CN1360558A - 用于生产碳纳米管的方法和催化剂 - Google Patents
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Abstract
一种通过使含碳气体与金属催化粒子接触来生产碳纳米管的催化剂和方法。催化粒子含有至少一种选自族VIII的金属,包括例如Co、Ni、Ru、Rh、Pd、Ir和Pt,和含有至少一种选自族VIb的金属,包括例如Mo、W和Cr。金属组分可以沉积在载体上。优选所形成的纳米管的显著部分是单壁碳纳米管。另外,还公开了一种用于确定催化剂组成和反应条件以优化单壁碳纳米管生产的方法。
Description
本申请是美国专利申请09/389553(1999年9月3日递交)和美国专利申请60/137206(1999年6月2日递交)的继续申请。
发明背景
本发明涉及用于生产碳纳米管的方法和催化剂,更具体地说,但不限制其范围,本发明涉及用于生产单壁碳纳米管的方法和催化剂。
碳纳米管(也称作碳原纤)是具有完全富勒烯罩的石墨片无缝管,在过渡金属催化剂存在下,它们首先是多层同心管或多壁碳纳米管,然后作为单壁碳纳米管。碳纳米管显示有前途的应用,包括纳米级电子设备、高强度材料、电子场发射、扫描探针显微镜的尖端以及气体储存。
一般来说,在这些应用中,单壁碳纳米管比多壁碳纳米管更优选,因为前者具有较少的缺陷,所以比相似直径的多壁碳纳米管的强度更高,传导性更强。与多壁碳纳米管相比,单壁碳纳米管不易于出现缺陷,因为多壁碳纳米管能通过在不饱和碳价之间形成桥而幸免于意外缺陷,而单壁碳纳米管没有可以补偿缺陷的隔壁。
但是,这些实际技术所需量的新单壁碳纳米管的可行性仍然存在问题。仍然需要用于生产高质量单壁碳纳米管的大规模方法。
目前,有三个合成碳纳米管的主要方法。这些包括碳的激光烧蚀(Thess,A等,Science 273,483(1996))、石墨棒的电弧放电(Journet,C等,Nature 388,756(1997))和烃的化学蒸气沉积(Ivanov,V等,Chem.Phys.Lett 223,329(1994);LiA等,Science274,1701(1996))。通过催化烃裂解生产多壁碳纳米管现在已达到工业规模(美国专利5578543),而单壁碳纳米管的生产仍然是通过激光(Rinzler,A.G.等,Appl.Phys.A,67,29(1998))和电弧(Haffner,J.H.等,Chem.Phys.Lett.296,195(1998))技术以克级规模生产。
与激光和电弧技术不同,在过渡金属催化剂上的碳蒸气沉积倾向于生成多壁碳纳米管作为主要产物,而不是单壁碳纳米管。但是,在从催化烃裂解方法生产单壁碳纳米管方面有一些成功。Dai等(Dai,H等,Chem.Phys.Lett.260,471(1996))证明由加热至1200℃的承载在氧化铝上的一氧化碳(CO)和钼(Mo)催化剂的歧化反应生产网状单壁碳纳米管。从报告的电子显微图象来看,Mo金属显然附着在纳米管的尖端。单壁碳纳米管的报告直径通常为1-5纳米,并通过Mo的粒径来控制。含有铁、钴或镍的催化剂在850-1200℃温度下使用,形成多壁碳纳米管(美国专利4663230)。最近,单壁碳纳米管的绳状束通过苯与铁催化剂和硫添加剂在1100-1200℃温度下的热裂解而生成(Cheng,H.M.等,Appl.Phys.Lett.72,3282(1998);Cheng,H.M.等,Chem.Phys.Lett.289,602(1998))。合成的单壁碳纳米管大致以束排列并纺织在一起,与从激光气化或电弧方法得到的那些相似。已提出使用这样的激光目标,它包括一种或多种族VI或族VIII过渡金属以形成单壁碳纳米管(WO98/39250)。已提出包括铁和选自族V(V、Nb和Ta)、族VI(Cr、Mo和W)、族VII(Mn、Tc和Re)或镧系元素的至少一种元素的金属催化剂的应用(美国专利5707916)。但是,使用这些催化剂的方法未教导生产具有单壁碳纳米管与多壁碳纳米管高比例的大量纳米管。
另外,在反应步骤之前或之后的分离步骤占去大部分生产碳纳米管所需的资金和操作成本。所以,从多壁碳纳米管和污染物(即无定形和石墨碳)提纯出单壁碳纳米管比碳纳米管的实际生产需要更多的时间和费用。
另外,目前技术中的最大限制之一是不能对特定合成中所含的不同形式的碳进行简单和直接的定量。目前,透射电子显微术(TEM)是最广泛用于确定在特定样品中的单壁碳纳米管分数的表征技术。但是,透射电子显微术只能提供所生产的碳物质类型的定性描述。难以确定给定的透射电子显微图象表示多少总产率。用任何统计数据半定量地确定样品中不同碳物质的分布是耗时的,且使用透射电子显微术的方法不能用作大规模操作的常规质量控制手段。
所以,需要新的和改进的生产纳米管的方法,该方法能在比现有方法更低的温度下合成工业规模量的基本上纯的单壁碳纳米管,以及需要对特定合成中碳的不同形式的直接定量方法。本发明涉及这种生产碳纳米管和对合成产物进行定量的方法。
发明概述
根据本发明,提供用于生产碳纳米管的催化剂和方法,该方法能避免现有技术的缺陷和缺点。具体地说,该方法包括在反应器单元中使金属催化粒子与有效量的含碳气体在足以催化生产碳纳米管的温度下接触,其中显著部分的碳纳米管是单壁碳纳米管,金属催化粒子包括除铁以外的族VIII金属和族VIb金属。
另外,根据本发明,提供确定催化剂组成和反应条件的方法,以优化单壁碳纳米管的生产。具体地说,该方法包括在反应器单元中使含碳纳米管的产物样品与有效量的含氧气体接触以氧化样品中存在的碳,同时提高反应器单元内的温度。检测由样品释放出的二氧化碳量,并通过在特定温度下从样品释放出的二氧化碳来确定样品中存在的特定碳物质。改变催化剂组成和/或反应条件,直至单壁碳纳米管的存在量显著高于含碳纳米管的产物样品中的所有其它碳物质。
