CN107008330B - 基于催渗原理的NiCoB纳米合金催化剂的制备方法和应用 - Google Patents
基于催渗原理的NiCoB纳米合金催化剂的制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种基于催渗原理的NiCoB纳米合金催化剂的制备方法,具体步骤如下:准确称取硼酐和铝粉,将硼酐、铝粉和清洗好的泡沫CoNi合金置入水热反应釜中,加入水搅拌均匀,密封后放入180‑220℃的烘箱中加热80‑100h,自然冷却至室温,取出泡沫CoNi合金;泡沫CoNi合金在开启式管式电炉内以8‑10℃/min的升温速度升至830‑870℃,恒温保持4‑6h,冷却至室温后,取出样品用清洗液清洗后即可得到粘接力良好的NiCoB纳米合金。由于在该工艺中B原子扩散到合金内部形成渗层,故形成的NiCoB合金催化剂和NiCo合金基体有良好的粘接力,不易脱落。
Description
技术领域
本发明属于纳米合金催化剂技术领域,具体涉及一种基于催渗原理的NiCoB纳米合金催化剂的制备方法和应用。
背景技术
NiCoB纳米合金由于具有独特的电子结构和优异的导电性能而被广泛用作NaBH4水解制氢中的催化剂。目前NiCoB纳米合金的制备一般采用化学、电化学或气相沉积的方法合成。用这些方法制备的NiCoB纳米合金都是粘附在NiCo合金基体表面,因此在析氢反应过程中,很容易脱落,这将导致NiCoB纳米合金的催化性能降低。
发明内容
为了解决上述问题,本发明提供一种基于催渗原理的NiCoB纳米合金催化剂的制备方法和应用。
本发明的目的是以下述方式实现的:
基于催渗原理的NiCoB纳米合金催化剂的制备方法,具体步骤如下:
(1)准确称取泡沫CoNi合金,用清洗液超声清洗8-12min;
(2)准确称取硼酐和铝粉,将硼酐、铝粉和清洗好的泡沫CoNi合金置入水热反应釜中,加入水搅拌均匀,密封后放入180-220℃的烘箱中加热80-100h,自然冷却至室温,取出泡沫CoNi合金,洗涤,干燥;
(3)将洗涤、干燥后的泡沫CoNi合金在开启式管式电炉内以8-10℃/min 的升温速度升至830-870℃,恒温保持4-6h,整个反应过程在氮气保护下进行;
(4)冷却至室温后,取出样品用清洗液清洗后即可得到粘接力良好的NiCoB纳米合金;
所述泡沫CoNi合金中Co和Ni的质量比为7:3-9:1,泡沫CoNi合金与硼酐的质量比为(2-3):1,铝粉的质量为硼酐质量的5%-10%。
所述泡沫CoNi合金中Co和Ni的质量比为7:3或9:1。
所述泡沫CoNi合金与硼酐的质量比为2:1。
所述清洗液为丙酮。
利用上述的基于催渗原理的NiCoB纳米合金催化剂的制备方法制备的NiCoB纳米合金催化剂在催化NaBH4水解制氢中的应用。
相对于现有技术,本发明采用新工艺,经过步骤(2)后,活性B原子粘附在泡沫CoNi合金表面,经过步骤(3)后,活性B原子扩散到泡沫CoNi合金内部,分别形成CoB、NiB相,最终形成NiCoB合金。由于在该工艺中B原子扩散到合金内部形成渗层,故形成的NiCoB合金催化剂和NiCo合金基体有良好的粘接力,不易脱落。
附图说明
图1是本发明制备的NiCoB纳米合金SEM形貌(200×)。
图2是本发明制备的NiCoB纳米合金SEM形貌(7000×)。
图3是图2中光标处能谱图。
图4是不同制备工艺制得的NiCoB催化剂的析氢速率。
具体实施方式
实施例1:
基于催渗原理的NiCoB纳米合金催化剂的制备方法,具体步骤如下:
(1)准确称取泡沫CoNi合金,用清洗液超声清洗8-12min;
(2)准确称取硼酐和铝粉,将硼酐、铝粉和清洗好的泡沫CoNi合金置入水热反应釜中,加入水搅拌均匀,密封后放入180-220℃的烘箱中加热80-100h,自然冷却至室温,取出泡沫CoNi合金,洗涤,干燥;
(3)将洗涤、干燥后的泡沫CoNi合金在开启式管式电炉内以8-10℃/min 的升温速度升至830-870℃,恒温保持4-6h,整个反应过程在氮气保护下进行;
