CN115003628A - 具有高氧迁移的基于铈-锆氧化物的氧离子导体(czoic)材料 - Google Patents
具有高氧迁移的基于铈-锆氧化物的氧离子导体(czoic)材料 Download PDFInfo
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- CN115003628A CN115003628A CN202180010931.8A CN202180010931A CN115003628A CN 115003628 A CN115003628 A CN 115003628A CN 202180010931 A CN202180010931 A CN 202180010931A CN 115003628 A CN115003628 A CN 115003628A
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- 239000000463 material Substances 0.000 title claims abstract description 97
- 239000010416 ion conductor Substances 0.000 title claims abstract description 12
- QWDUNBOWGVRUCG-UHFFFAOYSA-N n-(4-chloro-2-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1[N+]([O-])=O QWDUNBOWGVRUCG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 title claims description 45
- 239000001301 oxygen Substances 0.000 title claims description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims description 36
- 238000013508 migration Methods 0.000 title claims description 18
- 230000005012 migration Effects 0.000 title claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 11
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
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- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 4
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000000101 transmission high energy electron diffraction Methods 0.000 claims abstract 3
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- -1 oxygen ion Chemical class 0.000 claims description 11
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
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- 229910052727 yttrium Inorganic materials 0.000 claims description 4
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 150000002926 oxygen Chemical class 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
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- 230000004580 weight loss Effects 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种基于铈‑锆氧化物的离子导体(CZOIC)材料,包含:以所述CZOIC材料的总质量为基础,含量范围为5wt.%至95wt.%的氧化锆、含量范围为95wt.%至5wt.%的氧化铈、以及含量范围为30wt.%或更少的稀土金属的至少一种氧化物。所述CZOIC材料展示出的结构包括一个或多个膨胀晶胞和多个具有有序纳米域的微晶。所述CZOIC材料的结构呈现出由使用SAED技术在多个(hkl)位置测量的表现出畸变的d值所定义的晶格,使得相同(hkl)位置的d值与参照铈‑锆材料在相同(hkl)位置测量的d值相差约2%至约5%。
Description
技术领域
本公开大体涉及基于铈-锆氧化物的离子导体(CZOIC)材料,该材料用作氧传感器、用于固体氧化物燃料电池中、用作催化剂或用于其他需要快速氧迁移和传导的应用中。
背景技术
本节中的陈述仅提供与本公开相关的背景信息,可能不构成现有技术。在三元转化(TWC)催化剂中,基于铈-锆氧化物的离子导体(CZOIC)材料被广泛用作储氧材料。为在该应用中获得成功,CZOIC材料需展现出高储氧能力、高度的在宽泛温度范围内(例如一直到1150℃)的烧结抗性,形成中孔以展现出有效的传质特性,并提供与贵金属的兼容性。容易进行的氧迁移是对CZOIC材料的另一个重要要求。在废气中出现的为防止CO/HC突破的快速环境变化期间,尤其是在加速期间,氧迁移对于氧气的释放和再吸附都至关重要。
CZOIC材料的氧迁移取决于多种因素的相互作用,所述多种因素如氧化物组成、存在的稀土掺杂剂的类型和数量、晶相(如四方晶相、立方晶相、烧绿石等)和微晶尺寸。在过去25年中有关对CZOIC材料的氧迁移的广泛研究使得开发出允许TWC催化剂在300-600℃温度范围内有效运行的材料。
然而,有关CO、NOx、HC和烟灰排放水平的新的严格要求使得有必要寻找新的CZOIC材料,该材料展现出在显著较低的温度下(理想地在室温下)氧在材料的晶格结构内迁移和CeO2减少容易进行的性质。这种具有快速氧迁移的新CZOIC材料的研发不仅对于TWC催化剂应用很重要,对于在固体氧化物燃料电池(SOFC)中用作电解质也很重要,在该固体氧化物燃料电池(SOFC)中,还要求在低温下的高传导性。
从本文的描述将明显看出可应用的其他领域。应当理解,此处的描述及具体实施例仅用作说明目的,不用作限制本公开的范围。
附图说明
为使本公开被更好地理解,现将通过参考附图描述以示例方式给出的各种形式,其中:
图1为本公开的具有不同平均颗粒大小(d50)的两种CZOIC材料(CZ-1,CZ-2)与二氧化铈-氧化锆参照材料(CZ-参照)相比在1000℃老化六小时后的TPR-H2图谱的图示;
图2为CZOIC材料(CZ-1)的TPR-H2图谱的图示,连续运行以确定测得的Tmax的稳定性;
图3为在存在和不存在本公开中的CZOIC材料或二氧化铈-氧化锆参照材料的情况下炭黑氧化的微商热重分析(DTG)曲线的图示;
图4为由选区电子衍射(SAED)测量的二氧化铈-氧化锆参照材料的晶体结构的图示;
图5为由选区电子衍射(SAED)测量的本公开的CZOIC材料的晶体结构的图示;和
图6为由选区电子衍射(SAED)测量的本公开的另一CZOIC材料的晶体结构的图示。
本文所描述的附图仅用于说明目的,无意于以任何方式对本公开的范围进行限制。
具体实施方式
