CN109414682B - 具有增强稳定性的高温层化混合金属氧化物材料 - Google Patents

具有增强稳定性的高温层化混合金属氧化物材料 Download PDF

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CN109414682B
CN109414682B CN201780018094.7A CN201780018094A CN109414682B CN 109414682 B CN109414682 B CN 109414682B CN 201780018094 A CN201780018094 A CN 201780018094A CN 109414682 B CN109414682 B CN 109414682B
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metal oxide
mixed metal
particles
phase
ldh
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CN109414682A (zh
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加桑·塞尔曼·阿拉贝迪
约翰·阿德里安·霍尔
马诺哈拉·古蒂约尔·维拉巴德拉帕
休·克里斯托弗·格林威尔
安德鲁·怀廷
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University of Durham
Saudi Arabian Oil Co
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University of Durham
Saudi Arabian Oil Co
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Abstract

制备混合金属氧化物颗粒(ii)的方法，所述颗粒包含含有M、Al和C的混合金属氧化物相，所述方法通过在400℃至800℃的反应温度下加热金刚烷嵌入层化双氢氧化物(LDH)颗粒(i)以形成混合金属氧化物颗粒来进行，(i)具有通式[M(1‑x)Al(x)(OH)2]A(x).m H2O，其中x为0.14至0.33，m为0.33至0.50，M选自Mg、Ca、Co、Ni、Cu或Zn，并且A为金刚烷羧酸盐，并且纵横比，即颗粒的宽度/厚度大于100。进一步提供MMO颗粒(ii)本身以及通过与(ii)接触通过吸附从工艺流中除去成分的方法([优选CO2或有毒离子，尤其磷酸盐、砷酸盐、铬酸盐、溴化物、碘化物和硫化物。

Description

具有增强稳定性的高温层化混合金属氧化物材料
相关申请的交叉引用
本申请要求于2016年3月17日提交的美国临时申请62/309,647的权益，所述临时申请以全文引用的方式并入本文中。
技术领域
本公开的实施例一般涉及层化混合金属氧化物，并且具体来说，涉及具有高温稳定性的混合金属氧化物催化剂。
背景技术
负载金属或金属氧化物催化剂的合成在非均相催化中具有很大的工业重要性。高活性、高选择性和长催化剂寿命为任何工业催化剂的期望特性。在金属/金属氧化物负载催化剂中，Cu/ZnO/Al2O3体系和负载在各种载体(氧化铝、二氧化硅和碳)上的金属/金属氧化物(Pt、Pd、Rh和Au)体系具有很大的工业重要性。通常，这些催化体系通过如溶胶-凝胶、沉积-沉淀、沉积-还原和浸渍方法的方法来制备。这些合成方法面临如分布不均匀、活性金属物质沉积在载体上导致颗粒聚集和活性物质在较高温度下以及再循环期间烧结的问题。
