CN107867725A - 一种钴酸铜镍纳米线的制备方法及其在催化氨硼烷水解产氢上的应用 - Google Patents
一种钴酸铜镍纳米线的制备方法及其在催化氨硼烷水解产氢上的应用 Download PDFInfo
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- CN107867725A CN107867725A CN201711266886.4A CN201711266886A CN107867725A CN 107867725 A CN107867725 A CN 107867725A CN 201711266886 A CN201711266886 A CN 201711266886A CN 107867725 A CN107867725 A CN 107867725A
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- Prior art keywords
- nickel
- cobalt
- solution
- preparation
- nano wire
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 26
- 239000010941 cobalt Substances 0.000 title claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000002253 acid Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 12
- 239000001257 hydrogen Substances 0.000 title claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 10
- 230000007062 hydrolysis Effects 0.000 title claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 title claims description 7
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 title claims description 6
- 238000006555 catalytic reaction Methods 0.000 title description 6
- 239000010949 copper Substances 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 150000001868 cobalt Chemical class 0.000 claims abstract description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 3
- 239000012498 ultrapure water Substances 0.000 claims abstract description 3
- 239000003643 water by type Substances 0.000 claims abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims 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 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 69
- 238000000034 method Methods 0.000 abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 239000004312 hexamethylene tetramine Substances 0.000 abstract description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract description 2
- 150000004692 metal hydroxides Chemical class 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000002070 nanowire Substances 0.000 description 17