以下描述本质上仅是示例,且无意于限制本公开或其应用或用途。例如,在本公开通篇中描述了根据其中包含的教导制造和使用的基于铈-锆氧化物的离子导体(CZOIC)材料,同时还描述了用于减少车辆排放气体的三元催化剂(TWC),其目的是更加全面说明其组成及用途。在用于除去来自汽油或柴油发动机的HC、CO、NOx和烟灰的其他催化剂、柴油氧化催化剂和其他氧化催化剂或在其他应用如在固体氧化物燃料电池(SOFC)中使用的氧传感器或电解质中加入和使用所述CZOIC材料被认为在本公开的范围内。应当理解,在整个说明书中,相应的附图标记表示相同或相应的部件和特征。
本公开大体提供一种基于铈-锆氧化物的离子导体(CZOIC)材料,该材料展示出的结构包括一个或多个膨胀晶胞和多个具有有序纳米域的微晶。所述CZOIC材料可以包含氧化锆、氧化铈和至少一种除铈以外的稀土金属的氧化物,由氧化锆、氧化铈和至少一种除铈以外的稀土金属的氧化物组成,或者基本由氧化锆、氧化铈和至少一种除铈以外的稀土金属的氧化物组成。CZOIC材料可以包含氧化铈和氧化锆,使得该材料包含的铈与锆的质量比(Ce:Zr)范围为约0.2至约1.0。或者,所述铈与锆的质量比范围为0.3至0.9;或者,所述铈与锆的质量比范围为0.4至0.8。
就本公开的目的而言,本文中的术语“至少一个/种”和“一个/种或多个/种”可互换使用且可以具有相同的含义。这些术语当指单个元素或多个元素时,也可以由元素末尾的后缀“(s)”表示。例如,“至少一个晶胞”、“一个或多个晶胞”和“一个或多个晶胞(unitcell(s))”可互换使用且旨在具有相同的含义。
就本公开的目的而言,由于本领域技术人员已知的预期变化(例如,测量的局限性和变异性),在本文中对于可测量的数值和范围使用术语“约”和“基本上”。
此外,在本文中以“在[第一数字]和[第二数字]之间”或者“在[第一数字]至[第二数字]之间”表述的任何参数范围均包括所述及的数字。换言之,该范围意在相似地解释为指定为“从[第一个数字]至[第二个数字]”的范围。
所述CZOIC材料的氧化锆含量相对于所述CZOIC材料总重量为在约5wt.%和95wt.%之间。在需要时,所述CZOIC材料的氧化锆含量范围相对于所述CZOIC材料的总重量可以为从10wt.%至90wt.%或者在约20wt.%和约80wt.%之间。所述CZOIC材料中的氧化铈含量范围相对于所述CZOIC材料的总重量还可以是从5wt.%至95wt.%,或者在约10wt.%至约90wt.%之间,或者从约20wt.%至约80wt.%。
就本公开的目的而言,术语“重量”是指质量值,如具有克、千克等单位的质量值。此外,通过端点对数值范围的表述包括端点及该数值范围内的所有数字。例如,以重量计40%至以重量计60%的浓度范围(也写作40wt.%至60wt.%)包括以重量计40%、以重量计60%以及二者之间的所有浓度(例如,40.1%、41%、45%、50%、52.5%、55%、59%等)。
根据本公开的另一方面,所述CZOIC中存在的除了铈(Ce)之外的至少一种稀土金属可以包括镝(Dy)、铒(Er)、铕(Eu)、钆(Gd)、钬(Ho)、镧(La)、镥(Lu)、钕(Nd)、镨(Pr)、钷(Pm)、钐(Sm)、钪(Sc)、铽(Tb)、铥(Tm)、镱(Yb)、钇(Y)或其混合物。或者,所述CZOIC材料中存在的除铈之外的稀土金属选自镧、钕、镨、钇或其组合。CZOIC中的这些稀土金属的含量范围相对于所述CZOIC材料总重量可以为0wt.%至35wt.%,或者少于30wt.%,或者从约5wt.%至25wt.%。OSM中存在的稀土金属的量足以使所述CZOIC材料的晶格稳定。
当需要时,所述CZOIC材料还可以包含一种或多种过渡金属,所述过渡金属选自但不限于铜、铁、镍、钴、锰或其组合的组。所述CZOIC材料中存在的这些任选的过渡金属的含量范围可以为以重量计从0%至8%,或者约1wt.%至约7wt.%,或者约2wt.%至约5wt.%。
所述CZOIC材料展示出的氧迁移是由于在典型的废气混合物中出现的氧化/还原反应的容易进行性与在所述CZOIC材料的晶格结构中异价离子(aliovalent)(La3+、Nd3+、Y3+等)的存在的结合。这些异价离子的存在导致在晶格结构中形成氧空位,使得氧能够从微晶本体迁移到表面,并且使得相反过程能够实现。