(4)冷却至室温后,取出样品用清洗液清洗后即可得到粘接力良好的NiCoB纳米合金;
泡沫CoNi合金中Co和Ni的质量比为7:3-9:1,泡沫CoNi合金与硼酐的质量比为(2-3):1,铝粉的质量为硼酐质量的5%-10%。
泡沫CoNi合金中Co和Ni的质量比为7:3或9:1。
泡沫CoNi合金与硼酐的质量比为2:1。
清洗液为丙酮。
利用上述的基于催渗原理的NiCoB纳米合金催化剂的制备方法制备的NiCoB纳米合金催化剂在催化NaBH4水解制氢中的应用。
实施例2:
基于催渗原理的NiCoB纳米合金催化剂的制备方法,具体步骤如下:
(1)准确称取泡沫CoNi合金,用丙酮超声清洗8min;
(2)准确称取硼酐和铝粉,将硼酐、铝粉和清洗好的泡沫CoNi合金置入水热反应釜中,加入水搅拌均匀,密封后放入180℃的烘箱中加热80h,自然冷却至室温,取出泡沫CoNi合金,洗涤,干燥;
(3)将洗涤、干燥后的泡沫CoNi合金在开启式管式电炉内以8℃/min 的升温速度升至830℃,恒温保持4h,整个反应过程在氮气保护下进行;
(4)冷却至室温后,取出样品用丙酮清洗后即可得到粘接力良好的NiCoB纳米合金;
泡沫CoNi合金中Co和Ni的质量比为7:3,泡沫CoNi合金与硼酐的质量比为2:1,铝粉的质量为硼酐质量的5%。
实施例3:
基于催渗原理的NiCoB纳米合金催化剂的制备方法,具体步骤如下:
(1)准确称取泡沫CoNi合金,用丙酮超声清洗9min;
(2)准确称取硼酐和铝粉,将硼酐、铝粉和清洗好的泡沫CoNi合金置入水热反应釜中,加入水搅拌均匀,密封后放入190℃的烘箱中加热85h,自然冷却至室温,取出泡沫CoNi合金,洗涤,干燥;
(3)将洗涤、干燥后的泡沫CoNi合金在开启式管式电炉内以8.5℃/min 的升温速度升至840℃,恒温保持4.5h,整个反应过程在氮气保护下进行;
(4)冷却至室温后,取出样品用丙酮清洗后即可得到粘接力良好的NiCoB纳米合金;
泡沫CoNi合金中Co和Ni的质量比为8:3,泡沫CoNi合金与硼酐的质量比为2.2:1,铝粉的质量为硼酐质量的6%。
实施例4:
基于催渗原理的NiCoB纳米合金催化剂的制备方法,具体步骤如下:
(1)准确称取泡沫CoNi合金,用丙酮超声清洗10min;
(2)准确称取硼酐和铝粉,将硼酐、铝粉和清洗好的泡沫CoNi合金置入水热反应釜中,加入水搅拌均匀,密封后放入200℃的烘箱中加热90h,自然冷却至室温,取出泡沫CoNi合金,洗涤,干燥;
(3)将洗涤、干燥后的泡沫CoNi合金在开启式管式电炉内以9℃/min 的升温速度升至850℃,恒温保持5h,整个反应过程在氮气保护下进行;
(4)冷却至室温后,取出样品用丙酮清洗后即可得到粘接力良好的NiCoB纳米合金;
泡沫CoNi合金中Co和Ni的质量比为8:2,泡沫CoNi合金与硼酐的质量比为2.5:1,铝粉的质量为硼酐质量的7%。
实施例5:
基于催渗原理的NiCoB纳米合金催化剂的制备方法,具体步骤如下:
(1)准确称取泡沫CoNi合金,用丙酮超声清洗11min;
(2)准确称取硼酐和铝粉,将硼酐、铝粉和清洗好的泡沫CoNi合金置入水热反应釜中,加入水搅拌均匀,密封后放入210℃的烘箱中加热95h,自然冷却至室温,取出泡沫CoNi合金,洗涤,干燥;
(3)将洗涤、干燥后的泡沫CoNi合金在开启式管式电炉内以9.5℃/min 的升温速度升至860℃,恒温保持5.5h,整个反应过程在氮气保护下进行;
(4)冷却至室温后,取出样品用丙酮清洗后即可得到粘接力良好的NiCoB纳米合金;
泡沫CoNi合金中Co和Ni的质量比为9:2,泡沫CoNi合金与硼酐的质量比为2.8:1,铝粉的质量为硼酐质量的8%。
实施例6:
基于催渗原理的NiCoB纳米合金催化剂的制备方法,具体步骤如下:
(1)准确称取泡沫CoNi合金,用丙酮超声清洗12min;
(2)准确称取硼酐和铝粉,将硼酐、铝粉和清洗好的泡沫CoNi合金置入水热反应釜中,加入水搅拌均匀,密封后放入220℃的烘箱中加热100h,自然冷却至室温,取出泡沫CoNi合金,洗涤,干燥;
