CN112156794A - 一种多壁碳纳米管@过渡金属硫化物@二硫化钼三维异质结构的制备方法及其应用 - Google Patents
一种多壁碳纳米管@过渡金属硫化物@二硫化钼三维异质结构的制备方法及其应用 Download PDFInfo
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Abstract
本发明提供了一种多壁碳纳米管@过渡金属硫化物@二硫化钼三维异质结构的制备方法及其应用。此材料制备方法包括:(1)通过微乳液法制得金属甲酸框架化合物;(2)在金属甲酸框架化合物的溶液中引入羧基化多壁碳纳米管和硫代乙酰胺,通过溶剂热法、再经过煅烧制得多壁碳纳米管@过渡金属硫化物的复合材料;(3)在多壁碳纳米管@过渡金属硫化物的溶液中引入钼源和硫源,通过水热法、再经过煅烧获得多壁碳纳米管@过渡金属硫化物@二硫化钼三维异质结构。MCNTs@CoSx@MoS2优异的电化学性能主要归功于其新颖的结构优势,MCNTs、CoSx和MoS2之间的协同效应以及MCNTs的稳定性。本发明方法操作简单,可推广到一系列具有结构多功能优势的复合材料设计与合成中。
Description
技术领域
本发明属于纳米复合材料研究领域,特别是通过两步溶剂热法制备了一种多壁碳纳米管@过渡金属硫化物@二硫化钼三维异质结构,并作为电解水析氢析氧催化剂的应用。
背景技术
全球人口的迅速膨胀,经济的快速发展和人类需求的不断扩大,导致能源的需求量也在不断增加。作为世界能源主体的化石能源(煤、石油、天然气)的日渐枯竭和日益严重的生态环境问题严重限制了能源的开发利用。因此开发绿色,高效的可再生能源已经迫在眉睫。近年来,越来越多的科学家将目光聚集在氢能上,作为可再生能源之一的氢能被称为是二十一世纪最洁净的能源。电解水制氢具有产氢纯度高、操作简单、维护方便等优点。然而,水的实际分解电压总高于其理论值,这是由于析氢及析氧反应中存在过电位,因此开发能显著降低过电位的高效催化剂是很有必要的。
以MoS2为代表的过渡金属硫化物由于其在能源领域的巨大应用潜力,引起了国内外科学家的研究热潮。研究表明MoS2具有较小的吉布斯吸附能和化学稳定性,加之其催化活性高、成本低、资源丰富,被认为是一种很有前途的替代铂的HER催化剂。但MoS2本身也存在一定的局限性(催化活性位点数量较少、导电性较差等),这会限制它在催化领域中的应用。因此,我们需要对其改性,具体措施如下:一方面,可制备二硫化钼与其他物质的复合材料,增加本征催化活性位点,从而提高析氢性能。近年来,金属甲酸框架MFF具有较大的比表面积、均一可调的多孔结构,故得到了国内外的广泛应用。其中由MFF衍生的硫化钴具有更多的催化活性位点,进而展现出极好的电催化性能、较好的导电性,且其原材料丰富,价格便宜。因此,我们将MoS2与MFF衍生的过渡金属硫化物进行复合,从而提升MoS2的催化性能;另一方面,MoS2作为一种典型的半导体,提高其导电性的一种有效途径就是与导电性材料复合。到目前为止,科学家们已经通过多种方法实现了MoS2与多种导电材料相结合,如石墨烯、碳纳米管、碳纸等等。其中,多壁碳纳米管的管壁随着层数的增加,结构缺陷和化学反应性增强,具有较高的可修饰性。因此,我们购买商业的多壁碳纳米管并利用其特殊的表面缺陷结构进一步功能化处理,将其与MoS2复合以获得催化活性更优的复合催化剂。
综上所述,我们生产制备出一种多壁碳纳米管@过渡金属硫化物@二硫化钼三维异质结构来实现对二硫化钼的改性。
发明内容
本发明所要解决的技术问题是,为克服MoS2本身的局限性,提供一种多壁碳纳米管@过渡金属硫化物@二硫化钼三维异质结构的制备方法及其在电解水析氢析氧催化剂中的应用。本发明方法制得的复合材料本征催化活性位点丰富,导电性强以及稳定性好,该复合材料在催化析氢析氧方面展现出了便于大规模应用的优势。
