CN110743568B - 一种花状多孔Co3O4负载Pt粒子纳米材料及其制备方法和应用 - Google Patents
一种花状多孔Co3O4负载Pt粒子纳米材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种花状多孔Co3O4负载Pt粒子纳米材料及其制备方法和其作为电解水催化剂的应用,该方法包括利用吡嗪(C4H4N2)作为配位分子,与Pt盐和Co盐形成络合物沉淀,干燥后,再在氧气气氛下,升温煅烧氧化,即得所述花状多孔Co3O4负载Pt粒子纳米材料。本发明制备方法简单易行,原料成本低廉,可实现规模化生产。所得纳米材料中,Pt作为HER活性中心,Co3O4作为OER活性中心的同时与Pt有协同作用可以促进水的解离,其作为电解水催化剂表现处理优异的催化活性和稳定性。
Description
技术领域
本发明涉及一种花状多孔Co3O4负载Pt粒子纳米材料及其制备方法和其作为电解水催化剂的应用,属于Pt基电解水材料技术领域。
背景技术
能源危机和环境污染是目前人类所必须面对的两大难题,开发新技术、新能源是解决这两个问题的关键,也是科研领域的研究热点,诸如太阳能、风能、生物质能等一系列新能源应运而生,其中氢能作为一种高效清洁的可再生能源,被认为是未来最具发展前景的新型能源载体。在众多制氢的方法中,电解水制氢因其高效、绿色、环保、原料丰富等优点脱颖而出,电解所需要的电能可由太阳能、风能等供给,因此,电解水制氢也是一种重要的能源转换与存储的手段。到目前为止,贵金属(Pt)和贵金属氧化物(IrO2, RuO2)在酸性介质中具有最优异的HER或OER活性,但是它们昂贵的价格和匮乏的储量阻碍了它们商业发展。另外,相对于HER,OER反应动力学过程缓慢并且需要非常高的过电位来驱动电化学反应,这从而影响了电解水效率。因此开发高效、低成本的电催化剂是十分重要。
目前发展的电解水催化剂主要有金属合金、过渡金属硫化物、碳化物、氮化物、硒化物、氧化物、磷化物和杂原子掺杂碳等,但是它们的性能仍不能满足需求。因此在提高贵金属基催化剂性能的同时,降低贵金属的载量以降低成本也很重要。
发明内容
发明目的:为解决上述技术问题,本发明的目的在于提供了花状多孔Co3O4负载Pt粒子纳米材料和其制备方法,以及该方法制得的电极材料在电解水方面的应用。本发明通过一种简易通用的自牺牲模板法制备PtCo霍夫曼配合物前驱体,经过氧化生成花状的由表面粗糙多孔的Co3O4片负载Pt粒子的纳米材料,作为电解水材料表现出优异的 HER,OER性能和稳定性。
技术方案:为了达到上述发明目的,本发明所采用的技术方案如下:
一种花状多孔Co3O4负载Pt粒子纳米材料的制备方法,包括利用吡嗪(C4H4N2) 作为配位分子,与Pt盐和Co盐形成络合物沉淀,干燥后,再在氧气气氛下,升温煅烧氧化,即得所述花状多孔Co3O4负载Pt粒子纳米材料。
作为优选:
所述Pt盐选自K2[Pt(CN)4],Co盐选自Co(NO3)2或CoCl2。
所述吡嗪、Pt盐和Co盐的摩尔比为(0.01~1):(0.01~1):(0.01~1),优选1:1:1。
所述升温采用程序升温方法,升温速率为1~20℃·min-1。
所述煅烧氧化的温度为200-500℃,时间为1~4h。
优选,包括以下步骤:
制备吡嗪和K2[Pt(CN)]4的混合溶液A、以及Co(NO3)2溶液,将Co(NO3)2溶液滴加入混合溶液A中,反应后将沉淀干燥,然后在氧气气氛下,以1~20℃·min-1的速率程序升温,升温至200-500℃煅烧氧化1~4h,即得所述花状多孔Co3O4负载Pt粒子纳米材料。
进一步优选,所述混合溶液A和Co(NO3)2溶液的溶剂均选自水和甲醇的混合溶剂,其中,水和甲醇的体积比为(0.1~99):1。