在本发明的一方面,金属催化粒子是沉积在载体例如二氧化硅上的双金属催化剂。在双金属催化剂中的族VIII金属与族VIb金属之比在约1∶5至约2∶1的范围内。
本发明的一个目的是提供一种以较大量和在较低温度下生产单壁碳纳米管的方法。
本发明的另一个目的是提供定量地确定样品中存在的不同形式的碳,包括单壁碳纳米管、多壁碳纳米管以及无定形碳,进而确定特定催化剂的选择性和优化生产碳纳米管的反应条件的方法。
本发明的其它目的、特征和优点将从以下详细描述结合附图和所附权利要求中表现出来。
附图简述
图1是由通过在SiO2上的Co/Mo催化剂在约700℃下催化的CO歧化反应得到的单壁碳纳米管的透射电子显微图象(放大倍数约为100000)。
图2是图1中所用样品在更高分辨率下的透射电子显微图象(放大倍数约为400000),显示单壁碳纳米管的束(SWNTs)。
图3是图1中所用样品的透射电子显微图象,显示在束中增长的排列的单壁碳纳米管。
图4是图1中所用样品的透射电子显微图象,显示单壁碳纳米管束的端视图。
图5是图1中所用样品的扫描电子显微图象,显示从催化表面增长出来的单壁碳纳米管束。
图6是由Co∶Mo/SiO2催化剂在约700℃下催化的CO歧化反应得到的产物的温度程序氧化曲线。
图7是由在SiO2上的Co催化剂、在SiO2上的Mo催化剂和在SiO2上的Co∶Mo催化剂在约700℃下催化的CO歧化反应得到的产物的温度程序氧化曲线。
图8是由在SiO2上的Co∶Mo催化剂在约700℃下催化的CO歧化反应得到的产物的温度程序氧化曲线,其中改变Co∶Mo的摩尔比。
图9是由Co∶Mo/SiO2催化剂催化的CO歧化反应得到的产物的温度程序氧化曲线,其中改变反应温度。
图10是由Co∶Mo/SiO2催化剂在约700℃下催化的CO歧化反应得到的产物的温度程序氧化曲线,其中改变在CO歧化反应中所用的含碳气体中CO的百分比。
图11是由Co∶Mo/SiO2催化剂在约700℃下催化的CO歧化反应得到的产物的温度程序氧化曲线,其中改变CO歧化反应的时间。
发明详述
本发明涉及用于生产大量单壁碳纳米管的催化剂和方法,其中使有效量的含碳气体在较低温度下通过包括至少一种族VIII金属和至少一种族VIb金属的双金属催化粒子;和涉及能可靠地定量检测在含碳纳米管的产物中单壁碳纳米管产率的方法。
具体地说,用于生产单壁碳纳米管的方法包括使包括族VIII金属和族VIb金属的双金属催化粒子与有效量的含碳气体在被加热到约500-1200℃温度的反应器中接触,优选约600-850℃,更优选约650-750℃,最优选约700℃。含碳气体可以连续地供应到反应器中,或含碳气体可以在静止气氛中保持在反应器中。
本文所用的词语“有效量的含碳气体”指存在的足量的气态碳物质,以使碳在如下所述的较高温度下沉积在金属催化粒子上,从而形成碳纳米管。
本文所用的金属催化粒子包括催化剂组分。本发明提供和使用的催化剂是双金属的。双金属催化剂含有至少一种选自族VIII的除铁以外的金属,包括Co、Ni、Ru、Rh、Pd、Ir、Pt及其混合物,和含有至少一种选自族VIb的金属,包括Cr、W、Mo及其混合物。可用于本发明的双金属催化剂的具体实例包括Co-Cr、Co-W、Co-Mo、Ni-Cr、Ni-W、Ni-Mo、Ru-Cr、Ru-W、Ru-Mo、Rh-Cr、Rh-W、Rh-Mo、Pd-Cr、Pd-W、Pd-Mo、Ir-Cr、Ir-W、Ir-Mo、Pt-Cr、Pt-W和Pt-Mo。本发明特别优选的催化剂包括Co-Mo、Co-W、Ni-Mo和Ni-W。
双金属催化剂的两种金属组分之间存在增效作用,因为与含有族VIII金属或族VIb金属之一作为催化剂的金属催化粒子相比,含有双金属催化剂的金属催化粒子对于生产单壁碳纳米管更有效。该双金属催化剂的增效作用将在下面更详细地描述。
在金属催化粒子中族VIII金属与族VIb金属之比还影响本发明方法生产单壁碳纳米管的选择性。族VIII金属与族VIb金属之比优选是约1∶10至约15∶1,更优选是约1∶5至约2∶1。一般来说,在用于选择性地生产单壁碳纳米管的金属催化粒子中,族VIb金属(例如Mo)的浓度将超过族VIII金属(例如Co)的浓度。
金属催化粒子可以含有选自族VIII和族VIb两者的一种以上金属,只要存在至少一种选自其中每个族的金属即可。例如,金属催化粒子可以含有(1)一种以上的族VIII金属和一种族VIb金属,(2)一种族VIII金属和一种以上的族VIb金属,或(3)一种以上的族VIII金属和一种以上的族VIb金属。
双金属催化剂可以通过简单地将两种金属混合而制成。双金属催化剂还可以通过分解前体化合物而就地形成,前体化合物例如是二(环戊二烯基)钴或二(环戊二烯基)钼的氯化物。
催化剂优选沉积在载体上,载体例如是二氧化硅(SiO2)、MCM-41(Mobil结晶材料-41)、氧化铝(Al2O3)、MgO、Mg(Al)O(铝稳定的氧化镁)、ZrO2、分子筛沸石或本领域公知的其它氧化载体。
金属催化粒子,即沉积在载体上的催化剂,可以通过在平面基质如石英、玻璃、硅以及氧化硅表面上按照本领域一般技术人员公知的方式蒸发金属混合物而制成。
沉积在载体上的双金属催化剂的总量可以在宽范围内变化,但通常占金属催化粒子总重量的约1-20%,更优选占金属催化粒子总重量的约3-10%。
在本发明的另一种实施方案中,双金属催化剂可以不沉积在载体上,在这种情况下,金属组分含有基本上约100%的金属催化粒子。