混合金属氧化物材料可通过热分解层化双氢氧化物(LDH)材料获得。LDH也称为阴离子粘土，并且在结构和特性上为广泛使用的硅铝酸盐阳离子粘土的反电荷类似物。LDH在三个主要步骤中经历热分解：(a)室温至100℃，除去吸附/物理吸附的水；(b)100℃至220℃，除去嵌入水；和(c)220℃至400℃，除去嵌入阴离子并且使矿物层脱羟基，导致形成无定形混合金属氧化物残余物。由将LDH加热至220至400℃的温度范围而形成的混合金属氧化物材料通常均为无定形的并且由单金属氧化物相(MIIO)和尖晶石相(MIIM2 IIIO4)构成。存在于母体LDH材料中的阴离子通常不再存在于混合金属氧化物材料中或存在的程度如此之小以至于其不显著影响混合金属氧化物材料的特性。不幸的是，将LDH进一步加热到大于800℃可导致形成热力学稳定且不可逆的尖晶石相，伴随着相分离和烧结。
发明内容
因此，持续需要混合金属氧化物材料，其具有更好的热稳定性、改进的催化剂再生能力，以及较高温度下改进的抗烧结性，其中颗粒不可逆地熔合在一起。具体来说，需要混合金属氧化物材料，其在混合金属氧化物颗粒经受较高温度时，阻止尖晶石相的不可逆形成。
本公开的实施例涉及在高温下无烧结并且可重复使用的金属氧化物。具体来说，实施例涉及来自LDH的无烧结的混合金属氧化物，其可通过使用金刚烷作为客体阴离子进行再循环。阴离子在制备具有比LDH晶体化学中通常遇到的更大纵横比的晶体方面具有次要优势。
根据一个实施例，提供一种制备混合金属氧化物颗粒的方法。所述方法包含将金刚烷嵌入层化双氢氧化物(LDH)颗粒加热至高达400℃至800℃的反应温度以形成混合金属氧化物颗粒，其中金刚烷嵌入LDH颗粒具有通式[M1-xAlx(OH)2](A)x·mH2O，其中x为0.14至0.33，m为0.33至0.50，M选自Mg、Ca、Co、Ni、Cu或Zn，并且A为金刚烷羧酸盐。金刚烷嵌入LDH颗粒具有大于100的纵横比，其中纵横比界定为金刚烷嵌入LDH颗粒的宽度除以金刚烷嵌入LDH颗粒的厚度。混合金属氧化物颗粒包含含有M、Al或Fe和碳的混合金属氧化物相。
另一个实施例涉及混合金属氧化物颗粒。混合金属氧化物颗粒包含至少一种含有M、Al或Fe和碳的混合金属氧化物相，其中M选自Mg、Ca、Co、Ni、Cu或Zn。氧化物相具有式MO，并且混合金属氧化物相可夹在氧化物相的链之间。混合金属氧化物颗粒包含以混合金属氧化物颗粒总重量计的小于5wt％的具有式MAl2O4或MFe2O4的尖晶石相。在其它实施例中，混合金属氧化物颗粒不包括具有式MAl2O4或MFe2O4的任何尖晶石相。
根据另一个实施例，提供一种从过程流中除去成分的方法。所述方法包含使过程流与催化剂接触，其中催化剂包含前述混合金属氧化物颗粒。
所描述的实施例的其它特征和优点将在下面的具体实施方式中阐述，并且部分特征和优点对于本领域技术人员来说将从所述描述中显而易见，或者通过实践包括下面的具体实施方式、权利要求书以及附图的所描述的实施例而被认识到。
附图说明
图1为根据本公开的一个或多个实施例的Mg/Al-金刚烷酸酯LDH的粉末X射线衍射(PXRD)图；
图2为根据本公开的一个或多个实施例的Mg/Al-金刚烷酸酯LDH的红外(IR)光谱图；
图3为根据本公开的一个或多个实施例的Mg/Al-金刚烷酸酯LDH的1H固态核磁共振(NMR)光谱图；
图4为根据本公开的一个或多个实施例的Mg/Al-金刚烷酸酯LDH的13C固态NMR光谱图；
图5A和5B为根据本公开的一个或多个实施例生产的不同放大倍数的Mg/Al-金刚烷酸酯LDH的扫描电子显微镜(SEM)图像；
图6为根据本公开的一个或多个实施例的在400℃下热分解后(曲线a)和在800℃下热分解后(曲线b)的混合金属氧化物残余物的PXRD图；
图7为根据本公开的一个或多个实施例的在400℃下热分解后(曲线a)和在800℃下热分解后(曲线b)的混合金属氧化物残余物的IR光谱图；
图8为根据本公开的一个或多个实施例的从加热至800℃的氧化物残余物重建后的Mg/Al-金刚烷酸酯LDH的混合金属氧化物残余物的PXRD图；
