CN106698511B - 一种掺钇二氧化锆介观晶体及其制备方法和应用 - Google Patents
一种掺钇二氧化锆介观晶体及其制备方法和应用 Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 49
- NYWITVDHYCKDAU-UHFFFAOYSA-N oxygen(2-) yttrium(3+) zirconium(4+) Chemical compound [O--].[O--].[Y+3].[Zr+4] NYWITVDHYCKDAU-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 13
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000126 substance Substances 0.000 claims description 9
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- 229910021641 deionized water Inorganic materials 0.000 claims description 6
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- 230000035484 reaction time Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 3
- 208000011580 syndromic disease Diseases 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
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- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 25
- 238000002156 mixing Methods 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 13
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- 229910000431 copper oxide Inorganic materials 0.000 description 13
- 239000002245 particle Substances 0.000 description 10
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- 150000002500 ions Chemical class 0.000 description 8
- 229910052727 yttrium Inorganic materials 0.000 description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
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- 239000003795 chemical substances by application Substances 0.000 description 4
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 4
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- 230000003197 catalytic effect Effects 0.000 description 3
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- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical class [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 3
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- 238000004220 aggregation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- RVRKDGLTBFWQHH-UHFFFAOYSA-N yttrium zirconium Chemical compound [Y][Zr][Y] RVRKDGLTBFWQHH-UHFFFAOYSA-N 0.000 description 2
- 108010022579 ATP dependent 26S protease Proteins 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- CPKNPEXMGALOSZ-UHFFFAOYSA-N [Cu]=O.[Y] Chemical compound [Cu]=O.[Y] CPKNPEXMGALOSZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000001338 self-assembly Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种掺钇二氧化锆介观晶体及其制备方法，属于金属氧化物功能材料的制备领域。本发明将硝酸钇、氧氯化锆和尿素按比例溶解于水中形成混合溶液，经150℃水热反应24 h，制得所述掺钇二氧化锆介观晶体。本发明制备方法简便易行，成本低，介观晶体产率高；所制得的掺钇二氧化锆介观晶体具有良好的单分散性，呈橄榄状，内部多孔，比表面积高达150~161m2/g，是一种优良的水煤气变换催化剂载体。