合适的含碳气体的实例包括:饱和的和不饱和的脂族烃,例如甲烷、乙烷、丙烷、丁烷、己烷、乙烯和丙烯;一氧化碳;氧化的烃,例如丙酮、乙炔和甲醇;芳族烃,例如甲苯、苯和萘;以上物质的混合物,例如一氧化碳和甲烷。使用乙炔能促进形成多壁碳纳米管,而CO和甲烷是用于形成单壁碳纳米管的优选进料气体。含碳气体可以任选地与稀释剂气体混合,例如氦气、氩气或氢气。
在本发明的优选实施方案中,双金属催化粒子置于反应器单元内,例如置于炉或烘箱中的石英管,将含碳气体通入反应器单元内。或者,样品可以通过微波辐射加热。该方法可以是连续的,其中金属催化粒子和含碳气体连续地进料和在反应器内混合,或该方法可以是间歇方法,其中含碳气体和金属催化粒子置于反应器单元内,并在反应期间保留在反应器单元内。
或者,金属催化粒子可以与电弧放电系统中的电极混合,以生产单壁碳纳米管和/或多壁碳纳米管。或者,可以在暴露于微波诱导等离子体放电的系统中使用金属催化粒子。在完成催化过程之后,从反应器中取出金属催化粒子和纳米管。通过本领域普通技术人员公知的方法从金属催化粒子中分离出纳米管。在此处,没有必要进一步讨论从金属催化粒子中分离出碳纳米管的这种方法。
此处制得的单壁碳纳米管通常具有外径为约0.7-5纳米。此处制得的多壁碳纳米管通常具有外径为约2-50纳米。
用于对单壁碳纳米管进行可靠的定量检测方法是直接的和易于进行的,从而可以检测到选择性或稳态生产的变化,使重现性和质量控制易于实现。该方法基于温度程序氧化(TPO)技术(Krishnankutty,N等,Catalysis Today,37,295(1997))。该技术通常用于评估碳的结晶性,并基于这样的概念,即与具有短程结晶有序的材料相比,高度石墨材料的抗氧化性将更强。在本发明中,采用该技术来提供一种确定相对于多壁碳纳米管的生产单壁碳纳米管的选择性的方法,以及由每种碳物质占总固体产物的百分比,每种碳物质不仅包括单壁碳纳米管和多壁碳纳米管,而且包括无定形碳和石墨碳物质。所以,该方法与上述碳纳米管的生产方法相结合,将允许受控地生产单壁碳纳米管。但是,应该理解的是,该方法还能用于分析任何含有碳纳米管的样品。
具体地说,该方法包括使分散在载体气体中的含氧气体连续流,例如在氦气中的5%氧气,通过含碳纳米管的样品,例如含碳沉积物的催化剂,同时使温度从室温线性升高到约800℃。含氧气体的量能够有效地氧化在样品中存在的碳物质。碳物质的氧化导致生成二氧化碳,每种碳物质,例如单壁或多壁碳纳米管、无定形碳或石墨,在不同的温度下被氧化。通过样品中存在的每种碳物质的氧化作用生成的二氧化碳由质谱监测。所生成的二氧化碳通过用已知量的纯二氧化碳的脉冲和已知量的石墨的氧化来校正,从而直接检测在各温度下被氧化的碳的量。也就是说,由质谱测得的1摩尔二氧化碳对应于1摩尔在给定温度下被氧化的特定种类的碳。
采用温度程序氧化的定量方法在下文中称作温度程序氧化方法,该方法特别适用于定量表征单壁碳纳米管,这是因为单壁碳纳米管在较窄的温度范围内被氧化,该温度范围处于无定形碳的氧化温度以上,且处于多壁碳纳米管和石墨碳的氧化温度以下。例如,通过该方法,测得单壁碳纳米管的氧化温度比C60富勒烯的氧化温度高出约100℃,且比多壁碳纳米管的氧化温度低约100℃。通过热重分析法(TGA)得到相似的结果(Rinzler,A.G.等,Appl.Phys.A,67,29(1998)),确定该方法对于定量单壁碳纳米管的适用性。
此处所述的温度程序氧化分析方法可以用于快速检测不同的催化剂配方和碳纳米管生产方法的操作条件,以便优化单壁碳纳米管的生产。例如,在金属催化粒子中存在的最佳双金属催化剂,以及两种金属的最佳摩尔比,可以通过温度程序氧化来确定。温度程序氧化还可以用于优化反应条件,例如温度、时间和含碳气体中碳的浓度。例如,在不同反应温度下产物的温度程序氧化结果显示,碳的沉积量随着温度的降低而增加,但对生产单壁碳纳米管的选择性在低温下较低。所以,温度程序氧化可以用于发现对于任何特定催化剂的最佳反应温度。
现在将理解的是,尽管已详细讨论了单壁碳纳米管生产的优化,但相同的方法可以用于优化多壁碳纳米管的生产。
石墨、无定形碳和在催化过程中形成的其它碳残渣的量被最小化,这是因为使用了较低的温度。石墨或无定形碳的重量小于在该方法期间形成的总固体材料重量的约40%,更优选小于约10%。最优选,石墨、无定形碳和其它固体碳残渣的量小于催化过程的总固体产物的约5%。
此处所述的温度程序氧化方法看来是第一种能不仅确定样品中存在的碳物质、而且能确定样品中存在的每种碳物质百分比的方法。这特别有助于在单壁碳纳米管用于各种用途中之前确定应该采取何种纯化步骤(如果有的话)。因为与实际的碳纳米管生产本身相比,纯化步骤十分费时和昂贵,所以温度程序氧化方法的价值是显然的。
此处制得的碳纳米管可以用于各种用途。例如,它们可以用作纤维增强的复合材料结构或混杂复合材料结构(即除碳纳米管以外含有增强材料例如连续纤维的复合材料)中的增强材料。复合材料可以进一步含有填料,例如炭黑、二氧化硅及其混合物。可增强的基体材料的实例包括无机和有机聚合物、陶瓷(例如卜特兰水泥)、碳和金属(例如铅或铜)。当基体是有机聚合物时,可以是:热固性树脂例如环氧、双马来酰亚胺、聚酰亚胺、或聚酯树脂;热塑性树脂;或反应注射成型树脂。碳纳米管还可以用于增强连续的纤维。可被增强或包括在混杂复合材料中的连续纤维的实例包括芳族聚酰胺、碳、玻璃纤维及其混合物。连续纤维可以是织造的、编织的、卷曲的或直接的。
本发明将通过以下实施例更详细地说明。但是,实施例仅仅用于说明本发明的理想方面,而不用于限制本发明的范围。
实施例1:
含有约10重量%在二氧化硅基质上的混合钴和钼(约1∶1比率)的双金属催化粒子通过初期润湿浸渍方法制备,其中使适宜量的硝酸钴和七钼酸铵四水合物一起溶解在去离子水中,然后逐步滴加在二氧化硅上。陶瓷灰砂和研杵用于分散在二氧化硅上的金属。所得的双金属催化粒子然后于环境条件下干燥数小时。被部分干燥的双金属催化粒子然后在烘箱中于约80℃下干燥约12小时。干的双金属催化粒子然后在流动空气中于约450℃下煅烧。
为了生产碳纳米管,将约0.1克经煅烧的双金属催化粒子置于立式石英管反应器中,该反应器具有电弧内径为约8毫米。装有经煅烧的双金属催化粒子的立式石英管反应器置于炉内,该炉配备有热电偶和温度控制。使氢气(约85厘米3/分钟)从反应器顶部通入该反应器。炉温是以约20℃/分钟的速率从室温线性升高到约450℃。在达到约450℃之后,将氢气流再通入反应器中约30分钟。反应器温度然后升高到在氦气中的约600-700℃。然后,一氧化碳气体(约50%一氧化碳/50%氦气)以约100厘米3/分钟的流速通入反应器中。CO与经煅烧的双金属催化粒子的接触时间是约15分钟到约2小时。在经过上述接触时间之后,关闭该炉,并在氦气中将产物冷却到室温。
反应之后,样品的颜色恢复到深黑色。为了对产物进行透射电子显微镜分析,将一部分产物悬浮在蒸馏水中,用超声波辐照。将几滴该悬浮液沉积在承载在铜栅上的lacey碳上。然后干燥一部分产物,并用JEOL JEM-2000FX型透射电子显微镜在约200KV下观察。如透射电子显微镜图象所示(图1-4),可以清晰地看到大量单壁碳纳米管。观察到这些单壁碳纳米管层叠在一起,粗略地排列成束。透射电子显微镜图象还显示,单壁碳纳米管的束被无定形碳所包覆,与其它方法相似。大多数管具有约1纳米直径,少部分管具有较大的直径,最多约3.2纳米。
在透射电子显微镜分析之后,用JEOL JSM-880型扫描电子显微镜扫描产物。图5中的扫描电子显微镜图象显示在二氧化硅表面上的单壁碳纳米管的束。
实施例2:
含有承载于二氧化硅上的Ni、Co或Mo单金属催化剂的金属催化粒子也通过与实施例1所述相同的方法制备,将其催化性能与含有双金属催化剂的金属催化粒子的催化性能进行比较。在进行与实施例1所述相同的在700℃下CO处理之后,进行同样的透射电子显微镜分析,在这些样品中没有观察到单壁碳纳米管。该结果表示确实存在CO和Mo之间的增效作用使两种金属的结合成为很有效的配方,而在该温度下,单独的金属不能生产单壁碳纳米管。
实施例3:
在不同的载体(SiO2、MCM-41、Al2O3、Mg(Al)O和ZrO2)上制备一系列含有约6重量%Co-Mo双金属催化剂的金属催化粒子,并比较其碳纳米管的生产能力,然后采用与实施例1相同的CO歧化方法。表I概括了这些实验的结果。实施例4:
按照与实施例1相同的步骤,观察到含有沉积在SiO2上的Co-W双金属催化剂的金属催化粒子,其中Co/W摩尔比为约1.0,得到与Co-Mo/SiO2金属催化粒子相似的单壁碳纳米管产率。在Co-Mo系列的情况下,观察到仅仅含有W/SiO2、但不含Co的金属催化粒子不能形成单壁碳纳米管。
实施例5:
表I催化剂载体对碳沉积形态学的影响 | |
催化剂 | 观察到的碳沉积物的形态学 |
Co∶Mo/SiO2 | 主要量的单壁碳纳米管,少量多壁碳纳米管和石墨 |
Co∶Mo/MCM-41 | 主要量的单壁碳纳米管,少量多壁碳纳米管和石墨 |
Co∶Mo/Al2O3 | 少量的单壁碳纳米管、多壁碳纳米管和石墨 |
Co∶Mo/Mg(Al)O | 少量石墨、少量单壁碳纳米管 |
Co∶Mo/ZrO2 | 少量石墨、少量单壁碳纳米管 |
用温度程序氧化方法分析通过与实施例1所述相同的CO歧化方法用含有承载于二氧化硅上的约6重量%Co-Mo双金属催化剂(约1∶2比率)的金属催化粒子制成的碳物质,如图6所示。
为了进行温度程序氧化分析,将由约700℃下CO处理产物得到的约50毫克样品放置在与实施例1所用相似的石英管反应器中。将约5%氧气/95%氦气的连续流通入反应器中,炉温以约11℃/分钟的速率从室温升高到约800℃,然后在约800℃保持约1小时。所形成的CO2用质谱检测,以确定在各温度下被氧化的碳物质的量。
质谱检测CO2在石英管内的分压,得到绝对值。然后通过减去基线值来归一化该值,在用约100微升CO2脉冲和已知量的石墨氧化校正之后计算。调节后的值与在特定温度下被氧化的CO2摩尔量直接成比例,后者又与样品中存在的特定碳物质的摩尔量直接成比例。从这些数值可以计算催化方法总固体产物中的单壁碳纳米管百分比。
在Co∶Mo/SiO2金属催化粒子(标为“Co∶Mo 1∶2”)上制得的碳物质的温度程序氧化曲线表示为其中心处于约330℃的小氧化峰,该峰归属于无定形碳的氧化,以及其中心处于约510℃的主要峰,该峰在图中由箭头标出,并归属于单壁碳纳米管的氧化。
两个参比样品也通过温度程序氧化方法观察,其曲线如图6所示。第一个参比样品(标为“石墨”)是与Co∶Mo/SiO2金属催化粒子进行物理混合的石墨粉。这种形式的碳的氧化在很高的温度下进行,开始为约700℃,在约800℃保持约30分钟之后完成。
第二个参比样品是纯化的单壁碳纳米管的商业样品,购自TubesRice(Rice University,Houston,Texas)。该样品以约5.9克/升含有非离子表面活性剂Triton X-100的液体悬浮液形式提供。为了进行温度程序氧化分析,Co∶Mo/SiO2金属催化粒子用单壁碳纳米管悬浮液浸渍,其中液体/催化剂的重量比率为约1∶1,以便得到在样品上的约0.6重量%单壁碳纳米管。经浸渍的样品(标为“TubesRice”)的温度程序氧化曲线显示两个峰,低温峰对应于表面活性剂的氧化,第二个峰处于约510℃,完全对应于单壁碳纳米管的氧化。为了确定第一个峰确实归属于表面活性剂的氧化,制备具有相同浓度的仅含表面活性剂的空白溶液的样品。其温度程序氧化曲线(标为“空白溶液”)符合“TubesRice”曲线的第一个峰,证明该峰确实对应于表面活性剂Triton。