氧化铈有形成非化学计量的CeO2-x表面缺陷位点的能力,这会导致氧空位以及形成表面活性氧。氧化锆展示出类似的效果。当氧化铈和氧化锆结合形成CZOIC材料时,这种效果得到加强。除表面氧迁移外,由于Ce4+到Ce3+还原性的增加,氧化锆还使得晶格氧簇的迁移增加。立方氧化铈晶格中引入氧化锆增加了基于铈-锆氧化物的离子导体(CZOIC)材料中缺陷的产生,促进晶格氧的迁移,从而允许发生在CZOIC材料表面的氧化还原反应也发生在内部。氧化锆还有在高温使用期间稳定晶体结构的能力。
给出以下具体实施例以说明依据本公开的教导而形成的基于铈-锆氧化物的离子导体(CZOIC)及其性质,并不应被解释为限制本公开的范围。依据本公开,本领域技术人员将理解,在不背离或超出本公开的精神或范围的情况下,可以对文中公开的具体实施方式做出许多改变,并且仍能获得相同或相似的结果。本领域技术人员可进一步理解,本文中报道的任何性质表示常规测量的性质并且可通过多种不同方法获得。本文描述的方法代表一种这样的方法以及可以在不超出本公开范围的情况下使用的其他方法。
现参考图1,其中提供了本公开的具有不同平均颗粒大小(d50)的两种CZOIC材料(CZ-1、CZ-2)在1000℃老化六小时后获得的以及二氧化铈-氧化锆参照材料(CZ-参照)在1000℃老化六小时后的TPR-H2图谱的图示。Micromeritics Autochem 2920II仪器用于测试在25℃至900℃温度范围内的程序升温还原(TPR),升温速度为10℃/min,恒定90%Ar/10%H2气体流速为5cm3/min。TPR-H2提供了一种能够指示活性氧的量的测量以及金属氧化物还原过程中涉及的步骤。CZ-1和CZ-2间的差异是CZOIC材料展示出的平均颗粒大小(D50)。更具体地,CZOIC材料CZ-1和CZ-2的D50分别为1.1微米(μm)、0.5微米(μm)。CZ-参照代表常规的二氧化铈-氧化锆材料,例如在欧洲专利No.1 527 018B1中所给出的实施例中描述的内容,其全部内容通过引用整体并入本文。
在较高温度下发生的还原过程通常与金属氧化物结构中氧原子的迁移有关。本公开的CZOIC材料展示出快速氧离子迁移和传导性,表现为出现通过TPR-H2测量的在250℃或更低温度(参见CZ-1;CZ-2)出现的Tmax。相比之下,CZ-参照在约475℃的温度出现通过TPR-H2测量的Tmax。本公开的CZOIC材料在1000℃下老化六小时后通过TPR-H2测量的Tmax保持在250℃或更低的温度。此外,本公开的CZOIC材料(CZ-1;CZ-2)的TPR-H2图谱展示出在低于400℃的温度下存在至少80%或更多的可还原氧。最后,如图2中所示的对CZ-1的连续TPR-H2运行(运行#1到运行#6)的测量值表明,本公开的CZOIC材料的Tmax的出现保持相对恒定,只是略微向较高温度偏移。
现参考图3,其中提供了在存在和不存在本公开的CZOIC材料(CZ-1)或二氧化铈-氧化锆参照材料(CZ-参照)的情况下炭黑氧化的微商热重分析(DTG)曲线的图示。炭黑用作柴油发动机排放的模拟烟灰。本公开的CZOIC材料(CZ-1)和二氧化铈-氧化锆参照材料(CZ-参照)的DTG曲线是使用5%的炭黑与95%的混合氧化物材料(CZ-1或CZ-参照)混合得到的。使用以10℃/min的升温速度从25℃加热至700℃的Seiko EXTAR 7300TG/DTA/DSC仪器对25mg CZOIC材料样品测量DTG曲线。
DTG曲线表示在指定温度或时间里的加热或冷却等温线处的重量损失或增加的测量值(-dm/dt)。多个分解过程的出现可能会重叠,例如,一个分解反应在第二个(更高温度的分解过程)反应开始时可能还没有完成。然而,在大多数情况下,如果不测量其一阶导数(即DTG曲线),就不能对TG曲线进行可靠的定性和定量评估。任何温度下的DTG曲线的峰高都给出了质量损失率。
图3中,本公开的CZOIC材料(CZ-1)展示出快速氧离子迁移和传导,表现为在低于500℃氧化炭灰(carbon soot)或烃的能力。相比之下,二氧化铈-氧化锆参照材料(CZ-参照)在高于500℃的温度下氧化炭灰或烃,或者在低于300℃氧化饱和烃的能力。当没有CZOIC材料存在时,发现炭黑在接近600℃的温度氧化。DTG曲线进一步证明,至少10%的储氧容量(OSC)可用于一氧化碳(CO)在300℃或低于300℃的氧化。