本发明还提供了一种由上述方法制备的花状多孔Co3O4负载Pt粒子纳米材料。
本发明最后提供了所述的花状多孔Co3O4负载Pt粒子纳米材料作为电解水催化剂的应用。
本发明方法中,以K2[Pt(CN)]4和Co(NO3)2为金属源,吡嗪为配位剂,预先制备肉粉色的PtCo霍夫曼配合物,在通过自牺牲模板法氧化处理得到花状多孔Co3O4负载Pt 粒子纳米材料。该材料,具有独特的由二维片组装成的三维纳米花结构,粗糙的Co3O4片表面具有丰富的孔道,且均匀负载着高度分散的直径为3nm的Pt小粒子。
本发明中所制备花状多孔Co3O4负载Pt粒子纳米材料,具有以下几种优势:①独特的花状多级结构,由排列整齐的纳米片形成的多尺度结构具有丰富的暴露的可接近的活性位点,可以促进平面内的传质。②有机组分裂解时有效引入孔道,同时保留其独特的形貌,暴露出大的比表面积和丰富的活性位点,有助于气体和电解质的传输与扩散。③前驱体合成时,各元素均匀分布,氧化后,Pt粒子均匀的负载Co3O4片上,具有强烈的协同作用。④高度分散的Pt作为HER活性中心,Co3O4作为OER活性中心同时与 Pt的协同作用促进了水的解离,从而加快氢气的演化。
有益效果:相对于现有技术,本发明的优势在于:
本发明是一种新型的花状结构的电极材料的制备方法,通过简便、可实现规模化生产的自牺牲模板法制备花状多孔Co3O4负载Pt粒子纳米材料,该方法工艺简单易行、操作简单、可实现大规模生产;所制得的产物形貌规整、Pt纳米粒子尺寸均一地负载在多孔Co3O4片上,从而,所制得的材料具有活性位点多、循环稳定性良好和花状结构等特点。与常规铂基合金材料相比,所制备的花状多孔Co3O4负载Pt粒子纳米材料具备更为优异的结构特点和组分优势,是一种极有潜力的电解水催化材料,在未来的能源行业应用前景广阔。
附图说明
图1是根据本发明方法制备的花状PtCo霍夫曼配合物前驱体的SEM图谱;
图2是根据本发明方法制备的花状多孔Co3O4负载Pt粒子纳米材料的SEM图谱;
图3是根据本发明方法制备的花状多孔Co3O4负载Pt粒子纳米材料的HRTEM图谱;
图4是根据本发明方法制备的花状多孔Co3O4负载Pt粒子纳米材料的TG图谱;
图5是根据本发明方法制备的花状多孔Co3O4负载Pt粒子纳米材料的XRD图谱;
图6是根据本发明方法制备的花状多孔Co3O4负载Pt粒子纳米材料的EDS图谱;
图7是根据本发明方法制备的花状多孔Co3O4负载Pt粒子纳米材料的HER的LSV 图谱;
图8是根据本发明方法制备的花状多孔Co3O4负载Pt粒子纳米材料的循环1000圈前后的HER对比图谱;
图9是根据本发明方法制备的花状多孔Co3O4负载Pt粒子纳米材料的OER的LSV 图谱;
图10是根据本发明方法制备的花状多孔Co3O4负载Pt粒子纳米材料的循环1000 圈前后的OER对比图谱;
图11是根据本发明方法制备的花状多孔Co3O4负载Pt粒子纳米材料的电解水性能图谱;
图12是根据本发明方法制备的花状多孔Co3O4负载Pt粒子纳米材料的电解水的计时电流曲线。
具体实施方式
下面通过具体实施例对本发明所述的技术方案给予进一步详细的说明。
实施例1
一种花状多孔Co3O4负载Pt粒子纳米材料制备方法,包括以下步骤:
1)合成花状PtCo霍夫曼配合物:配制混合溶液(水:甲醇体积比=1:1),0.1mmol吡嗪和0.1mmol K2[Pt(CN)]4溶于35mL混合溶液记为溶液A,0.1mmol Co(NO3)2溶于35mL混合溶液记为溶液B,溶液B缓慢滴加于A中,搅拌1h,离心干燥得到肉粉色粉末,即花状PtCo霍夫曼配合物;
