CN109414686B - 高纵横比层状双氢氧化物材料和其制备方法 - Google Patents
高纵横比层状双氢氧化物材料和其制备方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 title claims description 15
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000002245 particle Substances 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
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- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
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- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 10
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- JIMXXGFJRDUSRO-UHFFFAOYSA-N adamantane-1-carboxylic acid Chemical compound C1C(C2)CC3CC2CC1(C(=O)O)C3 JIMXXGFJRDUSRO-UHFFFAOYSA-N 0.000 claims description 6
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- 230000035484 reaction time Effects 0.000 claims 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- -1 adamantane ions Chemical class 0.000 description 3
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- 125000000129 anionic group Chemical group 0.000 description 3
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- 239000001257 hydrogen Substances 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
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- 102000040954 LDH family Human genes 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 238000005470 impregnation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 239000011259 mixed solution Substances 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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Abstract
实施例涉及插入有金刚烷的层状双氢氧化物(LDH)颗粒和制备插入有金刚烷的LDH颗粒的方法。所述方法包含向水溶液中加入第一前体和第二前体以形成初始混合物，其中所述第一前体是Al(OH)3或Al2O3，所述第二前体是氢氧化物M(OH)2或氧化物MO，其中M是氧化态为+2的金属；且所述初始混合物的M/Al摩尔比为从1至5。所述方法还包含向所述初始混合物中加入一定量的金刚烷以形成Al/金刚烷摩尔比为从0.5至2的反应混合物；和加热所述反应混合物以制备插入有金刚烷的LDH颗粒，其中所述插入有金刚烷的LDH颗粒具有大于100的纵横比。
Description
相关申请的交叉引用
本申请要求2016年3月17日提交的美国临时申请62/309,645的权益，其以全文引用的方式并入本文中。
技术领域
本公开的实施例主要涉及层状双氢氧化物材料，并且具体地涉及高纵横比层状双氢氧化物材料和制备方法。
背景技术
负载金属或金属氧化物催化剂的合成在多相催化中具有极大的工业重要性。高活性、高选择性和长催化剂寿命是任何工业催化剂的期望特性。催化剂材料可以由层状双氢氧化物(LDH)制备。LDH，也称为阴离子粘土，是广泛使用的硅铝酸盐阳离子粘土在结构和特性上的反电荷类似物。一般来说，尽管存在许多制备金属氧化物颗粒的方法，但与通过合成方法例如湿法浸渍/固态制备获得的氧化物颗粒相比，通过分解LDH获得的氧化物具有几个优点。具体来说，LDH可以提供一种简单、节省成本且在环境上适合的方式以在原子水平上实现金属离子的均匀分布。为了将LDH层用于各种应用，人们需要能够剥离或分层这些层。由于碳酸盐LDH在热力学上更稳定，因此难以将其换成其他离子或难以剥离其中碳酸盐是电荷平衡离子的LDH层。结果，这些材料的使用受到限制。已经尝试从碳酸盐LDH开始制备高纵横比的非碳酸化LDH；但是，这种方法有多个步骤，而且很麻烦。
