CN102203031A - 有序中孔独立式碳膜和形状因子 - Google Patents
有序中孔独立式碳膜和形状因子 Download PDFInfo
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- CN102203031A CN102203031A CN2009801317459A CN200980131745A CN102203031A CN 102203031 A CN102203031 A CN 102203031A CN 2009801317459 A CN2009801317459 A CN 2009801317459A CN 200980131745 A CN200980131745 A CN 200980131745A CN 102203031 A CN102203031 A CN 102203031A
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Abstract
通过沉积包括水溶性碳前体,非离子表面活性剂,和油的前体混合物水溶液在基片或支架上,干燥该前体混合物,以及然后交联和热处理(碳化)该碳前体制备独立式有序中孔碳膜和形状因子。碳化后,有序中孔碳膜和形状因子包含有序中尺度孔的离散域。
Description
优先权
本申请要求美国专利申请号12/190,937,2008年8月13日提交的,标题是“有序中孔独立式碳膜和形状因子(form factor)”的优先权。
背景和概要
本发明涉及一种形成独立式有序中孔碳膜和形状因子的方法。该方法包含形成包含碳前体,至少一种表面活性剂,油和水的前体混合物,沉积该前体混合物到基片上,以及然后干燥,交联和热处理(碳化)该碳前体以形成碳膜或形状因子。本发明还涉及根据该方法制造的碳膜和形状因子。有利地,膜和形状因子的宏观和中孔形貌都可以通过改变工艺条件如前体混合物中碳前体∶表面活性剂∶油∶水的比值,基片的选择,以及干燥和碳化条件来控制。
有序中孔碳材料包括三维有序和相互连接的孔的阵列,孔的尺寸约在2到50纳米范围内。有序中孔碳可以表现出高达大约2200m2/g的BET比表面积,并且在惰性气氛中通常表现出优秀的热稳定性,和对酸和碱的强的抗腐蚀性。在优选的制造有序中孔碳的合成路线中,宏观几何形状,孔的几何形状和表面化学,包括表面活性物质的可选择的加入,可以根据所需的应用定制。
有序中孔碳可被用于多种应用,包括水/空气净化,气体分离,过滤,催化,吸附,色谱分离,电容去离子,电化学双电层电容器,超级电容器,和储氢。
依照本发明,申请人已经确定包括有序中孔碳材料的独立式碳膜和形状因子是可以制备的,例如,通过在基片或支架上沉积包括水溶性的碳前体,非离子表面活性剂,油和水的前体混合物水溶液,干燥和交联该前体混合物,以及热处理该涂层的基片或支架。前体混合物沉积后,但是在碳前体交联前,表面活性剂自组装形成碳前体的模板。碳化后,碳膜和形状因子包括中尺度孔隙率的有序域。
具有薄膜厚度从大约100到500微米的独立式碳膜可以利用本发明的方法形成。根据一种优选的形成独立式碳膜的方法,前体混合物薄层沉积在第一基片上,并且该沉积层夹在第一基片和第二基片之间。干燥和交联后,该沉淀层通过加热经由热致除去(例如,热解)溶剂和基于表面活性剂的有机模板变成独立式有序中孔碳膜。
形状因子可以利用类似的方法制备,其中前体混合物沉积在支架上。支架可以是有机的或无机的,并且可以包括纸、布或泡沫。一旦该沉积层涂布在支架上,就交联和通过加热碳化。由于支架可以是有机的,支架可以在热处理步骤中挥发和/或结合入形状因子中。由于前体混合物涂布支架的外露表面,形状因子包括了缘自支架的正面形象。
利用这样一种方法,复杂的几何结构比如有序中孔碳泡沫块,蜂窝,波纹板及其他网状结构是可以生产的。优选的形状因子包括碳膜涂层的网状支架,其中碳膜包括有序中孔碳。