2)制备花状多孔Co3O4负载Pt粒子纳米材料:将步骤1)制得的肉粉色粉末,在氧气气氛下,以1℃/min程序升温至400℃进行热处理,并在该温度下保持1h,然后冷却,即可得到最终产物。
实施例2
一种花状多孔Co3O4负载Pt粒子纳米材料制备方法,包括以下步骤:
1)合成花状PtCo霍夫曼配合物:配制混合溶液(水:甲醇体积比=1:1),0.1mmol吡嗪和0.1mmol K2[Pt(CN)]4溶于25mL混合溶液记为溶液A,0.1mmol Co(NO3)2溶于25mL混合溶液记为溶液B,溶液B缓慢滴加于A中,搅拌1h,离心干燥得到肉粉色粉末,即花状PtCo霍夫曼配合物;
2)制备花状多孔Co3O4负载Pt粒子纳米材料:将步骤1)制得的肉粉色粉末,在氧气气氛下,以1℃/min程序升温至400℃进行热处理,并在该温度下保持1h,然后冷却,即可得到最终产物。
实施例3
一种花状多孔Co3O4负载Pt粒子纳米材料制备方法,包括以下步骤:
1)合成花状PtCo霍夫曼配合物:配制混合溶液(水:甲醇体积比=1:1),0.1mmol吡嗪和1mmol K2[Pt(CN)]4溶于35mL混合溶液记为溶液A,1mmol Co(NO3)2溶于 35mL混合溶液记为溶液B,溶液B缓慢滴加于A中,搅拌1h,离心干燥得到肉粉色粉末,即花状PtCo霍夫曼配合物;
2)制备花状多孔Co3O4负载Pt粒子纳米材料:将步骤1)制得的肉粉色粉末,在氧气气氛下,以1℃/min程序升温至400℃进行热处理,并在该温度下保持1h,然后冷却,即可得到最终产物。
实施例4
一种花状多孔Co3O4负载Pt粒子纳米材料制备方法,包括以下步骤:
1)合成花状PtCo霍夫曼配合物:配制混合溶液(水:甲醇体积比=1:1),1mmol 吡嗪和0.1mmol K2[Pt(CN)]4溶于35mL混合溶液记为溶液A,0.1mmol Co(NO3)2溶于35mL混合溶液记为溶液B,溶液B缓慢滴加于A中,搅拌1h,离心干燥得到肉粉色粉末,即花状PtCo霍夫曼配合物;
2)制备花状多孔Co3O4负载Pt粒子纳米材料:将步骤1)制得的肉粉色粉末,在氧气气氛下,以1℃/min程序升温至400℃进行热处理,并在该温度下保持1h,然后冷却,即可得到最终产物。
实施例5
一种花状多孔Co3O4负载Pt粒子纳米材料制备方法,包括以下步骤:
1)合成花状PtCo霍夫曼配合物:配制混合溶液(水:甲醇体积比=1:1),0.1mmol吡嗪和0.1mmol K2[Pt(CN)]4溶于35mL混合溶液记为溶液A,0.2mmol Co(NO3)2溶于35mL混合溶液记为溶液B,溶液B缓慢滴加于A中,搅拌1h,离心干燥得到肉粉色粉末,即花状PtCo霍夫曼配合物;
2)制备花状多孔Co3O4负载Pt粒子纳米材料:将步骤1)制得的肉粉色粉末,在氧气气氛下,以1℃/min程序升温至400℃进行热处理,并在该温度下保持1h,然后冷却,即可得到最终产物。
实施例6
一种花状多孔Co3O4负载Pt粒子纳米材料制备方法,包括以下步骤:
1)合成花状PtCo霍夫曼配合物:配制混合溶液(水:甲醇体积比=1:1),0.1mmol吡嗪和0.2mmol K2[Pt(CN)]4溶于35mL混合溶液记为溶液A,0.1mmol Co(NO3)2溶于35mL混合溶液记为溶液B,溶液B缓慢滴加于A中,搅拌1h,离心干燥得到肉粉色粉末,即花状PtCo霍夫曼配合物;
2)制备花状多孔Co3O4负载Pt粒子纳米材料:将步骤1)制得的肉粉色粉末,在氧气气氛下,以1℃/min程序升温至400℃进行热处理,并在该温度下保持1h,然后冷却,即可得到最终产物。
实施例7
一种花状多孔Co3O4负载Pt粒子纳米材料制备方法,包括以下步骤:
1)合成花状PtCo霍夫曼配合物:配制混合溶液(水:甲醇体积比=1:1),0.1mmol吡嗪和0.1mmol K2[Pt(CN)]4溶于35mL混合溶液记为溶液A,0.1mmol Co(NO3)2溶于35mL混合溶液记为溶液B,溶液B缓慢滴加于A中,搅拌2h,离心干燥得到肉粉色粉末,即花状PtCo霍夫曼配合物;
2)制备花状多孔Co3O4负载Pt粒子纳米材料:将步骤1)制得的肉粉色粉末,在氧气气氛下,以1℃/min程序升温至400℃进行热处理,并在该温度下保持1h,然后冷却,即可得到最终产物。
实施例8
一种花状多孔Co3O4负载Pt粒子纳米材料制备方法,包括以下步骤:
1)合成花状PtCo霍夫曼配合物:配制混合溶液(水:甲醇体积比=1:1),0.1mmol吡嗪和0.1mmol K2[Pt(CN)]4溶于35mL混合溶液记为溶液A,0.1mmol Co(NO3)2溶于35mL混合溶液记为溶液B,溶液B缓慢滴加于A中,搅拌1h,离心干燥得到肉粉色粉末,即花状PtCo霍夫曼配合物;
2)制备花状多孔Co3O4负载Pt粒子纳米材料:将步骤1)制得的肉粉色粉末,在氧气气氛下,以1℃/min程序升温至300℃进行热处理,并在该温度下保持1h,然后冷却,即可得到最终产物。
实施例9
一种花状多孔Co3O4负载Pt粒子纳米材料制备方法,包括以下步骤:
1)合成花状PtCo霍夫曼配合物:配制混合溶液(水:甲醇体积比=1:1),0.1mmol吡嗪和0.1mmol K2[Pt(CN)]4溶于35mL混合溶液记为溶液A,0.1mmol Co(NO3)2溶于35mL混合溶液记为溶液B,溶液B缓慢滴加于A中,搅拌1h,离心干燥得到肉粉色粉末,即花状PtCo霍夫曼配合物;
2)制备花状多孔Co3O4负载Pt粒子纳米材料:将步骤1)制得的肉粉色粉末,在氧气气氛下,以1℃/min程序升温至500℃进行热处理,并在该温度下保持1h,然后冷却,即可得到最终产物。
实施例10
一种花状多孔Co3O4负载Pt粒子纳米材料制备方法,包括以下步骤:
1)合成花状PtCo霍夫曼配合物:配制混合溶液(水:甲醇体积比=1:1),0.1mmol吡嗪和0.1mmol K2[Pt(CN)]4溶于35mL混合溶液记为溶液A,0.1mmol Co(NO3)2溶于35mL混合溶液记为溶液B,溶液B缓慢滴加于A中,搅拌1h,离心干燥得到肉粉色粉末,即花状PtCo霍夫曼配合物;
2)制备花状多孔Co3O4负载Pt粒子纳米材料:将步骤1)制得的肉粉色粉末,在氧气气氛下,以1℃/min程序升温至40℃进行热处理,并在该温度下保持4h,然后冷却,即可得到最终产物。
实施例11
一种花状多孔Co3O4负载Pt粒子纳米材料制备方法,包括以下步骤:
1)合成花状PtCo霍夫曼配合物:配制混合溶液(水:甲醇体积比=1:1),0.1mmol吡嗪和0.1mmol K2[Pt(CN)]4溶于35mL混合溶液记为溶液A,0.1mmol Co(NO3)2溶于35mL混合溶液记为溶液B,溶液B缓慢滴加于A中,搅拌1h,离心干燥得到肉粉色粉末,即花状PtCo霍夫曼配合物;
2)制备花状多孔Co3O4负载Pt粒子纳米材料:将步骤1)制得的肉粉色粉末,在氧气气氛下,以5℃/min程序升温至400℃进行热处理,并在该温度下保持1h,然后冷却,即可得到最终产物。
实施例12
一种花状多孔Co3O4负载Pt粒子纳米材料制备方法,包括以下步骤:
1)合成花状PtCo霍夫曼配合物:配制混合溶液(水:甲醇体积比=1:1),0.1mmol吡嗪和0.1mmol K2[Pt(CN)]4溶于35mL混合溶液记为溶液A,0.1mmol Co(NO3)2溶于35mL混合溶液记为溶液B,溶液B缓慢滴加于A中,搅拌1h,离心干燥得到肉粉色粉末,即花状PtCo霍夫曼配合物;
2)制备花状多孔Co3O4负载Pt粒子纳米材料:将步骤1)制得的肉粉色粉末,在氧气气氛下,以10℃/min程序升温至400℃进行热处理,并在该温度下保持1h,然后冷却,即可得到最终产物。