现参考图4-6,其提供了使用选区电子衍射(SAED)测量的二氧化铈-氧化锆参照材料(图4)和本公开的CZOIC材料(图5和6)的晶体结构的图示。选区电子衍射(SAED)是一种晶体学实验技术,其中使薄晶体样品(约100nm厚)经受透射电子显微镜(TEM)的平行高能电子束处理,以使电子通过样本。由于与电子相关的波长通常约为千分之几纳米,并且晶体样品中原子间的间距大约是其一百倍,因此电子被衍射,原子充当衍射光栅。因此,一部分电子被散射到由样品的晶体结构所决定的特定角度,而其他电子则通过样品而不发生偏转。得到的TEM图像100(见图4-6)显示出一系列斑点,构成衍射图案。这些斑点中的每一个对应于样品晶体结构的衍射状况。SAED用于识别晶体结构和检查晶体缺陷111(见图4-6)。在这方面,SAED类似于X射线衍射,区别在于SAED可检查小至几百纳米大小的区域,而X射线衍射通常检查几厘米大小的区域。
本公开的CZOIC材料的结构(图5和6)展示出由使用SAED技术在多个(hkl)位置测量的d值定义的晶格。更具体地,在图5和图6中,沿着不同的晶带轴展示了CZ-1的不同微晶。本公开的CZOIC材料的实测d值表现出畸变。表1中提供了CZ-参照和本公开的CZOIC材料在多个(hkl)位置测量的d值。本公开的CZOIC材料在相同(hkl)位置的d值与参照铈-锆材料在相同(hkl)位置测量的d值相差约2%至约5%。
表1
根据本公开的另一方面,提供了一种催化剂,其包含至少一种铂族金属(PGM)以及如上文所述且在本文中进一步定义的基于铈-锆氧化物的离子导体(CZOIC)材料。催化剂可以是但不限于三元催化剂、四元催化剂、或柴油氧化催化剂。
CZOIC材料是三元催化剂(TWC)的组合物的重要部分,因为CZOIC材料在贫燃料和富燃料条件下对氧气储存和释放起主要作用,从而能够氧化CO和挥发性有机物,并且还原NOx。高效催化性能还与高比表面积和热稳定性以及高储氧能力有关。
该催化剂组合物包含一种或多种铂族金属(PGM),相对于全部催化剂组合物,其量在约0.01wt.%和10wt.%之间。或者,PGM存在量的范围是约0.05wt.%至约7.5wt.%,或者在1.0wt.%和约5wt.%之间。铂族金属可以包括但不限于铂(Pt)、钯(Pd)和铑(Rh)。
在本说明书中,已以能够清楚和简洁地书写说明书的方式对实施方案进行了描述,其目的是或者将理解的是,在不脱离本发明的情况下实施方案可以以各种方式组合或拆分。例如,将理解的是,本文描述的所有优选特征都适用于本发明的所有方面。
出于说明和描述的目的,前文的描述已呈现了本发明的各种形式。不旨在穷举或将本发明限制为所公开的精确形式。鉴于以上教导,存在许多修改或变化是可能的。选择和描述所讨论的形式,以提供对本发明原理及其实际应用的最佳说明,从而使本领域的普通技术人员能够以各种形式和适合预想的特定用途的各种修改来利用本发明。所有这些修改和变化在由随附权利要求根据公平、合法和公正地享有的范围内进行解释时所确定的本发明范围内。
Claims (21)
1.一种基于铈-锆氧化物的离子导体(CZOIC)材料,包含:以所述CZOIC材料的总重量为基础,含量范围为5wt.%至95wt.%的氧化锆、含量范围为95wt.%至5wt.%的氧化铈、以及含量范围为30wt.%或更少的除铈以外的稀土金属的至少一种氧化物;
其中所述CZOIC材料展示出的结构包含一个或多个膨胀晶胞和多个具有有序纳米域的微晶。
2.根据权利要求1所述的CZOIC材料,其中,所述CZOIC材料包含的铈与锆的质量比(Ce:Zr)为约0.2至约1.0。
3.根据权利要求1或2中任一项所述的CZOIC材料,其中,所述稀土金属选自镧(La)、钕(Nd)、镨(Pr)、钇(Y)或其组合的组。
4.根据权利要求1-3中任一项所述的CZOIC材料,其中,所述CZOIC材料的结构展示出由使用SAED技术在多个(hkl)位置测量的d值所定义的表现出畸变的晶格,使得相同(hkl)位置的d值与参照铈-锆材料在相同(hkl)位置测量的d值相差约2%至约5%。
