CN107321372B - CoS纳米颗粒/N掺杂RGO析氢复合材料的制备方法 - Google Patents
CoS纳米颗粒/N掺杂RGO析氢复合材料的制备方法 Download PDFInfo
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Abstract
本发明属于材料合成技术领域,公开了一种具有析氢效果的CoS纳米颗粒/N掺杂RGO复合材料的制备方法。本发明通过简单的一步溶剂热法合成前驱体,然后通过高温煅烧生成CoS纳米颗粒/N掺杂RGO复合材料,用于酸性条件下提高析氢性能。本发明的优点在于绿色环保,成本低,制备工艺简便,制得的催化剂易于大规模工业化生产并具备优异的电催化活性及良好的析氢稳定性。杂环原子N引入到CoS/RGO中,形成几何缺陷和杂原子的协同效应,能够降低碳材料对于氢离子的吸附自由能,更有利于氢气的析出,能够显著提高CoS的电化学性能。
Description
技术领域
本发明属于材料合成技术领域,具体涉及了CoS纳米颗粒/N掺杂RGO复合材料的制备方法及其用于电化学析氢的催化剂的用途。
背景技术
最近,人类面临着日益严重的环境污染和能源危机,当前开发和利用清洁有效的能源是解决目前危机的重要挑战之一。从能源清洁及可循环的角度考虑,氢能作为一种高效、清洁、环保的二次能源具有资源丰富,热值高,环保无污染,利用形式多样等特点,已被普遍认为氢是一种理想的新能源,有着无可比拟的巨大优势和无限广阔的应用前景。然而如何通过有效的途径获得较为廉价的氢能源,是目前科研工作者研究的主要内容之一,地球上水资源丰富,通过水的电解获得氢气是有效的途径之一,但是水的电解能源转化效率低是制约其工业化生产的因素之一,因此设计和开发高性能的电解水的催化剂具有极其重要的意义。
近几年,过渡金属硫化物在能源存储及在电催化中的潜在应用得到了研究工作者的广泛关注。过渡金属Co、Ni、Fe硫化物是一类重要的HER催化剂,对MEx(M:Fe、Co、Ni;E:S、N、P)一系列硫化物催化析氢性能研究表明,在酸性电解液中,CoS2、NiS2、CoP、NiP等具有较好的电化学析氢性能。最近,CoS纳米粒子析氢性能也被研究者所关注,Sun等人用微波加热法成功合成了CoS纳米粒子,并研究了微波加热时间不同对CoS在中性溶液中析氢性能的影响。但是CoS电子传递速率慢,易团聚,稳定性差等缺点,限制了其析氢性能。本发明通过还原氧化石墨烯对CoS进行改性,增大其电子传导速率,从而增大其导电性,通过引入杂环原子氮,改变纳米粒子间层间距,进一步扩大活性位点,有效的提高了CoS电化学析氢性能。
发明内容
本发明旨在提供CoS纳米颗粒/N掺杂还原氧化石墨烯(CoS纳米颗粒/N掺杂RGO)析氢复合材料的制备方法,该方法通过简单的溶剂热法制得前驱体,在通过高温煅烧的方法获得CoS纳米颗粒/N掺杂RGO复合材料。本发明制备的CoS纳米颗粒/N掺杂RGO复合材料可显著提高单体的析氢性能。
CoS纳米颗粒/N掺杂RGO析氢复合材料的制备,具体包括以下步骤:
(1)称取一定量的Co(NO3)2·6H2O溶解到去离子水中,得到分散液A;
(2)称取一定量的双氰胺(DCDA)溶解到去离子水中;将DCDA溶液缓慢注入到得到分散液A溶液中,充分搅拌均匀得到分散液B;
(3)然后取GO溶液缓慢注入分散液B溶液中,搅拌,在超声仪中超声,得到分散液C;
(4)在剧烈搅拌下,将NH3·H2O点滴注入到分散液C中,调节溶液pH到10,形成墨绿色溶液D;
(5)称取一定量的C2H5NS溶解在去离子水中,在剧烈搅拌下将溶液缓慢注入到墨绿色溶液D中,剧烈搅拌直至反应完全;然后将其转入水热釜中,水热反应结束后,待其冷却到室温将其取出,用去离子水和乙醇洗涤5次,冷冻干燥,得到黑色粉末;