图9A和9B为根据本公开的一个或多个实施例的在400℃下热分解后(图9A)和在800℃下热分解后(图9B)的混合金属氧化物残余物的13C固态NMR光谱图；
图10A-10D为根据本公开的一个或多个实施例的在400℃下热分解后的不同放大倍数的混合金属氧化物残余物的SEM图像；
图11A-12D为根据本公开的一个或多个实施例的在800℃下热分解后的不同放大倍数的混合金属氧化物残余物的SEM图像；
图13为根据本公开的一个或多个实施例的在400℃下热分解后的混合金属氧化物残余物的另一SEM图像；
图14A为根据本公开的一个或多个实施例的在400℃下热分解后的混合金属氧化物残余物的透射电子显微镜(TEM)亮视场图像；
图14B和14C为根据本公开的一个或多个实施例的图14A的混合金属氧化物残余物的高分辨率透射电子显微镜(HRTEM)图像；
图14D为根据本公开的一个或多个实施例的图14A的混合金属氧化物残余物的选定区域衍射图案(SADP)的TEM图像；
图15A-15C为根据本公开的一个或多个实施例的在800℃下热分解后的混合金属氧化物残余物的TEM亮视场图像；
图15D为根据本公开的一个或多个实施例的图15C的混合金属氧化物残余物的HRTEM图像；
图16A为根据本公开的一个或多个实施例的在800℃的温度下的混合金属氧化物残余物的MgO链的能量分散X射线(EDX)光谱图像；
图16B为根据本公开的一个或多个实施例的在800℃的温度下的混合金属氧化物残余物层的EDX图像；
图17A和17B为根据本公开的一个或多个实施例的在800℃下热分解之后的MgO链的TEM亮视场图像；
图17C为根据本公开的一个或多个实施例的图17B的MgO链的HRTEM图像；
图17D为根据本公开的一个或多个实施例的图17C的MgO链的SADP的TEM图像；
图18A-18D为在400℃下热分解后来自Mg/Al-NO3的不同放大倍数的混合金属氧化物残余物的SEM图像；
图19为根据本公开的一个或多个实施例的在从加热至1100℃的氧化物残余物重建之后重建的Mg/Al-金刚烷酸酯LDH的氧化物残余物的PXRD图；
图20为根据本公开的一个或多个实施例的在从加热至400℃的氧化物残余物重建之后重建的Mg/Al-金刚烷酸酯LDH的氧化物残余物的X射线光电子光谱(XPS)图；
图21为根据本公开的一个或多个实施例的在从加热至800℃的氧化物残余物重建之后重建的Mg/Al-金刚烷酸酯LDH的氧化物残余物的X射线光电子光谱(XPS)图；和
图22为根据本公开的一个或多个实施例的在从加热至1100℃的氧化物残余物重建之后重建的Mg/Al-金刚烷酸酯LDH的氧化物残余物的X射线光电子光谱(XPS)图。
具体实施方式
活性还原金属或金属氧化物颗粒在稳定载体上的分散为复杂且费力的过程。为此，需要考虑各种参数，如合成条件、载体的性质以及在载体上分散/分配活性催化剂的适当方式。一般来说，设计和合成催化体系的进行中的目标包括提供不受限制的催化剂，如不均匀分布、颗粒聚集、活性物质在较高温度下的烧结，以及回收贵金属的能力。
现在将详细参考混合金属氧化物颗粒的实施例，并且具体来说，由金刚烷嵌入层化双氢氧化物(LDH)颗粒生产的混合金属氧化物颗粒。
混合金属氧化物颗粒可包含至少一种含有M、Al或Fe和碳的混合金属氧化物相，其中M选自Mg、Ca、Co、Ni、Cu或Zn。在具体实施例中，M为Mg。混合金属氧化物颗粒还可包含具有式MO的氧化物相。混合金属氧化物相可夹在氧化物相的链之间。另外，混合金属氧化物颗粒包含以混合金属氧化物颗粒总重量计的小于5重量％(wt％)的具有式MAl2O4或MFe2O4的尖晶石相。在各种实施例中，混合金属氧化物颗粒包含以混合金属氧化物颗粒总重量计的小于3wt％、小于2wt％，或小于1wt％的具有式MAl2O4或MFe2O4的尖晶石相。混合金属氧化物颗粒也可不包含具有式MAl2O4或MFe2O4的尖晶石相。如图6所示，混合金属氧化物颗粒可限定在800℃下具有13.0+/-0.5的特征峰的粉末X射线衍射(PXRD)图谱。不受理论束缚，混合金属氧化物颗粒保持高达800℃的层化金属氧化物结构，并且即使在氧化气氛中高达800℃下也不聚集。