5.根据权利要求1-4中任一项所述的CZOIC材料,其中,所述CZOIC材料展示出快速氧离子迁移和传导,表现为出现通过TPR-H2测量的在250℃或更低的温度出现的Tmax。
6.根据权利要求1-5中任一项所述的CZOIC材料,其中,所述CZOIC材料在1000℃老化六小时后展示出快速氧离子迁移和传导,表现为出现通过TPR-H2测量的在250℃或更低的温度出现的Tmax。
7.根据权利要求1-6中任一项所述的CZOIC材料,其中,所述CZOIC材料展示出快速氧离子迁移和传导,表现为出现通过TPR-H2测量的在低于400℃的温度存在至少80%或更多的可还原氧。
8.根据权利要求1-7中任一项所述的CZOIC材料,其中,所述CZOIC材料展示出快速氧离子迁移和传导,表现为在低于500℃氧化炭灰或烃的能力。
9.根据权利要求1-8中任一项所述的CZOIC材料,其中,所述CZOIC材料展示出快速氧离子迁移和传导,表现为至少10%的储氧容量(OSC)可用于一氧化碳(CO)在300℃或低于300℃的氧化。
10.根据权利要求8所述的CZOIC材料,其中,所述氧化烃的能力表示在低于300℃氧化饱和烃的能力。
11.根据权利要求1-10中任一项所述的CZOIC材料在三元催化剂、四元催化剂或柴油氧化催化剂中的用途。
12.一种包含储氧材料的三元转化(TWC)催化剂,所述储氧材料包含根据权利要求1-10中任一项所述的CZOIC材料。
13.一种具有电解质的固体氧化物燃料电池(SOFC),所述电解质包含根据权利要求1-10中任一项所述的CZOIC材料。
14.一种具有快速氧离子迁移和传导的催化剂,所述催化剂包含:
至少一种铂族金属(PGM);以及
基于铈-锆氧化物的离子导体(CZOIC)材料,包含:以所述CZOIC材料的总质量为基础,含量范围为5wt.%至95wt.%的氧化锆、含量范围为95wt.%至5wt.%的氧化铈、以及含量范围为30wt.%或更少的除铈以外的稀土金属的至少一种氧化物;其中,所述CZOIC材料展示出的结构包含一个或多个膨胀晶胞和多个具有有序纳米域的微晶。
15.根据权利要求14所述的催化剂,其中,所述CZOIC材料包含的铈与锆的质量比(Ce:Zr)为约0.2至约1.0。
16.根据权利要求14或15中任一项所述的催化剂,其中,所述稀土金属选自镧(La)、钕(Nd)、镨(Pr)、钇(Y)或其组合的组。
17.根据权利要求14-16中任一项所述的催化剂,其中,所述CZOIC材料的结构展示出由使用SAED技术在多个(hkl)位置测量的表现出畸变的d值所定义的晶格,使得相同(hkl)位置的d值与参照铈-锆材料在相同(hkl)位置测量的d值相差约2%至约5%。
18.根据权利要求14-17中任一项所述的催化剂,其中,所述CZOIC材料展示出快速氧离子迁移和传导,表现为至少以下一项:
(i)出现通过TPR-H2测量的在250℃或更低的温度出现的Tmax;
(ii)出现通过TPR-H2测量的在低于400℃的温度存在至少80%或更多的可还原氧;
(iii)在低于500℃氧化炭灰或烃的能力;
(iv)至少10%的储氧容量(OSC)可用于一氧化碳(CO)在300℃或低于300℃的氧化。
19.根据权利要求14-18中任一项所述的催化剂,其中,CZOIC材料在1000℃老化六小时后展示出快速氧离子迁移和传导,表现为至少以下一项:
(i)出现通过TPR-H2测量的在250℃或更低的温度出现的Tmax;
(ii)出现通过TPR-H2测量的在低于400℃的温度存在至少80%或更多的可还原氧;
(ii)在低于500℃氧化炭灰或烃的能力;
(iv)至少10%的储氧容量(OSC)可用于一氧化碳(CO)在300℃或低于300℃的氧化。
20.根据权利要求18或19中任一项所述的催化剂,其中,所述氧化烃的能力表示在低于300℃氧化饱和烃的能力。
21.根据权利要求14-20中任一项所述的催化剂,其中,所述催化剂为三元催化剂、四元催化剂或柴油氧化催化剂。
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