- 238000013019 agitation Methods 0.000 description 14
- 230000008859 change Effects 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 7
- 229910005949 NiCo2O4 Inorganic materials 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 229940011182 cobalt acetate Drugs 0.000 description 7
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 7
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 229910003266 NiCo Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000000053 physical method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910016506 CuCo2O4 Inorganic materials 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000257465 Echinoidea Species 0.000 description 1
- 229910003203 NH3BH3 Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
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- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Classifications
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- C01G51/40—Cobaltates
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- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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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
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- H01F1/0036—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity
- H01F1/0072—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties showing low dimensional magnetism, i.e. spin rearrangements due to a restriction of dimensions, e.g. showing giant magnetoresistivity one dimensional, i.e. linear or dendritic nanostructures
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P2006/00—Physical properties of inorganic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
本发明提供了一种钴酸铜镍纳米线的制备方法,包括以下步骤:(1)、将可溶性镍盐、钴盐、铜盐溶于超纯水中,配置成混合盐溶液A;(2)、将1~4mmol十二烷基硫酸钠加入A溶液搅拌溶解;(3)、将12~30mmol六次甲基四胺溶于20mL超纯水形成B溶液;(4)、将B溶液通过分液漏斗缓慢滴加至A溶液混合形成C溶液,搅拌0~1h;(5)、再转移至100mL反应釜,100~160℃反应8~20h,抽滤洗涤,在真空烘箱40~60℃下烘干,再在马弗炉中350~800℃反应1~4h。本发明采用水热合成法,首先将原料按一定比例混合,六次甲基四胺作为沉淀剂生成多元金属氢氧化物,再经煅烧合成钴酸盐,此过程有效实现了原料中设定镍钴铜配比,整个制备过程操作简单,环境友好,实验重现性非常好,成本低、易于工业化生产,可规模化生产CuxNi1‑xCo2O4复合钴酸盐。