为实现上述技术目的,本发明提供了一种多壁碳纳米管@过渡金属硫化物@二硫化钼三维异质结构的制备方法,其方法包括:
(1)在室温下,以硝酸钴为金属盐,甲酸为配体、二甲胺为模板以及AEO3为乳化剂,通过微乳液法制得金属甲酸框架化合物(Co-MFF);
(2)将购买的多壁碳纳米管用混酸进行水浴处理,得到羧基化多壁碳纳米管;
(3)在金属甲酸框架化合物(Co-MFF)的溶液中引入多壁碳纳米管和硫代乙酰胺,将其进行超声处理使之均匀分散,再通过溶剂热法得到产物,经过煅烧制得多壁碳纳米管@过渡金属硫化物的复合材料;
(4)在多壁碳纳米管@过渡金属硫化物的溶液中引入钼源和硫源,通过水热法得到产物,经过煅烧获得多壁碳纳米管@过渡金属硫化物@二硫化钼异质结构。
优选地,在步骤(1)中,硝酸钴、二甲胺和甲酸的摩尔比为1 : 4 : 6。
优选地,在步骤(1)中,所用的二甲胺的质量分数为33wt %。
优选地,在步骤(1)中,所用的甲酸为无水甲酸。
优选地,在步骤(1)中所述的微乳液法是将溶液在室温下搅拌4小时,陈化12小时后,倒去上清液,保留沉淀物,再用甲醇对其洗涤数次,离心和干燥。
优选地,在步骤(2)中,于80℃的水浴下,将管径为20-50nm的多壁碳纳米管置于混酸(硝酸的体积:硫酸的体积=3:1)中连续搅拌3小时。
优选地,在步骤(3)中,溶剂热反应温度是120℃,反应时间是6小时。
优选地,在步骤(3)中,所述的煅烧方法为将干燥后的产物在N2气氛下350℃煅烧2小时(每分钟升温1℃),即得到多壁碳纳米管@过渡金属硫化物复合材料。其与步骤(4)中的煅烧方法一致。
优选地,在步骤(4)中,所述的钼源为二水合钼酸钠,硫源为硫脲。
优选地,在步骤(4)中,水热反应温度是200℃,反应时间是14小时。
本发明的有益效果在于:
1.我们采用了一种简单的方法,通过两步溶剂热法合成了一种新奇的MCNTs@CoSx@MoS2三维异质结构。
2.作为一种双功能催化剂,该催化剂同时具有OER和HER性能。与CoSx、MCNTs@CoSx、MCNTs@MoS2、CoSx@MoS2、MoS2相比,MCNTs@CoSx@MoS2具有更好的电催化活性。
3.由于其几何结构的优化以及MCNTs、CoSx和MoS2之间的协同效应,使MCNTs@CoSx@MoS2具有丰富的电化学活性位点,提高的导电性和稳定性,以及快速的质量传递和离子运输。
4.我们的研究为合成一系列具有异质结构和可控成分的复合材料提供了新的思路。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍。
图1为本发明一种实施例的流程示意图;
图2为MCNTs@Co9S8的扫描电镜图(a,b),X-衍射谱图(XRD)(c);MCNTs@CoSx@MoS2的扫描电镜图(d,e),X-衍射谱图(XRD)(f);
图3为在0.5 M H2SO4中,CoSx, CoSx@MoS2, MCNTs@CoSx@MoS2, MCNTs@Co9S8,MCNTs@MoS2, MoS2, MCNTs 和 Pt/C的极化曲线图(a),Tafel斜率图(b),电化学双电层电容(e);在1 M KOH中,CoSx, CoSx@MoS2, MCNTs@CoSx@MoS2, MCNTs@Co9S8, MCNTs@MoS2, MoS2,MCNTs和 Pt/C的极化曲线图(c),Tafel斜率图(d),电化学双电层电容(f)
具体实施方案
下面结合附图,通过实例进一步说明本发明的目的,技术方案和优点。
根据本发明的实施例,如图1所示为制备多壁碳纳米管@过渡金属硫化物@二硫化钼三维异质结构的流程,具体步骤包含:
(1)在80℃的水浴中,将0.3g多壁碳纳米管浸入在50ml包含硝酸和硫酸的混合溶液中(体积比为3:1),搅拌3小时,所得产物用蒸馏水洗涤,离心收集,并干燥。
(2)在室温下,将4mmol二甲胺、6mmol无水甲酸和5ml AEO3溶解在25ml正辛烷中;再将1mmol硝酸钴、5ml甲醇和5ml AEO3溶解于另一25ml正辛烷中,然后将粉色澄清液一次性倒入无色透明溶液中,磁力搅拌4小时,室温陈化12小时,所得产物用甲醇洗涤、离心,并干燥。得到Co-MFF前驱体。
(3)将30mg Co-MFF完全分散于30ml无水乙醇中,向其中加入30mg硫代乙酰胺和5mg碳纳米管,磁力搅拌10分钟后将该分散液转移至45ml反应釜中,于120℃下反应6小时,所得产物经离心洗涤,并干燥。将干燥后的产物在N2气氛下350℃煅烧2小时,即得到多壁碳纳米管@过渡金属硫化物(MCNTs@Co9S8)。
(4)将15mg MCNTs@CoSx,32mg二水合钼酸钠和64mg硫脲完全分散于16ml去离子水中,然后将该分散液转移至40ml反应釜中,于200℃下反应14小时,后续步骤同(3)。即得到多壁碳纳米管@过渡金属硫化物@二硫化钼三维复合材料(MCNTs@CoSx@MoS2)。
该实施例的MCNTs@Co9S8样品,其扫描电镜照片如图2a,b所示,由图2a,b可以看出,Co9S8颗粒均匀地生长在MCNTs的表面,其管径为65-105nm,此外,Co9S8颗粒的尺寸为20-30nm。
该实施例的MCNTs@Co9S8样品,其X射线衍射图如图2c所示,由图2c可以看出,碳(JCPDS No.46-0945)的强特征衍射峰位于26度处,对应于碳的(002)晶面;此外,其它衍射峰与Co9S8 (JCPDS No. 65-6801)的相关特征峰高度一致。因此,这证明我们成功制备出了MCNTs@Co9S8复合材料。
该实施例的MCNTs@CoSx@MoS2样品,其扫描电镜照片如图2d,e所示,由图2d,e可以看出MoS2纳米片均匀垂直的生长在MCNTs@Co9S8的表面,其管径为135nm左右,并且MoS2纳米片的厚度大约为15nm。
该实施例的MCNTs@CoSx@MoS2样品,其X射线衍射图如图2f所示,由图2f可以看出,金属硫化物的物相从Co9S8 (JCPDS No. 65-6801)转变为 CoS2 (JCPDS No. 14-1471)和Co3S4 (JCPDS No. 47-1738)。
本实施例得到的复合材料MCNTs@CoSx@MoS2的电催化性能如图2所示。由图2可以看出,MCNTs@CoSx@MoS2是一种同时具有HER和OER的双功能电催化剂。在0.5 M H2SO4中,当电流密度为10mA/cm2时,其过电位为206mV,塔菲尔斜率为69mV/dec。在1 M KOH中,当电流密度为10mA/cm2时,其过电位为296mV,塔菲尔斜率为92mV/dec。因此,本发明制备的复合材料具有优异的电催化性能。
对比例1:
(1)在室温下,将4mmol二甲胺、6mmol无水甲酸和5ml AEO3溶解在25ml正辛烷中;再将1mmol硝酸钴、5ml甲醇和5ml AEO3溶解于另一25ml正辛烷中,然后将粉色澄清液一次性倒入无色透明溶液中,磁力搅拌4小时,室温陈化12小时,所得产物用甲醇洗涤、离心,并干燥。得到Co-MFF前驱体。
(2)将30mg Co-MFF完全分散于30ml无水乙醇中,向其中加入30mg硫代乙酰胺,磁力搅拌10分钟后将该分散液转移至45ml反应釜中,于120℃下反应6小时,所得产物经离心洗涤,并干燥。将干燥后的产物在N2气氛下350℃煅烧2小时,即得到过渡金属硫化物(CoSx)。
对比例2:
将15mg MCNTs,32mg二水合钼酸钠和64mg硫脲完全分散于16ml去离子水中,然后将该分散液转移至40ml反应釜中,于200℃下反应14小时,所得产物经离心洗涤,并干燥。将干燥后的产物在N2气氛下350℃煅烧2小时,即得到多壁碳纳米管@二硫化钼复合材料(MCNTs@MoS2)。
对比例3:
将对比例1所得到的15mgCoSx与32mg二水合钼酸钠以及64mg硫脲完全分散于16ml去离子水中,然后将该分散液转移至40ml反应釜中,于200℃下反应14小时,所得产物经离心洗涤,并干燥。将干燥后的产物在N2气氛下350℃煅烧2小时,即得到过渡金属硫化物@二硫化钼复合材料(CoSx@MoS2)。
对比例4:
将32mg二水合钼酸钠和64mg硫脲完全分散于16ml去离子水中,然后将该分散液转移至40ml反应釜中,于200℃下反应14小时,所得产物经离心洗涤,并干燥。将干燥后的产物在N2气氛下350℃煅烧2小时,即得到二硫化钼(MoS2)。
在本发明中,由于几何结构的优化以及MCNTs、CoSx和MoS2之间的协同效应,使MCNTs@CoSx@MoS2具有丰富的电化学活性位点,电导率高,稳定性好,传质和离子传输快速。本发明为合成一系列具有异质结构和可控成分的复合材料提供了新的思路。以上所述是本发明优选的实例而已,但不应该认为是对本发明的限制,因此,对于本领域的一般技术人员来说,在依据本发明原理的情况下,做出的改进和修饰,仍属于本发明包括的范围。
Claims (11)
1.一种多壁碳纳米管@过渡金属硫化物@二硫化钼三维复合材料,其特征在于,它是一种管径具有纳米级尺寸的异质结构。
2.一种多壁碳纳米管@过渡金属硫化物@二硫化钼三维复合材料的制备方法,其特征包括以下步骤:
(1)在室温下,以硝酸钴为金属盐,甲酸为配体、二甲胺为模板以及AEO3为乳化剂,通过室温共沉淀法制得金属甲酸框架化合物(Co-MFF);
(2)在80℃下,将购买的多壁碳纳米管用混酸进行水浴处理,得到羧基化多壁碳纳米管;
(3)在金属甲酸框架化合物(Co-MFF)的溶液中引入多壁碳纳米管和硫代乙酰胺,将其进行超声处理使之均匀分散,再通过溶剂热法得到产物,经过煅烧制得多壁碳纳米管@过渡金属硫化物的复合材料;
(4)在多壁碳纳米管@过渡金属硫化物的溶液中引入钼源和硫源,通过水热法得到产物,经过煅烧获得多壁碳纳米管@过渡金属硫化物@二硫化钼异质结构。
3.根据权利要求2所述的方法,其特征在于:在步骤(1)中,金属盐、二甲胺和甲酸的摩尔比为1 : 4 : 6。
4.根据权利要求2所述的方法,其特征在于:在步骤(1)中,所用的二甲胺的质量分数为33 wt %。
5.根据权利要求2所述的方法,其特征在于:在步骤(1)中,所用的甲酸为无水甲酸。
6.根据权利要求2所述的方法,其特征在于:在步骤(1)中所述的室温沉淀法是将溶液室温搅拌4小时,在室温下陈化12小时后,倒去上清液,保留沉淀物。
7.根据权利要求2所述的方法,其特征在于:在步骤(2)中,在80℃的水浴下,将管径为20-50nm的多壁碳纳米管置于混酸(硝酸的体积:硫酸的体积=3:1)中搅拌3小时。
8.根据权利要求2所述的方法,其特征在于:在步骤(3)中,溶剂热反应温度是120℃,反应时间是6小时。
9.根据权利要求2所述的方法,其特征在于:在步骤(3)中,所述的煅烧方法为将干燥后的产物在N2气氛下350℃煅烧2小时(每分钟升温1℃),即得到多壁碳纳米管@过渡金属硫化物复合材料,其与步骤(4)中的煅烧方法一致。
10.根据权利要求2所述的方法,其特征在于:在步骤(4)中,所述的钼源为二水合钼酸钠,硫源为硫脲。
11.根据权利要求2所述的方法,其特征在于:在步骤(4)中,水热反应温度是200℃,反应时间是14小时。
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