发明内容
根据先前提出的背景技术，对具有高纵横比的LDH材料存在持续需求。
本公开的实施例涉及用调节高纵横比片层的生长的高对称金刚烷离子制备的LDH。此外，由于其亲有机性，金刚烷可以在有机溶剂中剥离。因此，这些LDH层可用于如先前提及的各种应用中。本公开的实施例涉及高纵横比的非碳酸化LDH，其仅使用一当量的阴离子盐。此外，这些LDH提供了工艺改进，因为它们能够实现“一锅”合成，并且由于使用金属氢氧化物作为起始材料和仅使用一当量的阴离子，在反应结束时洗涤工作较少(包括不洗涤)。所形成的材料一旦煅烧也具有期望特性。
根据一个实施例，提供了一种制备插入有金刚烷的层状双氢氧化物(LDH)颗粒的方法。所述方法包含向水溶液中加入第一前体和第二前体以形成初始混合物，其中第一前体是Al(OH)3或Al2O3，且第二前体是氢氧化物M(OH)2或氧化物MO，其中M是氧化态+2的金属。以初始混合物的总重量计，初始混合物具有1至5的M/Al摩尔比或小于10重量％固体的固体负载。所述方法还包含向初始混合物中加入一定量的金刚烷以形成具有从0.5至2的Al/金刚烷摩尔比的反应混合物，并加热反应混合物以制备插入有金刚烷的LDH颗粒，其中插入有金刚烷的LDH颗粒具有大于100的纵横比。纵横比通过插入有金刚烷的LDH颗粒的宽度除以插入有金刚烷的LDH颗粒的厚度来定义。
根据另一个实施例，提供了一种呈插入有金刚烷的LDH颗粒形式的插入有金刚烷的层状双氢氧化物(LDH)材料。插入有金刚烷的LDH颗粒包含由[M1-xAlx(OH)2](A)x·mH2O定义的通式，其中x是从0.14至0.33，m是从0.33至0.50，M选自Mg、Ca、Co、Ni、Cu或Zn，且A是金刚烷羧酸盐。插入有金刚烷的LDH颗粒进一步包含大于100的纵横比。纵横比通过插入有金刚烷的LDH颗粒的宽度除以插入有金刚烷的LDH颗粒的厚度来定义。
所描述的实施例的额外特征和优点将在下文的具体实施方式中阐述，并且将部分地由所属领域的技术人员从该描述容易了解或通过实践所描述的实施例(包括下文的具体实施方式、权利要求书以及附图)而认识到。
附图说明
图1A是通过阴离子交换制备的Mg/Al-CO3LDH的扫描电子显微法(SEM)图像；
图1B是通过共沉淀制备的Mg/Al-CO3LDH的SEM图像；
图2A和2B是根据本公开的一个或多个实施例制备的Mg/Al-金刚烷酸盐LDH的不同放大倍数的SEM图像；
图3是根据本公开的一个或多个实施例的Mg/Al-金刚烷酸盐LDH的粉末X射线衍射(PXRD)图；
图4是根据本公开的一个或多个实施例的Mg/Al-金刚烷酸盐LDH的红外(IR)光谱图；
图5是根据本公开的一个或多个实施例的Mg/Al-金刚烷酸盐LDH的1H固态核磁共振(NMR)光谱图；和
图6是根据本公开的一个或多个实施例的Mg/Al-金刚烷酸盐LDH的13C固态NMR光谱图。
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是复杂且费力的过程。为实现此目标，人们需要考虑各种参数，例如合成条件、载体的性质和在载体上分散/分布活性催化剂的适当方式。在金属/金属氧化物负载型催化剂中，负载于不同载体(氧化铝、二氧化硅和碳)上的Cu/ZnO/Al2O3系统和金属/金属氧化物(Pt、Pd、Rh和Au)系统具有很大的工业重要性。已知这些催化系统具有催化工业上重要反应的潜力，所述反应例如有甲醇的合成、水煤气变换反应、石油化学物流的脱硫、水的光化学/电化学分裂，和将二氧化碳光化学/电化学还原成有用的化学物质。
现在将详细参考具有高纵横比的插入有金刚烷的层状双氢氧化物(LDH)颗粒和其制备方法的实施例。具体来说，插入有金刚烷的LDH颗粒具有大于100的纵横比。如所定义的，纵横比由LDH颗粒的宽度除以LDH颗粒的厚度来定义。如所定义的，低于10的纵横比被认为是低的，小于100的纵横比被认为是中等的，并且100或更大的纵横比被认为是高纵横比。LDH颗粒可以从SEM图像计算。例如，参考图2B的实施例，显而易见的是，层状颗粒具有大的表面积，但缺乏厚度，从而导致高纵横比。另外，可以使用原子力显微法(AFM)来测量LDH颗粒的宽度和厚度并确定纵横比。
制备插入有金刚烷的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混合物的步骤。在一个实施例中，水溶液可以基本由水组成。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是氧化态+2的金属。虽然也考虑了各种其他金属，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，第二前体是Mg(OH)2或MgO。在一个实例中，第二前体是Mg(OH)2且第一前体是Al(OH)3。