生产混合金属氧化物的方法包含将金刚烷嵌入层化双氢氧化物(LDH)颗粒从约25℃的室温，如20℃至30℃加热至400℃至800℃的反应温度以形成混合金属氧化物颗粒。在其它实施例中，反应温度可为500℃至700℃。不希望受理论束缚，金刚烷嵌入LDH颗粒的加热速率被认为是决定所得氧化物颗粒的纳米晶性质的因素。举例来说，在一个或多个实施例中，可以约5℃/min，如4至6℃/min的加热速率发生加热。预期加热步骤可在反应温度下进行至少4小时。
无定形混合金属氧化物本质上通常为碱性的，并且可通过变化LDH前体中的阴离子的层组成和性质来调节混合金属氧化物的碱性。另外，许多混合金属氧化物材料具有再生回母体LDH材料的能力。举例来说，通过用阴离子水溶液(如母体LDH材料中存在的阴离子)处理许多混合金属氧化物材料，混合金属氧化物相可在被称为“重建”或“记忆效应”的过程中转变回母体LDH。某些特征在于强记忆效应的混合金属氧化物材料对于催化剂应用可为特别期望的，因为这种混合金属氧化物材料适合于催化剂再循环过程。然而，混合金属氧化物材料的记忆效应可受到在高温(例如800℃或更高)下形成不可逆的尖晶石相的限制。当形成不可逆的尖晶石相时，混合金属氧化物材料的溶液处理变得不能重建LDH材料，因为稳定的尖晶石相中的原子不再重新排列回LDH的层化结构。
金刚烷嵌入LDH颗粒可具有通式[M1-xAlx(OH)2](A)x·mH2O，其中x为0.14至0.33，m为0.33至0.50，M选自Mg、Ca、Co、Ni、Cu或Zn，并且A为金刚烷羧酸盐。金刚烷嵌入LDH颗粒具有大于100的纵横比。如所界定，纵横比为LDH颗粒的宽度除以LDH颗粒的厚度。如所界定，小于10的纵横比被认为是较低的，小于100的纵横比被认为是中等的，100或更大的纵横比被认为是高纵横比。可由SEM图像计算LDH颗粒。举例来说，参考图2B的实施例，显然层化颗粒具有大表面积，但缺乏厚度，这会导致高纵横比。类似地，原子力显微镜(AFM)可用于测量层化颗粒并且计算纵横比。
制备金刚烷嵌入LDH颗粒的方法可包括向水溶液中加入第一前体和第二前体以形成初始溶液的步骤。在一个实施例中，水溶液可基本上由水组成。第一前体可包含Al(OH)3或Al2O3。第二前体可包括含金属的化合物，例如氢氧化物M(OH)2或氧化物MO，其中M为氧化态为+2的金属。虽然也考虑各种其它金属，但M可选自Mg、Ca、Co、Ni、Cu、Zn或其组合。在一个或多个实施例中，第二前体可包括Mg(OH)2、Ca(OH)2、Co(OH)2、Ni(OH)2、Cu(OH)2、Zn(OH)2或其组合。在其它实施例中，第二前体为Mg(OH)2或MgO。在一个实例中，第二前体为Mg(OH)2，并且第一前体为Al(OH)3。
此外，在其它实施例中，初始溶液可具有1至5或1至3的M/Al摩尔比。此外，初始溶液可具有以初始溶液总重量计的小于10重量％固体的固体载量，或小于5重量％固体的固体载量。
随后，所述方法包括向初始溶液中加入一定量的金刚烷，以形成Al/金刚烷摩尔比为0.5至2的反应混合物。在一个或多个其它实施例中，Al/金刚烷摩尔比可为0.8至1.2或可为1至1。考虑各种金刚烷源。在一个实施例中，金刚烷可以羧酸的形式加入。任选地，可对反应进行搅拌。
通常，用无机客体阴离子制备用于转化为混合金属氧化物的LDH，其可在热处理下容易地除去。当使用有机阴离子，如羧酸官能化的金刚烷时，可实现改进的LDH特性。金刚烷的结构特征在于高对称性(Td)，没有分子内应变，并且因此，其为极其热力学稳定的。同时，金刚烷可被化学官能化。金刚烷的熔点为270℃，并且即使在室温下也缓慢升华。金刚烷难溶于水，但易溶于碳氢化合物。
