CN109364950A - 一种石墨烯/金属硫化物多级纳米材料及其绿色合成方法 - Google Patents
一种石墨烯/金属硫化物多级纳米材料及其绿色合成方法 Download PDFInfo
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Abstract
本发明涉及一种石墨烯/金属硫化物多级纳米材料及其绿色合成方法,该方法以氧化石墨烯、L‑组氨酸、金属盐、硫代乙酰胺为原料,利用微波辅助加热制备石墨烯/金属硫化物多级纳米材料。本发明最大的特点是利用L‑组氨酸中丰富的功能团,络合溶液中的金属离子并控制形核和晶粒生长过程,通过基团间互相作用力实现对纳米颗粒的自组装形成金属硫化物多级纳米材料,是一种无污染、环境友好的绿色合成技术。另外,利用氧化石墨烯大的比表面积作为载体,形成石墨烯/金属硫化物多级纳米材料,利用多级纳米材料高活性、石墨烯大的比表面积和高的导电性能结合,可有效地应用于污水处理、环境保护和和太阳能电池等领域。
Description
技术领域
本发明涉及一种石墨烯/金属硫化物多级纳米材料及其绿色合成方法,属于纳米材料领域。
背景技术
金属硫化物作为一种十分重要的半导体纳米材料,因其具有特异的光、电、热、磁等性质,在半导体发光器件、非线性光学材料、光催化等领域表现出巨大的应用前景。形貌是影响金属硫化物性能的主要因素,因此不同形貌的金属硫化物得到了大量的研究,金属硫化物多级纳米结构由于其本身的独特结构而表现出非常高的反应活性受到了科研工作者广泛关注。目前,人们通常加入表面活性剂生成多级纳米结构,但表面活性剂本身会对环境造成一定的污染。
石墨烯是由单层sp2杂化碳原子构成的蜂窝状二维平面晶体薄膜,在石墨烯二维平面内,C-C键使石墨烯具有良好的刚性。另外,石墨烯平面上形成的π电子可以自由移动,使石墨烯具有良好的导电性。当石墨烯与金属硫化物复合时,有助于提高金属硫化物的力学、热学、电学等性能,可更加有效地应用于污水处理、环境保护和太阳能电池等领域。
发明内容
针对现有技术的不足,本发明提供一种石墨烯/金属硫化物多级纳米材料及其绿色合成方法。
为了解决上述技术问题,本发明的技术方案如下:
一种石墨烯/金属硫化物多级纳米材料的绿色合成方法,包括如下步骤:
S1、将氧化石墨烯分散于去离子水中,获得氧化石墨烯分散液a;
S2、向S1中获得的氧化石墨烯分散液a中加入金属盐和氨基酸,混合均匀,获得溶液b;
S3、向S2中获得的溶液b中加入硫源,超声搅拌20-30min,获得溶液c;
S4、加热溶液c,反应25-35min后,固液分离,获得沉淀物质,洗涤,干燥,获得石墨烯/金属硫化物多级纳米材料。
S1中,将浓度为0.8-1.2 g/L的氧化石墨烯溶液与去离子水按体积比1-3:10混合,超声分散,优选地,超声分散时间为15-45min,进一步优选为20-40min,获得到氧化石墨烯分散液a。
S1中,溶液a中,氧化石墨烯的质量浓度为0.08-0.36 g/L。
S2中,溶液b中,氧化石墨烯、金属盐、氨基酸的质量比为0.02-0.06:1-3:1-3。
S2中,所述氨基酸为L-组氨酸。
S3中,所述硫源为硫代乙酰胺,优选地,溶液c中,氧化石墨烯、金属盐、氨基酸、硫源的质量比为0.02-0.06:1-3:1-3:0.3-1。
S4中,采用微波辅助加热方式加热。
S4中,控制反应温度为180-250℃。
S4中,洗涤时,依次用蒸馏水和无水乙醇洗涤5-6次。
所述金属盐包括二水合乙酸镉、一水合乙酸铜、二水合氯化亚锡中的至少一种。
基于同一发明构思,本发明还提供一种石墨烯/金属硫化物多级纳米材料,由如上所述的绿色合成方法制成。
生物分子含有丰富的官能团,能够有效地导向纳米材料的生长,本发明以氨基酸生物分子辅助纳米材料的合成,是一种无污染、环境友好的绿色合成技术。
本发明以L-组氨酸辅助、氧化石墨烯为载体,利用微波加热技术获得石墨烯/金属硫化物多级纳米材料。
