CN110404585B - 一种利用水浴加热在基底上制备mof片的方法 - Google Patents
一种利用水浴加热在基底上制备mof片的方法 Download PDFInfo
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Abstract
本发明涉及一种利用水浴加热在基底(泡沫镍、钢网、钛网、钼网等)上二次生长二维纳米MOF片的方法,属于材料科学与工程技术和化学领域。本发明制备的二维纳米MOF片涉及的金属有Fe、Co、Ni、Mn、Cu、Zn等元素。首先配置相应的一定浓度的反应物溶液A,把事先清洗干净的基底浸入上述溶液中,然后在一定温度下加热数十小时得到中间产物B;把制备好的中间产物B放入管式炉中,在惰性气体的条件下加热数小时,得到中间产物C;最后再重复得到中间产物B的方法。本方法具有操作简单、效率高、应用范围广等优点。
Description
(1)发明名称:一种利用水热法在基底上二次生长二维纳米MOF片的方法
(2)技术领域
本发明涉及利用水热法在基底上二次生长二维纳米MOF片的方法,属于材料科学与工程技术和化学领域。
(3)背景技术
自支撑电极,将活性组分或者电催化剂以某种共价键或化学键吸附的形式结合在能导电的基底电极(集流体或者电极上),可以达到既能传递电子,又能活化底物的双重目的。自支撑电极由集流体、电催化剂和复合三个部分组成。集流体:有铜箔、钴、石墨烯、氧化石墨烯、纳米炭纤维等导电性优良集流体,因为电极除了提供电化学反应的界面之外,还是导电的介质,将电子运输到反应界面;电催化剂:镍、四氧化三钴、CoO、NaS、ZnO、Ni1-xFeOOH、硫化亚铁等,起到加速电化学反应;复合:一般是在优良的集流体或者改性的集流体上原位生长或自组装上具有微纳米结构的催化性能优异的电催化剂。常用制备自支撑电极的方法有:自组装法-高温原位固化、静电自组装退货法、磷化法、水热原位制备法、直接退火处理法、水溶液和微乳液介导法等。其中,这里我们用到的是水热原位制备法。
水热法或溶剂热法,通常指的是直接将金属盐与有机桥联配体在特定的溶剂(如水或者有机溶剂)中混合,放入密闭的耐高压金属容器(即反应釜中)通过加热,反应物在体系的自产生压力下进行反应。对于MOF而言,反应及晶化温度通常在60~180℃之间,很多化合物可以在150℃左右的温度下合成。传统的加热方法采用平衡原理,将反应容器置于烘箱、油浴等装置中,通常进行一次反应需要半天至数天时间。由于相对较高的压力和高温,水(溶剂)热法有利于MOF产物的单晶生长,通过合理的反应温度等条件控制,可望获得较大尺寸的单晶,这是水(溶剂)热法的优点及其被广泛采用的主要原因。
将通过水热法制备好的自支撑MOF电极在惰性气体条件下进行煅烧,即进行碳化处理。碳化(carbonization)又称干馏、炭化、焦化,是指固体或有机物在隔绝空气条件下加热分解的反应过程或加热固体物质来制取液体或气体 (通常会变为固体)产物的一种方式。这个过程不一定会涉及到裂解或热解。本文专利此处是脱水碳化,指的是将有机物去掉其他元素留下碳。如浓硫酸具有很强的脱水能力在和有机物接触时,把有机物中的氢、氧元素按水的组成比 (2:1)脱去,留下黑色的碳,从而使对方碳化。实际脱的是氢和氧,并不是说该物质就含水。同时,高温下碳或不饱和的碳把一些金属还原出来。碳化后的自支撑MOF电极ORR电化学催化性能明显提升很多,但是OER电化学催化性能稍微降低了一些,通过本发明的二次生长MOF的方法,在碳化后的基底上再次生长MOF材料,既弥补了OER的电化学催化性能,也保证了ORR的电化学催化性能。
(4)发明内容
1、本发明的目标
本发明的目的是提出一种利用水热法在基底上二次生长二维纳米MOF片的方法。高温碳化虽然会提升样品ORR等催化性能,但同时也会使原样品的OER 等催化性能降低,通过二次生长二维纳米MOF片的方法,除了增强了ORR等催化性能外,同时还弥补了OER的电化学催化性能。
2、本技术的发明要点本发明要点如下:
(1)用金属盐溶液、有机物和溶剂配置成质量-体积浓度为6-10mg/ml的反应物溶液A,所述的金属盐元素为Fe、Co、Ni、Mn、Cu、Zn,所述的有机物为2,6-萘二羧酸二钾盐,所述的溶剂为去离子水。
(2)把清洗干净的基底放入实验步骤(1)所述溶液中(即放入反应釜中),最后把反应釜放入鼓风干燥机中,反应温度为60-180℃,反应时间为12-24h;将得到的基底放入真空管式炉中进行煅烧,一般使用氮气或氩气作为惰性气体,煅烧温度为600-900℃,而煅烧时间为4-10h。
(3)使用与步骤(1)相同的金属盐、有机物和溶剂,配置成质量-体积浓度为3.6-6mg/ml的反应物溶液B,然后把步骤(2)得到的泡沫镍放入溶液B中 (即反应釜中),再次放入鼓风干燥箱中,反应时间和温度与步骤(2)相同。
本发明提出的利用水热法在基底上二次生长二维纳米MOF片的方法,其优是:这种方法适用范围广泛,可以合成多种金属MOF材料,如Ni、Co、Fe、 Mn、Zn等,同时这种方法也适合多种基底,比如泡沫镍、钛网、钢网、镍网等,且材料结构坚固,导热和导电性能良好,化学性能稳定,合成工艺简单,可以大规模生产。
(5)本发明的附图
图1、2和3分别是本发明方法制备的第一次生长MOF、碳化后的MOF和第二次生长MOF的扫描透射电子显微镜图。图4和图5分别是OER和ORR电化学催化性能图;其中R-NCM@NF代表第二次生长MOF的泡沫镍,A- NCM@NF代表碳化后MOF的泡沫镍,NCM@NF代表第一次生长MOF的泡沫镍,而NF代表原始泡沫镍。
(6)本发明实施例
以下介绍本发明方法的实施例:
实施例1
Ni-Co-MOF/泡沫镍材料的制备
首先,把乙酸镍、硝酸钴、2,6-萘二羧酸二钾盐和去离子水充分混合,配置成6.7mg/ml的混合溶液A并倒入反应釜中,然后把清洗干净的泡沫镍放入反应釜中,在60℃条件下加热20h;待加热完毕后,取出泡沫镍并烘干,然后放入管式炉中,在650℃条件下煅烧4h;待煅烧完毕后,再配置3mg/ml的混合溶液A并倒入另一个反应釜中,把煅烧好的泡沫镍放入该反应釜中,在60℃条件下加热20h,待加热完毕后,取出泡沫镍并且烘干,得到最后的产物。
实施例2
Ni-Fe-MOF/泡沫镍材料的制备
首先,把乙酸镍、硝酸铁、2,6-萘二羧酸二钾盐和去离子水充分混合,配置成6.7mg/ml的混合溶液A并倒入反应釜中,然后把清洗干净的泡沫镍放入反应釜中,在60℃条件下加热20h;待加热完毕后,取出泡沫镍并烘干,然后放入管式炉中,在650℃条件下煅烧4h;待煅烧完毕后,再配置3mg/ml的混合溶液A并倒入另一个反应釜中,把煅烧好的泡沫镍放入该反应釜中,在60℃条件下加热20h,待加热完毕后,取出泡沫镍并且烘干,得到最后的产物。
实施例3
Ni-Co-MOF/钢网材料的制备
首先,把乙酸镍、硝酸钴、2,6-萘二羧酸二钾盐和去离子水充分混合,配置成6.7mg/ml的混合溶液A并倒入反应釜中,然后把清洗干净的钢网放入反应釜中,在60℃条件下加热20h;待加热完毕后,取出钢网并烘干,然后放入管式炉中,在650℃条件下煅烧4h;待煅烧完毕后,再配置3mg/ml的混合溶液A并倒入另一个反应釜中,把煅烧好的钢网放入该反应釜中,在60℃条件下加热20h,待加热完毕后,取出钢网并且烘干,得到最后的产物。
实施例4
Ni-Fe-MOF/钢网材料的制备
首先,把乙酸镍、硝酸铁、2,6-萘二羧酸二钾盐和去离子水充分混合,配置成6.7mg/ml的混合溶液A并倒入反应釜中,然后把清洗干净的钢网放入反应釜中,在60℃条件下加热20h;待加热完毕后,取出钢网并烘干,然后放入管式炉中,在650℃条件下煅烧4h;待煅烧完毕后,再配置3mg/ml的混合溶液A并倒入另一个反应釜中,把煅烧好的钢网放入该反应釜中,在60℃条件下加热20h,待加热完毕后,取出钢网并且烘干,得到最后的产物。
实施例5
Ni-Co-MOF/钛网材料的制备
首先,把乙酸镍、硝酸钴、2,6-萘二羧酸二钾盐和去离子水充分混合,配置成6.7mg/ml的混合溶液A并倒入反应釜中,然后把清洗干净的钛网放入反应釜中,在60℃条件下加热20h;待加热完毕后,取出钛网并烘干,然后放入管式炉中,在650℃条件下煅烧4h;待煅烧完毕后,再配置3mg/ml的混合溶液A并倒入另一个反应釜中,把煅烧好的钛网放入该反应釜中,在60℃条件下加热20h,待加热完毕后,取出钛网并且烘干,得到最后的产物。
