CN108483482A - 一种钴负载铝酸锌纳米粉体及其制备方法 - Google Patents
一种钴负载铝酸锌纳米粉体及其制备方法 Download PDFInfo
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- 239000011701 zinc Substances 0.000 title claims abstract description 73
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 69
- -1 zinc aluminate Chemical class 0.000 title claims abstract description 68
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000010941 cobalt Substances 0.000 title claims abstract description 54
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 54
- 239000011858 nanopowder Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 63
- 150000001868 cobalt Chemical class 0.000 claims abstract description 29
- 239000012266 salt solution Substances 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 23
- 238000013019 agitation Methods 0.000 claims description 19
- 239000000047 product Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 159000000013 aluminium salts Chemical class 0.000 claims description 13
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 13
- 150000003751 zinc Chemical class 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 229910001676 gahnite Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 claims 1
- DCAYPVUWAIABOU-UHFFFAOYSA-N alpha-n-hexadecene Natural products CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 1
- 239000006227 byproduct Substances 0.000 claims 1
- DCAYPVUWAIABOU-NJFSPNSNSA-N hexadecane Chemical group CCCCCCCCCCCCCCC[14CH3] DCAYPVUWAIABOU-NJFSPNSNSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 abstract description 6
- 238000001802 infusion Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 229910052596 spinel Inorganic materials 0.000 abstract description 3
- 239000011029 spinel Substances 0.000 abstract description 3
- 239000011540 sensing material Substances 0.000 abstract 1
- 235000013495 cobalt Nutrition 0.000 description 40
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 27
- 206010001497 Agitation Diseases 0.000 description 16