Description
技术领域
本发明涉及化合物制备技术领域,尤其涉及一种钴酸铜镍纳米线的制备方法及其在催化氨硼烷水解产氢上的应用。
背景技术
钴酸镍(NiCo2O4)是一种具有反尖晶石型结构的复合氧化物,近年来,各种方法用于控制合成具有良好形貌的NiCo2O4材料,其中可以分为物理方法和化学方法。物理方法主要包括:低温粉碎法、超声波粉碎法、冲击波破碎法等。但是用物理方法所制备的钴酸镍不纯、易有杂质。目前,化学方法是制备钴酸镍的主要方法,其中包括:共沉淀法、模板法、溶胶凝胶法、电沉积法、水热法和低温固相法等。溶胶凝胶法是把金属无机化合物经过溶液、溶胶、凝胶和固化后制备成前驱体,然后将前驱体热处理成氧化物或者其他化合物固体。但是其比较漫长的凝胶化过程和较长周期的合成过程,导致其生产成本较高。电化学沉积法是在实验过程中直接从水溶液中制备金属及其不同的致密度的离子薄膜的一种电化学方法。但在其生产过程中需要消耗大量电能,导致其生产成本昂贵,使其在工业中的应用备受阻碍。低温固相法是把金属盐或金属氧化物按照一定比例充分混合、研磨,然后进行煅烧使其发生固相反应,最后再经过研磨得到产物,是在不使用任何溶剂的前提下发生化学反应。但会引起研磨等后续处理所引起的杂质混合与结构缺陷。而共沉淀法与水热合成法可以在溶液中制备前驱体粉末,其成本低廉而且产物粉末颗粒细小均匀,形貌较好,非常适合工业化。钴酸镍的纳米线阵列、纳米片、海胆状、分级花状等形貌均有报道。
中国专利(CN201310594484.2,2014)提出一种多孔NiCo2O4纳米线阵列超级电容器电极材料的制备方法:;将六水合硝酸镍Ni(NO3)2·6H2O、六水合硝酸钴Co(NO3)2·6H2O和尿素溶解于水中,再放入清洗后的泡沫镍,在90~180℃进行水热反应3~18h,冷却至室温,取出泡沫镍,然后超声洗涤,干燥,煅烧即得,制备的多孔NiCo2O4纳米线阵列具有良好的电化学稳定性,但该方法直接在泡沫镍集流体上生长获得,这并不利于规模化生产。
中国专利(CN201510204162.1,2015)提出一种用作超级电容器电极的NiCo2O4@NiCo2O4纳米材料及其制备方法:通过水热反应法制得核结构NiCo2O4纳米线,在该纳米线上,进一步通过电化学沉积法制得壳结构的NiCo2O4纳米线,最终得到具有同质核壳结构的NiCo2O4@NiCo2O4纳米线,该发明有效的提高了电极的比表面积和空间利用率,提升了电极材料的比电容,但很明显工艺复杂且耗能。因此,研发一种形貌可控、成本较低、产品性能优良的能够用于工业化生产钴酸盐复合物的方法是本发明的所要解决的问题。
发明内容
本发明的目的在于着眼于节能、经济、简便、可规模化等,提供了一种利用简单、温和的水热法,在没有使用模板的条件下合成出CuxNi1-xCo2O4纳米线的制备方法。
为解决以上技术问题,本发明提供一种钴酸铜镍纳米线的制备方法,包括以下步骤:
(1)、将可溶性镍盐、钴盐、铜盐溶于超纯水中,配置成混合盐溶液A;
(2)、将1~4mmol十二烷基硫酸钠加入A溶液搅拌溶解;
(3)、将12~30mmol六次甲基四胺溶于20mL超纯水形成B溶液;
(4)、将B溶液通过分液漏斗缓慢滴加至A溶液混合形成C溶液,搅拌0~1h;
(5)、再转移至100mL反应釜,100~160℃反应8~20h,抽滤洗涤,在真空烘箱40~60℃下烘干,再在马弗炉中350~800℃反应1~4h。
优选的,步骤(1)中配置成含Co2+/(Ni2+、Cu2+)摩尔比为2:1的混合盐溶液A。
优选的,步骤(1)中所述的可溶性镍盐选自六水氯化镍、七水硫酸镍、六水硝酸镍、氯化镍、硫酸镍、硝酸镍中的一种。
优选的,步骤(1)中所述可溶性钴盐选自四水乙酸钴、氯化钴、硫酸钴、硝酸钴、六水氯化钴、七水硫酸钴、六水硝酸钴中的一种。
优选的,所述可溶性铜盐选自二水氯化铜、五水硫酸铜、硝酸铜中的一种。
本发明还公开了利用上述方法制得的钴酸铜镍纳米线作为催化剂在催化氨硼烷水解产氢上的应用。
综上所述,本发明的制备方法具有以下有益效果:
1.本发明采用水热合成法,首先将原料按一定比例混合,六次甲基四胺作为沉淀剂生成多元金属氢氧化物,再经煅烧合成钴酸盐,此过程有效实现了原料中设定镍钴铜配比,整个制备过程操作简单,环境友好,实验重现性非常好,成本低、易于工业化生产,可规模化生产CuxNi1-xCo2O4复合钴酸盐。
2.本发明制备的纳米线CuxNi1-xCo2O4复合钴酸盐材料,在催化氨硼烷水解产氢方面,表现出优异的性能,尤其Cu0.6Ni0.4Co2O4,催化活性最高,TOF值高达119.5molhydrogen min-1molcat -1,该值是目前文献报道的最高值,有望实现工业化制备催化产氢的催化剂。