不受理论束缚，使用热稳定金刚烷作为结构导向剂，其允许LDH在c结晶轴上的a和b结晶方向上优先生长。这导致观察到高纵横比的颗粒。此外，使用水热合成和金属氢氧化物前体在pH和动力学方面仔细控制生长条件。
嵌入金属氢氧化物层之间的金刚烷羧酸根离子可充当生长纳米MgO链的热稳定模板，并且还充当防止尖晶石相形成的屏障。所得MgO链具有晶界，与常规MgO或LDH相比，所述MgO链可示出更高的催化活性和更高的热稳定性。此外，金刚烷酸的热稳定性意味着它不同时分解到层中，导致中间层和电荷平衡得以保留。这似乎阻碍混合金属氧化物向尖晶石相的转化过程，并且结果证明在较高温度下的层化结构。
如前所述，混合金属氧化物颗粒在用于催化剂时为有效的。具体来说，此包含混合金属氧化物颗粒的催化剂可用于从气流中除去二氧化碳。此外，此包含混合金属氧化物颗粒的催化剂可用作吸附剂以从过程流中除去有毒离子。举例来说，从气流或水流中除去磷酸盐、砷酸盐、铬酸盐、溴化物、碘化物和硫化物。另外，金刚烷嵌入层化LDH前体可从混合金属氧化物中再生。在一个实例中，通过使用足以提供3倍摩尔过量的CO3 2-的量的碳酸钠溶液对在800℃下分解后获得的混合金属氧化物进行重建。
另外，LDH为环境友好且经济上可行的层化材料。由于它们易于变化的组成、良好分散的取代和层化性质，这些材料先前已被发现用于各种应用中。LDH的热分解将产生混合金属氧化物，其本质上为碱性的。这些氧化物在包括水煤气变换反应和光催化应用的各种催化反应中已用作非均相催化剂。此外，这些氧化物适合于从燃煤发电厂捕获CO2，所述燃煤发电厂向环境中排放大量的CO2。在一种或多种应用中，已发现从LDH获得的混合金属氧化物材料为用于捕获酸性CO2气体的合适吸附剂，并且能够从工业废水和饮用水中吸附有毒离子。
实例
通过以下实例将进一步阐明所描述的实施例。
实例1：金刚烷嵌入层化双氢氧化物的制备
为了制备根据前述实施例的金刚烷嵌入层化双氢氧化物材料，通过将5克(g)Mg(OH)2溶解在95g去离子水中制备5％wt/wt的Mg(OH)2溶液。向所得溶液中加入3.36g Al(OH)3，其量足以提供2的Mg/Al摩尔比。然后，向溶液加入9.31g金刚烷羧酸，其量足以在所得反应混合物中提供1:1的Al/金刚烷摩尔比。测量反应混合物的pH，发现为9.5。
然后将反应混合物在室温下剧烈搅拌1小时。将搅拌的反应混合物转移到特富龙衬里(Teflon-lined)的高压釜中，并且在150℃下加热24小时(h)。从混合物中过滤出层化双氢氧化物材料。测量滤液的pH，发现为8.6。在另一组实验中，通过使用5的Mg/Al摩尔比来重复先前讨论的程序。反应结束后，用水彻底洗涤产物并且在65℃下干燥。
所合成的LDH的PXRD图案在图1中给出，并且示出在
Figure BDA0001802610750000071
处的基础反射(001)对应于中间层中金刚烷离子的双层排列。在较高的2θ值处看到(001)的约数。参考图2，用IR光谱进一步表征金刚烷酸的嵌入。在1517cm-1和1395cm-1处的振动对应于COO-基团的反对称和对称伸缩振动。在2901cm-1和2847cm-1处的振动用于C-H振动。4302cm-1振动是由于层金属氢氧化物基团与中间层中嵌入水分子的氢键结合。
记录Mg/Al-金刚烷酸酯LDH的1H和13C固态NMR光谱，并且分别在图3和4中给出。在较低ppm值下在图3的1H光谱中的4个尖峰是由于金刚烷环中存在的氢。在3.8ppm和4.8ppm处的峰分别是由于嵌入水和金属氢氧化物的氢。参考图4，Mg/Al-金刚烷酸酯的13C NMR光谱示出在29.5ppm、37.3ppm、40.6ppm和42.8ppm处的4个峰是由于金刚烷分子中存在4种不同的碳。在186.98ppm处的峰是由于羧酸盐基团的碳。参考图5A和5B，所合成的LDH的SEM图像示出层化材料的典型的片晶形态。
