CN111203248A - 一种掺杂石墨烯包覆过渡金属碳化物纳米胶囊的制备方法及在微波催化中的应用 - Google Patents
一种掺杂石墨烯包覆过渡金属碳化物纳米胶囊的制备方法及在微波催化中的应用 Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
本发明涉及纳米材料制备技术及其应用领域,针对现有掺杂方法不适用于在纳米及原子尺度上进行调控的问题,提供一种掺杂石墨烯包覆过渡金属碳化物纳米胶囊的制备方法,将过渡金属块放在直流电弧氢等离子体设备上,通入氢气、惰性气体、含碳元素气体和掺杂异质元素气体使腔体总气压达0.005 Pa~9.5×104帕;接通电源形成稳定电弧,蒸发过渡金属块;冷却后引入空气钝化。本方法一步制备掺杂的石墨烯包覆过渡金属碳化物纳米胶囊,制备过程简单,可规模化制备;掺杂元素分布均匀,产物纯净;制备过程中可通过气氛进行形貌调控。本发明还提供了产物在微波催化领域的应用,反应时间短。
Description
技术领域
本发明属于纳米材料制备技术及其应用领域,涉及掺杂石墨烯包覆过渡金属碳化物纳米胶囊的制备方法及在微波催化中的应用。
背景技术
异质核@壳石墨烯包覆过渡金属碳化物纳米胶囊具有较好的化学稳定性,且其微观构型赋予了它具有特殊的多重介电极化效应,这将有可能导致更加有趣的微波辅助催化效果。从物理意义而言,核@壳结构构成了一种充满电介质的电容型结构,可以等效为电容和电阻的并联电路。在微波扰动下,极化电荷的电位移和外加磁场形成一定的相位差,可以诱导出界面极化、共振腔极化、甚至由异质单原子掺杂诱导的单原子极化等。因此,利用异质单原子对石墨烯包覆过渡金属碳化物纳米胶囊调控异质核@壳复合材料的微波吸收特性,进而调控微波催化性能,具有潜在的应用意义。
目前常用的掺杂方式有热扩散和离子注入等方法,主要用于块状晶体的掺杂;另外,对微米尺度材料的掺杂主要采用化学气相沉积法、磁控溅射法、化学法等方法,可定义为微米尺度上的调控。例如,在中国专利文献上公开的《一种过渡金属碳化物催化剂的处理方法》,其公告号CN1879964A,将过渡金属碳化物催化剂和硫/氮源在温度为273-973K、压力为0.1-10Mpa的条件下进行处理,最终在过渡金属碳化物催化剂表面形成具有组成为MOδYηC1-X的薄层,其中M为过渡金属元素;Y为元素S或N;δ=0-0.3;η=0.05-0.3;X=0.1-0.65。其中的硫源为H2S、硫化油与H2的混合物;氮源为NH3、NH3/H2混合物或是在氢气的存在下能产生NH3的有机氮化物。处理后的过渡金属碳化物催化剂不仅稳定性得到明显改善,催化活性也得到提高,可适用于催化石油馏份或煤的衍生油的加氢脱硫、加氢脱氮、烃的异构化和芳构化等反应,尤其适用于加氢脱硫、脱氮反应。但是该方法是对材料进行后处理,先将过渡金属碳化物合成出来后,再使用化学气相沉积法、磁控溅射法、化学法等方法对材料进一步掺杂。这些方法虽然在材料的掺杂中能够得到较好的掺杂效果,但是不适用于在纳米及原子尺度上进行掺杂的调控。据此需要一种理想的技术结构解决以上问题。
与传统加热方法相比,微波辐射具有更高的加热速率、高选择性、降低活化能和出色的可控性等优点。微波辅助催化实质上是电磁场、催化剂和反应物交互作用的结果,已被利用于促进固氮、有机合成、污染物降解等,以推进反应进程、提高产物选择性及产率。目前掺杂的过渡金属碳化物主要应用于锂空气电池、电催化产氢、催化生物质油加氢脱氧、肼分解等,在催化方面的应用也是用于催化石油馏份或煤的衍生油的加氢脱硫、加氢脱氮、烃的异构化和芳构化等反应。掺杂的石墨烯包覆过渡金属碳化物纳米胶囊在微波催化领域的应用研究还很少见。