附图说明
图1为本发明制备的Cu0.6Ni0.4Co2O4的SEM图。
图2为本发明制备的Cu0.6Ni0.4Co2O4的TEM图。
图3为本发明制备的Cu0.6Ni0.4Co2O4的BET测试曲线。
图4为本发明制备的Cu0.6Ni0.4Co2O4的XRD测试曲线。
图5为本发明制备的Cu0.6Ni0.4Co2O4和CuCo2O4、NiCo2O4的催化产氢性能对比。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,但不构成对本发明保护范围的限制。
实施例1
前驱体的制备:将乙酸钴(2mmol)、十二烷基硫酸钠(2mmol)、氯化镍(x mmol)、氯化铜(1-x mmol)溶于20mL水,其中0≤x≤1,磁力搅拌直至溶解,再加入1.2M六次甲基四胺溶液20mL,磁力搅拌30min,移至反应釜,120℃反应12h,抽滤洗涤,在真空烘箱40℃下烘干,得到前驱体M(OH)2,M为金属镍、铜、钴(即Ni(OH)2、Cu(OH)2、Co(OH)2)。
纳米线状CuxNi1-xCo2O4的制备:将烘干的前驱体置于研钵中研磨均匀,置于马弗炉中,以2℃/min升温速率升温至600℃,保持2h;待其冷却至室温后,取出样品得到目标产物CuxNi1-xCo2O4。
经测定,本发明所得CuxNi1-xCo2O4,形貌仍为纳米线的结构。
实施例2
前驱体的制备:将乙酸钴(2mmol)、十二烷基硫酸钠(2mmol)、氯化镍(x mmol)、氯化铜(1-x mmol)溶于20mL水,其中0≤x≤1,磁力搅拌直至溶解,再加入0.6M六次甲基四胺溶液20mL,磁力搅拌30min,移至反应釜,120℃反应12h,抽滤洗涤,在真空烘箱60℃下烘干,得到前驱体M(OH)2,M为金属镍、铜、钴(即Ni(OH)2、Cu(OH)2、Co(OH)2)。
纳米线状CuxNi1-xCo2O4的制备:将烘干的前驱体置于研钵中研磨均匀,置于马弗炉中,以2℃/min升温速率升温至600℃,保持2h;待其冷却至室温后,取出样品得到目标产物CuxNi1-xCo2O4。
经测定,本发明所得CuxNi1-xCo2O4,形貌仍为纳米线的结构。
实施例3
前驱体的制备:将乙酸钴(2mmol)、十二烷基硫酸钠(4mmol)、氯化镍(x mmol)、氯化铜(1-x mmol)溶于20mL水,其中0≤x≤1,磁力搅拌直至溶解,再加入1.2M六次甲基四胺溶液20mL,磁力搅拌60min,移至反应釜,120℃反应12h,抽滤洗涤,在真空烘箱40℃下烘干,得到前驱体M(OH)2,M为金属镍、铜、钴(即Ni(OH)2、Cu(OH)2、Co(OH)2)。
纳米线状CuxNi1-xCo2O4的制备:将烘干的前驱体置于研钵中研磨均匀,置于马弗炉中,以2℃/min升温速率升温至600℃,保持4h;待其冷却至室温后,取出样品得到目标产物CuxNi1-xCo2O4。
经测定,本发明所得CuxNi1-xCo2O4,形貌仍为纳米线的结构。
实施例4
前驱体的制备:将乙酸钴(2mmol)、十二烷基硫酸钠(2mmol)、氯化镍(x mmol)、氯化铜(1-x mmol)溶于20mL水,其中0≤x≤1,磁力搅拌直至溶解,再加入1.2M六次甲基四胺溶液20mL,磁力搅拌30min,移至反应釜,160℃反应8h,抽滤洗涤,在真空烘箱40℃下烘干,得到前驱体M(OH)2,M为金属镍、铜、钴(即Ni(OH)2、Cu(OH)2、Co(OH)2)。
纳米线状CuxNi1-xCo2O4的制备:将烘干的前驱体置于研钵中研磨均匀,置于马弗炉中,以2℃/min升温速率升温至600℃,保持2h;待其冷却至室温后,取出样品得到目标产物CuxNi1-xCo2O4。
经测定,本发明所得CuxNi1-xCo2O4,形貌仍为纳米线的结构。
实施例5
前驱体的制备:将乙酸钴(2mmol)、十二烷基硫酸钠(2mmol)、氯化镍(x mmol)、氯化铜(1-x mmol)溶于20mL水,其中0≤x≤1,磁力搅拌直至溶解,再加入1.5M六次甲基四胺溶液20mL,磁力搅拌30min,移至反应釜,100℃反应20h,抽滤洗涤,在真空烘箱40℃下烘干,得到前驱体M(OH)2,M为金属镍、铜、钴(即Ni(OH)2、Cu(OH)2、Co(OH)2)。
纳米线状CuxNi1-xCo2O4的制备:将烘干的前驱体置于研钵中研磨均匀,置于马弗炉中,以2℃/min升温速率升温至600℃,保持2h;待其冷却至室温后,取出样品得到目标产物CuxNi1-xCo2O4。
经测定,本发明所得CuxNi1-xCo2O4,形貌仍为纳米线的结构。