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 9
- 206010013786 Dry skin Diseases 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- 239000012456 homogeneous solution Substances 0.000 description 6
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
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- 210000000481 breast Anatomy 0.000 description 3
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- 230000005284 excitation Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- JPWJUWBXBXDIKJ-UHFFFAOYSA-N [Co++].[Co++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Co++].[Co++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JPWJUWBXBXDIKJ-UHFFFAOYSA-N 0.000 description 1
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 235000020280 flat white Nutrition 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- 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
- B01J23/80—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 zinc, cadmium or mercury
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/641—Chalcogenides
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- H01S3/00—Lasers, i.e. devices using stimulated emission of electromagnetic radiation in the infrared, visible or ultraviolet wave range
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Abstract
本发明公开一种钴负载铝酸锌纳米粉体及其制备方法,本发明采用表面活性剂辅助的水热法制备铝酸锌粉末,并用超声波辅助湿法浸渍法将铝酸锌粉末浸渍到钴盐溶液中,经陈化、干燥、焙烧,即可制备出钴负载铝酸锌纳米粉体;本发明的钴负载铝酸锌尖晶石纳米粉体,其纳米颗粒尺寸为20~200nm,表面存在Co3+离子,尖晶石型钴负载铝酸锌粉体是一种新型的催化剂、发光、湿敏传感材料。
Description
技术领域
本发明涉及一种钴负载铝酸锌纳米粉体及其制备方法,属于粉体材料制备技术领域。
背景技术
铝酸锌具有良好的物理性能和化学性能,如化学稳定性好,耐磨、耐腐蚀、热膨胀系数小,同时具有良好的力学性能,热振稳定性以及抗辐射性能等。可应用于催化剂、催化剂载体、耐火材料、光学材料和湿敏传感器等领域。
在铝酸锌粉体制备方法中,水热法是一种制备纳米粉体的常用方法。传统的水热法是将有机或无机化合物经过溶液、水热反应、干燥,焙烧等工艺程序而制备铝酸锌的一种方法。水热反应过程是基于金属盐的水解为离子、分子团在一定温度、压力下成核结晶的过程。因此去离子水的加入量、有机活性剂、温度、压力的控制对成核-结晶过程以及粉体的粒径和形貌有着至关重要的影响,并最终影响铝酸锌粉末的性能。除此之外,这种方法还有以下缺点:所需原材料种类较多,影响水热反应过程的因素较多不易有效控制,因而所制备粉体的粒径和形貌较难以有效控制。
在负载纳米粉体的制备方法中,湿法浸渍是一种常用的方法。传统的湿法浸渍操作简单,但存在负载金属在载体上分布不均匀、负载物与载体结合度较差的问题。
