CN108940333B - 一种双金属氧化物/碳氮/碳纳米管复合物的制备方法 - Google Patents
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Abstract
一种双金属氧化物/碳氮/碳纳米管复合物的制备方法,属于纳米复合材料制备技术领域。将两种不同金属盐、羧酸或羧酸盐在水中混合均匀,获得羧酸根络合的金属离子溶液;将碳纳米管、含氮聚合物在水‑醇溶液中混合,超声至稳定悬浊液;将上述两种液体混合,超声或搅拌至均匀分散;向混合液中加入硼氢化盐,发生原位反应,双金属氧化物/碳氮结构生成并附着于所述碳纳米管表面;经洗涤、干燥得到所述双金属氧化物/碳氮/碳纳米管复合物。本发明方法双金属氧化物呈薄片状且自组装形成多层组装体结构,组装体呈片层状、团簇状、花朵状或海胆状,附着于碳纳米管表面,组装体内两种金属元素、碳元素、氮元素、氧元素均匀分布。
Description
技术领域:
本发明涉及一种双金属氧化物/碳氮/碳纳米管复合物的制备方法,属于纳米复合材料制备技术领域。
背景技术
金属氧化物具有优异的化学、电化学性能,尤其是双金属氧化物性能突出,是催化及电化学反应领域的研究热点之一,但其导电性能差,严重影响了反应效率。碳纳米管具有比表面积大、电导率高、化学稳定性好等特点,将双金属氧化物与碳纳米管结合制备金属氧化物/碳纳米管复合纳米材料,可有效发挥二者各自的优势,获得良好的反应性能。向金属氧化物/碳纳米管复合材料中引入碳元素和氮元素的聚合物,不仅进一步提升了材料的导电性,还可增强材料的稳定性,并且有可能产生新的反应活性位点,提高材料的反应性能,表现出良好的催化及电化学活性。
现有技术中,金属氧化物/碳氮/碳纳米管复合物的制备方法主要是化学法。首先采用聚合法在碳纳米管表面包覆一层聚合物,然后向聚合物包覆碳纳米管的分散液中加入含金属离子的溶液,加入碱或氨水调控pH至碱性,加热溶液,形成金属氧化物担载于聚合物包覆的碳纳米管表面。但现有技术步骤较多,增加了合成过程的复杂性,且制备的金属氧化物/碳氮/碳纳米管复合物中,金属氧化物的尺寸较大,比表面积较小,氧化物与碳纳米管之间的结合不够稳定,从而影响该金属氧化物/碳氮/碳纳米管复合物的催化及电化学活性。
发明内容
本发明针对现有技术的不足,其目的在于提供过一种双金属氧化物/碳氮/碳纳米管复合物的制备方法。
为了实现上述目的,本发明采取的技术方案如下:
一种双金属氧化物/碳氮/碳纳米管复合物的原位制备方法,其特征在于,所述制备方法包括以下步骤:
(1)将两种金属盐与羧酸或羧酸盐混合后加到去离子水中形成混合溶液,混合溶液中的羧酸根过量使金属离子能够完全被络合;将混合溶液在室温下超声分散至稳定,得到羧酸根络合的金属离子溶液A;
(2)将碳纳米管、含氮聚合物单体混合后加至去离子水与醇的混合溶液中,超声分散1.5小时以上,获得稳定悬浊液B;
(3)将溶液A与悬浊液B混合,超声或搅拌至碳纳米管分散均匀,得到溶液C;
(4)在持续超声或搅拌条件下,向溶液C中加入过量硼氢化盐粉末或硼氢化盐水溶液,反应至溶液中无气泡产生,得到溶液D;
(5)将溶液D用去离子水及乙醇离心或抽滤清洗,过滤,获得的固体置于烘箱中40℃-80℃干燥,所得的黑色粉末即为金属氧化物/碳氮/碳纳米管复合物。
步骤(1)中所述的金属盐,所述金属元素为金、银、铂、钯、铜、钌、铁、钴、镍以及锌的离子中的两种,其摩尔比范围为0.01~100。
步骤(1)中所述的羧酸盐为柠檬酸盐、乙二酸盐、丁二酸盐、戊二酸盐、苯甲二酸盐、酒石酸盐中的一种或多种。
步骤(1)中所述的羧酸为柠檬酸、乙二酸、丁二酸、戊二酸、苯甲二酸、酒石酸中的一种或多种。
步骤(1)中所述的金属离子与羧酸根离子的摩尔比为1:1~1:10。