实施例6
前驱体的制备:将乙酸钴(2mmol)、十二烷基硫酸钠(2mmol)、氯化镍(x mmol)、氯化铜(1-x mmol)溶于20mL水,其中0≤x≤1,磁力搅拌直至溶解,再加入1.2M六次甲基四胺溶液20mL,磁力搅拌30min,移至反应釜,120℃反应12h,抽滤洗涤,在真空烘箱40℃下烘干,得到前驱体M(OH)2,M为金属镍、铜、钴(即Ni(OH)2、Cu(OH)2、Co(OH)2)。
纳米线状CuxNi1-xCo2O4的制备:将烘干的前驱体置于研钵中研磨均匀,置于马弗炉中,以2℃/min升温速率升温至800℃,保持2h;待其冷却至室温后,取出样品得到目标产物CuxNi1-xCo2O4。
经测定,本发明所得CuxNi1-xCo2O4,形貌仍为纳米线的结构。
实施例7
前驱体的制备:将乙酸钴(2mmol)、十二烷基硫酸钠(2mmol)、氯化镍(x mmol)、氯化铜(1-x mmol)溶于20mL水,其中0≤x≤1,磁力搅拌直至溶解,再加入1.2M六次甲基四胺溶液20mL,磁力搅拌30min,移至反应釜,110℃反应12h,抽滤洗涤,在真空烘箱40℃下烘干,得到前驱体M(OH)2,M为金属镍、铜、钴(即Ni(OH)2、Cu(OH)2、Co(OH)2)。
纳米线状CuxNi1-xCo2O4的制备:将烘干的前驱体置于研钵中研磨均匀,置于马弗炉中,以2℃/min升温速率升温至350℃,保持2h;待其冷却至室温后,取出样品得到目标产物CuxNi1-xCo2O4。
经测定,本发明所得CuxNi1-xCo2O4,形貌仍为纳米线的结构。
下面以纳米线状Cu0.6Ni0.4Co2O4为例,对本发明制备的复合钴酸盐的结构和性能进行分析和测试。
1、SEM分析
图1为本发明制备的Cu0.6Ni0.4Co2O4的SEM图。从扫描图中可以看出,通过水热合成的Cu0.6Ni0.4Co2O4形貌呈直径约为30nm的纳米线。
2、TEM测试
图2为本发明制备的Cu0.6Ni0.4Co2O4的TEM图,从投射图中可以进一步证实纳米线状的催化剂。
3、BET测试
图3为本发明制备的Cu0.6Ni0.4Co2O4的氮气吸附脱附等温曲线及孔径分布曲线,从图中可以看出,等温线被归类为Ⅳ型等温线,且等温曲线在相对压力为0.45~0.98的范围内有一个明显的迟滞环,表明材料中有中孔的存在。从孔径分布曲线可以发现孔主要集中在4nm。
4、XRD
图4为本发明制备的Cu0.6Ni0.4Co2O4的XRD测试。图中所标示出的为Cu0.6Ni0.4Co2O4不同晶面的特征峰。
5、催化产氢性能的测试
图5为本发明制备的Cu0.6Ni0.4Co2O4作为催化剂催化氨硼烷水解产氢的性能测试,NH3BH3用量3mmol,NaOH 20mmol,催化剂5mg。测得25℃下Cu0.6Ni0.4Co2O4作为催化剂第一分钟产氢55mL,而CuCo2O4作为催化剂第一分钟产氢约24mL、NiCo2O4作为催化剂第一分钟无氢气产生。
以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也视为本发明的保护范围。
Claims (6)
1.一种钴酸铜镍纳米线的制备方法,其特征在于,包括以下步骤:
(1)、将可溶性镍盐、钴盐、铜盐溶于超纯水中,配置成混合盐溶液A;
(2)、将1~4mmol十二烷基硫酸钠加入A溶液搅拌溶解;
(3)、将12~30mmol六次甲基四胺溶于20mL超纯水形成B溶液;
(4)、将B溶液通过分液漏斗缓慢滴加至A溶液混合形成C溶液,搅拌0~1h;
(5)、再转移至100mL反应釜,100~160℃反应8~20h,抽滤洗涤,在真空烘箱40~60℃下烘干,再在马弗炉中350~800℃反应1~4h。
2.根据权利要求1所述的一种钴酸铜镍纳米线的制备方法,其特征在于:步骤(1)中配置成含Co2+/(Ni2+、Cu2+)摩尔比为2:1的混合盐溶液A。
3.根据权利要求1所述的一种钴酸铜镍纳米线的制备方法,其特征在于:步骤(1)中所述的可溶性镍盐选自六水氯化镍、七水硫酸镍、六水硝酸镍、氯化镍、硫酸镍、硝酸镍中的一种。
4.根据权利要求1所述的一种钴酸铜镍纳米线的制备方法,其特征在于:步骤(1)中所述可溶性钴盐选自四水乙酸钴、氯化钴、硫酸钴、硝酸钴、六水氯化钴、七水硫酸钴、六水硝酸钴中的一种。
5.根据权利要求1所述的一种钴酸铜镍纳米线的制备方法,其特征在于:所述可溶性铜盐选自二水氯化铜、五水硫酸铜、硝酸铜中的一种。
6.如权利要求1-5任一项所述的制备方法所制备的钴酸铜镍纳米线作为催化剂在催化氨硼烷水解产氢上的应用。
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