Description
技术领域
本发明属于金属氧化物功能材料的制备领域，具体涉及一种掺钇二氧化锆介观晶体及其制备方法和应用。
背景技术
介观晶体（简称介晶）是指纳米晶基元按照特定晶体取向有序堆积而成的纳米晶超结构或有序聚集体，是由纳米晶粒通过自组装形成一个较大的微纳晶体。宏观上，微纳晶体因纳米晶粒的有序外延排列而呈单晶形态；微观上，微纳晶体内部纳米晶粒之间存在清晰可见的界面或空隙。介晶材料由于其特殊的结构使其在工业上具有重要的应用价值，成为单晶和多晶材料的有力竞争者。目前，有关功能性氧化物介晶材料的可控制备和性能研究仍是一个颇具挑战性的研究课题。
二氧化锆（ZrO2）是一种十分重要的结构和功能材料，它不但具有良好的热稳定性、而且同时具有表面酸性、碱性和氧化性、还原性，还富含表面羟基，这些性能使二氧化锆成为一种很重要的催化剂材料。由于Y3+与Zr4+具有相似的离子半径，Y3+很容易置换ZrO2中的Zr4+形成置换固溶体，同时在其表面和内部形成氧空位，因而Y元素常被作为助剂来调变ZrO2或含锆催化剂的结构性能。然而，目前尚未有钇掺杂的ZrO2介观晶体及其制备技术和应用的公开报道。
发明内容
本发明的目的在于提供一种掺钇二氧化锆介观晶体及其制备方法和应用，其制备方法简便易行，适合规模化生产，制得的掺钇二氧化锆介观晶体产品单分散性好，比表面积高达150～161m2/g，内部具有丰富孔道，是一种优良的催化剂材料，特别适合用作水煤气变换催化剂载体。
为实现上述目的，本发明采用如下技术方案：
一种掺钇二氧化锆介观晶体的制备方法，其包括以下步骤：
（1）将硝酸钇、氧氯化锆和尿素溶解于去离子水中，室温下搅拌后制得混合溶液；
（2）将步骤（1）所得混合溶液转入高温反应釜中，控制反应温度为150 ℃，反应时间为24 h；所得反应产物经离心分离、洗涤、干燥后得到掺钇二氧化锆介观晶体。
步骤（1）混合溶液中硝酸钇与氧氯化锆的物质的量浓度之和为0.75 mol/L；尿素的物质的量浓度为1.5 mol/L；硝酸钇的物质的量占硝酸钇与氧氯化锆总物质的量的2%～10%。
所得掺钇二氧化锆介观晶体为单斜晶相，形貌为橄榄状，长度为50～150 nm，直径为20～80 nm；比表面积为150～161 m2/g，内部多孔，最可几孔径为2 nm。
所得掺钇二氧化锆介观晶体可用作载体制备水煤气变换催化剂，其制备方法为：在超声波破碎辅助条件下，将所述掺钇二氧化锆介观晶体分散于硝酸铜水溶液中，然后向上述溶液中滴加碱液至溶液pH=9.0，所得沉淀经离心洗涤、干燥、焙烧后制得水煤气变换催化剂；所用碱液为碳酸钠、碳酸钾、氢氧化钾或氢氧化钠的水溶液。
本发明制备过程中硝酸钇及氧氯化锆与尿素在水热条件下均匀反应，反应遵循“原位结晶”机制，即经均匀沉淀生成的氢氧化物前驱物经过脱去羟基（或脱水），原子原位重排而转变为结晶态掺钇二氧化锆，析出掺钇二氧化锆一次纳米晶粒，一次晶粒在反应体系固有场（纳米晶固有偶极矩）下实现晶体学取向聚集，形成掺杂钇的二氧化锆介观晶体超结构。
本发明的显著优点在于：
（1）本方法首次制备出橄榄状掺杂钇的二氧化锆介观晶体，其制备方法简便易行，适合规模化生产，在较宽的钇含量（2%～10%）掺杂范围内，所得掺钇二氧化锆介晶产率高，单分散性好，结晶性好，比表面积高达150～161 m2/g，产物颗粒内部孔道丰富，颗粒内部最可几孔径为2 nm。
（2）本发明所制备的掺钇二氧化锆介晶是一种优良的催化剂载体，以其为载体制备的铜基催化剂表现出优异的水煤气变换反应制氢催化性能，当氧化铜质量含量为10%时，掺钇二氧化锆介晶负载氧化铜催化剂在反应温度为240℃时的CO转化率高达91%，明显高于无掺杂钇的二氧化锆介晶负载氧化铜催化剂（反应温度为240℃时，CO转化率为83%）和传统多晶二氧化锆负载氧化铜催化剂（反应温度为240℃时，CO转化率为69%）。
附图说明
图1是实施例1制备的掺钇二氧化锆介观晶体的XRD图。
图2是实施例1制备的掺钇二氧化锆介观晶体的SEM图。
图3是实施例1制备的掺钇二氧化锆介观晶体的TEM图。
图4是实施例1制备的掺钇二氧化锆介观晶体的选区电子衍射（SAED）图。
图5是实施例2制备的掺钇二氧化锆介观晶体的SEM图。
图6是实施例3制备的掺钇二氧化锆介观晶体的SEM图。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例1
将0.40 g硝酸钇，16.58 g氧氯化锆及6.31 g尿素溶于50mL去离子水中，室温下搅拌后制得混合溶液（硝酸钇的物质的量占硝酸钇与氧氯化锆总物质的量的2%），将上述混合液用去离子水标定到70mL后转入容积为100mL的高温反应釜中。将反应釜放入鼓风干燥箱内，控制反应温度为150℃，反应时间为24小时。所得产物经离心洗涤脱除杂质离子后于60℃干燥8小时得到掺钇二氧化锆介观晶体。
图1是本实施例制备的掺钇二氧化锆介观晶体的XRD图。由图1可知，所制备的掺钇二氧化锆呈单斜晶相。
图2、图3分别是本实施例制备的掺钇二氧化锆介观晶体的SEM图和TEM图。由图2和图3可知，掺钇二氧化锆颗粒呈橄榄状且由众多小晶粒聚集而成，橄榄状颗粒的长度为50～150 nm，直径为20～80 nm。