步骤(1)中所述的络合反应的反应温度范围为4℃~100℃。
步骤(2)中所述的碳纳米管为单壁、双壁或多壁碳纳米管,或几种碳纳米管不同含量的组合;通过化学气相沉积法、石墨电弧法、模板法或高温热解法合成。优选碳纳米管表面接枝有亲水基团;
步骤(2)中所述的碳纳米管经酸洗或氧化处理后,其在去离子水中的分散度提高。
步骤(2)中所述的含氮聚合物单体为苯胺、吡咯、噻吩、酰胺、丙烯亚胺、乙酰苯胺、甲基吡咯。
步骤(2)中所述的醇为甲醇、乙醇、异丙醇、乙二醇中的一种,或几种醇不同含量的组合。
步骤(2)中所述的去离子水与醇的混合溶液,醇与去离子水的体积比取值范围为0.01~100。
步骤(4)中所述的硼氢化盐为NaBH4或KBH4,BH4 —与金属离子的摩尔比大于10。
步骤(4)中所述的反应温度范围为4℃~60℃。
双金属氧化物的存在形式为:厚度1nm~10nm的纳米薄片,或由上述薄片自组装形成的组装体,组装体呈片层状、团簇状、花朵状或海胆状;组装体尺寸5nm~500nm,双金属氧化物占该复合物的质量百分比为10%~70%。
在复合物中,碳氮聚合物为层状结构,层状结构厚度小于5nm,与双金属氧化物组装体部分结合在一起,二者共同均匀附着于碳纳米管表面。步骤(2)中碳纳米管与含氮聚合物单体质量比取值范围为0.01~100。
一种催化剂材料,包括所述双金属氧化物/碳氮/碳纳米管复合物。
本发明所用的制备方法具有如下优点:制备方法简单,流程短,在制备过程中,金属离子由羧酸根络合形成络合结构,聚合物单体吸附于碳纳米管表面,羧酸根与聚合物通过化学键结合或静电作用力相互吸引,可使金属及氮元素在碳纳米管表面均匀分布;聚合物单体的聚合与所述金属离子由高价态向低价态的还原同时进行,避免了金属团聚形成大颗粒;另外,硼氢化盐溶于混合溶液后提供了过量OH—离子与金属离子键合,同时发生快速还原反应的同时还进行氧化,可使金属离子形成卷曲的氧化物薄片,且自组装形成多层组装体结构,组装体呈片层状、团簇状、花朵状或海胆状,与含碳氮的聚合物层一起附着于碳纳米管表面;金属元素、氮元素、碳元素、氧元素在组装体结构内均匀分布,含碳、氮聚合物的引入提升了材料的导电性,增强了复合材料的稳定性,而且增加了活性中心;氧化物薄片结构提供了更多的活性缺陷位点,从而可提高该金属氧化物/碳氮/碳纳米管复合物的催化及电化学性能。
附图说明:
图1为本发明实施例提供的双金属氧化物/碳氮/碳纳米管复合物的制备方法流程图。
图2为本发明实施例1提供的双金属氧化物/碳氮/碳纳米管复合物的扫描电镜照片。
图3为本发明实施例1提供的双金属氧化物/碳氮/碳纳米管复合物的透射电镜照片及元素分布扫描。
图4为本发明实施例2提供的双金属氧化物/碳氮/碳纳米管复合物的扫描电镜照片。
图5为本发明实施例3提供的双金属氧化物/碳氮/碳纳米管复合物的扫描电镜照片。
图6为本发明实施例3提供的双金属氧化物/碳氮/碳纳米管复合物的扫透电镜照片。
图7为本发明实施例1提供的双金属氧化物/碳氮/碳纳米管复合物在1M KOH溶液中催化氧析出反应的极化曲线。
图8为本发明实施例2提供的双金属氧化物/碳氮/碳纳米管复合物在0.1M KOH溶液中催化氧析出反应的极化曲线。
图9为本发明实施例3提供的双金属氧化物/碳氮/碳纳米管复合物在0.1M KOH溶液中催化氧还原反应的极化曲线。
图10本发明实施例1提供的双金属氧化物/碳氮/碳纳米管复合物的X射线光电子能谱(xps)图。
具体实施方式:
如下结合具体的实施例进一步说明本发明,指出的是:以下实施例只用于说明本发明的具体实施方法,并不能限制本发明权利保护范围。
实施例1:
铁钴氧化物/碳氮/多壁碳纳米管复合物的制备:
将0.02mol FeCl3、0.02mol CoCl2、0.1mol柠檬酸钠加入100mL去离子水中,超声至其完全溶解,得到FeCl3-CoCl2-柠檬酸钠水溶液,即溶液A。