发明内容
本发明的目的在于提供一种钴负载铝酸锌纳米粉体及其制备方法,该纳米粉体以锌盐、铝盐、钴盐为原料,采用表面活性剂十六烷基三甲基溴化铵(CTAB)辅助水热法制备ZnAl2O4粉体,得到的ZnAl2O4粉体置于钴盐溶液中经磁力搅拌、超声辅助湿法浸渍、干燥、烧结,即可得到钴负载铝酸锌纳米粉体;本发明钴负载铝酸锌纳米粉体能够改善由于钴负载不均匀和负载物和载体结合强度不高的问题,纳米粉体的粒径为20nm~200nm,形貌为球粒状。
本发明提供钴负载铝酸锌纳米粉体,该纳米粉体以锌盐、铝盐、钴盐为原料并加入表面活性剂制备得到,纳米粉体颗粒尺寸为20~200nm,纳米粉体表面钴主要以Co3+离子形式存在。
所述锌盐为硝酸锌、醋酸锌或氯化锌,所述铝盐为硝酸铝、醋酸铝或氯化铝,所述钴盐为硝酸钴、乙酸钴或氯化钴。
所述表面活性剂为十六烷基三甲基溴化铵(CTAB)。
本发明还提供所述钴负载铝酸锌纳米粉体的制备方法,具体包括以下步骤:
(1)采用新型的表面活性剂十六烷基三甲基溴化铵(CTAB)辅助的水热法,将锌盐、铝盐和表面活性剂按比例溶于去离子水中,调节溶液的pH值,使pH值为7~10;
(2)将步骤(1)中调节完pH值的溶液在室温下磁力搅拌4~8小时,得到均匀白色粘稠状乳浊液,将此乳浊液置于反应釜中,200~220℃保温8~10小时得到白色沉淀,用乙醇和去离子水反复洗涤5~7次,将洗涤后的产物置于干燥箱内,80~120℃干燥6~10小时,将干燥后的产物球磨成均匀粉末,放入马弗炉中于700~900℃下焙烧4~6小时,得到ZnAl2O4粉末样品;
(3)将1g步骤(2)所得到的ZnAl2O4粉末样品置于50mL钴盐溶液中,室温下充分磁力搅拌2~4小时后,超声波条件下超声浸渍1~3小时,室温陈化,随后在80~100℃下磁力搅拌直至溶液蒸发,将蒸发后所得产物置于干燥箱内80~100℃干燥4~6小时,取出产物,球磨成均匀粉末,在马弗炉中600~800℃焙烧4~6小时,研磨得到钴负载铝酸锌纳米粉体。
步骤(1)采用NaOH溶液、KOH溶液或浓氨水调节pH值。
步骤(1)所述锌盐、铝盐、表面活性剂和去离子水的摩尔比为1:2:0.5~1:450~625。
步骤(3)所述钴盐溶液的摩尔浓度为0.065mol/L~0.969mol/L。
步骤(3)所述的超声波频率为30~50Hz。
步骤(3)所述的陈化时间为10~15小时。
本发明使用表面活性剂十六烷基三甲基溴化铵(CTAB)辅助水热法制备尖晶石钴负载铝酸锌纳米粉体;采用廉价易得的锌盐、铝盐、钴盐、表面活性剂、溶剂(去离子水)进行制备,优点包括其一,金属前驱体离子可以在表面活性剂CTAB上成核成结晶,使晶粒自发生长为均匀球粒状;其二,大部分CTAB可在去离子水和乙醇洗涤过程中去除,另外残留的CTAB也可在焙烧时,转变为气体排出,无残留;其三,操作流程简单可靠,反应过程可控性高,其四,钴在铝酸锌粉体表面形成尖晶石型四氧化三钴,由于其相同的晶体结构,铝酸锌粉体与负载钴有良好的结合度。
本发明采用CTAB作为表面活性剂,将CTAB溶解在去离子水中,混合均匀,调节溶液使pH值,磁力搅拌,得到白色粘稠状的乳浊液,这是CTAB辅助水热法的关键所在;在磁力搅拌下,金属离子前驱体充分扩散并在CTAB上成核,有利前驱体金属离子和原子团的均匀混合,之后在恒温不加压水热条件下自发在CTAB上结晶,得到均匀的球型纳米颗粒,该方法可更加有效的控制形成颗粒的粒径,使得制备的粉体粒径更均匀、细小、弥散。
本发明湿法浸渍过程为均匀磁力搅拌,超声条件下浸渍,磁力搅拌使铝酸锌纳米粉体和钴盐溶液充分接触,超声波条件下,溶液中的钴离子运动加速,使其能更充分负载铝酸粉体上,同时改善钴负载不均匀的问题。
本发明的有益效果:
(1)本发明所述方法更加有效的控制形成颗粒的粒径,使得制备的粉体粒径更均匀,细致,有利前驱体金属离子和原子团的均匀混合。
(2)本发明制备的钴负载铝酸锌纳米粉体,所制备粉体颗粒细小、弥散、均匀,钴均匀负载铝酸锌粉体上。
(3)本发明制备的钴负载铝酸锌纳米粉体,铝酸锌粉体表面被四氧化三钴包覆,钴与铝酸锌的结合强度高。
(4)本发明钴负载铝酸锌纳米粉体,钴负载铝酸锌粉体表面钴主要以Co3+离子存在,可应用于催化剂、发光材料、湿敏传感器等领域。
(5)本发明所述方法中钴负载铝酸锌纳米粉体在283nm的紫外光激发下,在波长为350nm(UV-A)、470nm(蓝光区)和685nm(红光区)可实现发射峰强度的调节,该方法合成的钴负载铝酸锌纳米粉体可用于制备固体激光器件。
附图说明
图1为实施例1不同浓度钴盐溶液制备得到的钴负载铝酸锌粉体的XRD图;