采用TEM、SEM、XRD、XPS和TG等途径对以上实施例制备的花状多孔Co3O4负载Pt粒子纳米材料进行物理表征。从SEM图谱(图1,2),可以看出所制备前驱体和氧化后催化剂的三维花状结构,进一步放大的高倍TEM图(图3)显示Pt纳米粒子均匀地负载在多孔Co3O4片上,粒径约为3nm。图4是所制备的前驱体的热重谱图,从图中,可以得到催化剂最佳氧化温度为400℃。由图5,XRD图谱可以看出,催化剂的衍射峰可与Pt和Co3O4的标准卡片吻合。EDS谱图(图6)表明,最终催化剂中Pt和 Co的比例与投料比一致。最后,以商业化20%Pt/C和RuO2为参照催化剂,将所制备的花状多孔Co3O4负载Pt粒子纳米材料应用在HER和OER反应上。图7,8和图9,10 分别是两种催化剂的HER/OER性能和稳定性对比,从图7可以看出,在10mA cm-2处,花状多孔Co3O4负载Pt粒子纳米材料过电势为34mV,接近是商业化Pt/C催化剂(10 mV)。图8表明,经过1000圈的加速耐久力稳定性测试后过电位仅稍有改变。图9看出在10mA cm-2处,花状多孔Co3O4负载Pt粒子纳米材料过电势为390mV,接近是商业化RuO2催化剂(340mV)。大电流密度下(50mA cm-2)过电势比RuO2。图10表明,经过1000圈的加速耐久力稳定性测试后过电位仅稍有改变。图11是花状多孔Co3O4负载Pt粒子纳米材料的电解水性能图,在10mAcm-2处,电池电压为1.6V。图12表明,该材料具有良好的电解水稳定性。这表明状多孔Co3O4负载Pt粒子纳米材料兼具HER 和OER双功能。
Claims (9)
1.一种花状多孔Co3O4负载Pt粒子纳米材料的制备方法,其特征在于,包括利用吡嗪C4H4N2作为配位分子,与Pt盐和Co盐形成络合物沉淀,干燥后,再在氧气气氛下,升温煅烧氧化,即得所述花状多孔Co3O4负载Pt粒子纳米材料;其中所述Pt盐为K2[Pt(CN)4]。
2.根据权利要求1所述的花状多孔Co3O4负载Pt粒子纳米材料的制备方法,其特征在于,所述Co盐选自Co(NO3)2或CoCl2。
3.根据权利要求1所述的花状多孔Co3O4负载Pt粒子纳米材料的制备方法,其特征在于,所述吡嗪、Pt盐和Co盐的摩尔比为(0.01~1):(0.01~1):(0.01~1)。
4.根据权利要求1所述的花状多孔Co3O4负载Pt粒子纳米材料的制备方法,其特征在于,所述升温采用程序升温方法,升温速率为1~20℃·min-1。
5.根据权利要求1所述的花状多孔Co3O4负载Pt粒子纳米材料的制备方法,其特征在于,所述煅烧氧化的温度为200-500℃,时间为1~4h。
6.根据权利要求1所述的花状多孔Co3O4负载Pt粒子纳米材料的制备方法,其特征在于,包括以下步骤:
制备吡嗪和K2[Pt(CN)]4的混合溶液A、以及Co(NO3)2溶液,将Co(NO3)2溶液滴加入混合溶液A中,反应后将沉淀干燥,然后在氧气气氛下,以1~20℃·min-1的速率程序升温,升温至200-500℃煅烧氧化1~4h,即得所述花状多孔Co3O4负载Pt粒子纳米材料。
7.根据权利要求6所述的花状多孔Co3O4负载Pt粒子纳米材料的制备方法,其特征在于,所述混合溶液A和Co(NO3)2溶液的溶剂均选自水和甲醇的混合溶剂,其中,水和甲醇的体积比为(0.1~99):1。
8.一种由权利要求1~7任一项所述的方法制备的花状多孔Co3O4负载Pt粒子纳米材料。