本发明的技术构思是:L-组氨酸分子携带许多官能团(如-NH2,-COOH,-SH,-OH等),能与金属离子以配位键结合,同时各基团间与水溶剂间的氢键、范德华力、疏水作用等可使纳米粒子以多级结构方式进行自组装,因此利用L-组氨酸辅助的方法可以合成金属硫化物多级纳米材料。氧化石墨烯表面具有丰富的带负电的功能团,通过静电相互作用很容易吸引溶液中的金属离子,达到形成的金属硫化物多级纳米材料稳定地锚定在石墨烯表面,有效地提高金属硫化物的导电性,并阻止硫化物的团聚。
本发明最大的特点是利用L-组氨酸中丰富的功能团,络合溶液中的金属离子并控制形核和晶粒生长过程,通过基团间互相作用力实现对纳米颗粒的自组装形成金属硫化物多级纳米材料,是一种无污染、环境友好的绿色合成技术。另外,利用氧化石墨烯大的比表面积作为载体,形成石墨烯/金属硫化物多级纳米材料,利用多级纳米材料高活性、石墨烯大的比表面积和高的导电性能结合,可有效地应用于污水处理、环境保护和和太阳能电池等领域。
与现有技术相比,本发明的有益效果如下:
1、从环保的角度出发,选取对人体无毒害、无环境污染且具有良好生物相容性的生物小分子L-组氨酸为基质,辅助纳米材料的合成,发展环境友好、条件温和、成本低廉、操作简单,是一种易于大规模工业生成的通用合成技术。
2、本发明的绿色合成方法适用面广,可应用于石墨烯/硫化镉多级纳米材料、石墨烯/硫化铜多级纳米材料、石墨烯/硫化亚锡多级纳米材料等多种纳米材料的制备;
3、通过本发明的方法获得的石墨烯/金属硫化物多级纳米材料形貌好且无杂质,制备过程可控性强;
4、本发明得到石墨烯/金属硫化物多级纳米材料,利用金属硫化物多级纳米材料高活性、石墨烯大的比表面积和高的导电性能结合,在污水处理、环境保护和太阳能电池等方面具有重要的意义。
附图说明
图1 是实施例1中石墨烯/硫化镉多级纳米材料的SEM图像;
图2是实施例1中石墨烯/硫化镉多级纳米材料的TEM图像;
图3是实施例1中石墨烯/硫化镉多级纳米材料的HRTEM图像;
图4是实施例2中石墨烯/硫化铜多级纳米材料的XRD图;
图5是实施例2中石墨烯/硫化铜多级纳米材料的SEM图像;
图6是实施例3中石墨烯/硫化亚锡多级纳米材料的XRD图;
图7是实施例3中石墨烯/硫化亚锡多级纳米材料的SEM图像。
具体实施方式
以下将结合实施例来详细说明本发明。
实施例1
石墨烯/硫化镉多级纳米材料的制备方法如下:
(1)将10mL浓度为1 g/L的氧化石墨烯溶液加入到50 mL去离子水中超声分散得到氧化石墨烯分散液a;
(2)在上述分散均匀的溶液a中加入0.83 g的二水合乙酸镉和1 g的L-组氨酸,超声分散,得到分散均匀的溶液b;
(3)在所述分散均匀的溶液b中加入0.3 g硫代乙酰胺,超声搅拌30 min,得分散均匀的溶液c;
(4)将对溶液c进行微波辅助加热,在200℃下反应30 min后,固液分离,得到黄色的沉淀物质;
(5)将所得沉淀物质用蒸馏水和无水乙醇洗涤6次,得到无杂质的石墨烯/硫化镉多级纳米材料;
参见附图1,它是本实施例中石墨烯/硫化镉多级纳米材料的SEM图,图中可以看到,均匀分布着大量的球状颗粒,直径大约在200 nm左右,并且每个球体的表面粗糙。
参见附图2,它是本实施例中石墨烯/硫化镉多级纳米材料的TEM图,图中可以看到,纳米球是一种超细纳米颗粒组成的多级纳米球。
参见附图3,它是本实施例中石墨烯/硫化镉多级纳米材料的HRTEM图,图中可以看到,组成多级纳米球的超细纳米颗粒的晶格线,晶格间距0.33 nm,对应于硫化镉的(002)晶面。
实施例2
石墨烯/硫化铜多级纳米材料的光催化材料的制备方法如下:
(1)将10mL浓度为1 g/L的氧化石墨烯溶液加入到50 mL去离子水中超声分散得氧化石墨烯分散液a;
(2)在上述分散均匀的溶液a中加入0.8 g的一水合乙酸铜和1 g的L-组氨酸,超声分散,得到分散均匀的溶液b;
