CN106745238B - 一种Mg掺杂ZrO2介观晶体及其制备方法和应用 - Google Patents
一种Mg掺杂ZrO2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 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011777 magnesium Substances 0.000 claims abstract description 52
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 41
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000011148 porous material Substances 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
- 238000003756 stirring Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 208000011580 syndromic disease Diseases 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000010949 copper Substances 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
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- 238000002525 ultrasonication Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 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
- 239000002178 crystalline material Substances 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
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 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
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- 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
- B01J23/78—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 alkali- or alkaline earth metals
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Abstract
本发明公开了一种Mg掺杂ZrO2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。本发明将硝酸镁、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5h，制得所述Mg掺杂ZrO2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Mg掺杂ZrO2介观晶体具有良好的单分散性，呈类球状，直径为50～100 nm，BET比表面积高达155～164 m2/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Mg掺杂ZrO2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）是一种新型的晶体材料，它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，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。这种新型材料具有高晶化度、高孔隙度和由亚单元有序排列而成的结构特点，在催化、传感、光电器件、生物医学材料以及能源存储与转化等诸多领域有着广阔的应用前景。目前，有关功能性氧化物介晶材料的可控制备和性能研究是一个颇具挑战性的研究课题。
二氧化锆（ZrO2）是一种十分重要的功能材料，它同时具有表面酸性、碱性和氧化性、还原性，它还具有良好的热稳定性，这些性能使ZrO2成为一种很重要的催化剂材料。Mg元素常被作为助剂来调变ZrO2或含锆催化剂的物理和化学性能。由Mg助剂改性的ZrO2基催化剂在乙醇一步法合成乙酸乙酯、甲烷重整制合成气、乙醇重整制氢等反应中表现优异的催化性能。Mg掺杂的ZrO2介观晶体同样可能具有重要的潜在应用价值。然而，截止目前尚未有Mg掺杂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Mg掺杂ZrO2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Mg掺杂ZrO2介观晶体产品单分散性好，比表面积高达155～164m2/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Mg掺杂ZrO2介观晶体的制备方法，其包括以下步骤：
（1）将硝酸镁、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）所得混合溶液转入水热反应釜中，控制反应温度为150 ℃，反应时间为5 h；所得反应产物经离心洗涤、干燥后得到Mg掺杂ZrO2介观晶体。
步骤（1）混合溶液中硝酸镁与氧氯化锆的物质的量浓度之和为0.5 mol/L，硝酸镁的物质的量占硝酸镁与氧氯化锆总物质的量的5%～9%；尿素的物质的量浓度为1 mol/L。
所得Mg掺杂ZrO2介观晶体为单斜晶相，形貌为类球状，类球状直径为50～100 nm；BET比表面积为155～164 m2/g，内部多孔，最可几孔径为2 nm。
所得Mg掺杂ZrO2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Mg掺杂ZrO2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镁及氧氯化锆与尿素在水热条件下均匀沉淀反应生成氢氧化物，氢氧化物前驱物经过脱水，原子原位重排而转变为结晶态Mg掺杂ZrO2，即析出Mg掺杂ZrO2一次纳米晶粒。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Mg的ZrO2介观晶体超结构。