如同碳膜一样,申请人已经发现有序域的中等尺度的孔保留在这些复杂几何结构中,即使是在碳化以后。因此,根据本发明的有序中孔碳膜和形状因子可以被在纳米范围和更大尺度,如,微观尺度排序的对应于基片或支架的结构确定。
一旦形成,有序中孔碳膜和形状因子可以被活化。可以包括部分氧化碳材料的表面并通常涉及到表面积随之增加的可选的活化,可以包括热和/或化学活化。
本发明的附加功能和优势将在以下的详细说明中阐明,并且对于本领域技术人员,在说明书中部分地将是迅速显而易见的,或者通过实践在此描述的本发明确认的,包括以下的详细说明,权利要求书,以及附图。
可以理解无论是上述的一般说明和以下的详细说明都提出本发明的实施方式,并且旨在提供一个概述或框架来理解本发明的如其所声称的性质和特性。附图提供对本发明进一步的了解,纳入并构成本说明书的一部分。附图说明本发明不同的实施方式,并与说明书一起用来解释本发明的原则和操作。
附图简要说明
图1是形成有序中孔(mesoporous)碳膜和形状因子的方法的示意流程图;
图2A-2C显示了利用(A)泡沫,(B)布,和(C)纸巾有机支架制备的有序中孔碳形状因子的扫描电子显微镜照片;
图3显示了有序中孔碳(A)粉末,(B)碳化泡沫,和(C)碳化布的X-射线衍射数据图;
图4显示了利用泡沫支架(比较例)制备的碳材料的扫描电子显微镜照片;
图5是显示独立式有序中孔碳膜中孔的方向的一系列扫描电子显微镜照片;
图6是显示在铝和Pyrex品牌基片上的有序中孔碳膜的(a)横截面视图,(b)底面,和(c)顶面的一系列扫描电子显微镜照片;
图7显示了有序中孔碳粉末和独立式膜的X-射线衍射图显示出(a)粉末,(b)膜的顶面,和(c)膜的底面的衍射;
详细说明
图1是描述形成有序中孔碳膜和形状因子的方法的例子的示意流程图。参考图1,包括碳前体,表面活性剂,和油的混合物水溶液的前体混合物100涂布在基片120或支架140上,并且干燥来形成由介观结构相(mesostructure phase)组成的交联涂层150。介观结构相被包括表面活性剂的有机模板(例如,液晶相)自组装定义。由有机模板定向的碳前体在碳化步骤145中通过加热碳化来形成具有有序孔190的域180的有序中孔碳膜160或形状因子170。在热处理步骤中,基片120或支架140至少可以部分地挥发和/或结合入膜160或形状因子170中。
特别地,有序中孔碳材料是从包括:i)水溶性碳前体/水溶液,ii)非离子表面活性剂,和iii)油的浓缩的前体混合物中形成的,该前体混合物干燥以形成基于表面活性剂的自组装,其中表面活性剂定义,并且交联碳前体稳定介观结构相。由于加热的结果,介观结构相通过溶剂和基于表面活性剂的模板的连续清除转化成有序中孔碳膜或形状因子。
通过选择前体混合物的合适的组成和浓度,可能控制所产生的有序中孔碳材料的物理特性,如宏观形貌,域的大小,和孔径及孔径分布。选择碳前体/水∶表面活性剂∶油的适当比例的技术,和控制基于这些比例的有序中孔碳的物理性能的方法在普遍拥有的美国专利申请No.11/899,002中公开,其全部内容通过参考全文明确地引入本文。
根据本发明制备的有序中孔碳膜和形状因子优选具有定向的,均匀,中孔直径(2-50nm)的孔,高表面积,和良好的机械强度。除了控制前体混合物的组成和浓度之外,这些物理属性可以通过调节其他过程变量来控制,如湿度,pH值,干燥条件,交联条件,热处理条件,和基片或支架的选择。
本发明的其他方面和优势公开如下:
材料
用来形成有序中孔碳膜和形状因子的前体混合物包括碳前体/水,表面活性剂,和油。碳前体的一个例子是510D50酚醛树脂(Georgia Pacific),包括两种不同分子量的物质(GPC数据,Mn约2800和约1060)。另外的合适的水溶性碳前体包括热固性碳水化合物,聚乙烯醇,间苯二酚甲醛,双亲肽,脂类,和其他酚醛树脂。
