CN108479832A - 一种非金属元素掺杂负载纳米零价镍碳纤维复合材料的制备方法 - Google Patents
一种非金属元素掺杂负载纳米零价镍碳纤维复合材料的制备方法 Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/16—Reducing
Abstract
本发明公开了一种非金属元素掺杂负载纳米零价镍碳纤维复合材料的制备方法,包括如下步骤:首先将经硝酸修饰改性后的活性碳纤维浸渍于含镍离子的N,N‑二甲基甲酰胺溶液中,预氧化后得前驱体;然后将所得前驱体与无机非金属盐一起转移至管式炉中,在惰性气体保护下进行煅烧热解即可获得目标产物。本发明中,经硝酸修饰改性后的碳纤维表面具有大量高度分散的活性中心,为金属颗粒的分散及其生长成核提供了有利条件;原位控制合成有效避免了零价镍的团聚、氧化以及反应过程中活性中心的流失;本发明所制备的复合材料具有优异的性能,可被用于挥发性有机气体的净化、催化加氢、磁性材料、超级电容器等领域。
Description
技术领域
本发明属于碳纤维材料技术领域,具体涉及一种非金属元素掺杂负载纳米零价镍(Ni0)碳纤维复合材料的制备方法。
背景技术
零价镍(Ni0)因其价态低、尺寸小、表面活性位多等独特的性质,在催化、磁性材料、光电子、磁流体和信息贮存等诸多领域具有广泛的应用前景。零价镍(Ni0)的常用制备方法包括溶胶凝胶法、水热法、化学还原法和气相沉积法等。这些常用制备方法装置简单、操作方便,但利用其合成的零价镍(Ni0)易发生团聚,在空气中不能够稳定存在,容易被氧化成氧化镍。
为了克服零价镍(Ni0)的上述缺点,将其负载到载体上再进行使用,不仅可以提高镍的负载量,同时载体的存在还可有效避免零价镍(Ni0)的团聚、氧化以及反应过程中活性中心的流失。碳材料通常具有发达的孔隙结构、高的化学稳定性以及独特的电子传导性质,从而成为一种理想的载体选择。目前,常用的碳载体有碳纳米管、石墨烯和多孔碳等。但这些碳基材料通常是由高温煅烧含碳前驱体而得到的,在这一过程中会产生挥发性有机物、CO、CO2等有毒有害物质,从而引发环境问题。因此迫切需要寻找一种廉价易得、性能优越的材料作为载体。
碳纤维是一种主要由sp2杂化碳原子组成的高度石墨化碳材料,其作为载体具有比表面积大、耐高温、耐酸碱、柔韧性好等优点,在复合材料领域有着广泛的应用。但由于碳纤维表面碳元素之间以非极性共价键相连接,晶界间呈平行的石墨微晶乱层结构,导致其浸润性较差,与金属的相容性不佳,不易形成牢固的粘合界面,因此碳纤维在复合材料领域的应用受到了一定限制。为进一步扩大碳纤维的应用范围,通常采用后处理的方式将杂原子(N、S、P、B等)掺杂到碳纤维的表面或内部结构中,使其各方面的性能得到改进和提高。
目前已有许多关于镍基复合材料的研究报道:
专利号CN 105513819 A公开了一种镍钴双金属氢氧化物纳米片/氮掺杂碳纤维杂化材料及其制备方法。该发明中的杂化材料由镍盐、钴盐和六亚甲基四胺为前驱体,在具有三维网络结构的氮掺杂碳纤维表面原位生长镍钴双金属氢氧化物纳米片而得到。通过这种方法制得的氮掺杂碳纤维复合材料具有较好的氧化还原活性和稳定性,但复合材料中的镍元素均以化合物的形式存在,而非单质,这限制了该类复合材料的进一步应用。
专利号CN 106540699 A公开了一种利用自生长碳纳米管制备高活性镍基催化剂的制备方法,首先将常规镍基催化剂放入反应器中,经还原性气体处理后得到零价镍;再通入水蒸气和有机物,高温煅烧实现碳纳米管的生长。在这种制备工艺中,零价镍纳米颗粒暴露于空气中易被氧化。同时,制备过程中需要切换不同组成的载气,操作复杂。
发明内容
为克服现有技术的不足,本发明的目的在于提供一种非金属元素掺杂负载纳米零价镍(Ni0)碳纤维复合材料的制备方法,旨在使制得的复合材料具有较高的催化活性和稳定性。
本发明为实现发明目的,采用如下技术方案:
本发明非金属元素掺杂负载纳米零价镍碳纤维复合材料的制备方法,其特点在于,按如下步骤进行:
(1)碳纤维的预处理
将0.13g碳纤维置于乙醇溶液中超声去除表面杂质,然后置于硝酸溶液中,室温下浸泡处理1~5小时,再水洗至中性后烘干,得经硝酸修饰改性后的活性碳纤维;