通过温度程序氧化方法从CO2对“TubesRice”参比样品中的单壁碳纳米管的量进行定量,得到约0.64重量%的值,这很好地符合在样品中承载的单壁碳纳米管的量(约0.6重量%)。该结果证明本发明的温度程序氧化方法可以用于直接定量特定碳物质的百分比,例如由纳米管生产方法得到的产物中存在的单壁碳纳米管、多壁碳纳米管和无定形碳。目前,还没有其它能直接定量特定碳物质占纳米管生产所得总固体产物的分数的方法。实施例6:
由含有承载于二氧化硅上Co或Mo单金属催化剂的金属催化粒子催化的CO歧化所得产物的温度程序氧化曲线用实施例5的方法得到,并与由双金属催化剂催化的CO歧化所得产物的温度程序氧化曲线进行比较。温度程序氧化方法清楚地证明Co和Mo所显示的增效作用,这在实施例2中也由透射电子显微镜观察到。
如图7所示,含有Mo/SiO2金属催化粒子的样品(标为“Mo”)的温度程序氧化曲线表明单独的Mo不能生产碳纳米管;“Mo”温度程序氧化曲线仅仅包括小的低温峰,对应于无定形碳。相似地,含有Co/SiO2金属催化粒子的样品(标为“Co”)的温度程序氧化曲线表明单独的Co对生产单壁碳纳米管没有选择性,并主要生成石墨碳和多壁碳纳米管,如上所述,其在比单壁碳纳米管更高的温度下氧化。相比之下,两种金属的组合得到对单壁碳纳米管的高选择性,含有Co∶Mo/SiO2金属催化粒子的样品(标为“Co∶Mo=1∶2”,其中Co∶Mo比率是约1∶2)显示其中心位于约510℃的大峰,归属于单壁碳纳米管。因为没有其它明显的峰,所以可以假设单壁碳纳米管占碳纳米管生产所得总固体产物的大部分百分比。
在催化产物中存在的单壁碳纳米管、无定形碳、多壁碳纳米管和石墨的百分比列于表II中,其中所有数字和测量值是近似值。
实施例7:
表II Co和Mo所表现的增效作用 | |||
催化剂 | 无定形碳% | 单壁碳纳米管% | 多壁碳纳米管和石墨% |
Co | 38 | 11 | 51 |
Mo | 95 | 5 | 0 |
Co∶Mo(1∶2) | 8 | 88 | 4 |
将由含有Co∶Mo双金属催化剂的金属催化粒子催化的CO歧化产物的温度程序氧化曲线进行比较,其中Co∶Mo比率为约1∶4、约1∶2、约1∶1和约2∶1,以确定改变Co∶Mo/SiO2金属催化粒子中Co∶Mo摩尔比的作用。通过与实施例5所述相同的方法得到温度程序氧化曲线。如图8所示,含有Co∶Mo摩尔比为约1∶2和约1∶4的Co∶Mo/SiO2金属催化粒子显示对单壁碳纳米管的最高选择性。箭头表示对应于单壁碳纳米管氧化的峰中心。这些样品的温度程序氧化曲线表明这些催化剂制得大部分单壁碳纳米管和少量无定形碳。Co∶Mo比率的增加不会提高单壁碳纳米管的产率,但确实加速形成多壁碳纳米管和石墨碳,如在标为“Co∶Mo=2∶1”的程序温度氧化曲线的约600-700区域中的峰尺寸增加所示。
从图8的程序温度氧化曲线估计每种催化剂的选择性值,并列于表III中,其中所有数字和测量值是近似值。
实施例8:
表III Co∶Mo摩尔比对单壁碳纳米管生产的作用 | |||
Co∶Mo催化剂的摩尔比 | 无定形碳% | 单壁碳纳米管% | 多壁碳纳米管和石墨% |
2∶1 | 12 | 57 | 31 |
1∶1 | 16 | 80 | 4 |
1∶2 | 8 | 88 | 4 |
1∶4 | 5 | 94 | 1 |
图9-11表明采用温度程序氧化技术来优化反应条件。CO歧化反应用Co∶Mo/SiO2金属催化粒子(约1∶1摩尔比)催化,且所用的方法与实施例1中所述相似,不同的是在图9中改变反应温度,在图10中改变CO的浓度,在图11中改变反应时间。CO歧化产物用实施例5所述的温度程序氧化方法分析。
在图9中,显示当反应器温度为约600℃、约700℃和约800℃时制得的碳物质的温度程序氧化曲线。这些曲线证明碳的沉积量随着温度的降低而增加;但是在较低的温度下,对单壁碳纳米管的选择性较低。温度程序氧化可以用于确定任何特定催化剂的最佳反应温度,在这种情况下,最佳温度是约700℃。单壁碳纳米管、无定形碳、多壁碳纳米管和石墨占催化产物的百分比列于表IV中,其中所有的数字和测量值是近似值。
在图10中,显示当含碳气体中CO浓度为约1%、约20%、约35%和约50%时制得的碳物质的温度程序氧化曲线。这些曲线证明单壁碳纳米管的产量与含碳气体中CO浓度有很大的关系。
表IV反应器温度对单壁碳纳米管生产的作用 | |||
温度 | 无定形碳% | 单壁碳纳米管% | 多壁碳纳米管和石墨% |
600℃ | 16 | 55 | 29 |
700℃ | 16 | 80 | 4 |
800℃ | 25 | 61 | 14 |
在图11中,显示当反应时间为约3分钟、约10分钟和约1小时时制得的碳物质的温度程序氧化曲线。反应时间指使反应器保持在约700℃且CO与金属催化粒子接触的时间。这些温度程序氧化曲线证明单壁碳纳米管的产率在第一个大约10分钟期间随着时间的延长而显著增加,但超过该时间后,增长的幅度不太显著。
现在应该理解的是,温度程序氧化方法是一种催化方法,其中样品中存在的金属催化了碳物质的氧化。所以,如果催化剂的性质显著改变,则氧化峰的位置可以从上述实施例所述的峰位置发生位移,尽管该峰所表示的碳结构是相同的。例如,已观察到,催化剂载体的改变可以导致这种位移。所以,对于本发明方法中所用的每种催化剂,催化剂的完整温度程序氧化曲线以及操作条件应该用适宜的参比来进行,以确定峰的位移以及最佳操作条件。