此外，在其它实施例中，初始混合物可具有1至5或1至3的M/Al摩尔比。此外，以初始混合物的总重量计，初始混合物可具有小于10重量％固体的固体负载，或小于5重量％固体的固体负载。
随后，所述方法包括向初始混合物中加入一定量的金刚烷，以形成Al/金刚烷摩尔比为从0.5至2的反应混合物。在一个或多个另外的实施例中，Al/金刚烷的摩尔比可以为从0.8至1.2，或可以为1比1。考虑了各种金刚烷源。在一个实施例中，金刚烷可以以羧酸的形式加入。任选地，反应可被搅拌。
一般来说，用无机客体阴离子制备用于转化成混合型金属氧化物催化剂的LDH，所述无机客体阴离子可以在热处理下容易地除去。当使用有机阴离子例如羧酸官能化的金刚烷时，可以实现LDH的特性的改善。金刚烷具有以高对称性(Td)为特征的结构，没有分子内应变，因此具有极高的热力学稳定性。同时，金刚烷可以被化学官能化。金刚烷的熔点为270℃，并且即使在室温下也会缓慢升华。金刚烷难溶于水，但易溶于烃。
在不受理论束缚的情况下，使用热稳定的金刚烷作为结构导向剂，这允许在c结晶轴上的a和b结晶方向上LDH的优先生长。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和动力学方面小心控制生长条件。
接下来，所述方法包括加热反应混合物以产生插入有金刚烷的LDH颗粒，其中插入有金刚烷的LDH颗粒具有大于100的纵横比。如所定义的，插入有金刚烷的LDH颗粒意谓将金刚烷插入LDH颗粒基质中。在其它实施例中，插入有金刚烷的LDH颗粒的纵横比大于125，或大于150，或大于200。此外，插入有金刚烷的LDH颗粒具有2至12μm或5至10μm的粒径。加热步骤可以在110℃至180℃的反应温度下进行，反应时间为12小时至48小时，或者在130℃至170℃的反应温度下进行，反应时间为20小时至30小时。
LDH族材料的最大群组包括具有组成[MII 1-xMIII x(OH)2]x+或[MI xMIII 1-x(OH)2]x+(MI＝Li；MII＝Mg、Ca、Co、Ni、Zn；MIII＝Al、Cr、Fe；0.14≤x≤0.33)。的带正电荷的金属氢氧化物层层上的正电荷由中间层中存在的阴离子平衡。阴离子被命名为阴离子粘土。一组阴离子粘土包括具有通式[MII 1-xMIII x(OH)2](An-)x/n·mH2O或[MI xMIII 1-x(OH)2]x+(An-)x/n·mH2O(m＝0.33–0.50)的材料，其中A是阴离子，例如硝酸盐或卤素。
插入有金刚烷的LDH颗粒可具有通式[M1-xAlx(OH)2](A)x·mH2O，其中x是从0.14至0.33，m是从0.33至0.50，M选自Mg、Ca、Co、Ni、Cu或Zn，且A是金刚烷羧酸盐。
具有高纵横比的LDH在包装中的氧气屏障的发展中起一定作用，在纳米复合材料中作为填充剂，以及作为阻燃剂等。对于所有这些应用，可以容易地分散在聚合物基质中的高纵横比的片层是所期望的，但是不容易获得。阴离子(阴离子的电荷和对称性)在LDH晶体的成核和生长中起关键作用。碳酸盐离子在自然界中普遍存在，具有与LDH的层间对称性良好匹配的D3h对称性，并且与其他阴离子相比具有更高的电荷密度。结果，LDH优选碳酸盐离子而不是其他离子，并且这调节了层的有序堆叠。图1A和1B的SEM展示分别经由阴离子交换和共沉淀制备的Mg/Al-碳酸盐LDH。
与本发明实施例相反，LDH通常通过共沉淀技术制备，其中将金属盐的均匀混合溶液加入另一种含有氢氧化钠和待掺入的过量客体阴离子的溶液中。由于快速的多次成核和结晶事件，从该方法获得的LDH总是显示具有亚微米尺寸的微晶。共沉淀的晶体可具有约1-10或更小的纵横比。这表明晶体具有窄的宽度并且优先沿c轴生长。这反映了阴离子和阳离子的高过饱和度和在反应器的混合区中许多晶体的快速成核。
为了说明，通过共沉淀和阴离子交换方法制备的Mg/Al-CO3LDH样品的SEM图像提供于图1A和1B中。如图所示，这些颗粒是不规则的较厚团聚物。由于此厚度，Mg/Al-CO3LDH样品的纵横比很低。相反，如图2A和2B所示产生的Mg/Al-金刚烷酸盐LDH的SEM显微照片描绘了具有比Mg/Al-CO3小得多的厚度的片状层。鉴于这些低厚度，这些Mg/Al-金刚烷酸盐LDH颗粒具有高纵横比。
实例
所描述的实施例将通过以下实例进一步阐明。
实例1
层状双氢氧化物的制备
在一种典型的制备中，通过将5克(g)Mg(OH)2溶解在95g去离子水中制备5重量％的Mg(OH)2溶液。向其中加入3.36g Al(OH)3以达到Mg/Al摩尔比为2。然后，将9.31g金刚烷羧酸加入到相同的溶液中(Al/金刚烷摩尔比＝1)，并将所得反应混合物在室温下剧烈搅拌1小时。此后，将溶液转移到Teflon衬里的高压釜中并在150℃下加热24小时(h)。测量初始反应混合物和最终滤液的pH，结果分别为9.5和8.6。在另一组实验中，通过使Mg/Al摩尔比达到5重复上述工序。反应结束后，用水彻底洗涤产物并在65℃下干燥。
为了比较，通过更常规的氨沉淀法从金属硝酸盐开始合成Mg/Al-NO3LDH(Mg/Al摩尔比＝2)。
所合成的LDH的PXRD图谱示于图3中，并且显示了在
