CN110787816B - 一种四重修饰的二硫化钼电催化剂及制备方法 - Google Patents
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical class S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims abstract description 4
- 239000002096 quantum dot Substances 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 230000007547 defect Effects 0.000 claims description 3
- 238000013532 laser treatment Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 238000011282 treatment Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 5
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- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 1
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Abstract
本发明公开一种四重修饰二硫化钼电催化剂的方法，包括以下步骤：前驱体的准备；脉冲激光辐照处理。本发明还公开一种四重修饰的二硫化钼电催化剂，其采用如上所述的方法制备而成，运用于催化析氢领域。
Description
技术领域
本发明涉及一种四重修饰的二硫化钼电催化剂及制备方法。
技术背景
日益严重的环境危机和全球能源短缺迫使人们寻找可替代传统燃料的可持续再生的新能源。氢能因为其无污染的燃烧产物，高燃烧值和大规模稳定储存的特点，已成为传统燃料能源替代品之一。通过电催化分解水制氢是一种环境友好且高效的制氢方法。
电催化制氢的效率取决于用于加速制氢反应进程的电催化剂。用于表征电催化剂性能好坏的标准之一是过电位。过高的过电位将会使电催化分解水制氢的过程中消耗过多的电能，因此，如何进一步降低电催化剂的过电位成为了该领域的难点。
发明内容
本发明的目的是降低二硫化钼电催化剂的过电位，提出一种高效制备四重修饰二硫化钼电催化剂的方法。本发明的实现包括以下步骤：将所得到的前驱体1克平整地铺在SiO2成分的凹槽内，凹槽的大小为1平方厘米；采用功率密度为2.5瓦/平方厘米，波长为532纳米的脉冲激光，在样品上进行均匀地扫描式照射，然后将样品重新铺平，对样品进行重复式激光扫描，共重复5次，保证样品被激光均匀地扫描过；经过激光处理后获得所需的四重修饰的二硫化钼电催化剂。
与现有技术相比，本发明所述的样品具有以下的优点：一、能够获得具有更低过电位的二硫化钼电催化剂。二、四重修饰的二硫化钼暴露出更多的反应界面和边界原子。
附图说明
图1 是对比例和实施例的X射线衍射图谱。
图2 是对比例和实施例的普通透射电镜图。
图3 是实施例的高分辨透射电镜图；其中，图3A、图3C和图3E分别是实施例的三个特征区域的透射电镜图;图3B是图3A的局部放大图；图3D是图3C的局部放大图；图3F是图3E的局部放大图。
图4 是对比例和实施例的过电位曲线图。
具体实施方式
以下结合具体实施例对本发明的实现进行详细的描述。
本实施例的具体步骤如下：将所得到的前驱体1克平整地铺在SiO2成分的凹槽内，凹槽的大小为1平方厘米；采用功率密度为2.5瓦/平方厘米，波长为532纳米的脉冲激光，在样品上进行均匀地扫描式照射，然后将样品重新铺平，对样品进行重复式激光扫描，共重复5次，保证样品被激光均匀地扫描过；经过激光处理后获得所需的四重修饰的二硫化钼电催化剂。
为了说明本实施例的技术效果，将购买得到的未经进一步处理的二硫化钼作为本实施例的对比例。
对按照实施例和对比例获得的样品，用X射线衍射方法测得衍射数据。可以看到对比例样品具有很好的结晶性，几个明显的特征衍射峰位于14.4°、29.0°、39.6°、44.2°、49.8°和60.2°,与PDF#37-1492（MoS2, P63/mmc, a = 3.161 Å, c = 12.299 Å）中（002）、（004）、（103）、（006）、（105）和（008）的衍射峰对应地很好。实施例中的样品的衍射峰的位置基本不变，但是强度发生了明显的变化，最强的（002）衍射峰的强度不到未经四重修饰的MoS2的三分之一。
图2是对比例和实施例的普通透射电镜图。图2A显示对比例具有明显的片状结构，尺寸为纳米到微米之间。图2B显示实施例也是具有明显的片状结构。在激光的作用下，部分小尺寸的二硫化钼纳米片呈现出圆片状。值得特别注意的是，实施例表面出现了直径在几十纳米的纳米颗粒。
图3是实施例的高分辨透射电镜图。图3A和3B中可以看出表面的直径为几十纳米的纳米颗粒是由直径小于10纳米的二硫化钼量子点组成的；图3C和3D中可以看到在纳米颗粒旁边分布着离散的二硫化钼量子点，对应于放大图3D中的阴影部分；图3E和3F中清楚地看到相邻的量子点之间界面存在明显的缺陷，量子点之间的晶界是非晶化的。量子点聚集成纳米颗粒、离散的二硫化钼量子点及量子点之间晶界的非晶化和缺陷是来由于去除激光辐照之后骤冷导致的。二硫化钼电催化剂表面的四重修饰将为其带来更多的反应界面和边界原子，将有利于电催化性能的提升。
图4对比研究了实施例和对比例的过电位，通常采用在电流密度为-10 mA/cm2时的过电位进行对比。对比例的过电位为461 mV，实施例的过电位得到了明显的优化，过电位的值直接降低到217 mV。
综上所述，通过如实施例所述的方法可以制备四重修饰的二硫化钼电催化剂。
本发明还公开了一种四重修饰二硫化钼电催化剂，其采用如实施例所述的方法制备而成。四重修饰二硫化钼电催化剂具有217 mV的过电位（在-10 mA/cm2电流密度下），明显优于未修饰的二硫化钼。
需要声明的是，以上所述的仅是本发明的优选实施方式，本发明不限于以上实施例。可以理解，本领域技术人员在不脱离本发明的基本构思的前提下直接导出或联想到的其他改进和变化，均应认为包含在本发明的保护范围之内。
Claims (2)
1.一种四重修饰二硫化钼电催化剂的方法，包括以下步骤：将购买得到的未经进一步处理的二硫化钼作为前驱体；将所得到的前驱体1克平整地铺在SiO2成分的凹槽内，凹槽的大小为1平方厘米；采用功率密度为2.5瓦/平方厘米，波长为532纳米的脉冲激光，在样品上进行均匀地扫描式照射，然后将样品重新铺平，对样品进行重复式激光扫描，共重复5次，保证样品被激光均匀地扫描过；经过激光处理后获得所需的四重修饰的二硫化钼电催化剂。
2.如权利要求1所述的方法制备得到的二硫化钼电催化剂，其特征在于，在二硫化钼片层上原位形成了直径小于10纳米的二硫化钼量子点；量子点聚集成直径为几十纳米的二硫化钼纳米颗粒，量子点之间的晶界是非晶化的；存在缺陷；存在离散的二硫化钼量子点。
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