实施例9:
在本发明方法的一个特别优选的实施方案中,催化剂组成是Co-Mo/二氧化硅催化剂,其中Co∶Mo摩尔比为约1∶2。单金属Co催化剂或具有较高Co∶Mo摩尔比的催化剂倾向于得到低的选择性,显著制得不利的多壁碳纳米管和石墨。在研究的温度范围内,在没有Co的情况下,Mo基本上对纳米管生产呈惰性。催化剂在氢气中进行预处理,例如在约500℃下,以便部分还原Mo,但不还原Co。在没有该预处理步骤的情况下,或在较高温度下进行预还原的情况下(即,不足以还原或过多的还原),催化剂没有效果,且生成较少的SWNT。其它载体例如氧化铝可以导致差的Co-Mo相互作用,使选择性和产率受到损失。
高空速(在约30000小时-1以上)是优选的,以使CO2的浓度最小化,CO2是反应的副产物,它抑制向纳米管的转化。高的CO浓度是优选的,以使无定形碳沉积物的形成最小化,因为这种沉积物的形成在低CO浓度下发生。优选的温度范围的特征在于,低于约650℃时,对SWNT的选择性低;而高于约850℃时,转化率低,这是因为反应的可逆性(放热)和催化剂的去活化。所以,最佳温度为约700-800℃;更优选为约725-775℃,和最优选约750℃。
生产方法设计成这样的方式,使得优选的催化剂配料与高度浓缩的CO流在约750℃下快速接触。否则,产率和选择性将受到很大的影响。由该方法制得的SWNT的质量可以通过包括拉曼光谱、温度程序氧化(TPO)和电子显微术(TEM)的表征技术的组合来确定。
优选的方法所以包括使CO气体流(高浓度)与催化粒子在约750℃下以高空速(高于约30000小时-1)在高压下(高于约4826322.99Pa(即高于约4826322.99N·m-2(70psi)))接触约1小时。
如果按照上述条件,将得到高产率的SWNT(约20-25克SWNT/约100克在反应器中所装载的初始催化剂)和高选择性(大于约90%)。
在不偏离所附权利要求限定的本发明精神和范围的情况下,可以对所述各种组分、元素和组合或所述方法的步骤或步骤顺序进行改变。
此处描述的本发明可以在没有其中未具体公开的任何因素的情况下适宜地实施。
以下权利要求包括本申请的最宽的可能范围。权利要求应该不是必要地受限于优选的实施方案或实施例所示的实施方案。
Claims (52)
1.一种生产碳纳米管的方法,包括:
在反应器单元中使含有至少一种除铁以外的族VIII金属与至少一种族VIb金属的金属催化粒子与有效量的含碳气体在足以催化生产碳纳米管的温度下接触,以使显著部分的碳纳米管是单壁碳纳米管。
2.根据权利要求1的方法,其中族VIII金属选自Co、Ni、Ru、Rh、Pd、Ir、Pt及其混合物。
3.根据权利要求1或2中任一项的方法,其中族VIb金属选自Cr、Mo、W及其混合物。
4.根据权利要求1的方法,其中族VIII金属选自Co、Ni、Ru、Rh、Pd、Ir、Pt及其混合物,其中族VIb金属选自Cr、Mo、W及其混合物。
5.根据权利要求1-4中任一项的方法,其中所述金属催化粒子进一步含有沉积金属的的载体。
6.根据权利要求5的方法,其中载体选自二氧化硅、MCM-41、氧化铝、MgO、Mg(Al)O、ZrO2和分子筛沸石。
7.根据权利要求1-6中任一项的方法,其中族VIII金属与族VIb金属的比率是约1∶10至约15∶1。
8.根据权利要求1-7中任一项的方法,其中族VIII金属与族VIb金属的比率是约1∶5至约2∶1。
9.根据权利要求5或6中任一项的方法,其中催化粒子含有约1-20重量%的金属。
10.根据权利要求1-9中任一项的方法,其中含碳气体选自饱和的烃、脂族烃、氧化的烃、芳族烃、一氧化碳及其混合物。
11.根据权利要求1-9中任一项的方法,其中含碳气体进一步含有稀释剂气体。
12.根据权利要求1-11中任一项的方法,其中温度足够地低于所述含碳气体的热分解温度以便避免显著形成热解的碳。
13.根据权利要求1-12中任一项的方法,其中所述温度为约500-1200℃。
14.根据权利要求1-13中任一项的方法,其中所述温度为约600-850℃。
15.根据权利要求1-14中任一项的方法,其中所述温度为约650-750℃。
16.根据权利要求1-15中任一项的方法,其中催化制得的碳纳米管进一步包括多壁碳纳米管。
17.根据权利要求1-16中任一项的方法,其中单壁碳纳米管占催化制得的纳米管的至少约60%到至少约95%。
18.根据权利要求1-17中任一项的方法,其中族VIII金属是Co。
19.根据权利要求1-17中任一项的方法,其中族VIII金属是Ni。
20.根据权利要求1-17中任一项的方法,其中族VIII金属是Ru。
21.根据权利要求1-17中任一项的方法,其中族VIII金属是Rh。
22.根据权利要求1-17中任一项的方法,其中族VIII金属是Pd。
23.根据权利要求1-17中任一项的方法,其中族VIII金属是Ir。
24.根据权利要求1-17中任一项的方法,其中族VIII金属是Pt。
25.根据权利要求1-24中任一项的方法,其中族VIb金属是Cr。
26.根据权利要求1-24中任一项的方法,其中族VIb金属是Mo。
27.根据权利要求1-24中任一项的方法,其中族VIb金属是W。
28.根据权利要求1-27中任一项的方法,其中金属催化粒子含有至少一种额外的族VIII金属。
29.根据权利要求1-28中任一项的方法,其中金属催化粒子含有至少一种额外的族VIb金属。