实例2：混合金属氧化物材料的制备
通过在空气气氛中将实例1样品以5℃/min的加热速率从室温加热至高达800℃的最大值持续4小时来获得混合金属氧化物。在另一组实验中，通过在空气气氛中将实例1样品以5℃/min的加热速率从室温加热至400℃持续4小时来获得混合金属氧化物。通过使用足以提供3倍摩尔过量的CO3 2-的量的碳酸钠溶液对在800℃下分解后获得的混合金属氧化物进行重建。
将制备的Mg/Al-金刚烷酸酯LDH在空气气氛下在400℃和800℃下热分解4小时。在热分解时，LDH产生混合金属氧化物，其本质上为碱性的。在Mg/Al-金刚烷酸酯LDH的情况下，期望MgO和MgAl2O4氧化物。
两种分解的氧化物的PXRD图案示出由于MgO在43°2θ和61°2θ处引起的反射(图6)。对于基于LDH的氧化物，大约13°2θ的宽反射为令人惊讶和出乎意料的，因为在高于400℃下的热处理时，总是失去层化结构。如通过IR分析进一步证明的，反射是由于形成层化氧化物类型的层化材料。
这里，记录分解样品的IR光谱并且在图7中示出。曲线(b)中示出的800℃样品的IR光谱未示出任何可与LDH起始材料相关的峰，因此表明不存在LDH相。400℃的IR光谱在1405cm-1处示出峰，但不是由于LDH相，如前所示。此峰可以是由于金刚烷酸离子的CH弯曲振动。
令人惊讶的是，分解的氧化物残余物(在800℃下)的PXRD图案没有示出由于MgAl2O4或MgFe2O4尖晶石相引起的反射。如图8所示，用碳酸钠水溶液处理后的此氧化物残余物得到所描绘的碳酸盐嵌入LDH(参见图8)。PXRD用于表征固体，并且样品中存在的任何结晶材料将示出PXRD图案中的特征反射。在PXRD图案中不存在由于MgAl2O4或MgFe2O4尖晶石引起的反射被认为是所述尖晶石在样品中不存在。此外，尖晶石为比氢氧化物或LDH更热力学稳定的相，并且因此将不恢复到LDH相。这进一步证实在氧化物残余物中不存在MgAl2O4或MgFe2O4尖晶石相，因为极其稳定的分离后尖晶石将不重建成LDH。
总之，PXRD证明，对于Mg/Al-金刚烷酸酯LDH前体，层状材料仍然存在于800℃下，据我们所知，在所述温度下先前报道的每种LDH材料不仅失去其层结构而且开始烧结并且分离成尖晶石相。从IR光谱，显然层化相不是由于任何残余的LDH材料，而是由于另一相。
为了检查金刚烷部分存在的可能性，所得产物进一步用13C固态NMR表征，所述金刚烷部分可以在形成组合混合金属氧化物和MgO的层化相中起关键作用。400℃和800℃氧化物残余物两者的13C NMR光谱分别在图9A和9B中示出。参考图9A，在400℃下获得的氧化物残余物在25ppm和64ppm处示出两个峰，表明存在两种不同类型的碳环境。在110ppm和190ppm处的峰是由于用于测量的特富龙胶囊。参考图9B，在800℃下获得的氧化物残余物中，在25ppm和64ppm处的峰强度增强。在25ppm处的峰为sp3杂化碳的特征，并且在64ppm处的峰为sp杂化碳的特征。因此，这些结果清楚地表明存在两种不同类型的碳。
为了观察混合金属氧化物以及MgO的可能生长，进行形成的氧化物相的SEM分析。图10A-10D示出在400℃下获得的氧化物残余物的SEM图像。氧化物残余物在结构上层化，如图10A和10B所示。氧化物链以及层的生长描绘于图10C中并且图10D的SEM证明金刚烷充当氧化物残余物的模板或生长导向剂。在800℃下获得的氧化物残余物的SEM图像在图11A-12D中提供。
参考图13，本例中的高温层化氧化物的形成机理可基于由在400℃下分解4小时的Mg/Al-金刚烷酸酯LDH获得的混合金属氧化物残余物的SEM图像来解释。SEM描绘氧化物残余物的边缘上以及基础表面上的MgO链。存在于LDH中间层中的金刚烷部分充当MgO链的生长模板，这反过来防止层的聚集，从而导致尖晶石相形成的抑制。
