壳-核纳米球的EDS谱图和组成元素分布图；
图5为四元铋基硫族壳-核纳米球的XPS谱图；
图6为四元铋基硫族壳-核纳米球对罗丹明B的光催化活性图。
具体实施方式
为了对本发明的技术特征、目的和效果有更加清楚的理解，现对照附图详细说明本发明的具体实施方式。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
四元铋基硫族壳-核纳米晶体的制备方法，包括以下步骤：在高温惰性气氛(氮气)下，按照2：1：1的摩尔比混合乙酰丙酮铜，醋酸锌，硝酸铋，并加入油胺和1-十八碳烯在150℃下反应形成金属油胺络合物，冷却至125℃，并注入十二烷硫醇(DDT)和叔十二烷基硫醇(t-DDM)，所述十二烷硫醇和叔十二烷基硫醇的质量比为1：2，再反应1h，分离得到四元铋基硫族壳-核纳米晶体1。
上述四元铋基硫族壳-核纳米晶体的合成示意图如图1所示，反应过程中铜、锌、铋、硫的合成占比随时间变化的曲线如图2所示。
实施例2
四元铋基硫族壳-核纳米晶体的制备方法，包括以下步骤：在高温惰性气氛(氮气)下，按照2：1：1的摩尔比混合乙酰丙酮铜，醋酸锌，硝酸铋，并加入油胺和1-十八碳烯在180℃下反应形成金属油胺络合物，冷却至130℃，并注入十二烷硫醇(DDT)和叔十二烷基硫醇(t-DDM)，所述十二烷硫醇和叔十二烷基硫醇的质量比为1：2，再反应2h，分离得到四元铋基硫族壳-核纳米晶体2。
实施例3
四元铋基硫族壳-核纳米晶体的制备方法，包括以下步骤：在高温惰性气氛(氮气)下，按照2：1：1的摩尔比混合乙酰丙酮铜，醋酸锌，硝酸铋，并加入油胺和1-十八碳烯在200℃下反应形成金属油胺络合物，冷却至150℃，并注入十二烷硫醇(DDT)和叔十二烷基硫醇(t-DDM)，所述十二烷硫醇和叔十二烷基硫醇的质量比为1：2，再反应3h，分离得到四元铋基硫族壳-核纳米晶体3。
一、四元铋基硫族壳-核纳米晶体的表征
(1)对实施例1-实施例3制备得到的四元铋基硫族壳-核纳米晶体进行透射电镜(TEM)表征，分析得出的纳米晶体的平均粒径为52nm的单分散纳米晶体(图3左上)；高分辨率TEM(图3右上)显示出纳米晶体为为壳-核形态；电子衍射图谱中图案是随机的亮点，表明制备得到的纳米球在不同的晶向都有良好的晶体特征(图3左下)，通过绘制吸收光谱的Tauc曲线(图3右下)得到，纳米球的光学带隙为1.57eV，这个带隙值对大多数光催化应用都是有效的。
(2)通过X射线能量色散光谱图(EDS)(图4)按其化学计量比显示出了相应元素的存在。EDS光谱中硅的存在可归因于测试使用的是硅晶片基板。
(3)用X射线光电子能谱(XPS)(图5)分析得到组成晶体的四种元素分别处于其氧化态。Cu的2p图谱中，分别在932.2eV(2p3/2)和951.9eV(2p1/2)出现特征峰，其峰距为19.7eV，这表明CZBS中铜的存在形式是Cu(I)。Zn的2p图谱中，1021.7eV和1044.7eV处显示出特征峰，其峰距为23eV，表明锌的存在形式是Zn(II)。在Bi的4f谱图中，在158.9eV(4f5/2)和164.2eV(4f7/2)显示出Bi(III)的特征峰。S的2p谱图中在159.1eV和164.2eV观察到了特征峰，表明了硫化物的存在。
二、四元铋基硫族壳-核纳米晶体的光催化实验
以罗丹明B为例，测试了上述实施例制备得到的四元铋基硫族壳-核纳米晶体对含有有机污染物的溶液的光催化降解作用。在光降解性能测试实验中，将25mg四元铋基硫族壳-核纳米晶体悬浮在含10ppm罗丹明B的100mL水溶液中，在黑暗条件下搅拌24小时以达到平衡吸附。然后用300W氙(Xe)灯照射溶液，每隔30min测量一次550nm处的光吸收度以检测罗丹明B浓度的变化。将光照30min后，罗丹明的浓度降低约60％，当光照200min后，罗丹明的浓度仍然降低约60％，这说明制备得到的四元铋基硫族壳-核纳米晶体具有光催化活性。
将光降解曲线用拟一级朗格缪尔-欣谢尔伍德(L-H)动力学方程(方程1)进行拟合，公式如下：
in(C0/C)＝Kappi (1)
公式中，kapp是表观伪一阶速率常数(min-1)，C0是罗丹明B的初始浓度(mg/L)，C是在t时间时罗丹明B的浓度(mg/L)可以观察到光降解曲线与拟一级反应动力学方程具有良好的相关性(R>0.95)，其表观速率常数为0.007min-1(图6)。
另外，还利用上述制备得到的四元铋基硫族壳-核纳米晶体重复上述光催化实验(重复三次)，结果显示每次催化实验后四元铋基硫族壳-核纳米晶体对罗丹明B的降解率均在60％左右，表明制备得到的四元铋基硫族壳-核纳米晶体具有很好的光催化稳定性。
Claims (5)
1.一种四元铋基硫族壳-核纳米球，其特征在于，所述纳米球以Cu2ZnS3为核，以BiS3为壳，所述纳米球的直径为50～55nm；
所述四元铋基硫族壳-核纳米球通过以下方法制备得到：在惰性气氛下，以乙酰丙酮铜，醋酸锌，硝酸铋为反应原料，同时加入油胺反应形成金属油胺络合物，冷却后加入硫前体反应1～3h，分离后即得；
所述乙酰丙酮铜，醋酸锌，硝酸铋的摩尔比为2：1：1；加入油胺的同时，还加入1-十八碳烯；所述硫前体为十二烷硫醇和叔十二烷基硫醇，所述十二烷硫醇和叔十二烷基硫醇的质量比为1：2，所述形成金属油胺络合物的反应温度为150～200℃，所述冷却后的的温度为125～140℃。
2.根据权利要求1所述一种四元铋基硫族壳-核纳米球，其特征在于，所述惰性气氛选自氮气、氩气。
3.权利要求1所述的四元铋基硫族壳-核纳米球在制备光催化降解材料中的应用。
4.权利要求1所述的四元铋基硫族壳-核纳米球在在光催化降解染料中的应用。
5.根据权利要求4所述的应用，其特征在于，所述染料为罗丹明B。
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