30.根据权利要求1-29中任一项的方法,其中金属催化粒子含有至少一种额外的族VIII金属和至少一种额外的族VIb金属。
31.根据权利要求1-30中任一项的方法,其中金属催化粒子基本上连续地供应到含碳气体流中。
32.根据权利要求1-31中任一项的方法,其中含碳气体供应到其中装有催化粒子的反应器单元中。
33.一种确定催化剂组成以优化单壁碳纳米管生产的方法,包括:
提供单壁碳纳米管生产的产物,其中在生产中使用具有这样组成的金属催化粒子,它包括除铁以外的族VIII金属和族VIb金属,且族VIII金属和族VIb金属之间具有预定的比率;
取出含有单壁碳纳米管的产物样品;
在反应器单元中使含有单壁碳纳米管的产物样品与有效量的含氧气体接触以便氧化样品中存在的碳物质;
将反应器单元内的温度从约室温升高到约800℃;
检测在约室温至约800℃的给定温度下由样品释放出的二氧化碳量;
通过在检测温度下从样品释放出的二氧化碳量来确定样品中存在的特定碳物质;和
通过改变族VIII金属、改变族VIb金属和改变两种金属的预定比率中的至少一种方式来改变金属催化粒子的组成,使得单壁碳纳米管的存在量显著高于含碳纳米管的产物样品中的所有其它碳物质。
34.一种具有根据权利要求33方法确定的组成的金属催化粒子,其中所述金属催化粒子制得这样的产物,其中存在的碳物质的至少约60%到至少约95%是单壁碳纳米管。
35.根据权利要求34的金属催化粒子,其中催化剂组成包括Co和Mo,其中Co和Mo的预定比率是约1∶10至约15∶1。
36.根据权利要求33的确定催化剂组成以优化单壁碳纳米管生产的方法,其中在提供单壁碳纳米管生产的产物、其中在生产中使用金属催化粒子的步骤中,生产单壁碳纳米管的方法包括在反应器单元中使金属催化粒子与有效量的含碳气体在足以催化生产含单壁碳纳米管的产物的温度下接触。
37.一种在生产单壁碳纳米管的方法中优化反应条件的方法,包括:
提供单壁碳纳米管生产的产物,其中使用一组反应条件,包括温度、时间和在含碳气体中碳浓度中的至少一种;
取出含有单壁碳纳米管的产物样品;
在反应器单元中使含有单壁碳纳米管的产物样品与有效量的含氧气体接触以便氧化样品中存在的碳物质;
将反应器单元内的温度从约室温升高到约800℃;
检测在约室温至约800℃的给定温度下由样品释放出的二氧化碳量;
通过在检测温度下从样品释放出的二氧化碳量来确定样品中存在的特定碳物质;和
通过改变温度、时间和含碳气体中碳浓度中的至少一种来改进反应条件,使得单壁碳纳米管的存在量显著高于含碳纳米管的产物样品中的所有其它碳物质。
38.根据权利要求37的在生产单壁碳纳米管的方法中优化反应条件的方法,其中在提供单壁碳纳米管产物的步骤中,生产单壁碳纳米管的方法包括在反应器单元中使金属催化粒子与有效量的含碳气体在足以催化生产含单壁碳纳米管的产物的温度下接触,其中金属催化粒子包括除铁以外的族VIII金属和族VIb金属。
39.一种用于生产碳纳米管的催化粒子,包括至少一种除铁以外的族VIII金属和至少一种族VIb金属。
40.根据权利要求39的催化粒子,其中族VIII金属选自Co、Ni、Ru、Rh、Pd、Ir、Pt及其混合物。
41.根据权利要求39或40的催化粒子。
42.根据权利要求39-41中任一项的催化粒子,其中所述粒子进一步含有沉积金属的的载体。
43.根据权利要求42的催化粒子,其中载体选自二氧化硅、MCM-41、氧化铝、MgO、Mg(Al)O、ZrO2和分子筛沸石。
44.根据权利要求39-43中任一项的催化粒子,其中族VIII金属与族VIb金属的比率是约1∶10至约15∶1。
45.根据权利要求39-44中任一项的催化粒子,其中族VIII金属与族VIb金属的比率是约1∶5至约2∶1。
46.根据权利要求42或43中任一项的催化粒子,其中催化粒子含有约1-20重量%的金属。
47.根据权利要求39-46中任一项的催化粒子,其中催化粒子含有至少一种额外的族VIII金属。
48.根据权利要求39-47中任一项的催化粒子,其中催化粒子含有至少一种额外的族VIb金属。
49.一种生产碳纳米管的方法,包括:
在反应器单元中使含有至少一种金属的金属催化粒子与有效量的气体在足以催化生产碳纳米管的温度下接触。
50.一种确定催化剂组成的方法,包括:
提供纳米管生产的产物,其中在生产中使用金属催化粒子;
取出产物样品;
在反应器单元中使产物样品与有效量的气体接触以便氧化样品中存在的碳物质;
将反应器单元内的温度升高到约室温以上;
确定样品中存在的特定碳物质;和
改变金属催化粒子的组成。
51.一种在生产纳米管的方法中优化反应条件的方法,包括:
提供碳纳米管生产的产物,其中使用一组反应条件,包括温度、时间和在含碳气体中碳浓度中的至少一种;
取出产物样品;
在反应器单元中使产物样品与有效量的气体接触以便氧化样品中存在的碳物质;
将反应器单元内的温度升高到约室温以上;
确定样品中存在的特定碳物质;和
通过改变温度、时间和在含碳气体中碳浓度中的至少一种来改进反应条件。
52.一种用于生产碳纳米管的催化粒子,包含至少一种金属。
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2004
- 2004-01-08 US US10/754,002 patent/US6962892B2/en not_active Expired - Lifetime
- 2004-08-25 US US10/926,317 patent/US7094386B2/en not_active Expired - Lifetime
-
2006