将0.1g多壁碳纳米管及0.1g苯胺加入至25mL去离子水/25mL乙醇的混合溶液中,室温下超声3小时以上,使碳纳米管分散均匀,获得悬浊液B。
取10mL溶液A与50mL悬浊液B混合,室温下超声1.5小时以上,获得溶液C。在持续超声条件下,向溶液C中缓慢加入3g KBH4,反应过程至少保持2小时,直至溶液中无气泡冒出,获得溶液D。
将溶液D分别使用去离子水及乙醇进行抽滤清洗,获得的固体置于50℃的烘箱中干燥,所得的黑色固体即为铁钴氧化物/碳氮/多壁碳纳米管复合物。参阅图2可以看出,氧化物薄片自组装成花朵状结构,尺寸大约为200nm,负载于碳纳米管表面上。参阅图3可以看出,此花朵结构内碳、氮、氧、铁、钴元素均匀分布。
实施例2:
铁镍氧化物/碳氮/多壁碳纳米管复合物的制备:
该实施例制备过程与实施例1基本相同,区别在于,所述金属盐及量分别为0.03mol NiCl2和0.01mol FeCl3,络合反应的温度为45℃。参阅图4可以看出,所获得铁镍氧化物自组装体尺寸大约为300nm,负载于碳纳米管表面上。
实施例3:
钴镍氧化物/碳氮/多壁碳纳米管复合物的制备:
该实施例制备过程与实施例1基本相同,区别在于,所述金属盐及量分别为0.02mol NiCl2和0.02mol CoCl2,络合反应的温度为40℃。参阅图5及图6可以看出,所获得钴镍氧化物自组装体尺寸大约为100~300nm,负载于碳纳米管表面上。
尽管这里已详细列出并说明了优选实施案例,但本领域技术人员可知,可在不脱离本发明精髓的情况下进行各种改进、添加、替换等方式,这些内容都被认定为属于权利要求所限定的本发明的范围之内。
Claims (9)
1.一种双金属氧化物/碳氮/碳纳米管复合物的制备方法,其特征在于,所述的复合物结构为:双金属氧化物的存在形式为:厚度1 nm~10 nm的纳米薄片,或由上述薄片自组装形成的组装体,组装体呈片层状、团簇状、花朵状或海胆状;组装体尺寸5 nm ~ 500 nm;所述制备方法包括以下步骤:
将两种金属盐与羧酸或羧酸盐混合后加到去离子水中形成混合溶液,混合溶液中的羧酸根过量使金属离子能够完全被络合;将混合溶液在室温下超声分散至稳定,得到羧酸根络合的金属离子溶液A;
将碳纳米管、含氮聚合物单体混合后加至去离子水与醇的混合溶液中,超声分散1.5小时以上,获得稳定悬浊液B;
将溶液A与悬浊液B混合,超声或搅拌至碳纳米管分散均匀,得到溶液C;
在持续超声或搅拌条件下,向溶液C中加入过量硼氢化盐粉末或硼氢化盐水溶液,反应至溶液中无气泡产生,得到溶液D;其中反应温度范围为4℃~60℃;
将溶液D用去离子水及乙醇离心或抽滤清洗,过滤,获得的固体置于烘箱中40℃-80℃干燥,所得的黑色粉末即为双金属氧化物/碳氮/碳纳米管复合物。
2.按照权利要求1所述的方法,其特征在于,步骤(1)中所述的两种金属盐,金属元素为金、银、铂、钯、铜、钌、铁、钴、镍以及锌中的两种,其摩尔比范围为0.01~100。
3.按照权利要求1所述的方法,其特征在于,步骤(1)中所述的羧酸盐为柠檬酸盐、乙二酸盐、丁二酸盐、戊二酸盐、酒石酸盐中的一种或多种;步骤(1)中所述的羧酸为柠檬酸、乙二酸、丁二酸、戊二酸、酒石酸中的一种或多种。
4.按照权利要求1所述的方法,其特征在于,步骤(1)中所述的金属离子与羧酸根离子的摩尔比为1:1~1:10;步骤(1)中所述的络合反应的反应温度范围为4℃~100℃。
5.按照权利要求1所述的方法,其特征在于,步骤(2)中所述的碳纳米管为单壁、双壁或多壁碳纳米管,或几种碳纳米管的组合;通过化学气相沉积法、石墨电弧法、模板法或高温热解法合成;所述的碳纳米管经酸洗或氧化处理。