9.权利要求8所述的花状多孔Co3O4负载Pt粒子纳米材料作为电解水催化剂的应用。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104803818A (zh) * | 2015-03-27 | 2015-07-29 | 中国石油大学(北京) | 在金属有机骨架材料存在下进行液相乙烯齐聚和聚合的方法 |
CN105514369A (zh) * | 2015-12-07 | 2016-04-20 | 南京师范大学 | 一种中空SnO2/Co3O4杂化纳米管及其制备方法和应用 |
CN106824224A (zh) * | 2017-01-25 | 2017-06-13 | 中国科学院上海高等研究院 | 贵金属负载型四氧化钴纳米催化剂的制备方法及应用 |
CN108689786A (zh) * | 2018-05-08 | 2018-10-23 | 中国科学院青岛生物能源与过程研究所 | 一种借氢还原偶联合成亚胺和胺类化合物的方法 |
CN108736028A (zh) * | 2018-05-31 | 2018-11-02 | 深圳大学 | 一种多孔氮掺杂碳负载钴纳米材料、制备方法及其应用 |
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-
2019
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104803818A (zh) * | 2015-03-27 | 2015-07-29 | 中国石油大学(北京) | 在金属有机骨架材料存在下进行液相乙烯齐聚和聚合的方法 |
CN105514369A (zh) * | 2015-12-07 | 2016-04-20 | 南京师范大学 | 一种中空SnO2/Co3O4杂化纳米管及其制备方法和应用 |
CN106824224A (zh) * | 2017-01-25 | 2017-06-13 | 中国科学院上海高等研究院 | 贵金属负载型四氧化钴纳米催化剂的制备方法及应用 |
CN108689786A (zh) * | 2018-05-08 | 2018-10-23 | 中国科学院青岛生物能源与过程研究所 | 一种借氢还原偶联合成亚胺和胺类化合物的方法 |
CN108736028A (zh) * | 2018-05-31 | 2018-11-02 | 深圳大学 | 一种多孔氮掺杂碳负载钴纳米材料、制备方法及其应用 |
Non-Patent Citations (2)
Title |
---|
"Design and self-assembly of metal-organicframework-derived porous Co3O4 hierarchical structures for lithium-ionb atteries";Longmei Zhang et al;《Ceramics International》;20151214;第42卷;第5160-5170页 * |
"Synthesis and Characterization of New Cobalt(II)-Pyrazine Coordination Polymer as Precursor for Preparation of Co(II) Oxide Nanoparticles: Surprising Coordination, DFT Calculation and Spectroscopic Studies";Nafise Modanlou Juibari et al;《J Inorg Organomet Polym》;20170724;第27卷;第124-130页 * |
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