有用的表面活性剂是可以从BASF公司中获得的PEOy-PPOx-PEOy三嵌段共聚物。特别地,PluronicTM F127(x=106,y=70)和PluronicTM F108(x=127,y=50)被用来与本发明的方法结合以制造独立式碳膜和形状因子。其他的非离子表面活性剂包括PluronicTM P123的(x=20,y=70)和PluronicTM F88(x=104,y=39)。
对于碳前体,表面活性剂起可移除的有机模板的作用。加入到前体混合物中的水和油的量可通过其液晶相用于操作表面活性剂的自组装,和反过来,由此产生的中孔碳材料的中孔结构和性能。特别地,前体混合物的化学性质,可用于控制,例如,由此产生的孔径和孔容。
在包括PEOy-PPOx-PEOy三嵌段聚合物的前体混合物中,油充当PPO块的溶胀剂。在前体混合物中油的浓度可用于控制胶束结构的疏水部分的溶胀,还可以控制由此产生的有序中孔碳的孔的大小和孔的介观结构。油的加入使混合物水溶液从两相体系变为三相体系。油还扩大了水,表面活性剂和碳前体组分的范围,在此之中特定的介观结构是稳定的。
油的一个例子是丁醇。然而,作为替代或除丁醇之外,其他合适的油(与水不混溶的液体)包括对二甲苯,辛烷,十六烷,己醇,戊醇,醋酸丁酯和均三甲苯。
前体混合物中水的浓度可用于控制交联材料和热处理(碳化)产物中中孔孔道的组装。在包括PEOy-PPOx-PEOy三嵌段共聚物的前体混合物中,水与PEO块相互作用并且,通过溶胀包含碳前体的相,可以影响表面活性剂模板的自组装。组分中碳前体∶水的比例可以在很大的范围内改变。例如,前体混合物的碳前体∶水的比例范围可以从5∶0到1∶4(例如,5∶0,4∶1,3∶2,2∶3,和1∶4)。
合成
在典型的合成中,PEOx-PPOy-PEOx三嵌段共聚物(如,3.7gPluronicTM F127)添加到无水乙醇(18%F127在20ml乙醇中)中,加热搅拌,直到共聚物至少部分溶解于乙醇中。已知量的去离子水(例如,1.4ml)加入到混合物中,导致共聚物的进一步溶解。经过几分钟的搅拌,酚醛树脂(3.0ml)慢慢加入到混合物中随后剧烈搅拌。然后,丁醇(1.5ml)加入到混合物中继续搅拌以产生前体混合物A。可选的,5N盐酸(0.6ml)可以被加入到前体混合物A中以完全溶解共聚物。前体混合物使用前优选在室温下搅拌20-30分钟。
涂布
优选的用前体混合物涂布基片或支架的方法是浸涂。浸涂时,基片或支架沉浸到前体混合物浴中,由此前体混合物在基片或支架外露表面上形成涂层。在支架的实施方案中,涂布表面包括可见表面和支架的内表面,即,经由前体混合物渗透和/或注入涂布的表面。浸涂步骤可以重复,从而导致较厚的涂层。单独的浸涂步骤可以连续进行,或由一个或多个干燥,交联,和热处理步骤分隔开。
除浸涂之外,前体混合物可以通过旋转涂布,喷涂,浇铸,等涂布到基片或支架上,并且然后干燥,交联和热处理以形成碳膜和形状因子。可选地,在干燥前,可以利用多种方法将过量的前体混合物从基片或支架上除去。例如,弹性泡沫基片可以被按下以除去多余的前体。
如上所述,基片或支架可以包括有机或无机材料,可以是多孔或基本上无孔的材料。合适的(多孔或无孔)有机材料的例子包括聚合物泡沫,珠子,纤维,片材和涂层,纸张,布,和其他纤维素基的材料。合适的无机材料的例子包括碳,玻璃,陶瓷,半导体,和金属。此外,可以使用多种不同的支架结构或几何形状。例如,合适的支架可以包括蜂窝,泡沫,纤维,波纹板或平板,等。
干燥和交联
干燥包括水和其他挥发性液体的蒸发以形成有序预碳化介观结构相。在优选的干燥步骤中,涂布的基片或支架在室温下干燥特定的时间(如1,2,3小时或更长时间)。有序预碳化介观结构相被自组装的表面活性剂(如,三嵌段共聚物)和至少部分交联的碳前体(如,酚醛树脂)定义。自组装的表面活性剂起到模板的作用,促进预碳化介观结构相中碳前体的排序。
干燥步骤后,碳前体交联。在一个实施例中,为了进行交联,样品被放置在干燥器中并且按照表1中公开的交联周期加热。
表1.树脂交联的加热周期
交联稳定预碳化介观结构相。热处理前,交联膜可以有大约150至700微米的厚度,如下文所公开的,其厚度由于碳化减少约20-30%。