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值处可以看到(001)的约数。金刚烷酸的插入进一步用IR光谱表征，如图4所示。1517cm-1和1395cm-1处的振动对应于COO-基团的反对称和对称伸展振动。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的插入水分子的氢键结合。
记录Mg/Al-金刚烷酸盐LDH的1H和13C固态NMR光谱，并在图5和6中分别给出。图5的1H光谱中的在较低ppm值下的4个尖峰是由于金刚烷环中存在的氢。3.8ppm和4.8ppm的峰分别是因为插入的水和金属氢氧化物的氢。参考图6，Mg/Al-金刚烷酸盐的13C NMR光谱在29.5ppm、37.3ppm、40.6ppm和42.8ppm处显示出4个峰，这是由于金刚烷分子中存在4种不同的碳。186.98ppm处的峰是因为羧酸盐基团的碳。所合成的LDH的扫描电子显微镜(SEM)图像显示了层状材料的典型的片层形态(图2A和2B)。
本领域的技术人员将清楚，在不脱离要求保护的主题的精神和范围的情况下，可以对本文中所描述的实施例进行各种修改和变化。因此希望本说明书涵盖本文中描述的各种实施例的修改和变化，条件是此类修改和变化落在所附权利要求书和其等效物的范围内。
Claims (15)
1.一种制备插入有金刚烷的层状双氢氧化物(LDH)颗粒的方法，所述方法包含：
向水溶液加入第一前体和第二前体以形成初始混合物，其中：
所述第一前体是Al(OH)3或Al2O3；
所述第二前体是氢氧化物M(OH)2或氧化物MO，其中M是氧化态+2的金属；和
所述初始混合物具有从1至5的M/Al摩尔比；
以初始溶液的总重量计，所述初始混合物具有小于10重量％固体的固体负载；
向所述初始混合物中加入一定量的金刚烷以形成具有从0.5至2的Al/金刚烷摩尔比的反应混合物；和
加热所述反应混合物以制备所述插入有金刚烷的LDH颗粒，其中所述插入有金刚烷的LDH颗粒具有大于100的纵横比，所述纵横比通过插入有金刚烷的LDH颗粒的宽度除以所述插入有金刚烷的LDH颗粒的厚度来定义。
2.如权利要求1所述的方法，还包含搅拌所述反应混合物。
3.如权利要求1所述的方法，其中所述金刚烷以羧酸的形式加入。
4.如权利要求1所述的方法，其中所述加热步骤在从110℃至180℃的反应温度下进行，反应时间为12小时至48小时。
5.如权利要求1所述的方法，其中M选自Mg、Ca、Co、Ni、Cu或Zn。
6.如权利要求1所述的方法，其中所述第二前体是Mg(OH)2、Ca(OH)2、Co(OH)2、Ni(OH)2、Cu(OH)2或Zn(OH)2。
7.如权利要求1所述的方法，其中所述第二前体是Mg(OH)2或MgO。
8.如权利要求1所述的方法，其中所述第二前体是Mg(OH)2，且所述第一前体是Al(OH)3。
9.如权利要求1所述的方法，其中所述Al/金刚烷的摩尔比为从0.8至1.2。
10.如权利要求1所述的方法，其中所述插入有金刚烷的LDH颗粒具有通式[M1-xAlx(OH)2](A)x·mH2O，其中x是从0.14至0.33，m是从0.33至0.50，M选自Mg、Ca、Co、Ni、Cu或Zn，且A是金刚烷羧酸盐。
11.如权利要求1所述的方法，其中以所述初始混合物的总重量计，所述初始混合物具有小于5重量％固体。
12.如权利要求1所述的方法，其中所述纵横比大于125。
13.一种呈插入有金刚烷的LDH颗粒形式的插入有金刚烷的层状双氢氧化物(LDH)材料，其中所述插入有金刚烷的LDH颗粒包含：
由[M1-xAlx(OH)2](A)x·mH2O定义的通式，其中x是从0.14至0.33，m是从0.33至0.50，M选自Mg、Ca、Co、Ni、Cu或Zn，且A是金刚烷羧酸盐；和
大于100的纵横比，所述纵横比通过插入有金刚烷的LDH颗粒的宽度除以所述插入有金刚烷的LDH颗粒的厚度来定义。
14.如权利要求13所述的插入有金刚烷的LDH材料，其中所述纵横比大于125。
15.如权利要求13所述的插入有金刚烷的LDH材料，其中所述插入有金刚烷的LDH颗粒具有5至10μm的粒径。
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| PCT/US2017/022485 WO2017160965A1 (en) | 2016-03-17 | 2017-03-15 | High aspect ratio layered double hydroxide materials and methods for preparation thereof |
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| JP6674068B2 (ja) * | 2016-03-17 | 2020-04-01 | サウジ アラビアン オイル カンパニーＳａｕｄｉ Ａｒａｂｉａｎ Ｏｉｌ Ｃｏｍｐａｎｙ | 遷移金属アダマンタンカルボン酸塩及び酸化物ナノ複合材料の合成 |
| US10138199B2 (en) | 2016-03-17 | 2018-11-27 | Saudi Arabian Oil Company | High aspect ratio layered double hydroxide materials and methods for preparation thereof |