图4是本实施例制备的掺钇二氧化锆介观晶体的选区电子衍射（SAED）图。由图4可见单个掺钇二氧化锆颗粒呈现类单晶电子衍射行为，即颗粒内部一次晶粒间的晶格高度匹配，表明掺钇二氧化锆为介观晶体。
N2-物理吸脱附实验表明，该掺钇二氧化锆介晶的BET比表面积为150 m2/g，颗粒内部最可几孔径为2 nm。
实施例2
将1.00 g硝酸钇，16.07 g氧氯化锆及6.31 g尿素溶于50mL去离子水中，室温下搅拌后制得混合溶液（硝酸钇的物质的量占硝酸钇与氧氯化锆总物质的量的5%），将上述混合液用去离子水标定到70mL后转入容积为100mL的高温反应釜中。将反应釜放入鼓风干燥箱内，控制反应温度为150℃，反应时间为24小时。所得产物经离心洗涤脱除杂质离子后于60℃干燥8小时得到掺钇二氧化锆介观晶体。
图5是本实施例制备的掺钇二氧化锆介观晶体的SEM图。图5表明，所制备的掺钇二氧化锆颗粒同样为橄榄状介观晶体。
N2-物理吸脱附实验表明，该掺钇二氧化锆介晶的BET比表面积为157 m2/g，颗粒内部最可几孔径为2 nm。
实施例3
将2.01 g硝酸钇，15.23 g氧氯化锆及6.31 g尿素溶于50mL去离子水中，室温下搅拌后制得混合溶液（硝酸钇的物质的量占硝酸钇与氧氯化锆总物质的量的10%），将上述混合液用去离子水标定到70mL后转入容积为100mL的高温反应釜中。将反应釜放入鼓风干燥箱内，控制反应温度为150℃，反应时间为24小时。所得产物经离心洗涤脱除杂质离子后于60℃干燥8小时得到掺钇二氧化锆介观晶体。
图6是本实施例制备的掺钇二氧化锆介观晶体的SEM图。图6表明，所制备的掺钇二氧化锆颗粒同样为橄榄状介观晶体。
N2-物理吸脱附实验表明，该掺钇二氧化锆介晶的BET比表面积为161 m2/g，颗粒内部最可几孔径为2 nm。
应用实施例1
以实施例1制得的掺钇二氧化锆介观晶体为载体负载氧化铜制备铜基介晶催化剂，方法如下：在超声破碎的辅助下将3g 250℃焙烧后的掺钇二氧化锆介观晶体分散于200mL 0.021mol/L的三水合硝酸铜水溶液中，然后向上述溶液中滴加0.5mol/L的氢氧化钾水溶液至终点pH = 9.0。所得产物经洗涤脱除杂质离子后于120℃干燥8小时，再于400℃焙烧4小时制得掺钇二氧化锆介晶负载氧化铜催化剂。
应用实施例2
以实施例2制得的掺钇二氧化锆介观晶体为载体负载氧化铜制备铜基介晶催化剂，其制备方法和条件与应用实施例1相同。
应用实施例3
以实施例3制得的掺钇二氧化锆介观晶体为载体负载氧化铜制备铜基介晶催化剂，其制备方法和条件与应用实施例1相同。
应用对比例1：二氧化锆多晶负载氧化铜催化剂
将7.85g 八水合氧氯化锆溶解于200mL去离子水中制得反应底液，将0.5mol/L的氢氧化钾水溶液加入上述反应底液至终点pH = 9.0。所得产物经洗涤脱除杂质离子后于60℃干燥8小时，再于250℃焙烧4小时制得二氧化锆多晶。
在超声波破碎的辅助下将3g 二氧化锆多晶分散于200mL 0.021mol/L的三水合硝酸铜水溶液中，然后向上述溶液中滴加0.5mol/L的氢氧化钾水溶液至终点pH = 9.0。所得产物经洗涤脱除杂质离子后于120℃干燥8小时，再于400℃焙烧4小时制得二氧化锆多晶负载氧化铜催化剂。
应用对比例2：二氧化锆介晶负载氧化铜催化剂
将16.92g氧氯化锆及6.31 g尿素溶于50mL去离子水中，室温下搅拌后制得混合溶液。将上述混合液用去离子水标定到70mL后转入容积为100mL的高温反应釜中。将反应釜放入鼓风干燥箱内，控制反应温度为150℃，反应时间为24小时。所得产物经离心洗涤脱除杂质离子后于60℃干燥8小时得到二氧化锆介观晶体。
在超声波破碎的辅助下将3g 250℃焙烧后的不掺钇的二氧化锆介观晶体分散于200mL 0.021mol/L的三水合硝酸铜水溶液中，然后向上述溶液中滴加0.5mol/L的氢氧化钾水溶液至终点pH = 9.0。所得产物经洗涤脱除杂质离子后于120℃干燥8小时，再于400℃焙烧4小时制得二氧化锆介晶负载氧化铜催化剂。
活性评价
以水煤气变换反应为探针反应测试催化剂的催化活性，活性评价在常压固定床反应器上进行，评价条件：原料气为模拟甲烷重整气，其体积百分含量组成为15% CO，55% H2，7% CO2，23% N2。
以CO转化率表示催化活性，对应用实施例1-3及应用对比例1-2所得催化剂的活性进行评价，其结果如表1。
由此可见，与传统二氧化锆多晶负载氧化铜催化剂及未掺钇的二氧化锆介晶负载氧化铜催化剂相比，以本发明掺钇二氧化锆介观晶体为载体制备的铜基催化剂对水煤气变换反应具有更高的催化活性，即说明本发明所制备的掺钇二氧化锆介观晶体是一种优良的催化剂载体。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (1)
1.一种掺钇二氧化锆介观晶体，其特征在于，其制备方法包括以下步骤：
（1）将硝酸钇、氧氯化锆和尿素溶解于去离子水中，室温下搅拌后制得混合溶液；
（2）将步骤（1）所得混合溶液转入高温反应釜中，控制反应温度为150℃，反应时间为24h；所得反应产物经离心分离、洗涤、干燥后得到所述掺钇二氧化锆介观晶体；
步骤（1）混合溶液中硝酸钇与氧氯化锆的物质的量浓度之和为0.75 mol/L；尿素的物质的量浓度为1.5 mol/L；硝酸钇的物质的量占硝酸钇与氧氯化锆总物质的量的2%～10%；
所述晶体形貌为橄榄状，长度为50～150 nm，直径为20～80 nm；比表面积为150～161m2/g，内部多孔，最可几孔径为2 nm。
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