发明内容
针对现有技术的不足,本发明提供一种掺杂石墨烯包覆过渡金属碳化物纳米胶囊的方法,使石墨烯包覆过渡金属碳化物纳米胶囊的尺寸、石墨烯壳层厚度和性能得到精确控制的同时,实现掺杂石墨烯包覆过渡金属碳化物纳米胶囊的规模化制备。
为了实现上述目的,本发明采用以下技术方案:一种掺杂石墨烯包覆过渡金属碳化物纳米胶囊的制备方法,其特征在于,包括以下步骤:
1)在直流电弧氢等离子体设备的阳极上放置5-200 g过渡金属块,通入氢气、惰性气体、含碳元素气体和含掺杂异质元素气体,其中掺杂异质元素选自N、B、P三种元素,氢气的体积为掺杂异质元素气体的0-100倍,惰性气体的体积为掺杂异质元素气体的0-500倍,含碳元素气体的体积为掺杂异质元素气体的20-200倍,反应腔体的总气压保持在0.005 Pa-9.5×104 Pa;
2)接通电源形成稳定电弧,蒸发过渡金属块,控制电弧反应时间为5-20 min;待反应产物冷却至室温后,引入少量空气进行钝化处理,得到异质元素掺杂的石墨烯包覆过渡金属碳化物纳米胶囊。
首先使用自动控制直流电弧等离子体设备,再通入一定比例的氢气、惰性气体、含碳元素气体和含掺杂异质元素气体的混合气氛中,以石墨电极为电弧阴极,过渡金属块为电弧阳极,引弧蒸发过渡金属块原料,在原位制备的基础上一次性得到异质元素掺杂的石墨烯包覆过渡金属碳化物纳米胶囊。本发明在合成的过程中对石墨烯包覆过渡金属碳化物纳米胶囊进行原位可控异质元素掺杂,进而调控石墨烯包覆过渡金属碳化物纳米胶囊的微波吸收性能,从而调控催化剂的催化性能。本方明在制备的石墨烯包覆过渡金属碳化物纳米胶囊中掺杂的元素为N、B、P三种非金属元素;掺入方式为在反应气氛中引入含非金属掺杂元素的气体;掺杂元素主要存在于石墨烯包覆过渡金属碳化物纳米胶囊中,在表面形成M-NH、M-NH2、M-N-M、C-NH、C-NH2、C-N-C、M-B-M、M-BH、M-BH2、M-N-M、C-BH、C-BH2、C-B-C、M-P-M、M-PH3、M-PH2、M-PH化学键,M为上述过渡金属元素。这些表面暴露的化学键在微波辐照下,发生电偶极子极化,从而影响石墨烯包覆过渡金属碳化物纳米胶囊的微波吸收性能。因此,石墨烯包覆过渡金属碳化物纳米胶囊的微波吸收性能可以通过上述化学键的类型及浓度来进行调控。
作为优选,所述过渡金属块的质量百分数为99.9%及以上。
作为优选,所述的过渡金属块为固体过渡金属块或由过渡金属粉体压制而成的金属块。
作为优选,所述过渡金属块为钛、钒、铬、锰、铁、钇、锆、铌、钼、钽、钨中的一种或多种混合物。
作为优选,所述的惰性气体为氦气、氖气或氩气的一种或多种混合气体。
作为优选,所述的含碳元素气体为:甲烷、乙烷、乙炔、乙烯、丙烯、丙炔、丙烷、丁烷、丁烯的一种或多种混合气体。
作为优选,所述的掺杂异质元素气体为:氮气、氨气、乙硼烷、磷烷的一种或多种混合气体。
本发明还提供上述制备方法得到的异质元素掺杂的石墨烯包覆过渡金属碳化物纳米胶囊在微波催化领域的应用,包括以下步骤:
1)将上述得到的掺杂石墨烯包覆过渡金属碳化物纳米胶囊均匀分散于含有污染物的溶液中,放置于三口烧瓶中制成微波反应悬浮液,所述的掺杂石墨烯包覆过渡金属碳化物纳米胶囊的浓度为1-5000 mg/L,所述的污染物的浓度为0.1-1000 mmol/L;