(2)零价镍纳米颗粒的负载
将所述经硝酸修饰改性后的活性碳纤维置于含1~10mmol水溶性镍盐和0.2~2g表面活性剂的10~50mL N,N-二甲基甲酰胺溶液中,搅拌1~6小时后转移至马弗炉中,在250~350℃预氧化1~4小时,得前驱体;
称取0.2~2g含氮、含硼或含硫无机非金属盐于石英舟中,将所得前驱体平铺于无机非金属盐上层,然后整体转移至管式电阻炉中,在惰性气体保护下进行煅烧热解,反应结束后冷却至室温,即得目标产物;
其中,所述煅烧热解的过程为:先以5~10℃/min的升温速率升温至400℃,恒温1~3小时;再以5~10℃/min的升温速率升温至700~900℃,恒温1~3小时。
进一步地,所述碳纤维为碳毡、碳纸、碳泡沫或碳纤维布中的至少一种。
进一步地,步骤(1)中硝酸溶液的质量浓度为20~60%。
进一步地,步骤(2)中所述水溶性镍盐为氯化镍、硝酸镍或醋酸镍中的至少一种。
进一步地,步骤(2)中所述表面活性剂为聚乙烯吡咯烷酮、聚乙烯醇或聚乙二醇中的至少一种。
进一步地,步骤(2)中所述无机非金属盐为双氰胺、尿素或硫脲中的至少一种。
本发明建立了一种新型非金属元素掺杂碳纤维载镍复合材料的制备方法,通过原位控制合成一步实现镍离子的负载及其还原,同时采用后处理的方法实现了碳纤维中非金属元素的均匀掺杂。该制备方法和复合材料的结构新颖独特,在挥发性有机气体的净化、催化加氢、磁性材料、超级电容器等领域具有广阔的应用前景。
与现有技术相比,本发明具有以下优点和有益效果:
(1)碳纤维布作为载体具有比表面积大、耐高温、柔韧性好等优点,经硝酸处理后的碳纤维布表面具有大量高度分散的活性位点,可以有效锚定零价镍纳米颗粒。同时碳纤维布的交错纹理结构使其碳化后还能保持一定的整体结构,为分散活性金属及其在基底上生长成核提供了有利条件。
(2)采用原位控制合成法一步实现金属镍的负载及还原,避免了传统镍基复合材料合成过程中需要频繁更换反应设备或原料、操作复杂、耗时长等缺点。同时,原位控制合成避免了零价镍纳米颗粒暴露于空气中,有效抑制了零价镍纳米颗粒的氧化。
(3)本发明中,双氰胺作为有效氮源在热解过程中形成自下而上的富氮气氛,一步实现了氮元素在碳纤维中的均匀掺杂以及镍离子的还原。金属纳米颗粒、非金属元素以及碳纤维三者之间以Ni-N-C共价键的方式结合,既可以防止纳米颗粒的团聚又有利于电荷的转移从而提升复合材料的性能。
附图说明
图1为实施例1制备所得的氮掺杂负载纳米零价镍(Ni0)碳纤维复合材料的SEM图;
图2为实施例1制备所得的氮掺杂负载纳米零价镍(Ni0)碳纤维复合材料的XRD图;
图3为实施例1制备所得的氮掺杂负载纳米零价镍(Ni0)碳纤维复合材料的EDS元素面扫描图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图和实施例对本发明进行进一步详细说明,但本发明的保护范围不限于此。
实施例中未注明条件者,可按照常规条件进行;所用试剂或仪器未注明生产商者,均为可以通过市售购买获得的常规产品。
实施例1
(1)碳纤维布的预处理
将0.13g碳纤维布置于乙醇溶液中超声去除表面杂质,然后置于质量浓度为32%的硝酸溶液中,室温下浸泡处理3小时,水洗至中性后烘干,得经硝酸修饰改性后的活性碳纤维布;
(2)零价镍(Ni0)纳米颗粒的负载
将经硝酸修饰改性后的活性碳纤维布置于含2.3769g(10mmol)NiCl2·6H2O(AR)和1g聚乙烯吡咯烷酮的20mL N,N-二甲基甲酰胺(AR)溶液中,搅拌200min后转移至马弗炉中,在350℃预氧化2小时,得复合材料前驱体;
称取1g(12mmol)双氰胺于石英舟中,将所得前驱体平铺于双氰胺上层,然后整体转移至管式电阻炉的恒温区,在氮气气氛中先以5℃/min升温至400℃、恒温2小时,再以5℃/min升温至700℃、恒温2小时。反应结束后冷却至室温,即得氮掺杂负载纳米零价镍(Ni0)碳纤维复合材料。
本实施例所制得的复合材料质量为~0.136g,氮的掺杂率为~5%。
