CN106517298A - 一种CeO2介观晶体及其制备方法与应用 - Google Patents
一种CeO2介观晶体及其制备方法与应用 Download PDFInfo
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims description 47
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 230000002776 aggregation Effects 0.000 claims description 3
- 238000004220 aggregation Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000006259 organic additive Substances 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 abstract 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000008204 material by function Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 239000013598 vector Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 9
- 239000008187 granular material Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 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 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 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 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- FZIZEIAMIREUTN-UHFFFAOYSA-N azane;cerium(3+) Chemical compound N.[Ce+3] FZIZEIAMIREUTN-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 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
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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Abstract
本发明公开了一种CeO2介观晶体及其制备方法与应用，属于金属氧化物功能材料制备领域。本发明将硝酸铈铵、硝酸铵、可溶性硫酸盐按比例溶解于水中形成混合溶液，经150~200℃水热反应5～72 h制得所述CeO2介观晶体。本发明制备方法简便易行，成本低，无需添加有机添加剂，绿色环保。所制得的CeO2介观晶体具有良好的单分散性，呈球状，内部多孔，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制备领域，具体涉及一种CeO2介观晶体及其制备方法与应用。
背景技术
二氧化铈（CeO2）是一种廉价的轻稀土氧化物，其具有优良的储氧能力（OSC）、Ce3+与Ce4+之间的快速变换能力，以及比较多的氧空位（Oxygen Vacancy）等优点，广泛作为载体或者助剂用于制备催化剂，如汽车尾气净化催化剂。
介观晶体（简称介晶）是一种不同于传统多晶和单晶的新型晶体，一般是由纳米晶按照一定的取向自组装形成具有超结构的晶体，其内部通常存在大量堆积孔并可以显示类单晶的电子衍射行为。介观晶体作为一种新的晶体形式，有望取代单晶和多晶在催化、能量储存和转换以及传感器等领域得到广泛应用。目前，已报到的介观晶体的制备方法多需要引入有机添加剂，不但成本昂贵，还会污染环境。
发明内容
本发明的目的在于提供一种CeO2介观晶体及其制备方法与应用，其制备方法简便易行，绿色环保，无需引入有机添加剂，产品单分散性好，内部孔道丰富，是一种良好的催化剂材料，可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CeO2介观晶体的制备方法，其特征在于，包括以下步骤：
（1）将硝酸铈铵、硝酸铵、可溶性硫酸盐溶解于去离子水中制得混合溶液；
（2）将步骤（1）的混合溶液转入高温反应釜中，控制反应温度为150~200℃，反应时间为5～72 h；所得反应产物经离心洗涤、干燥后得到所述CeO2介观晶体。
步骤（1）混合溶液中硝酸铈铵的浓度为0.2 mol/L；硝酸铈铵与硝酸铵、可溶性硫酸盐的摩尔比为1:0~0.2:3。所述可溶性硫酸盐为硫酸钠、硫酸钾或硫酸铵。
所得CeO2介观晶体为球状，直径为100～600 nm，由小晶粒取向聚集而成；可用作载体制备水煤气变换催化剂，其制备方法为：将所述CeO2介观晶体分散于Cu(NO3)2·3H2O水溶液中，然后向其中滴加碱液至溶液pH=9，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，硝酸铈铵在水热条件下发生水解反应，通过“均匀饱和析出”机制，析出大量CeO2纳米晶基元，纳米晶基元在硫酸盐的诱导作用下实现晶体学取向聚集，形成多孔性CeO2介观晶体超结构。
本发明的显著优点在于：
（1）本发明在不添加任何有机添加剂的条件下制备出纳米球状CeO2介观晶体，其制备方法简便易行，绿色环保，适合规模化生产。且所得CeO2介晶产率高，单分散性好，结晶性好，产物颗粒内部孔道丰富。