| US10087355B2 (en) | 2016-03-17 | 2018-10-02 | Saudi Arabian Oil Company | Oil-based drilling fluids containing an alkaline-earth diamondoid compound as rheology modifier |
| US10106482B2 (en) * | 2016-03-17 | 2018-10-23 | Saudi Arabian Oil Company | Synthesis of magnesium adamantane salts and magnesium oxide nanocomposites, and systems and methods including the salts or the nanocomposites |
| US10252245B2 (en) | 2016-03-17 | 2019-04-09 | Saudi Arabian Oil Company | High temperature layered mixed-metal oxide materials with enhanced stability |
| US10875092B2 (en) | 2017-05-19 | 2020-12-29 | Saudi Arabian Oil Company | Methods for preparing mixed-metal oxide diamondoid nanocomposites and catalytic systems including the nanocomposites |
| WO2018213007A1 (en) | 2017-05-19 | 2018-11-22 | Saudi Arabian Oil Company | Synthesis of transition-metal adamantane salts and oxide nanocomposites |
| EP3527536A1 (en) * | 2018-02-15 | 2019-08-21 | Scg Chemicals Co. Ltd. | Method for preparing a camgal mixed oxide, a camgal mixed oxide obtainable this way and the use thereof for oligomerization of glycerol |
| CN108963277B (zh) * | 2018-07-02 | 2021-03-23 | 河南师范大学 | 一种可充式锌空电池双功能催化剂的制备方法及其应用 |
| CN109133200B (zh) * | 2018-08-31 | 2021-11-05 | 哈尔滨理工大学 | 一种花状Ni-Co水滑石电极材料的制备 |
| CN114507534B (zh) * | 2022-04-02 | 2023-05-12 | 陕西科技大学 | 一种氢氧化镍改性镁铝水滑石/蒙脱土纳米材料的制备方法 |
| CN114950547B (zh) * | 2022-06-01 | 2024-04-02 | 常州大学 | 酚钠盐改性水滑石的制备方法及其在制备酚醚类香料中的应用 |
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| Publication number | Publication date |
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| EP3429749B1 (en) | 2020-08-12 |
| WO2017160965A1 (en) | 2017-09-21 |
| US20170267623A1 (en) | 2017-09-21 |
| JP6914282B2 (ja) | 2021-08-04 |
| CN109414686A (zh) | 2019-03-01 |
| US10906859B2 (en) | 2021-02-02 |
| SG11201807817SA (en) | 2018-10-30 |
| JP2019512453A (ja) | 2019-05-16 |
| SA518392386B1 (ar) | 2021-12-14 |
| US20190039988A1 (en) | 2019-02-07 |
| EP3429749A1 (en) | 2019-01-23 |
| KR102164758B1 (ko) | 2020-10-13 |
| US10138199B2 (en) | 2018-11-27 |
| KR20190049620A (ko) | 2019-05-09 |
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