图1为本实施例制备所得的氮掺杂负载纳米零价镍(Ni0)碳纤维复合材料的SEM图像。从扫描电镜图中可以看出,碳纤维布表面有大量孔洞生成,零价镍(Ni0)纳米颗粒均匀生长在碳纤维上并牢牢嵌入在孔洞中。
图2为本实施例制备所得的氮掺杂负载纳米零价镍(Ni0)碳纤维复合材料的XRD衍射图谱。从图中可以看出,26°对应的衍射峰是石墨碳,其余三个衍射峰与Ni0(JCPDS 65-2865)完全吻合,表明由该实施例制备所得的复合材料为高纯Ni0材料。此外,氮元素的掺杂不影响产物晶型。
图3为本实施例制备所得的氮掺杂负载纳米零价镍(Ni0)碳纤维复合材料的EDS元素面扫描图。从图中可以看出,氮元素均匀地掺杂到碳纤维中。
实施例2
本实施例与实施例1的制备方法相同,区别仅在于步骤(2)中的煅烧热解过程为:先以5℃/min升温至400℃,恒温2小时;再以5℃/min升温至800℃,恒温2小时。反应结束后冷却至室温,即得氮掺杂负载纳米零价镍(Ni0)碳纤维复合材料。
本实施例所制得的复合材料质量为~0.134g,氮的掺杂率为~4%。
实施例3
本实施例与实施例1的制备方法相同,区别仅在于步骤(2)中的煅烧热解过程为:先以5℃/min升温至400℃,恒温2小时;再以5℃/min升温至900℃,恒温2小时。反应结束后冷却至室温,即得氮掺杂负载纳米零价镍(Ni0)碳纤维复合材料。
本实施例所制得的复合材料质量为~0.133g,氮的掺杂率为~4%。
实施例4
本实施例与实施例1的制备方法相同,区别仅在于步骤(2)中双氰胺的含量为0.1g(1mmol),制得氮掺杂负载纳米零价镍(Ni0)碳纤维复合材料。
本实施例所制得的复合材料质量为~0.134g,氮的掺杂率为~2%。
实施例5
本实施例与实施例1的制备方法相同,区别仅在于步骤(2)中双氰胺的含量为0.5g(6mmol),制得氮掺杂负载纳米零价镍(Ni0)碳纤维复合材料。
本实施例所制得的复合材料质量为~0.134g,氮的掺杂率为~3%。
实施例6
本实施例与实施例1的制备方法相同,区别仅在于步骤(2)中双氰胺的含量为2g(24mmol),制得氮掺杂负载纳米零价镍(Ni0)碳纤维复合材料。
本实施例所制得的复合材料质量为~0.137g,氮的掺杂率为~5%。
以上仅为本发明的示例性实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (6)
1.一种非金属元素掺杂负载纳米零价镍碳纤维复合材料的制备方法,其特征在于,按如下步骤进行:
(1)碳纤维的预处理
将0.13g碳纤维置于乙醇溶液中超声去除表面杂质,然后置于硝酸溶液中,室温下浸泡处理1~5小时,再水洗至中性后烘干,得经硝酸修饰改性后的活性碳纤维;
(2)零价镍纳米颗粒的负载
将所述经硝酸修饰改性后的活性碳纤维置于含1~10mmol水溶性镍盐和0.2~2g表面活性剂的10~50mL N,N-二甲基甲酰胺溶液中,搅拌1~6小时后转移至马弗炉中,在250~350℃预氧化1~4小时,得前驱体;
称取0.2~2g含氮、含硼或含硫无机非金属盐于石英舟中,将所得前驱体平铺于无机非金属盐上层,然后整体转移至管式电阻炉中,在惰性气体保护下进行煅烧热解,反应结束后冷却至室温,即得目标产物;其中,所述煅烧热解的过程为:先以5~10℃/min的升温速率升温至400℃,恒温1~3小时;再以5~10℃/min的升温速率升温至700~900℃,恒温1~3小时。
2.根据权利要求1所述的制备方法,其特征在于:步骤(1)中所述碳纤维为碳毡、碳纸、碳泡沫或碳纤维布中的至少一种。
3.根据权利要求1所述的制备方法,其特征在于:步骤(1)中所述硝酸溶液的质量浓度为20~60%。
4.根据权利要求1所述的制备方法,其特征在于:步骤(2)中所述水溶性镍盐为氯化镍、硝酸镍或醋酸镍中的至少一种。
5.根据权利要求1所述的制备方法,其特征在于:步骤(2)中所述表面活性剂为聚乙烯吡咯烷酮、聚乙烯醇或聚乙二醇中的至少一种。
6.根据权利要求1所述的制备方法,其特征在于:步骤(2)中所述无机非金属盐为双氰胺、尿素或硫脲中的至少一种。
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