（2）本发明所制备的CeO2介观晶体是一种优良的水煤气变换催化剂载体，以其为载体制备的CuO/CeO2催化剂表现出优异的水煤气变换反应催化性能，当CuO含量为10 wt%时，CuO/CeO2催化剂在250 ℃时的CO转化率高达85%。
附图说明
图1是实施例1制备的CeO2介观晶体的XRD图。
图2是实施例1制备的CeO2介观晶体的SEM图。
图3是实施例1制备的CeO2介观晶体的HRTEM图。
图4是实施例1制备的CeO2介观晶体的选区电子衍射（SAED）图。
图5是实施例2制备的CeO2介观晶体的SEM图。
图6是实施例3制备的CeO2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7.68 g硝酸铈铵和5.97 g硫酸钠溶于50 mL去离子水中，将上述混合液用去离子水标定到70 mL后转入容积为100 mL的高温反应釜中（即硝酸铈铵摩尔浓度为0.2 mol/L，硝酸铈铵与硫酸钠的摩尔比为1:3）。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5 h。所得产物经离心洗涤脱除杂质离子后于60℃干燥8 h，得到CeO2介观晶体。
图1是本实施例制备的CeO2介观晶体的XRD图。由图1可知，本实施例所制备的产品为纯CeO2。
图2是本实施例制备的CeO2介观晶体的SEM图。由图2可知，CeO2颗粒呈纳米球状，球体直径约为100～200 nm，具有良好的单分散性。
图3是本实施例制备的CeO2介观晶体的HRTEM图。由图3可知，球状CeO2颗粒由众多CeO2小晶粒取向聚集而成，即其颗粒内部一次晶粒间的晶格高度匹配，且颗粒内部布满孔道。
图4是本实施例制备的CeO2介观晶体的选区电子衍射（SAED）图。由图4可见，单个CeO2颗粒呈现类单晶电子衍射行为，表明所得CeO2为介观晶体。
实施例2
将7.68 g硝酸铈铵、0.11 g硝酸铵、7.32 g硫酸钾溶于50 mL去离子水中，将上述混合液用去离子水标定到70 mL后转入容积为100 mL的高温反应釜中（即硝酸铈铵摩尔浓度为0.2 mol/L，硝酸铈铵、硝酸铵与硫酸钾的摩尔比为1:0.1:3）。将反应釜放入鼓风干燥箱内，控制反应温度为170℃，反应时间为24 h。所得产物经离心洗涤脱除杂质离子后于60℃干燥8 h，得到CeO2介观晶体。
图5是本实施例制备的CeO2介观晶体的SEM图。从图5可见，所制备的CeO2颗粒同样为纳米球状介观晶体，球体直径约为300～600 nm。
实施例3
将7.68 g硝酸铈铵、0.22 g硝酸铵、5.55 g硫酸铵溶于50 mL去离子水中，将上述混合液用去离子水标定到70 mL后转入容积为100 mL的高温反应釜中（即硝酸铈铵摩尔浓度为0.2 mol/L，硝酸铈铵、硝酸铵与硫酸铵的摩尔比为1:0.2:3）。将反应釜放入鼓风干燥箱内，控制反应温度为200℃，反应时间为72 h。所得产物经离心洗涤脱除杂质离子后于60℃干燥8 h，得到CeO2介观晶体。
图6是本实施例制备的CeO2介观晶体的SEM图。从图6可见，所制备的CeO2颗粒同样为纳米球状介观晶体，球体直径约为200～600 nm。
应用实施例1
以实施例1制得的CeO2介观晶体为载体负载CuO制备CuO/CeO2介晶催化剂，方法如下：在超声波破碎的辅助下将3g 250℃焙烧后的CeO2介观晶体分散于200 mL 0.021 mol/L的Cu(NO3)2·3H2O水溶液中，然后向上述溶液中滴加0.5 mol/L的KOH水溶液至终点pH=9。所得产物经洗涤脱除杂质离子后于120℃干燥8 h，再于400℃焙烧4 h制得CuO/CeO2介晶催化剂。
应用实施例2
以实施例2制得的CeO2介观晶体为载体负载CuO制备CuO/CeO2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CeO2介观晶体为载体负载CuO制备CuO/CeO2介晶催化剂，其制备方法和条件与应用实施例1相同。
活性评价
以水煤气变换反应为探针反应测试所得催化剂的催化活性，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所得催化剂的活性进行评价，其结果如表1。
表1 应用实施例1-3所得催化剂的活性评价结果
由表1可见，本发明以CeO2介观晶体为载体制备的CuO/CeO2介晶催化剂对水煤气变换反应具有较高催化活性。
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 (6)
1.一种CeO2介观晶体的制备方法，其特征在于，包括以下步骤：
（1）将硝酸铈铵、硝酸铵、可溶性硫酸盐溶解于去离子水中制得混合溶液；
（2）将步骤（1）的混合溶液转入高温反应釜中，控制反应温度为150~200℃，反应时间为5～72 h；所得反应产物经离心洗涤、干燥后得到所述CeO2介观晶体。
2. 根据权利要求1所述的CeO2介观晶体的制备方法，其特征在于，步骤（1）混合溶液中硝酸铈铵的浓度为0.2 mol/L；硝酸铈铵与硝酸铵、可溶性硫酸盐的摩尔比为1:0~0.2:3。
3.根据权利要求1所述的CeO2介观晶体的制备方法，其特征在于，所述可溶性硫酸盐为硫酸钠、硫酸钾或硫酸铵。
4. 一种如权利要求1所述方法制得的CeO2介观晶体，其特征在于，其形貌为球状，直径为100～600 nm，由小晶粒取向聚集而成。
5.一种如权利要求4所述CeO2介观晶体的应用，其特征在于，用作载体制备水煤气变换催化剂。
6.根据权利要求5所述CeO2介观晶体的应用，其特征在于，其制备方法为：将所述CeO2介观晶体分散于Cu(NO3)2·3H2O水溶液中，然后向其中滴加碱液至溶液pH=9，所得沉淀经离心洗涤、干燥、焙烧后制得水煤气变换催化剂。
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