通过TEM和HRTEM进一步表征氧化物残余物，以分析混合金属氧化物和MgO链的逐层组装。图14A和14B示出在400℃下获得的氧化物残余物的TEM图像。图14C的HRTEM图像及其图14D的选定区域电子衍射图案进一步证明图14C和14D中所描绘的层化结构。参考图15A-15C的TEM图像和图15D的HRTEM图像，在800℃下的氧化物残余物保持与图14A-14D中所描绘的层结构类似的层结构。
在本实施例中，由于金刚烷离子的聚合，即使在800℃下，碳也以片状结构存在。为了定性地证明这一点，混合金属氧化物的EDX光谱在图16B中提供。图16A为EDX光谱，其将一条链与800℃的混合金属氧化物样品隔离。链状结构的EDX光谱揭示存在Mg和O，表明它由MgO构成，而不是如预期的那样由碳构成。然而，层化材料的EDX光谱令人惊讶地示出存在C、O、Mg和Al，表明即使在800℃下氧化物残余物中也存在碳。
MgO链的TEM和HRTEM分析以及选定区域衍射图案在图17A-17D中提供。通过将一种混合金属氧化物颗粒与另一种混合金属氧化物颗粒连接，生长MgO氧化物链，如图17C所示。这种生长导致在两个氧化物颗粒之间产生晶界，预期所述氧化物颗粒示出高催化活性。
为了探测材料在升高的温度下的稳定性，进行从Mg/Al-金刚烷LDH(400℃)获得的氧化物相的表面表征(使用BET)；这示出表面积为200m2/g，具有IV型等温线，表明形成的氧化物本质上为中孔的。
比较实例：由氨沉淀形成的Mg/Al-NO3层化双氢氧化物的混合金属氧化物
通过常规氨沉淀法从金属硝酸盐开始合成Mg/Al-NO3(Mg/Al＝2)层化双氢氧化物，并且在400℃下热分解4小时。分解的Mg/Al-NO3LDH的SEM图像在图18A-18D中提供。这些说明通常在分解时LDH如何失去其层化结构以产生无定形氧化物。如SEM显微照片所示，已经失去层化结构并且颗粒开始熔合在一起。
比较实例：由氨沉淀和金刚烷嵌入层化双氢氧化物形成的Mg/Al-NO3层化双氢氧化物重建混合金属氧化物
使用由本公开的LDH产生的氧化物的重复重建实验与从常规LDH获得的氧化物进行比较。用于重建研究的LDH为Mg/Al-CO3(Mg/Al＝2)，并且使用共沉淀技术在pH 10下制备。通过在400、800和1100℃下加热氧化物并且然后使用Na2CO3溶液重建回LDH来获得混合金属氧化物。由在1100℃下共沉淀的LDH形成的氧化物的PXRD图案示出材料转化为尖晶石相，在再水化时很少重建回母体LDH。在混合金属氧化物形成期间，Al3+将其配位几何形状从八面体(Oh)改变为四面体(Td)配位，并且在重建时恢复到八面体配位。在不同步骤(混合金属氧化物相和重建相)中测量这些几何形状中的Al3+提供这些氧化物的可再循环性或相分离的直接测量。使用固态NMR技术，量化在氧化物形成和重建步骤期间存在于Oh和Td中的Al3 +的量。通过将本公开的LDH和常规LDH加热至高达期望温度并且回到室温来形成氧化物。在重建时Al3+将恢复到Oh配位，并且在Td配位中留下的任何Al3+被认为是相分离/不可再循环相。如表1和2中所说明，由本公开的LDH获得的氧化物表现出比由常规混合金属氧化物获得的氧化物更好的重建。第一列(氧化物Td％)示出氢氧化物中的Al进入尖晶石相的趋势。然而，第二列(重建Td％)示出重建后的残余Al。两列中的数据清楚地示出，金刚烷嵌入LDH具有在热处理期间减少Al从氢氧化物相(向尖晶石)迁移的能力，以及与常规LDH颗粒相比，具有在尖晶石相(分离的相)中重建留下较少量的Al的能力。
表1-金刚烷嵌入LDH颗粒
Figure BDA0001802610750000111
表2-常规LDH颗粒
Figure BDA0001802610750000112