图2为实施例1浓度为0.323mol/L和0.969mol/L钴盐溶液制备得到的钴负载铝酸锌粉体的XPS 图;
图3为实施例1步骤(2)所制备的铝酸锌纳米粉体的SEM图;
图4为实施例1不同浓度钴盐溶液制备得到的钴负载铝酸锌粉体的SEM图;
图5为实施例1不同浓度钴盐溶液制备得到的钴负载铝酸锌粉体的发射光谱图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容。
实施例1
本实施例以Zn(NO3)2·6H2O、Al(NO3)3·8H2O、Co(NO3)2·6H2O和十六烷基三甲基溴化铵(CTAB)制备得到,具体制备步骤如下:
(1)按锌盐、铝盐、表面活性剂和去离子水的摩尔比为1:2:1:625的比例,称取 Zn(NO3)2·6H2O、Al(NO3)3·8H2O和表面活性剂十六烷基三甲基溴化铵(CTAB)溶于去离子水中,在室温下磁力搅拌得到均匀溶液,将浓度为4mol/L 的NaOH溶液滴加到均匀溶液中,使pH值为9;
(2)将步骤(1)中调节完pH值的溶液在室温条件下磁力搅拌4小时,得到白色粘稠状乳浊液,将白色粘稠状乳浊液置于反应釜内,220℃恒温8小时,取出产物,用乙醇和去离子水反复洗涤5次,得到白色沉淀,将得到的白色沉淀置于干燥箱内80℃干燥10小时,将干燥后的产物球磨至均匀粉末,将均匀粉末置于马弗炉中900℃焙烧6小时,取出粉末,再次球磨至粉末均匀,得到铝酸锌粉体;
(3)取1g步骤(2)得到的铝酸锌粉末浸渍于50mL浓度为0.065mol/L的硝酸钴溶液中,然后在室温下磁力搅拌4小时,超声条件下浸渍3小时,超声波频率为40Hz,随后室温陈化13小时,之后80℃磁力搅拌直至溶液蒸发,将蒸发后所得产物放入干燥箱内90℃干燥5小时,取出产物,球磨2小时成均匀粉末,置于马弗炉内800℃焙烧6小时,研磨得到钴负载的铝酸锌粉体。
在相同的制备条件下,取同质量步骤(2)制备的铝酸锌粉末浸渍于浓度分别为0.323mol/L、0.646mol/L、0.969mol/L的50mL硝酸钴溶液中,制备得到不同浓度钴盐溶液浸渍的钴负载铝酸锌粉体,钴盐溶液浓度越高制备得到的钴负载铝酸锌粉体其钴负载量越高。
图1为实施例1中,不同浓度钴盐溶液制备得到的钴负载铝酸锌粉体的XRD图,从图1可看出,钴负载铝酸锌粉体已经形成了尖晶石结构,无其他杂相,随着钴盐溶液浓度的增加,衍射峰强度降低,表明钴形成尖晶石型四氧化三钴,其包覆铝酸锌粉体表面,此外,XRD半高宽较宽。
图2为实施例1中,浓度0.323mol/L和0.969mol/L的硝酸钴溶液制备得到的铝酸锌粉体的XPS图,可看出,钴主要以Co3+离子形式存在,随着浸渍钴盐溶液浓度的逐渐增大,表面Co3+离子含量增加;同时,Co3O4逐渐包覆铝酸锌粉体,此结论与图1相同。
图3为实施例1中,步骤(2)制备得到的铝酸锌粉体的SEM图,从图2可看出,铝酸锌粉体为均匀球状颗粒、细小弥散,颗粒尺寸约为12nm。
图4为实施例1中,不同浓度钴盐溶液制备得到的钴负载量的铝酸锌粉体的SEM图,从图4可看出,随着浸渍钴盐溶液浓度的增加,粉末颗粒的尺寸增加,在钴盐溶液浓度为0.065mol/L~0.646mol/L时,该粉体为均匀球状颗粒,细小弥散分布,颗粒尺寸为20~50nm,在用0.969mol/L的钴硝酸钴溶液浸渍时,纳米颗粒由球形转变为不规则的多边形,颗粒尺寸约为200nm。
图5为实施例1中,不同浓度钴盐溶液制备得到的钴负载铝酸锌粉体,在波长为283nm的紫外光激发下,在波长为350nm(UV-A)、470nm (蓝光区)和685nm(红光区)有发射峰,发射峰的强度随着浸渍钴盐溶液的浓度增加而降低。
实施例2
本实施例以ZnCl2、AlCl3、CoCl2·6H2O和十六烷基三甲基溴化铵(CTAB)制备得到,具体制备步骤如下:
(1)按锌盐、铝盐、表面活性剂和去离子水的摩尔比为1:2: 0.8: 600的比例,称取ZnCl2、AlCl3和表面活性剂十六烷基三甲基溴化铵(CTAB)溶于去离子水中,在室温下搅拌得到均匀溶液,将浓度为3mol/L 的KOH溶液滴加到均匀溶液中,使溶液pH值为8;
(2)将步骤(1)中调节完pH值的溶液在室温条件下磁力搅拌5小时,得到白色粘稠状乳浊液,将白色粘稠状乳浊液置于反应釜内,200℃恒温10小时,取出产物,用乙醇和去离子水反复洗涤6次,得到白色沉淀,将得到的白色沉淀置于干燥箱内120℃干燥6小时,将干燥后的产物球磨至均匀粉末,将均匀粉末置于马弗炉中800℃焙烧4小时,取出粉末,再次球磨至粉末均匀,得到铝酸锌粉体;