2)将步骤1)制得的悬浮液与搅拌、冷却装置连接后置于微波反应器中制成微波反应装置,使用设置好频率的微波电磁波照射悬浮液,辐照一段时间后测试催化剂对污染物的微波催化降解性能,所述的微波频率为1-20 GHz、辐照时间为0.01-180 min。
掺杂石墨烯包覆过渡金属碳化物纳米胶囊催化剂吸收微波后,催化剂表面局部产生高温引起热效应使污染物分子发生分解,或者催化剂表面化学键发生能级变化从而降低污染物分子内部化学键强度促进分子分解,从而把电磁波能转换成化学能。
本发明的有益效果为:(1)在反应气氛中引入含有掺杂元素的气体,一步制备含有N、B、P一种或者多种非金属元素掺杂的石墨烯包覆过渡金属碳化物纳米胶囊,制备过程简单,可规模化制备;(2)掺杂元素分布均匀,产物纯净;(3)制备过程中可通过气氛进行形貌调控;(4)原料来源丰富,成本低廉;(5)产物环境友好无污染,结构新颖;(6)产物可吸收微波催化分解有机污染物,反应时间短。
附图说明
图1是实施例一合成的氮掺杂石墨烯包覆碳化钛纳米胶囊的X射线衍射(XRD)图谱。
图2是实施例一合成的氮掺杂石墨烯包覆碳化钛纳米胶囊的透射电镜(TEM)及N元素分布图。
图3是实施例二合成的氮掺杂石墨烯包覆碳化锰纳米胶囊的微波吸收图。
具体实施方式
下面结合具体实施例,对本发明的技术方案进一步说明。
实施例一
取约40 g钛块置于自动控制直流电弧等离子体设备阳极上,钛为纯度99.9%的固体金属块。以石墨电极作为电弧阴极,通入体积比为400:200:1的氩气:甲烷:氮气,使反应腔体的气压达到5×104 Pa。接通电源起弧蒸发钛块反应10 min,制得的氮掺杂石墨烯包覆碳化钛纳米胶囊沉积在炉腔壁上。待反应产物冷却至室温后,引入少量空气进行钝化操作,获得氮掺杂石墨烯包覆碳化钛纳米胶囊。
配制100 mg/L的氮掺杂石墨烯包覆碳化钛纳米胶囊和5 mmol/L的罗丹明B水分散液,使用500 W、2.45 GHz的微波辐照分散液5 min,测试罗丹明B的含量,计算其微波催化性能。
实例一得到的氮掺杂石墨烯包覆碳化钛纳米胶囊的XRD图如图1所示。由图中衍射峰确定氮掺杂石墨烯包覆碳化钛纳米胶囊结构中主相为碳化钛,氮元素含量很少,无法在XRD中体现出来。
实例一得到的氮掺杂石墨烯包覆碳化钛纳米胶囊的TEM图及N元素分布图如图2所示。可以看出碳化钛纳米颗粒外面包覆了2~3层石墨烯碳,且石墨烯碳层随着碳化钛晶体表面的弯曲而发生弯曲。N元素在石墨烯包覆碳化钛纳米胶囊中分布较均匀。
实施例二
取约200 g钛块置于自动控制直流电弧等离子体设备阳极上,以石墨电极作为电弧阴极,通入体积比20:10:1的氩气:甲烷:氮气,使反应腔体的气压达到3.5×104 Pa。接通电源起弧蒸发钛块反应20 min,制得的氮掺杂石墨烯包覆碳化钛纳米胶囊沉积在炉腔壁上。待反应产物冷却至室温后,引入少量空气进行钝化操作,获得氮掺杂石墨烯包覆碳化钛纳米胶囊。
配制50 mg/L的氮掺杂石墨烯包覆碳化钛纳米胶囊和100 mmol/L的罗丹明B水分散液,使用700 W、2.45 GHz的微波辐照分散液10 min,测试罗丹明B的含量,计算其微波催化性能。
实例二得到的氮掺杂石墨烯包覆碳化钛纳米胶囊的微波吸收性能图如图3所示。可以看出氮掺杂石墨烯包覆碳化钛纳米胶囊具有很好的微波吸收特性,达到-47.1 dB,在-10 dB时的频率宽度为5 GHz。
实施例三