(3)将洗涤、干燥后的泡沫CoNi合金在开启式管式电炉内以10℃/min 的升温速度升至870℃,恒温保持6h,整个反应过程在氮气保护下进行;
(4)冷却至室温后,取出样品用丙酮清洗后即可得到粘接力良好的NiCoB纳米合金;
泡沫CoNi合金中Co和Ni的质量比为9:1,泡沫CoNi合金与硼酐的质量比为3:1,铝粉的质量为硼酐质量的10%。
实施例7:
基于催渗原理的NiCoB纳米合金催化剂的制备方法,具体步骤如下:
(1)准确称取泡沫CoNi合金,用丙酮超声清洗10min;
(2)准确称取硼酐和铝粉,将硼酐、铝粉和清洗好的泡沫CoNi合金置入水热反应釜中,加入水搅拌均匀,密封后放入200℃的烘箱中加热96h,自然冷却至室温,取出泡沫CoNi合金,洗涤,干燥;
(3)将洗涤、干燥后的泡沫CoNi合金在开启式管式电炉内以10℃/min 的升温速度升至850℃,恒温保持5h,整个反应过程在氮气保护下进行;
(4)冷却至室温后,取出样品用丙酮清洗后即可得到粘接力良好的NiCoB纳米合金,测试结果如图1-4和表1所示;
泡沫CoNi合金中Co和Ni的质量比为9:1,泡沫CoNi合金与硼酐的质量比为2:1,铝粉的质量为硼酐质量的8%。
由图1-2可知,本发明在泡沫CoNi合金上制备出蠕虫状的合金;由图3和表1可知,蠕虫状的合金即为NiCoB纳米合金催化剂。
将本发明制备的NiCoB纳米合金催化剂和传统方法制备的NiCoB合金催化剂同时用于催化NaBH4水解制氢的反应,其析氢速率如图4所示。由图4可知,本发明制备的NiCoB纳米合金催化剂与传统方法制备的NiCoB合金催化剂相比,具有更加优异的催化析氢性能。
以上所述的仅是本发明的优选实施方式,应当指出,对于本领域的技术人员来说,在不脱离本发明整体构思前提下,还可以作出若干改变和改进,这些也应该视为本发明的保护范围。
Claims (5)
1.基于催渗原理的NiCoB纳米合金催化剂的制备方法,其特征在于:具体步骤如下:
(1)准确称取泡沫CoNi合金,用清洗液超声清洗8-12min;
(2)准确称取硼酐和铝粉,将硼酐、铝粉和清洗好的泡沫CoNi合金置入水热反应釜中,加入水搅拌均匀,密封后放入180-220℃的烘箱中加热80-100h,自然冷却至室温,取出泡沫CoNi合金,洗涤,干燥;
(3)将洗涤、干燥后的泡沫CoNi合金在开启式管式电炉内以8-10℃/min 的升温速度升至830-870℃,恒温保持4-6h,整个反应过程在氮气保护下进行;
(4)冷却至室温后,取出样品用清洗液清洗后即可得到粘接力良好的NiCoB纳米合金;
所述泡沫CoNi合金中Co和Ni的质量比为7:3-9:1,泡沫CoNi合金与硼酐的质量比为(2-3):1,铝粉的质量为硼酐质量的5%-10%。
2.根据权利要求1所述的基于催渗原理的NiCoB纳米合金催化剂的制备方法,其特征在于:所述泡沫CoNi合金中Co和Ni的质量比为7:3或9:1。
3.根据权利要求1所述的基于催渗原理的NiCoB纳米合金催化剂的制备方法,其特征在于:所述泡沫CoNi合金与硼酐的质量比为2:1。
4.根据权利要求1所述的基于催渗原理的NiCoB纳米合金催化剂的制备方法,其特征在于:所述清洗液为丙酮。
5.利用权利要求1所述的基于催渗原理的NiCoB纳米合金催化剂的制备方法制备的NiCoB纳米合金催化剂在催化NaBH4水解制氢中的应用。
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Non-Patent Citations (1)
Title |
---|
Two - stage gas boriding of Nisil in N;Kulka M,Makuch N,Poplawski M;《Surface and Coatings Technology》;Elsevier Science;20140204;第78-86页 |
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