热处理(碳化)
为了碳化碳前体,交联膜涂层的基片或支架可以,例如,按事先确定的加热廓线在炉内在氮气气氛中加热。根据一个实施例,样品以第一加热速率升温至400℃加热3小时挥发表面活性剂,然后以第二加热速率升温至800℃加热3小时碳化碳前体。热重分析数据表明,表面活性剂模板在300℃和400℃温度之间分解和挥发。
第一和第二加热速率的范围可以从0.1到5℃/分。例如,第一加热速率可以是约2℃/分,并且第二加热速率可以是约1℃/分。优选的热处理步骤包括开始按2℃/分升温至400℃加热3小时,然后在冷却到室温之前,按1℃/分升温至800℃加热3小时。
在有机支架被使用的实施例中,大多数的有机支架(碳材料)可以被结合入有序中孔碳产品的网状结构。
一旦形成,有序中孔碳材料就包括排列良好的中尺度孔的域。在基片或支架上形成碳膜的过程会导致一般是垂直于基片或支架表面的后碳化孔排布方式。形成有序中孔碳膜的方法进一步包括从基片上移出膜以形成独立式的膜。
由于孔排布的均匀性,本发明的方法可以生产具有比传统方法生产的碳更高的效率因子的碳材料。效率因子与可以进入或暴露在反应或吸附物质中的表面面积比例有关。
本发明的有序中孔碳膜和形状因子可以具有大于约75%的效率因子。由于更高的可用表面积,和与将膜和形状因子结合入过滤装置和反应器有关的相对容易以及增强的效率,这种结构作为过滤器或催化剂基体使用能比常规的碳粉末更有效。例如,通过最小化堵塞和流动模式的干扰,网状形状因子如泡沫块,波纹板,蜂窝,和交错的纤维可以提供灵活的反应器设计,容易的物料装卸,以及流量条件的更好的时间控制。孔的有序阵列允许工程师设计适应流量条件和利用有序中孔碳活性表面的优势的反应器几何形状。这种结构还可以提高对反应物的接触,并且将传质限制减至最小。有序中孔碳(后碳化)膜的厚度范围可以从约100至500微米。
活化/功能化(可选的)
经热处理步骤产生的有序中孔碳材料可以选择性地活化,以增加其可用表面面积或以提高其活性。活化步骤也可以在有序中孔碳内修饰孔径的分布。例如,活化可以将微孔(<2nm)引入中孔结构。
活化步骤可以包括一个或多个热活化步骤或化学活化步骤。例如,有序中孔碳材料可以通过在CO2或水蒸气(H2O)气氛中加热到高温(如,500-1000℃)被活化。另一个实施例,该结构的碳可以通过使用氧化剂经由溶液氧化还原化学反应被活化。除了增加碳材料的表面积,氧化剂还可用于控制孔径大小和孔径分布。
活化部分氧化碳材料的表面,但有利地留下完整的组织化的碳孔道阵列。活化过程还在孔道内沿内表面提供与活性物质或催化剂离子交换的活性部位。作为碳化和活化过程的结果,碳材料可以作为活性过滤器,膜,或催化剂载体使用。
另外,或者除了有序中孔碳材料的化学或热活化以外,碳表面可以,如果需要,在后碳化步骤中被化学官能化和/或通过利用静电使其带电。下面公开的一个实施例中,有序中孔碳膜被活化和功能化。
根据一种形成独立式有序中孔碳膜的方法,前体混合物涂布到两个不同基片中的至少一个上,并在碳化前,基片被放在一起以使沉积层夹于基片之间。在基片/沉积层/基片叠块内的沉积层的随后的干燥,交联,以及热处理可以产生独立式有序中孔碳膜。
根据另一个实施例,前体混合物浸涂在陶瓷蜂窝基片上,干燥,交联以及热处理。碳膜涂层的蜂窝基片在流动的CO2/N2中在900℃下通过加热被活化。样品然后浸入pH<4的HAuCl4和尿素的室温的溶液中,在不断搅拌下溶液温度升高至约80℃。温度的升高引起尿素的分解,pH值随之增加,以及细小的金颗粒沉淀和沉积在碳上。
在有序中孔碳的外露表面沉积催化剂颗粒的其他方法包括离子交换和催化剂(金属)溶胶固定化。
根据以上所述,独立式,有序中孔碳(OMC)薄膜由具有形成纳米级(中孔级)孔的有序域的平行孔或孔道的无定形碳的网络组成。单个孔直径的范围可以从约2到50纳米,而单个孔长度的范围可以从约50纳米到几微米。分隔相邻孔的碳壁厚度的范围可以从约2到10纳米。有序中孔碳薄膜能够化学活化来离子交换和表面吸附以及可以具有大于约300m2/g的表面积。