实施例6
Ni-Fe-MOF/钛网材料的制备
首先,把乙酸镍、硝酸铁、2,6-萘二羧酸二钾盐和去离子水充分混合,配置成6.7mg/ml的混合溶液A并倒入反应釜中,然后把清洗干净的钛网放入反应釜中,在60℃条件下加热20h;待加热完毕后,取出钛网并烘干,然后放入管式炉中,在650℃条件下煅烧4h;待煅烧完毕后,再配置3mg/ml的混合溶液A并倒入另一个反应釜中,把煅烧好的钛网放入该反应釜中,在60℃条件下加热20h,待加热完毕后,取出钛网并且烘干,得到最后的产物。
实施例7
Ni-Co-MOF/钼网材料的制备
首先,把乙酸镍、硝酸钴、2,6-萘二羧酸二钾盐和去离子水充分混合,配置成6.7mg/ml的混合溶液A并倒入反应釜中,然后把清洗干净的钼网放入反应釜中,在60℃条件下加热20h;待加热完毕后,取出钼网并烘干,然后放入管式炉中,在650℃条件下煅烧4h;待煅烧完毕后,再配置3mg/ml的混合溶液A并倒入另一个反应釜中,把煅烧好的钼网放入该反应釜中,在60℃条件下加热20h,待加热完毕后,取出钼网并且烘干,得到最后的产物。
实施例8
Ni-Fe-MOF/钼网材料的制备
首先,把乙酸镍、硝酸铁、2,6-萘二羧酸二钾盐和去离子水充分混合,配置成6.7mg/ml的混合溶液A并倒入反应釜中,然后把清洗干净的钼网放入反应釜中,在60℃条件下加热20h;待加热完毕后,取出钼网并烘干,然后放入管式炉中,在650℃条件下煅烧4h;待煅烧完毕后,再配置3mg/ml的混合溶液A并倒入另一个反应釜中,把煅烧好的钼网放入该反应釜中,在60℃条件下加热20h,待加热完毕后,取出钼网并且烘干,得到最后的产物。
实施例9
Ni-Co-MOF/镍网材料的制备
首先,把乙酸镍、硝酸钴、2,6-萘二羧酸二钾盐和去离子水充分混合,配置成6.7mg/ml的混合溶液A并倒入反应釜中,然后把清洗干净的镍网放入反应釜中,在60℃条件下加热20h;待加热完毕后,取出镍网并烘干,然后放入管式炉中,在650℃条件下煅烧4h;待煅烧完毕后,再配置3mg/ml的混合溶液A并倒入另一个反应釜中,把煅烧好的镍网放入该反应釜中,在60℃条件下加热20h,待加热完毕后,取出镍网并且烘干,得到最后的产物。
实施例10
Ni-Fe-MOF/镍网材料的制备
首先,把乙酸镍、硝酸铁、2,6-萘二羧酸二钾盐和去离子水充分混合,配置成6.7mg/ml的混合溶液A并倒入反应釜中,然后把清洗干净的镍网放入反应釜中,在60℃条件下加热20h;待加热完毕后,取出镍网并烘干,然后放入管式炉中,在650℃条件下煅烧4h;待煅烧完毕后,再配置3mg/ml的混合溶液A并倒入另一个反应釜中,把煅烧好的镍网放入该反应釜中,在60℃条件下加热20h,待加热完毕后,取出镍网并且烘干,得到最后的产物。
Claims (1)
1.一种利用水浴加热在基底上二次生长二维纳米MOF片的方法, 其特征在于该方法包括以下步骤:
(1)用金属盐溶液、有机物和溶剂配置成质量-体积浓度为6-10 mg/mL的反应物溶液A,然后把溶液A倒入反应釜中;
所述的金属盐元素为Fe、Co、Ni、Mn、Cu、Zn,所述的有机物为2,6-萘二羧酸二钾盐,所述的溶剂为去离子水;
(2)把清洗干净的基底放入实验步骤(1)反应釜中的溶液A中,最后把反应釜放入鼓风干燥机中,反应温度为60-180 ℃,反应时间为12-24 h;将得到的基底放入真空管式炉中进行煅烧,使用氮气或氩气作为隔绝空气的气体,煅烧温度为600-900 ℃,而煅烧时间为4-10h;
(3)使用与步骤(1)相同的金属盐、有机物和溶剂,配置成质量-体积浓度为3.6-6mg/mL的反应物溶液B,并把溶液B倒入反应釜中,然后把步骤(2)煅烧后的基底放入反应釜中的溶液B中,再次将反应釜放入鼓风干燥箱中,反应温度为60-180 ℃,反应时间为12-24 h。
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