取约80 g钒块置于自动控制直流电弧等离子体设备阳极上,钒块由粉体压制而成,纯度大于99.9%。以石墨电极作为电弧阴极,通入体积比200:100:1的氦气:乙炔:乙硼烷,使反应腔体的气压达到2×104 Pa。接通电源起弧蒸发钒块反应8 min,制得的硼掺杂石墨烯包覆碳化钒纳米胶囊沉积在炉腔壁上。待反应产物冷却至室温后,引入少量空气进行钝化操作,获得硼掺杂石墨烯包覆碳化钒纳米胶囊。
配制50 mg/L的硼掺杂石墨烯包覆碳化钒纳米胶囊和3 mmol/L的2,4-二氯苯酚水分散液,使用400 W、5 GHz的微波辐照分散液8 min,测试2,4-二氯苯酚的含量,计算其微波催化性能。
实施例四
取约60 g锰块置于自动控制直流电弧等离子体设备阳极上,以石墨电极作为电弧阴极,通入体积比60:20:1的氢气:丙烷:乙硼烷,使反应腔体的气压达到60 Pa。接通电源起弧蒸发锰块反应10 min,制得的硼掺杂石墨烯包覆碳化锰纳米胶囊沉积在炉腔壁上。待反应产物冷却至室温后,引入少量空气进行钝化操作,获得硼掺杂石墨烯包覆碳化锰纳米胶囊。
配制150 mg/L的硼掺杂石墨烯包覆碳化锰纳米胶囊和200 mmol/L的2,4-二氯苯酚水分散液,使用600W、14 GHz的微波辐照分散液180 min,测试2,4-二氯苯酚的含量,计算其微波催化性能。
实施例五
取约130 g钼块置于自动控制直流电弧等离子体设备阳极上,以石墨电极作为电弧阴极,通入体积比3:2:1:0.05的氢气:氖气:乙烯:磷烷,使反应腔体的气压达到4700 Pa。接通电源起弧蒸发钼块反应20 min,制得的磷掺杂石墨烯包覆碳化钼纳米胶囊沉积在炉腔壁上。待反应产物冷却至室温后,引入少量空气进行钝化操作,获得磷掺杂石墨烯包覆碳化钼纳米胶囊。
配制80 mg/L的磷掺杂石墨烯包覆碳化钼纳米胶囊和150 mmol/L的亚甲基蓝水分散液,使用800 W、8 GHz的微波辐照分散液30 min,测试亚甲基蓝的含量,计算其微波催化性能。
实施例六
取约5 g铬块和铁块的混合物(质量比1:2)置于自动控制直流电弧等离子体设备阳极上,以石墨电极作为电弧阴极,通入体积比100:100:150:1的氢气:惰性气体:含碳元素气体:氨气,其中惰性气体由体积比1:2的氦气和氖气组成,含碳元素气体由体积比1:3:1的乙烷、丙烯和丙炔组成,使反应腔体的气压达到0.005 Pa。接通电源起弧蒸发过渡金属块反应5 min,制得的氮掺杂石墨烯包覆碳化物纳米胶囊沉积在炉腔壁上。待反应产物冷却至室温后,引入少量空气进行钝化操作,获得氮掺杂石墨烯包覆碳化物纳米胶囊。
配制1 mg/L的氮掺杂石墨烯包覆碳化物纳米胶囊和0.1 mmol/L的亚甲基蓝水分散液,使用200 W、1 GHz的微波辐照分散液0.01 min,测试亚甲基蓝的含量,计算其微波催化性能,微波吸收特性达到-43.6 dB,在-10 dB时的频率宽度为3.1 GHz。
实施例七
取约130 g钽块、钇块和锆块的混合物(质量比1:0.1:1)置于自动控制直流电弧等离子体设备阳极上,以石墨电极作为电弧阴极,通入体积比20:500:50:1的氢气:惰性气体:含碳元素气体:掺杂异质元素气体,其中惰性气体由体积比1:1:1的氦气、氖气和氩气组成,含碳元素气体由体积比3:1的丁烷和丁烯组成,掺杂异质元素气体由体积比1:5的乙硼烷和甲烷组成,使反应腔体的气压达到9.5×104 Pa。接通电源起弧蒸发过渡金属块反应20 min,制得的掺杂石墨烯包覆碳化物纳米胶囊沉积在炉腔壁上。待反应产物冷却至室温后,引入少量空气进行钝化操作,获得掺杂石墨烯包覆碳化物纳米胶囊。