根据一个实施例,有序中孔碳形状因子包括具有有序中孔碳在其上形成涂层的无机支架。无机支架可以具有平面,纤维状,针状,或管状结构,和/或可以具有网状结构,如固体泡沫,蜂窝阵列,波纹板,等。
无机支架可以包括一种或多种玻璃或氧化物晶体,碳(如石墨),氮化物,碳化物,等。优选的无机支架材料粘附OMC前体涂层,并且被设置为机械地和化学地承受涂布,干燥,交联和在超过1200℃温度下热处理的步骤。特别地,优选的无机支架材料对化学和热分解包括熔化是惰性的,并且不经历形状因子合成中不受控制的或不希望的化学反应。
根据另一个实施例,有序中孔碳形状因子是如上所述,但包括有机支架,第一碳材料(从有机支架派生),和第二碳材料(从碳前体衍生)。如同无机支架一样,有机支架可以具有平面,纤维状,针状,或管状结构,和/或可以具有网状结构,如固体泡沫,蜂窝阵列,波纹板,等。
在这个实施例中,有机支架可以由聚合物制成,如聚丙烯,聚苯乙烯,或纤维素或其他有机物质,并且可以包括被制作成各种形式的有机纤维,包含合成纤维在内,如编织纤维结构,麻线,聚合物(塑料)结构,聚合物泡沫,海绵,等。
有机支架优选地在整个涂布,干燥,交联和热处理的步骤中粘附OMC前体涂层,并且设置为在与有序中孔碳前体同样的温度状态下碳化,同时保留其预碳化的结构。
在包括无机或有机支架的有序中孔碳形状因子中,支架优选地是起到有序中孔碳涂层结构支撑的功能。
实施例
本发明将通过下列实施例进一步阐明
实施例1-基于有机支架的形状因子
图2显示了利用有机,网状支架如(A)泡沫,(B)布,或(C)纸巾制备的有序中孔碳形状因子的扫描电子显微镜照片。图2(A)和2(C)分别显示了由泡沫和纸制得的有序中孔碳的宏观图像和中尺度结构的高分辨率图像。图2(B)显示了基于布的有序中孔碳形状因子的高分辨率SEM图像。每个形状因子都包括贯穿整个材料的有序中孔结构,它是由有机模板保留的,以及与初始支架相应的大孔结构。在图2中,从罗马数字(Ⅰ)至(Ⅲ)以逐渐增大的放大倍数显示显微照片。
使用前体混合物A通过浸涂方法涂布每个支架。过量的前体混合物被清除,随后每个样品在室温下干燥一夜。干燥后的涂层根据表1中公开的时间表通过加热交联,以及然后在流动的氮气中900℃热处理产生有序中孔碳形状因子。
碳化泡沫和碳化布的X-射线衍射(XRD)数据显示了六方有序的孔结构。还获得了有序中孔碳材料粉末样品的XRD数据。图3显示了对于碳化泡沫和碳粉都很好分辨的位于约处的d(100)峰,和两个更高次序的峰,分别对应于位于1.7和2.42θ处的d(110)约和d(210)约碳化布的XRD强度较小,这被认为是由于材料相对较低的孔隙率和因此减少的涂层量。在图3中,数据显示了(A)粉末,(B)碳化泡沫,和(C)碳化布样品的X-射线衍射。
实施例1A-碳涂层的有机支架(比较例)
图4显示了利用泡沫支架制备的比较碳材料的扫描电子显微镜照片(如图1(A))。代替前体混合物A,但是,使用只包含碳前体的混合物。按照实施例1用于有序中孔碳形状因子的同样的合成方案,在比较样品中只观察到大孔(从泡沫支架衍生)和一些微孔(250-350微米)。与利用前体混合物A得到的形状因子相反,没有观察到中孔隙,也没有有序中孔结构。在图4中,从罗马数字(Ⅰ)至(Ⅱ)以逐渐增大的放大倍数显示显微照片。
实施例2-独立式有序中孔碳膜
前体混合物A(含和不含盐酸)涂布到Pyrex或铝基片上,并且溶剂在室温下蒸发一夜以产生粘的,黄色涂层。每层涂层按照表1中公开的时间表加热交联。交联膜切割成特定的大小,放置于两个厚板之间以及在冷却到室温之前通过加热到预定的温度碳化。
如表2中数据所示,从交联状态到碳化状态,独立式有序中孔碳膜表现出了约60%的横向尺寸变化(收缩)和约75%的重量损失。正常厚度的变化(Z方向)在20到30%之间。
表2.交联/碳化的尺寸变化和重量损失。