(3)在所述分散均匀的溶液b中加入0.3 g硫代乙酰胺,超声搅拌20 min ~30 min,得分散均匀的溶液c;
(4)对溶液c进行微波辅助加热,在200℃下反应30 min后,固液分离,得到黑色的沉淀物质;
(5)将所得黑色沉淀物质用蒸馏水和无水乙醇洗涤6次,得到无杂质的石墨烯/硫化铜多级纳米材料;
参见附图4,X射线衍射仪分析结果得出,获得复合材料为硫化铜晶体的晶面衍射峰。
参见附图5,它是本实施例中石墨烯/硫化铜多级纳米球的SEM图,图中可以看到,硫化铜多级球由片状的硫化铜组成。
实施例3
石墨烯/硫化亚锡多级纳米材料的制备方法如下:
(1)将10mL浓度为1 g/L的氧化石墨烯溶液加入到50 mL去离子水中超声分散得氧化石墨烯分散液a;
(2)在上述分散均匀的溶液a中加入0.9 g的二水合氯化亚锡和1 g的L-组氨酸,超声分散,得到分散均匀的溶液b;
(3)在所述分散均匀的溶液b中加入0.3 g硫代乙酰胺,超声搅拌20 min ~30 min,得分散均匀的溶液c;
(4)对溶液c进行微波辅助加热,在200℃下反应30 min后,固液分离,得到沉淀物质;
(5)将所得的沉淀物质用蒸馏水和无水乙醇洗涤5~6次,得到无杂质的石墨烯/硫化亚锡多级纳米材料;
参见附图6,它是本实施例中石墨烯/硫化亚锡多级纳米材料的SEM图,图中可以看到,均匀分布着大量的硫化亚锡微米花,微米花花瓣为片状的硫化亚锡。
本发明以L-组氨酸辅助、氧化石墨烯为载体合成石墨烯/金属硫化物多级纳米材料;同时,相比溶液法制备金属硫化物多级纳米材料中采用表面活性剂造成的环境造污染问题,通过生物分子辅助合成纳石墨烯/金属硫化物多级纳米材料,简单、高效、无污染。所述材料可应用于污水处理、环境保护和太阳能电池等领域。
上述实施例阐明的内容应当理解为这些实施例仅用于更清楚地说明本发明,而不用于限制本发明的范围,在阅读了本发明之后,本领域技术人员对本发明的各种等价形式的修改均落入本申请所附权利要求所限定的范围。
Claims (10)
1.一种石墨烯/金属硫化物多级纳米材料的绿色合成方法,其特征在于,包括如下步骤:
S1、将氧化石墨烯分散于去离子水中,获得氧化石墨烯分散液a;
S2、向S1中获得的氧化石墨烯分散液a中加入金属盐和氨基酸,混合均匀,获得溶液b;
S3、向S2中获得的溶液b中加入硫源,超声搅拌20-30min,获得溶液c;
S4、加热溶液c,反应25-35min后,固液分离,获得沉淀物质,洗涤,干燥,获得石墨烯/金属硫化物多级纳米材料。
2.根据权利要求1所述的绿色合成方法,其特征在于,S1中,将浓度为0.8-1.2 g/L的氧化石墨烯溶液与去离子水按体积比1-3:10混合,超声分散,获得到氧化石墨烯分散液a。
3.根据权利要求1所述的绿色合成方法,其特征在于,S1中,溶液a中,氧化石墨烯的质量浓度为0.08-0.36 g/L。
4.根据权利要求1所述的绿色合成方法,其特征在于,S2中,溶液b中,氧化石墨烯、金属盐、氨基酸的质量比为0.02-0.06:1-3:1-3。
5.根据权利要求1所述的绿色合成方法,其特征在于,S2中,所述氨基酸为L-组氨酸。
6.根据权利要求1所述的绿色合成方法,其特征在于,S3中,所述硫源为硫代乙酰胺。
7.根据权利要求1所述的绿色合成方法,其特征在于,溶液c中,氧化石墨烯、金属盐、氨基酸、硫源的质量比为0.02-0.06:1-3:1-3:0.3-1。
8.根据权利要求1所述的绿色合成方法,其特征在于,S4中,控制反应温度为180-250℃,优选地,采用微波辅助加热方式加热。
9.根据权利要求1-8任一项所述的绿色合成方法,其特征在于,所述金属盐包括二水合乙酸镉、一水合乙酸铜、二水合氯化亚锡中的至少一种。
10.一种石墨烯/金属硫化物多级纳米材料,其特征在于,由如权利要求1-9任一项所述的绿色合成方法制成。
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