CN106542576A - 一种二氧化锆介观晶体及其制备方法与应用 - Google Patents
一种二氧化锆介观晶体及其制备方法与应用 Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000013078 crystal Substances 0.000 title claims abstract description 50
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 238000000527 sonication Methods 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims 1
- 239000003245 coal Substances 0.000 claims 1
- 230000009466 transformation Effects 0.000 claims 1
- 239000002107 nanodisc Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000008187 granular material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000003643 water by type Substances 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000523 sample Substances 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 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
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-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
- WGKMWBIFNQLOKM-UHFFFAOYSA-N [O].[Cl] Chemical group [O].[Cl] WGKMWBIFNQLOKM-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 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
- 230000008569 process Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000839 emulsion Substances 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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Abstract
本发明公开了一种二氧化锆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。本发明将十六烷基三甲基溴化铵与氧氯化锆按比例溶解于水中形成混合溶液,经145~150℃水热反应5~8小时制得所述二氧化锆介观晶体。本发明制备方法简便易行,成本低,介观晶体产率高,所制得的二氧化锆介观晶体具有良好的单分散性,呈纳米圆片状,内部多孔,BET比表面积高达152~158 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制备领域,具体涉及一种二氧化锆介观晶体及其制备方法和应用。
背景技术
二氧化锆(ZrO2)具有独特的物理化学性质,它是唯一同时具有表面酸性、表面碱性、氧化性和还原性四种性能的金属氧化物,控制不同的焙烧温度可以实现其在单斜相、四方相和立方相三种晶相间的转化。这些特殊的性能使其被广泛用作催化剂载体,在很多领域中甚至表现出了优于传统的氧化硅、氧化铝等载体的催化性能。因此,以二氧化锆为载体制备的催化剂受到越来越多的关注。
介观晶体(简称介晶)是由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,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。这种有序组装结构集合了多晶和单晶的结构特点,可以同时具有高孔隙率、高比表面积、高缺陷浓度、高晶度化、特定的暴露晶面。因此,将二氧化锆制备成介观晶体结构有望大大提高以其为载体的负载型金属催化剂的性能。然而,目前尚未有二氧化锆介观晶体及其制备技术的公开报道。
发明内容
本发明的目的在于提供一种二氧化锆介观晶体及其制备方法与应用,其制备方法简便易行,产品单分散性好,BET比表面积高达152~158 m2/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:
一种二氧化锆介观晶体,其为单斜晶相,圆片状,厚度为30~50 nm,直径为100~150nm,BET比表面积为152~158 m2/g,内部多孔,最可几孔径为2~3 nm。
所述二氧化锆介观晶体的制备方法包括以下步骤:
(1)将十六烷基三甲基溴化铵、氧氯化锆溶解于去离子水中制得混合溶液;
(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145~155 ℃,反应时间为5~8 h;所得反应产物经离心分离、洗涤、干燥后得到所述二氧化锆介观晶体。
步骤(1)混合溶液中氧氯化锆的浓度为0.4~0.5 mol/L,十六烷基三甲基溴化铵与氧氯化锆的摩尔比为0~0.4:1。
所得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,将所述二氧化锆介观晶体分散于氯金酸水溶液中,然后向上述溶液中滴加碱液至溶液pH=8,所得沉淀经离心洗涤、干燥、焙烧后制得水煤气变换介晶催化剂Au/ZrO2;所用碱液为碳酸钠、碳酸钾、氢氧化钾或氢氧化钠的水溶液。
本发明首次实现了二氧化锆介观晶体的一步法可控制备。其制备过程中,氧氯化锆在水热条件下发生水解反应,通过“均匀饱和析出”机制,析出大量二氧化锆纳米晶基元,纳米晶基元在反应体系固有场(纳米晶固有偶极矩)的作用下及十六烷基三甲基溴化铵的诱导下实现晶体学取向聚集,形成多孔性二氧化锆介观晶体超结构。
本发明的显著优点在于:
(1)本方法首次制备出纳米圆片状二氧化锆介观晶体,其制备方法简便易行,所得二氧化锆介晶产率高,单分散性好,结晶性好,产物暴露晶面均一,BET比表面积高达152~158m2/g,产物颗粒内部孔道丰富,颗粒内部最可几孔径为2~3 nm。
(2)本发明所制备的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Au/ZrO2催化剂表现出优异的水煤气变换反应制氢催化性能,当Au的含量为1 wt%时,Au/ZrO2催化剂在150℃就表现出优异的催化性能,其CO转化率可达59%;反应温度为270 ℃时的CO转化率更是高达93%,接近于该反应温度下的平衡转化率,明显优于以传统多晶ZrO2为载体的Au/ZrO2催化剂,显示了该二氧化锆介观晶体作为催化剂载体的优越性。