扫描电子显微术(SEM)用于评价和测量膜的几何结构,包括孔径大小和方向。如图5和6所示,沉积在Pyrex和铝上的膜厚度大约125微米,并且每个独立式膜由贯穿整个厚度的有序中孔结构组成同时孔的方向大致平行于基片。图5A显示了沿着顶部边缘的横截面图像,而图5B显示了沿着底部边缘的横截面图像。图5C是横截面视图。
Pyrex基片上的膜底面纹理比使用铝基片制备的膜更为平滑。参考图6,横截面(A),顶面(B)和底面(C)图像显示了一些纹理和,在某些情况下的大孔。在图6中,基片通过附注数字200(Pyrex)和300(铝)确定。在底面观察到的Divots是氯化钠晶体的痕迹,这是由于Georgia Pacific树脂中的氯化钠造成的。
图7显示了有序中孔碳粉末和独立式膜的X-射线衍射图,所示的衍射为(a)粉末,(b)膜的顶面,以及(c)膜的底面。如同实施例1中的形状因子一样,独立式碳膜的X-射线衍射数据显示了在每一个膜的顶面和底面上的六方有序的孔结构。六方排序在粉末样品中也能观察到。顶面和底面具有很好分辨的位于约(顶面)和(底面)处的d(100)反射,和更高次序的位于约(顶面)和约(底面)处的d(200)峰。
孔容分布(PVD)数据通过将单独的独立式膜分割成较小的部分而获得。孔径从2到7纳米不等且分布较窄。非活化样品表面积的范围约450-600m2/g,而活化样品表面积的范围约1000-1800m2/g。压汞法结果表明,非活化的膜包括60-70%的孔隙率,并且通过在前体混合物中引入盐酸该孔隙率可以提高至70%以上的值。
为了评价独立式膜的电性能,进行了平面和穿透电阻率测量。电阻率测量包括将银导电涂料应用到碳膜上形成电极,银线与电极连接,用数字万用表(4线配置)测量电阻,以及由使用样品和电极结构测量的电阻计算电阻率。
表3显示了样品1-9的平面和穿透电阻率和电导率的测量数据。通过控制盐酸的用量改变样品1-9中前体混合物的pH值。虽然没有测量,样品1-5的pH值被认为是在大约1-2的范围。样品6具有0.96的pH值且标准差为0.2。制备的样品7不含盐酸,并且具有8.5的pH值同时标准差为0.2。样品8和9的pH值分别为8.37和8.33。样品1-4和6-9在900℃热处理,而样品5在1200℃热处理。
表3.在平面上和通过平面的电气测量。
一般来说,电阻随膜的厚度增加而增加。然而,通过从900℃到1200℃增加热处理温度(样品5)平面电阻率却大幅度下降。
对本领域的技术人员而言,对本发明所作的不同的修改或改变都将是显而易见的,并没有脱离本发明的精神和范围。因为包含本发明精神和实质的公开实施方式的修改,组合,子组合和改变,对本领域技术人员都可能会出现,本发明应解释为包括所附的权利要求及其等值范围的一切内容。
Claims (20)
1.一种形成有序中孔碳膜或形状因子的方法,包括:
形成包括碳前体,表面活性剂,油和水的前体混合物;
沉积所述前体混合物到基片或支架上以形成基片或支架外露表面上的涂层;
干燥所述涂层和交联所述碳前体以形成基于表面活性剂的自组装模板和由模板排序的基于碳前体的介观结构相;和
热处理所述碳前体以形成有序中孔碳膜或形状因子。
2.根据权利要求1的方法,其中所述碳前体包括酚醛树脂以及所述表面活性剂包括三嵌段共聚物。
3.根据权利要求1的方法,其中所述沉积包括浸涂。
4.根据权利要求1的方法,其中在沉积步骤和干燥步骤之间将过量的前体混合物从所述基片或支架上清除。
5.根据权利要求1的方法,其中所述支架具有一个或多个平面,纤维状,针状,管状或网状结构。
6.根据权利要求1的方法,其中所述基片或支架包括多孔材料。
7.根据权利要求1的方法,其中所述基片或支架包括选自由聚合物泡沫,珠子,纤维,片材和涂层,纸,布,以及纤维素基材料组成的组的有机材料。
8.根据权利要求1的方法,其中所述基片或支架在热处理步骤中至少部分挥发。
9.根据权利要求1的方法,其中至少部分所述基片或支架结合入有序中孔碳膜或形状因子。
10.根据权利要求1的方法,其中所述有序中孔碳包括无定形碳。