通过XPS光谱进一步表征碳载体对混合金属氧化物的存在和性质。母体LDH的XPS光谱示出单峰，其结合能以285.3eV为中心。由于金刚烷羧酸盐的C-C和O-C＝O键特征，此峰具有碳组分。通过在400、800和1100℃(分别为图20、21和22)下加热样品获得的混合金属氧化物示出以285和289.5eV为中心的两个结合能峰。在285eV处的峰与在母体LDH中观察到的峰相似，并且是由于金刚烷羧酸盐。在289.5eV处的峰是由于构成有机聚合链的碳，并且在这种情况下是由于金刚烷链。基于XPS光谱，可以得出结论，混合金属氧化物锚定在纳米类金刚石(金刚烷)的长链上。
对于本领域技术人员显而易见的是，在不脱离所要求保护的主题的精神和范围的情况下，可以对所描述的内容进行各种修改和变化。因此，本说明书旨在覆盖各种描述的实施例的修改和变化，只要这些修改和变化落入所附权利要求及其等同物的范围内。

Claims (15)

1.一种制备混合金属氧化物颗粒的方法，所述方法包含：
将金刚烷嵌入层化双氢氧化物（LDH）颗粒加热至高达400℃至800℃的反应温度以形成混合金属氧化物颗粒，
其中：
所述金刚烷嵌入LDH颗粒具有
一定长度和宽度；
通式[M1−xAlx(OH)2](A)x⋅mH2O，其中x为0.14至0.33，m为0.33至0.50，M选自Mg、Ca、Co、Ni、Cu或Zn，并且A为金刚烷羧酸盐；和
大于100的纵横比，其中所述纵横比由金刚烷嵌入LDH颗粒的所述宽度除以所述金刚烷嵌入LDH颗粒的厚度来界定；和
所述混合金属氧化物颗粒包含含有M、Al和碳的混合金属氧化物相。
2.根据权利要求1所述的方法，其中所述混合金属氧化物颗粒进一步包含具有式MO的氧化物相。
3.根据权利要求1所述的方法，其中所述混合金属氧化物颗粒包含以所述混合金属氧化物颗粒重量计的小于5 wt%的具有式MAl2O4的尖晶石相。
4.根据权利要求3所述的方法，其中所述混合金属氧化物相位于所述具有式MO的氧化物相的链之间。
5.根据权利要求1所述的方法，其中所述加热至高达所述反应温度的加热速率为4至6℃/min。
6.根据权利要求5所述的方法，其中所述加热包括在所述反应温度下保持至少4小时。
7.根据权利要求1所述的方法，其中所述金刚烷嵌入层化双氢氧化物（LDH）颗粒的所述加热为20℃至30℃的初始温度到400℃至800℃的所述反应温度。
8.根据权利要求5所述的方法，其中M为Mg。
9.一种混合金属氧化物颗粒，其包含：
至少一种含有M、Al和碳的混合金属氧化物相，其中M选自Mg、Ca、Co、Ni、Cu或Zn；和
至少一种具有式MO的氧化物相，其中所述混合金属氧化物相夹在所述氧化物相的链之间，
其中所述混合金属氧化物颗粒包含以所述混合金属氧化物颗粒重量计的小于5 wt%的具有式MAl2O4的尖晶石相。
10.根据权利要求9所述的混合金属氧化物颗粒，其中所述混合金属氧化物颗粒限定在800℃下具有13.0 +/- 0.5的特征峰的粉末X射线衍射（PXRD）图谱。
11.根据权利要求9所述的混合金属氧化物颗粒，其中所述混合金属氧化物颗粒基本上由所述混合金属氧化物相和所述具有式MO的氧化物相的层组成。
12.一种从过程流中除去成分的方法，所述方法包含：
使所述过程流与催化剂接触，其中所述催化剂包含混合金属氧化物颗粒，所述混合金属氧化物颗粒包含：
至少一种含有M、Al和碳的混合金属氧化物相，其中M选自Mg、Ca、Co、Ni、Cu或Zn；和
至少一种具有式MO的氧化物相，其中所述混合金属氧化物相夹在所述氧化物相的链之间，并且其中所述混合金属氧化物颗粒不包括具有式MAl2O4的任何尖晶石相。
13.根据权利要求12所述的方法，其中M为Mg。
14.根据权利要求12所述的方法，其中所述过程流为气流并且除去的所述成分为二氧化碳。
15.根据权利要求12所述的方法，其中所述过程流为气流或水流并且除去的所述成分为有毒离子，其中所述有毒离子为磷酸盐、砷酸盐、铬酸盐、溴化物、碘化物和硫化物中的一种或多种。
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