本发明的显著优点在于：
（1）本方法首次制备出类球状Mg掺杂ZrO2介观晶体，其制备方法简便易行，适合规模化生产，介晶产物产率高，单分散性好，结晶性好，BET比表面积高达155～164 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Mg掺杂ZrO2介观晶体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CuO质量含量为10%时，Mg掺杂ZrO2负载CuO催化剂在反应温度为270℃时的CO转化率高达86%，明显优于以传统ZrO2多晶为载体的CuO/ZrO2催化剂（270℃时的CO转化率为69%）。
附图说明
图1是实施例1制备的Mg掺杂ZrO2介观晶体的XRD图。
图2是实施例1制备的Mg掺杂ZrO2介观晶体的SEM图。
图3是实施例1制备的Mg掺杂ZrO2介观晶体的选区电子衍射（SAED）图。
图4是实施例2制备的Mg掺杂ZrO2介观晶体的SEM图。
图5是实施例3制备的Mg掺杂ZrO2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0.45 g硝酸镁，10.715 g氧氯化锆及4.20 g尿素溶于50 mL去离子水中，室温下搅拌后制得混合溶液（即硝酸镁的物质的量占硝酸镁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70 mL后转入容积为100 mL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Mg掺杂ZrO2介观晶体。
图1是本实施例制备的Mg掺杂ZrO2介观晶体的XRD图。由图1可知，所制备的Mg掺杂ZrO2呈单斜晶相。
图2是本实施例制备的Mg掺杂ZrO2介观晶体的SEM图。由图2可知，Mg掺杂ZrO2颗粒呈类球状，类球状颗粒的直径为50～100 nm。
图3是本实施例制备的Mg掺杂ZrO2介观晶体的选区电子衍射（SAED）图。由图3可见单个Mg掺杂ZrO2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Mg掺杂ZrO2为介观晶体。
N2-物理吸脱附实验表明，该Mg掺杂ZrO2介晶的BET比表面积为155 m2/g，颗粒内部最可几孔径为2 nm。
实施例2
将0.63 g硝酸镁，10.49 g氧氯化锆及4.20 g尿素溶于50 mL去离子水中，室温下搅拌后制得混合溶液（即硝酸镁的物质的量占硝酸镁与氧氯化锆总物质的量的7%），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。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Mg掺杂ZrO2介观晶体。
图4是本实施例制备的Mg掺杂ZrO2介观晶体的SEM图。图4表明，所制备的Mg掺杂ZrO2颗粒同样为类球状介观晶体，其直径为50～100 nm。
N2-物理吸脱附实验表明，该Mg掺杂ZrO2介晶的BET比表面积为159 m2/g，颗粒内部最可几孔径为2 nm。
实施例3
将0.82 g硝酸镁，10.264 g氧氯化锆及4.20 g尿素溶于50 mL去离子水中，室温下搅拌后制得混合溶液（即硝酸镁的物质的量占硝酸镁与氧氯化锆总物质的量的9%），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。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Mg掺杂ZrO2介观晶体。
图5是本实施例制备的Mg掺杂ZrO2介观晶体的SEM图。图5表明，所制备的Mg掺杂ZrO2颗粒同样为类球状介观晶体，其直径为50～100 nm。
N2-物理吸脱附实验表明，该Mg掺杂ZrO2介晶的BET比表面积为164 m2/g，颗粒内部最可几孔径为2 nm。
应用实施例：Mg掺杂ZrO2介晶负载CuO催化剂
以实施例1制得的Mg掺杂ZrO2介观晶体为载体负载CuO后制得Cu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Mg掺杂ZrO2介观晶体分散于200 mL0.021 mol/L的三水合硝酸铜水溶液中，然后向上述溶液中滴加0.5 mol/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 h，再于400℃焙烧4 h制得Mg掺杂ZrO2介晶负载CuO催化剂。
应用对比例：ZrO2多晶负载CuO催化剂
将7.85 g氧氯化锆溶解于200 mL去离子水中制得反应底液，将0.5 mol/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 h，再于250℃焙烧4 h制得ZrO2多晶。
在超声破碎的辅助下将3g ZrO2多晶分散于200 mL 0.021 mol/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 h，再于400℃焙烧4 h制得ZrO2多晶负载CuO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，对应用实施例及应用对比例所得催化剂的活性进行评价，其结果如表1。
表1 应用实施例及应用对比例所得催化剂的活性评价结果
由此可见，与传统ZrO2多晶负载CuO催化剂相比，以本发明Mg掺杂ZrO2介观晶体为载体制备的负载CuO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Mg掺杂ZrO2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Mg掺杂ZrO2介观晶体的制备方法，其特征在于：包括以下步骤：
（1）将硝酸镁、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）所得混合溶液转入水热反应釜中，控制反应温度为150 ℃，反应时间为5h；所得反应产物经离心洗涤、干燥后得到所述Mg掺杂ZrO2介观晶体;
步骤（1）混合溶液中硝酸镁与氧氯化锆的物质的量浓度之和为0.5 mol/L；硝酸镁的物质的量占硝酸镁与氧氯化锆总物质的量的5%～9%；尿素的物质的量浓度为1 mol/L;
所得Mg掺杂ZrO2介观晶体，形貌为类球状，直径为50～100 nm；BET比表面积为155～164m2/g，内部多孔，最可几孔径为2 nm。
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