11.根据权利要求1的方法,进一步地包括活化所述有序中孔碳膜或形状因子。
12.根据权利要求1的方法,进一步地包括从所述基片上移除有序中孔碳膜。
13.独立式,有序中孔碳膜或形状因子,包括:形成在基片或支架上的无定形碳层,其中所述碳包括中尺度孔隙率的有序域。
14.根据权利要求13的有序中孔碳膜,其中所述基片包括基本上平坦的表面并且孔取向基本上平行于基片表面。
15.根据权利要求13的有序中孔碳膜或形状因子,其中所述支架具有一个或多个平面,纤维状,针状,管状或网状结构。
16.根据权利要求13的有序中孔碳膜或形状因子,其中所述基片或支架包括多孔材料。
17.根据权利要求13的有序中孔碳膜或形状因子,其中所述基片或支架包括选自由聚合物泡沫,珠子,纤维,片材和涂层,纸,布,以及纤维素基材料组成的组的有机材料。
18.根据权利要求17的有序中孔碳形状因子,其中所述形状因子包括:来源于有机材料的第一碳材料;和
来源于碳前体的第二碳材料,其中第一碳材料和第二碳材料中至少一个包括多个有序中尺度孔隙率的域。
19.根据权利要求13的有序中孔碳膜或形状因子,其中至少部分所述基片或支架结合入有序中孔碳膜或形状因子。
20.根据权利要求13的有序中孔碳膜或形状因子,其中有序中孔碳包括无定形碳。
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- 2009-08-12 EP EP09789109A patent/EP2331481A1/en not_active Withdrawn
- 2009-08-12 WO PCT/US2009/004597 patent/WO2010019221A1/en active Application Filing
- 2009-08-12 JP JP2011522985A patent/JP2011530480A/ja active Pending
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Cited By (6)
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CN103623872A (zh) * | 2013-12-17 | 2014-03-12 | 安徽理工大学 | 用于TiO2光催化剂的具有有序介孔结构活性碳纸载体及其制备方法 |
CN106457201A (zh) * | 2014-03-11 | 2017-02-22 | 乌第有限合伙公司 | 多孔碳膜 |
CN106457201B (zh) * | 2014-03-11 | 2019-11-15 | 南京动量材料科技有限公司 | 多孔碳膜 |
CN106554205A (zh) * | 2016-11-25 | 2017-04-05 | 厦门大学 | 一种SiCO微米级多孔中空陶瓷球的制备方法 |
CN106554205B (zh) * | 2016-11-25 | 2019-09-10 | 厦门大学 | 一种SiCO微米级多孔中空陶瓷球的制备方法 |
CN111285688A (zh) * | 2020-02-10 | 2020-06-16 | 北方民族大学 | 生物质碳膜及其制备方法和应用 |
Also Published As
Publication number | Publication date |
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WO2010019221A1 (en) | 2010-02-18 |
JP2011530480A (ja) | 2011-12-22 |
US20100040861A1 (en) | 2010-02-18 |
EP2331481A1 (en) | 2011-06-15 |
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