(3)取1g步骤(2)得到的铝酸锌粉末浸渍于50mL浓度为0.323mol/L氯化钴溶液中,然后在室温下磁力搅拌3小时,超声条件下浸渍2小时,超声波频率为30Hz,随后室温陈化10小时,之后90℃磁力搅拌直至溶液蒸发,将蒸发后所得产物放入干燥箱内80℃干燥6小时,取出产物,球磨2小时成均匀粉末,置于马弗炉内750℃焙烧4小时,研磨得到钴负载铝酸锌粉体。
实施例3
本实施例以Zn (CH3COO)2·2H2O、Al (CH3COO)3、C4H6O4Co·4(H2O)和十六烷基三甲基溴化铵(CTAB)制备得到,具体制备步骤如下:
(1)按锌盐、铝盐、表面活性剂和去离子水的摩尔比为1:2:0.5:450的比例,称取 Zn(CH3COO)2·2H2O、Al (CH3COO)3、表面活性剂十六烷基三甲基溴化铵(CTAB)溶于去离子水中,在室温下搅拌得到均匀溶液,将浓氨水滴加到均匀溶液中,使溶液pH值为7;
(2)将步骤(1)中调节完pH值的溶液在室温条件下磁力搅拌8小时,得到白色粘稠状乳浊液,将白色粘稠状乳浊液置于反应釜内,210℃恒温9小时,取出产物,用乙醇和去离子水反复洗涤7次,得到白色沉淀,将得到的白色沉淀置于干燥箱内100℃干燥8小时,将干燥后的产物球磨至均匀粉末,将均匀粉末置于马弗炉中700℃焙烧5小时,取出粉末,再次球磨至粉末均匀,得到铝酸锌粉体;
(3)取1g步骤(2)得到的铝酸锌粉末浸渍于50mL浓度为0.969mol/L乙酸钴溶液中,然后在室温下磁力搅拌2小时,超声条件下浸渍1小时,超声波频率为50Hz,随后室温陈化15小时,之后100℃磁力搅拌直至溶液蒸发,将蒸发后所得产物放入干燥箱内100℃干燥4小时,取出产物,球磨2小时成均匀粉末,置于马弗炉内600℃焙烧5.5小时,研磨得到钴负载铝酸锌。
本发明提供的制备方法制备出了表面富含活性Co3+、颗粒均匀细小分散的钴负载铝酸锌粉体,当钴盐溶液的浓度小于0.323mol/L时,钴弥散分布在铝酸锌表面;当钴盐溶液的浓度为0.323mol/L~0.969mol/L时,尖晶石相四氧化三钴形成并逐渐包裹铝酸锌纳米颗粒,同时钴负载铝酸锌纳米粉体在283nm的紫外光激发下,350nm(UV-A)470nm(蓝光区)和685nm(红光区)可实现发射峰强度的调节,表明本发明提供的改进方法是有效的,鉴于此,尖晶石型钴负载铝酸锌粉体可用于制备新型潜在催化剂、固体激光器件、湿敏传感器。
Claims (9)
1.一种钴负载铝酸锌纳米粉体,其特征在于,该纳米粉体以锌盐、铝盐、钴盐为原料并加入表面活性剂制备得到,纳米粉体颗粒尺寸为20~200nm,纳米粉体表面存在Co3+离子。
2.根据权利要求1所述钴负载铝酸锌纳米粉体,其特征在于,所述锌盐为硝酸锌、醋酸锌或氯化锌,所述铝盐为硝酸铝、醋酸铝或氯化铝,所述钴盐为硝酸钴、乙酸钴或氯化钴。
3.根据权利要求1所述钴负载铝酸锌纳米粉体,其特征在于,所述表面活性剂为十六烷基三甲基溴化铵。
4.权利要求1所述钴负载铝酸锌纳米粉体的制备方法,其特征在于,具体包括以下步骤:
(1)将锌盐、铝盐和表面活性剂按比例溶于去离子水中,调节溶液的pH值,使pH值为7~10;
(2)将步骤(1)中调节完pH值的溶液置于室温下,磁力搅拌4~8小时,之后将混合液置于反应釜内,在200~220℃保温8~10小时得到白色沉淀,将所得沉淀用乙醇和去离子水反复洗涤5~7次,将洗涤后的产物在80~120℃干燥6~10小时,将干燥后的产物球磨成均匀粉末,在700~900℃下焙烧4~6小时,得到ZnAl2O4纳米粉末;
(3)将1g步骤(2)所得到的ZnAl2O4纳米粉末样品置于50mL钴盐溶液中,室温下磁力搅拌2~4小时后,超声波条件下超声浸渍1~3小时,随后室温陈化,在80~100℃下磁力搅拌直至溶液蒸发,将蒸发后所得产物,在80~100℃干燥4~6小时,取出产物,球磨成均匀粉末,在600~800℃焙烧4~6小时,研磨得到钴负载铝酸锌纳米粉体。
5.根据权利要求4所述钴负载铝酸锌纳米粉体的制备方法,其特征在于,步骤(1)所述锌盐、铝盐、表面活性剂和去离子水的摩尔比为1:2:0.5~1:450~625。
6.根据权利要求4所述钴负载铝酸锌纳米粉体的制备方法,其特征在于,步骤(1)采用NaOH溶液、KOH溶液或浓氨水调节pH值。
7.根据权利要求4所述钴负载铝酸锌纳米粉体的制备方法,其特征在于,步骤(3)所述钴盐溶液的浓度为0.065mol/L~0.969mol/L。
8.根据权利要求4所述钴负载铝酸锌纳米粉体的制备方法,其特征在于,步骤(3)所述的超声波频率为30~50Hz。
9.根据权利要求4所述钴负载铝酸锌纳米粉体的制备方法,其特征在于,步骤(3)所述的陈化时间为10~15小时。
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