附图说明
图1是实施例1制备的二氧化锆介观晶体的XRD图。
图2是实施例1制备的二氧化锆介观晶体的SEM图。
图3是实施例1制备的二氧化锆介观晶体的TEM图。
图4是实施例1制备的二氧化锆介观晶体的选区电子衍射(SAED)图。
图5是实施例2制备的二氧化锆介观晶体的SEM图。
图6是实施例3制备的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9.02 g 氧氯化锆溶于50 mL去离子水中,将上述溶液液用去离子水标定到70mL后转入容积为100mL的高温反应釜中(即氧氯化锆摩尔浓度为0.4 mol/L,十六烷基三甲基溴化铵与氧氯化锆的摩尔比为0:1)。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6 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ZrO2介观晶体。
图1是本实施例制备的二氧化锆介观晶体的XRD图。由图1可知,所制备的ZrO2呈单斜晶相。
图2、图3分别是本实施例制备的二氧化锆介观晶体的SEM图和TEM图。由图2和图3可知,ZrO2颗粒呈纳米圆片状且由众多小晶粒聚集而成,圆片厚度约为30~50 nm,直径约为100~150 nm。
图4是本实施例制备的二氧化锆介观晶体的选区电子衍射(SAED)图。由图4可见,单个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ZrO2为介观晶体。
N2-物理吸脱附实验表明,该ZrO2介晶的BET比表面积为152 m2/g,颗粒内部最可几孔径为2 nm。
实施例2
将4.59 g十六烷基三甲基溴化铵和10.15 g氧氯化锆溶于50 mL去离子水中制得混合溶液,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(即氧氯化锆摩尔浓度为0.45 mol/L,十六烷基三甲基溴化铵与氧氯化锆的摩尔比为0.4:1)。将反应釜放入鼓风干燥箱内,控制反应温度为145℃,反应时间为8 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ZrO2介观晶体。
图5为本实施例制备的二氧化锆介观晶体的SEM图。图5表明所制备的ZrO2颗粒同样为纳米圆片状介观晶体。
N2-物理吸脱附实验表明,该ZrO2介晶的BET比表面积为158 m2/g,颗粒内部最可几孔径为2 nm。
实施例3
将2.55 g十六烷基三甲基溴化铵和11.28 g氧氯化锆溶于50 mL去离子水中制得混合溶液,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(即氧氯化锆摩尔浓度为0.5 mol/L,十六烷基三甲基溴化铵与氧氯化锆的摩尔比为0.2:1)。将反应釜放入鼓风干燥箱内,控制反应温度为155℃,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ZrO2介观晶体。
图6为本实施例制备的二氧化锆介观晶体的SEM图。图6表明所制备的ZrO2颗粒同样为纳米圆片状介观晶体。
N2-物理吸脱附实验表明,该ZrO2介晶的BET比表面积为157 m2/g,颗粒内部最可几孔径为3 nm。
应用实施例1
以实施例1制得的ZrO2介观晶体为载体负载Au制备Au/ZrO2介晶催化剂,方法如下:首先将2 g 于350 ℃焙烧4 h的ZrO2介观晶体分散到100 mL去离子水中,超声处理10 min后转移到三口烧瓶中。将0.52 mL氯金酸溶液(0.2 mol/L)滴加入已超声分散后的ZrO2载体乳浊液中,搅拌十分钟后,开始滴加0.5 mol/L的KOH溶液,控制终点pH=8,沉淀温度为60 ℃,搅拌器转速为600 r/min。然后在60 ℃陈化1 h,并保持pH=8。陈化结束后对沉淀进行离心洗涤数次,以AgNO3检测不出Cl-为止。所得沉淀在50 ℃下干燥8 h,制得Au/ZrO2介晶催化剂。
应用实施例2
以实施例2制得的ZrO2介观晶体为载体负载Au制备Au/ZrO2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ZrO2介观晶体为载体负载Au制备Au/ZrO2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
取60 mL 0.4 mol/L的ZrOCl2·8H2O水溶液,与1 mol/L的氨水并流沉淀。控制反应条件如下:底液为100 mL去离子水,沉淀温度60 ℃,终点pH=8,陈化1 h。将沉淀物洗涤至无Cl-后,经120 ℃干燥8 h,350 ℃焙烧4 h后,制得ZrO2多晶。
将2 g ZrO2多晶研磨后分散到100 mL去离子水中,超声处理10 min后转移到三口烧瓶中。将0.52 mL氯金酸溶液(0.2 mol/L)滴加入已超声分散后的ZrO2载体乳浊液中,搅拌十分钟后,开始滴加0.5 mol/L的KOH溶液,控制终点pH=8,沉淀温度为60 ℃,搅拌器转速为600 r/min。然后在60 ℃陈化1 h,并保持pH=8。陈化结束后对沉淀进行离心洗涤数次,以AgNO3检测不出Cl-为止。所得沉淀在50 ℃下干燥8 h,制得Au/ZrO2多晶催化剂。
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和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1-3及应用对比例所得催化剂的活性评价结果
由此可见,与Au/ZrO2多晶催化剂相比,以本发明ZrO2介观晶体为载体制备的Au/ZrO2介晶催化剂对水煤气变换反应具有更高的催化活性,说明本发明所制备的ZrO2介晶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 (5)
1. 一种二氧化锆介观晶体,其特征在于,其晶相为单斜相,形貌为圆片状,厚度为30~50 nm,直径为100~150 nm,BET比表面积为152~158 m2/g,内部多孔,最可几孔径为2~3nm。
2.一种如权利要求1所述二氧化锆介观晶体的制备方法,其特征在于,包括以下步骤:
(1)将十六烷基三甲基溴化铵、氧氯化锆溶解于去离子水中制得混合溶液;
(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145~155℃,反应时间为5~8 h;所得反应产物经离心分离、洗涤、干燥后得到所述二氧化锆介观晶体。
3. 根据权利要求2所述二氧化锆介观晶体的制备方法,其特征在于,步骤(1)混合溶液中氧氯化锆的浓度为0.4~0.5 mol/L,十六烷基三甲基溴化铵与氧氯化锆的摩尔比为0~0.4:1。
4.一种如权利要求1所述的二氧化锆介观晶体的应用,其特征在于,用作载体制备水煤气变换催化剂。
5.根据权利要求4所述的二氧化锆介观晶体的应用,其特征在于,其制备方法为:在超声波破碎辅助条件下,将所述二氧化锆介观晶体分散于氯金酸水溶液中,然后向上述溶液中滴加碱液至溶液pH=8,所得沉淀经离心洗涤、干燥、焙烧后制得水煤气变换介晶催化剂Au/ZrO2。
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