(6)将冷冻干燥后的黑色粉末转移到坩埚中,在N2范围中程序升温至煅烧温度,煅烧结束后,取出研磨,得到CoS纳米颗粒/N掺杂RGO析氢复合材料。
不加DCDA,GO溶液,用同样的方法合成CoS单体;
不加DCDA,用同样的方法合成CoS/RGO。
所述GO溶液的浓度为2mg/ml,所述Co(NO3)2·6H2O,C2H5NS,GO溶液的用量比例为:0.75mmol:4mmol:20ml。
步骤(2)中DCDA的量与步骤(3)中石墨烯的质量比分别为1:2,1:1,2:1,4:1。
步骤(4)中,所述NH3·H2O的质量分数为25-28%。
步骤(5)中,所述搅拌时间30min,所述水热反应的温度为180℃,水热反应的时间为14h。
步骤(6)中,所述煅烧温度分别为300℃、600℃或800℃,煅烧时间均为4h,所述程序升温的升温速率4℃/min。
本发明所述CoS纳米颗粒/N掺杂RGO析氢复合材料,用于电化学析氢的催化剂的用途。
CoS纳米颗粒/N掺杂RGO析氢复合材料,有效提高了硫化钴单体的电化学析氢性能,相较于贵金属催化剂Pt、Rh、Ru等,具有催化活性高、反应条件温和,合成工艺简便,方法简单等优点。
本发明的有益效果为:
(1)本发明制备的CoS纳米颗粒/N掺杂RGO析氢复合材料的制备,其制备工艺简单,成本低,易于大规模工业化生产,该材料具有良好的电化学稳定性和析氢性能,在解决环境污染和能源危机方面有良好的应用前景。
(2)电化学体系中的氮掺杂有效的增大了粒子间的层间距,增加了催化剂与电解液的接触面积,CoS纳米颗粒/N掺杂RGO析氢复合材料起始过电位70.6mV,塔菲尔斜率74.4mV dec-1,电流密度为10mA/cm2时的过电位为187.3mV;单体硫化钴的起始过电位为306.3mV,塔菲尔斜率153.5mV dec-1;CoS纳米颗粒/N掺杂RGO析氢复合材料与单体CoS在析氢方面相比较性能有了明显的提高。
(3)CoS纳米颗粒/N掺杂RGO析氢复合材料可作为性能优良的电化学析氢催化剂。氮掺杂的RGO与CoS复合所产生的协同效应既有利于提高了光生电子和空穴的寿命,促进电荷的传输,又有效地提升了复合后催化剂的稳定性。因此,CoS纳米颗粒/N掺杂RGO复合材料显著地提升了催化剂对电解水析氢性能,在电催化实际应用领域具有广阔的前景。
附图说明
图1为实施例1所制备的样品的XRD图谱,与CoS,CoS/RGO的XRD图的对比图;
图2为实施例1所制备的样品的扫描电镜图,A为单体CoS扫描电镜图,B为CoS纳米颗粒/N掺杂RGO复合材料的扫描电镜图;
图3为实施例1所制备的CoS纳米颗粒/N掺杂RGO复合材料在酸性溶液中电化学析氢效果图。
具体实施方式
下面结合说明书附图以及具体实施例对本发明作进一步说明。
实施例1:
制备CoS纳米颗粒/N掺杂RGO析氢复合材料的:
称取0.75mmol(0.2183g)的Co(NO3)2·6H2O溶解到去离子水中,搅拌直至形成均一溶液;
称取0.96mmol(0.08072g)的DCDA溶解到去离子水中,形成均一溶液;
将DCDA溶液缓慢注入到Co(NO3)2·6H2O溶液中;然后取20ml GO(2mg/ml)溶液缓慢注入上述均一的混合溶液中,剧烈搅拌,在超声仪中超声30min;在剧烈搅拌下,将NH3·H2O点滴注入到均一混合溶液中(PH=10),形成墨绿色溶液;