- 2006-01-24 US US11/338,170 patent/US7563428B2/en not_active Expired - Fee Related
-
2007
- 2007-05-25 US US11/805,917 patent/US20080107588A1/en not_active Abandoned
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CN101176181B (zh) * | 2003-12-24 | 2011-08-03 | 辛泰克公司 | 具有电场发射性质的小直径碳纳米管的合成方法 |
CN101023027B (zh) * | 2004-09-22 | 2012-07-18 | 昭和电工株式会社 | 气相法碳纳米管的制造方法 |
CN102216212A (zh) * | 2008-11-18 | 2011-10-12 | 马来西亚理科大学 | 一种生产碳纳米管(CNTs)的方法 |
CN102762296A (zh) * | 2009-10-29 | 2012-10-31 | 英弗勒科技有限公司 | 用于催化co和h2合成碳氢化合物的催化剂及其制备方法 |
CN102762296B (zh) * | 2009-10-29 | 2015-03-25 | 英弗勒Xtl科技有限公司 | 用于催化co和h2合成碳氢化合物的催化剂及其制备方法 |
CN103518238A (zh) * | 2011-05-13 | 2014-01-15 | 国立大学法人熊本大学 | 碳纳米管复合电极及其制造方法 |
CN103518238B (zh) * | 2011-05-13 | 2017-02-15 | 国立大学法人熊本大学 | 碳纳米管复合电极及其制造方法 |
US9583231B2 (en) | 2011-05-13 | 2017-02-28 | National University Corporation Kumamoto University | Carbon nanotube composite electrode and method for manufacturing the same |
CN103958061A (zh) * | 2012-01-11 | 2014-07-30 | Lg化学株式会社 | 用于碳纳米管的均相负载型催化剂的制备方法 |
CN103958061B (zh) * | 2012-01-11 | 2016-09-21 | Lg化学株式会社 | 用于碳纳米管的均相负载型催化剂的制备方法 |
CN106102906A (zh) * | 2015-02-06 | 2016-11-09 | Lg化学株式会社 | 包含不定形α-氧化铝的碳纳米管合成用催化剂及利用所述催化剂的碳纳米管的制备方法 |
CN106102906B (zh) * | 2015-02-06 | 2019-11-26 | Lg化学株式会社 | 包含不定形α-氧化铝的碳纳米管合成用催化剂及利用所述催化剂的碳纳米管的制备方法 |
Also Published As
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CA2375887C (en) | 2008-09-23 |
MXPA01012386A (es) | 2002-11-07 |
US6962892B2 (en) | 2005-11-08 |
CN100564251C (zh) | 2009-12-02 |
US20070116630A1 (en) | 2007-05-24 |
AU780726B2 (en) | 2005-04-14 |
EP1192104B1 (en) | 2007-08-08 |
US20040070009A1 (en) | 2004-04-15 |
WO2000073205A9 (en) | 2002-06-20 |
EP1192104A1 (en) | 2002-04-03 |
US20050025696A1 (en) | 2005-02-03 |
US6333016B1 (en) | 2001-12-25 |
BR0011106A (pt) | 2002-03-05 |
CN1495127A (zh) | 2004-05-12 |
US7563428B2 (en) | 2009-07-21 |
CA2375887A1 (en) | 2000-12-07 |
JP4777518B2 (ja) | 2011-09-21 |
US7094386B2 (en) | 2006-08-22 |
AU5462200A (en) | 2000-12-18 |
ES2291212T3 (es) | 2008-03-01 |
WO2000073205A1 (en) | 2000-12-07 |
DE60035875D1 (de) | 2007-09-20 |
DE60035875T2 (de) | 2008-04-30 |
JP2003500326A (ja) | 2003-01-07 |
ATE369314T1 (de) | 2007-08-15 |
US20040186011A1 (en) | 2004-09-23 |
US20080107588A1 (en) | 2008-05-08 |
US20020165091A1 (en) | 2002-11-07 |
US6994907B2 (en) | 2006-02-07 |
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