配制5000 mg/L的掺杂石墨烯包覆碳化物纳米胶囊和1000 mmol/L的亚甲基蓝水分散液,使用1200 W、20 GHz的微波辐照分散液30 min,测试亚甲基蓝的含量,计算其微波催化性能,微波吸收特性达到-39.5 dB,在-10 dB时的频率宽度为4.2 GHz。
本发明在反应气氛中引入含有掺杂元素的气体,一步制备含有N、B、P一种或者多种非金属元素掺杂的石墨烯包覆过渡金属碳化物纳米胶囊,制备过程简单,可规模化制备;掺杂元素分布均匀,产物纯净;制备过程中可通过气氛进行形貌调控。产物可吸收微波催化分解有机污染物,反应时间短。
Claims (8)
1.一种掺杂石墨烯包覆过渡金属碳化物纳米胶囊的制备方法,其特征在于,包括以下步骤:
1)在直流电弧氢等离子体设备的阳极上放置5-200 g过渡金属块,通入氢气、惰性气体、含碳元素气体和含掺杂异质元素气体,其中掺杂异质元素选自N、B、P三种元素,氢气的体积为掺杂异质元素气体的0-100倍,惰性气体的体积为掺杂异质元素气体的0-500倍,含碳元素气体的体积为掺杂异质元素气体的20-200倍,反应腔体的总气压保持在0.005 Pa-9.5×104 Pa;
2)接通电源形成稳定电弧,蒸发过渡金属块,控制电弧反应时间为5-20 min;待反应产物冷却至室温后,引入少量空气进行钝化处理,得到异质元素掺杂的石墨烯包覆过渡金属碳化物纳米胶囊。
2.根据权利要求1所述的一种掺杂石墨烯包覆过渡金属碳化物纳米胶囊的制备方法,其特征在于,所述过渡金属块的质量百分数为99.9%及以上。
3.根据权利要求1或2所述的一种掺杂石墨烯包覆过渡金属碳化物纳米胶囊的制备方法,其特征在于,所述的过渡金属块为固体过渡金属块或由过渡金属粉体压制而成的金属块。
4.根据权利要求1所述的一种掺杂石墨烯包覆过渡金属碳化物纳米胶囊的制备方法,其特征在于,所述过渡金属块为钛、钒、铬、锰、铁、钇、锆、铌、钼、钽、钨中的一种或多种混合物。
5.根据权利要求1所述的一种掺杂石墨烯包覆过渡金属碳化物纳米胶囊的制备方法,其特征在于,所述的惰性气体为氦气、氖气或氩气的一种或多种混合气体。
6.根据权利要求1所述的一种掺杂石墨烯包覆过渡金属碳化物纳米胶囊的制备方法,其特征在于,所述的含碳元素气体为:甲烷、乙烷、乙炔、乙烯、丙烯、丙炔、丙烷、丁烷、丁烯的一种或多种混合气体。
7.根据权利要求1所述的一种掺杂石墨烯包覆过渡金属碳化物纳米胶囊的制备方法,其特征在于,所述的掺杂异质元素气体为:氮气、氨气、乙硼烷、磷烷的一种或多种混合气体。
8.根据权利要求1-7所述的制备方法得到的一种掺杂石墨烯包覆过渡金属碳化物纳米胶囊在微波催化中的应用,其特征在于,包括以下步骤:
1)将掺杂石墨烯包覆过渡金属碳化物纳米胶囊均匀分散于含有污染物的溶液中,放置于三口烧瓶中制成微波反应悬浮液,所述的掺杂石墨烯包覆过渡金属碳化物纳米胶囊的浓度为1-5000 mg/L,所述的污染物的浓度为0.1-1000 mmol/L;
2)将步骤1)制得的悬浮液与搅拌、冷却装置连接后置于微波反应器中制成微波反应装置,使用设置好频率的微波电磁波照射悬浮液,辐照一段时间后测试催化剂对污染物的微波催化降解性能,所述的微波频率为1-20 GHz、辐照时间为0.01-180 min。
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