称取4mmol(0.3005g)的C2H5NS溶解在去离子水中,在剧烈搅拌下将溶液缓慢注入到墨绿色溶液中,搅拌30min;然后将其转入100ml水热釜中,在180℃加热14h;待其冷却到室温将其取出,用去离子水和乙醇洗涤5次,冷冻干燥。将冷冻干燥后的黑色粉末转移到坩埚中,在N2范围中煅烧,在300℃,600℃,800℃温度下煅烧4h,升温速率4℃/min。然后取出研磨,得到CoS纳米颗粒/N掺杂RGO析氢复合材料。经过X射线衍射图谱(XRD)对比不同煅烧温度下的复合材料,300℃下煅烧出来的物质晶相杂乱,析氢稳定性差,原因是由于煅烧温度低,部分未完全反应的C2H5NS没有充分分解;进一步提高煅烧温度,至煅烧温度升高到600℃时,所对应的XRD图晶相较好,与标准卡片(JCPDS NO.75-0605)完全吻合,显示出CoS纳米颗粒/N掺杂RGO复合材料的成功合成;当进一步提高煅烧温度至800℃时,XRD图谱显示部分CoS转变为Co9S8,并非想要得到的物质。通过不同的煅烧温度梯度,我们初步确认了合成CoS纳米颗粒/N掺杂RGO析氢复合材料合适的煅烧温度为600℃,在以下的合成CoS纳米颗粒,CoS/RGO纳米颗粒,所用的煅烧温度均为600℃。
实施例2:
制备单体CoS纳米颗粒:
称取0.75mmol(0.2183g)的Co(NO3)2·6H2O溶解到去离子水中,搅拌形成均一混合溶液;在剧烈搅拌下,将NH3·H2O点滴注入到均一混合溶液中(PH=10),形成墨绿色溶液;称取4mmol(0.3005g)的C2H5NS溶解在去离子水中,在剧烈搅拌下将溶液缓慢注入到墨绿色溶液中,搅拌30min;然后将其转入100ml水热釜中,在180℃加热14h;待其冷却到室温将其取出,用去离子水和乙醇洗涤5次,冷冻干燥。将冷冻干燥后的黑色粉末转移到坩埚中,在N2范围中煅烧,在600℃温度下煅烧4h,升温速率4℃/min。然后取出研磨,得到单体CoS纳米颗粒。
实施例3:
制备CoS/RGO纳米颗粒:
称取0.75mmol(0.2183g)的Co(NO3)2·6H2O溶解到去离子水中,搅拌形成均一溶液;然后取20ml GO(2mg/ml)溶液缓慢注入上述均一的溶液中,剧烈搅拌,在超声仪中超声30min;在剧烈搅拌下,将NH3·H2O点滴注入到均一混合溶液中(调节PH=10),形成墨绿色溶液;称取4mmol(0.3005g)的C2H5NS溶解在去离子水中,在剧烈搅拌下将溶液缓慢注入到墨绿色溶液中,搅拌30min;然后将其转入100ml水热釜中,在180℃加热14h;待其冷却到室温将其取出,用去离子水和乙醇洗涤5次,冷冻干燥。将冷冻干燥后的黑色粉末转移到坩埚中,在N2范围中煅烧,在600℃温度下煅烧4h,升温速率4℃/min。然后取出研磨,得到CoS/RGO纳米颗粒。
实施例4:
制备不同氮掺杂含量的CoS纳米颗粒/N掺杂RGO复合材料
称取0.75mmol(0.2183g)的Co(NO3)2·6H2O溶解到去离子水中,搅拌形成均一溶液;分别称取一定量的DCDA溶解到去离子水中;将DCDA溶液缓慢注入到Co(NO3)2·6H2O溶液中;然后取20ml GO(2mg/ml)溶液缓慢注入上述均一的溶液中,剧烈搅拌,在超声仪中超声30min;在剧烈搅拌下,将NH3·H2O点滴注入到均一混合溶液中(PH=10),形成墨绿色溶液;称取4mmol(0.3005g)的C2H5NS溶解在去离子水中,在剧烈搅拌下将溶液缓慢注入到墨绿色溶液中,搅拌30min;然后将其转入100ml水热釜中,在180℃加热14h;待其冷却到室温将其取出,用去离子水和乙醇洗涤5次,冷冻干燥。将冷冻干燥后的黑色粉末转移到10ml的坩埚中,在N2范围中煅烧,在600℃下煅烧4h,升温速率4℃/min。然后取出研磨,得到CoS/N-dopeRGO-1,CoS/N-dope RGO-2,CoS/N-dope RGO-3,CoS/N-dope RGO-4。
其中CoS/N-dope RGO-1,CoS/N-dope RGO-2,CoS/N-dope RGO-3,CoS/N-dopeRGO-4中DCDA与GO的质量比分别为1:2,1:1,2:1,4:1。