6.按照权利要求1所述的方法,其特征在于,步骤(2)中所述的含氮聚合物单体选自苯胺、吡咯、酰胺、丙烯亚胺、甲基吡咯。
7.按照权利要求1所述的方法,其特征在于,步骤(2)中所述的醇为甲醇、乙醇、异丙醇、乙二醇中的一种,或几种醇的组合;步骤(2)中所述的去离子水与醇的混合溶液,醇与去离子水的体积比取值范围为0.01~100。
8.按照权利要求1所述的方法,其特征在于,步骤(4)中所述的硼氢化盐为NaBH4或KBH4,BH4 —与金属离子的摩尔比大于10。
9.按照权利要求1所述的方法,其特征在于,步骤(2)中碳纳米管与含氮聚合物单体质量比取值范围为0.01~100。
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103012786A (zh) * | 2012-11-12 | 2013-04-03 | 南昌航空大学 | 一种石墨烯/CoFe2O4/聚苯胺复合吸波材料的制备方法 |
CN104209515A (zh) * | 2014-09-12 | 2014-12-17 | 北京工业大学 | 一种碳纳米管包覆金属颗粒的制备方法 |
CN107845814A (zh) * | 2017-11-12 | 2018-03-27 | 湖南科技大学 | 一种酸性碱性溶液中高效电催化氧还原反应催化剂及其制备方法 |
CN108091892A (zh) * | 2016-11-23 | 2018-05-29 | 韩会义 | 一种Fe/Co/N/MWCNTs催化剂 |
-
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103012786A (zh) * | 2012-11-12 | 2013-04-03 | 南昌航空大学 | 一种石墨烯/CoFe2O4/聚苯胺复合吸波材料的制备方法 |
CN104209515A (zh) * | 2014-09-12 | 2014-12-17 | 北京工业大学 | 一种碳纳米管包覆金属颗粒的制备方法 |
CN108091892A (zh) * | 2016-11-23 | 2018-05-29 | 韩会义 | 一种Fe/Co/N/MWCNTs催化剂 |
CN107845814A (zh) * | 2017-11-12 | 2018-03-27 | 湖南科技大学 | 一种酸性碱性溶液中高效电催化氧还原反应催化剂及其制备方法 |
Non-Patent Citations (2)
Title |
---|
A facile preparation of CoFe2O4 nanoparticles on polyaniline-functionalised carbon nanotubes as enhanced catalysts for the oxygen evolution reaction;Yang Liu et al.;《Journal of Materials Chemistry A》;20160211;第4卷;摘要,第4472页右栏倒数第2段,第4473页右栏第1段至第4474页左栏第1段 * |
Preparation of highly active and stable polyaniline-cobalt-carbon nanotube electrocatalyst for oxygen reduction reaction in polymer electrolyte membrane fuel cell;Zhong-shu Yin et al.;《Electrochimica Acta》;20131227;第119卷;摘要,第145页第2.1节 * |
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