图1是在煅烧温度为600℃下,CoS单体,CoS/RGO复合材料,CoS/N-RGO复合材料的XRD图谱,如图所示CoS单体XRD图谱与标准卡片(JCPDS NO.75-0605)能够完全吻合,说明我们成功合成了CoS单体;还原氧化石墨烯(RGO)的引入,并没有改变CoS单体的晶相,在2θ为11.5°左右有个明显的C峰,说明RGO的成功引入,杂环原子氮的引入并没有明显改变CoS/RGO复合材料XRD图谱。图1显示我们在煅烧温度为600℃时,成功合成了CoS单体,CoS/RGO复合材料,CoS/N-RGO复合材料。
图2为CoS单体(A),CoS/N-RGO复合材料(B)的SEM图,图(A)显示CoS单体为无规则的颗粒状,部分形成片状,图(A)中能明显看出CoS单体团聚在一块。图(B)中我们能够清晰的看到CoS纳米颗粒成功的负载在氮掺杂还原氧化石墨烯(N-RGO)上,氮掺杂还原氧化石墨烯的引入,显著地增加了复合材料的片层状结构,有效抑制了CoS纳米颗粒的团聚,增大了复合材料与电解液的接触面积,有效的增大了催化活性面积,有利于电催化析氢活性的提高。
图3为CoS单体,CoS/RGO复合材料,CoS/N-RGO复合材料在0.5mol/L的H2SO4溶液中的极化曲线图,CoS纳米颗粒/N掺杂RGO析氢复合材料起始过电位70.6mV,塔菲尔斜率74.4mV dec-1,电流密度为10mA/cm2时的过电位为187.3mV;单体硫化钴的起始过电位为306.3mV,塔菲尔斜率153.5mV dec-1;CoS纳米颗粒/N掺杂RGO析氢复合材料与单体CoS在析氢方面相比较性能有了明显的提高。
Claims (8)
1.CoS纳米颗粒/N掺杂RGO析氢复合材料的制备方法,其特征在于,包括如下步骤:
(1)称取一定量的Co(NO3)2·6H2O溶解到去离子水中,得到分散液A;
(2)称取一定量的双氰胺(DCDA)溶解到去离子水中;将DCDA溶液缓慢注入到得到分散液A溶液中,充分搅拌均匀得到分散液B;
(3)然后取GO溶液缓慢注入分散液B溶液中,搅拌,在超声仪中超声,得到分散液C;
(4)在剧烈搅拌下,将NH3·H2O点滴注入到分散液C中,调节溶液pH到10,形成墨绿色溶液D;
(5)称取一定量的C2H5NS溶解在去离子水中,在剧烈搅拌下将溶液缓慢注入到墨绿色溶液D中,剧烈搅拌直至反应完全;然后将其转入水热釜中,水热反应结束后,待其冷却到室温将其取出,用去离子水和乙醇洗涤5次,冷冻干燥,得到黑色粉末;
(6)将冷冻干燥后的黑色粉末转移到坩埚中,在N2范围中程序升温至煅烧温度,煅烧结束后,取出研磨,得到CoS纳米颗粒/N掺杂RGO析氢复合材料。
2.根据权利要求1所述的CoS纳米颗粒/N掺杂RGO析氢复合材料的制备方法,其特征在于,所述GO溶液的浓度为2mg/ml,所述Co(NO3)2·6H2O,C2H5NS,GO溶液的用量比例为:0.75mmol:4mmol:20ml。
3.根据权利要求1所述的CoS纳米颗粒/N掺杂RGO析氢复合材料的制备方法,其特征在于,步骤(2)中DCDA的量与步骤(3)中GO溶液中GO的质量比分别为1:2,1:1,2:1,4:1。
4.根据权利要求1所述的CoS纳米颗粒/N掺杂RGO析氢复合材料的制备方法,其特征在于,步骤(4)中,所述NH3·H2O的质量分数为25-28%。
5.根据权利要求1所述的CoS纳米颗粒/N掺杂RGO析氢复合材料的制备方法,其特征在于,步骤(5)中,所述搅拌时间30min,所述水热反应的温度为180℃,水热反应的时间为14h。
6.根据权利要求1所述的CoS纳米颗粒/N掺杂RGO析氢复合材料的制备方法,步骤(6)中,所述煅烧温度分别为300℃、600℃或800℃,煅烧时间均为4h,所述程序升温的升温速率4℃/min。
7.根据权利要求1~6任一项所述制备方法制得的CoS纳米颗粒/N掺杂RGO析氢复合材料。
8.将权利要求7所述的CoS纳米颗粒/N掺杂RGO析氢复合材料用于电化学析氢的催化剂的用途。
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