CN105858632A - 一种磷酸钴纳米管材料及其制法和其用于光解水制氧气 - Google Patents
一种磷酸钴纳米管材料及其制法和其用于光解水制氧气 Download PDFInfo
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- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002071 nanotube Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 19
- 239000001301 oxygen Substances 0.000 title claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000725 suspension Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 16
- 230000001699 photocatalysis Effects 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 6
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims 1
- 235000011007 phosphoric acid Nutrition 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 238000009388 chemical precipitation Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 229910021389 graphene Inorganic materials 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 238000001514 detection method Methods 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- REERVHLUKHFRQT-UHFFFAOYSA-N cobalt phosphoric acid Chemical compound [Co].P(O)(O)(O)=O REERVHLUKHFRQT-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910003071 TaON Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- -1 octylame Chemical compound 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
一种磷酸钴纳米管材料,其特征是:直径为5~50纳米,长度为100~2000纳米的中空管状结构。本发明利用廉价易得的磷源,钴源和有机胺为反应物,通过液相化学沉淀和水热合成法,就可以制备本发明的磷酸铁锂/石墨烯复合材料。制备方法工艺简单、适用于工业化大量生产、且成本低、基本没有环境污染。本发明中所得到的磷酸钴纳米管材料用于光解水制氧气,过程简单、环保、高效。本发明公开了其制法。
Description
技术领域:
本发明涉及一种磷酸钴纳米管材料及其生产方法和其用于光解水制氧气。
背景技术:
近来,能源与环境两大主题成为了人们关注的焦点,其中,能源材料和环保材料的创新是其关键问题之一。磷酸盐材料在这两方面发挥了独特的优势,例如,磷酸铁锂材料应用于锂离子电池方面和磷酸银材料应用于光解水制氧气等。在磷酸盐材料中,磷酸钴材料催化剂既可以用于锂离子电池的正极材料,也可以用于光解水制氧气的催化剂。另外,磷酸钴材料也可用作陶瓷颜料和釉药等。
因此,人们在磷酸钴材料的合成和应用方面做了大量的工作。例如,2004年,重庆师范大学的杜小旺在《重庆师范大学学报》上发表的一篇文章,报道了利用微波合成出了平均粒径为50.64 nm 的球形的磷酸钴纳米颗粒。2008年,Daniel G. Nocera发表在Science上的一篇题为“In Situ Formation of an Oxygen-Evolving Catalyst in NeutralWater Containing Phosphate and Co2+”文章中,报道了磷酸钴材料具有优异的电催化水分解制氧的性能。2014年,白珍辉等人申请了“一种磷酸钴粉体材料的制备方法(申请号:CN201410453227.1)”的发明专利,其发明中公开的是一种磷酸钴微米级颗粒的制备方法以及其用于锂离子电池材料的用途。2014年,陈刚等人申请了“一步法附载磷酸钴助催化剂的制备方法(申请号:CN201410255708.1)”的发明专利,其发明中公开的是一种将磷酸钴沉积生长到TaON催化载体上的制备方法,在此发明中,磷酸钴作为助催化剂,提高TaON光催化制氧气的能力。
总结近多年以来关于磷酸钴材料制备及应用的文献结果,可以发现还没有一种方法制备出磷酸钴纳米管材料,而本发明提供了磷酸钴纳米管材料及其制法和其用于光解水制氧气。
发明内容:
本发明的目的可通过如下技术方案实现:
一种磷酸钴纳米管材料,它具有直径为5~50纳米,长度为100~2000纳米的中空管状结构。
一种上述磷酸钴纳米管材料的制法,包括以下步骤:
步骤1. 在含有浓度为0.025-1.5 mol/L的磷酸二氢根离子和0.02-1.2 mol/L的钴离子溶液中,加入磷酸二氢根离子物质的量0.6-8倍的有机胺作为模板剂,混合均匀;
步骤2. 将步骤1中的悬浊液转移到有聚四氟乙烯内衬的水热釜中,密封后,150~200 °C下水热12~72小时。之后,冷却至室温,打开水热釜,得到紫色、红色或蓝色的悬浊液。
步骤3. 将步骤2中的悬浊液抽滤,并用乙醇多次洗涤,80 °C下干燥,得到的紫色、红色或蓝色的粉末即为磷酸钴纳米管材料。
上述的制法,步骤1所述的磷酸二氢根离子和钴离子的溶液,优选的是磷酸、磷酸二氢铵、磷酸二氢钠、磷酸二氢钾、硝酸钴、氯化钴、硫酸钴和醋酸钴的水溶液。
上述的制法,步骤1所述的有机胺,优选的是乙二胺、丁二胺、戊二胺、四甲基氢氧化铵、苯胺、环己胺、己胺、辛胺、癸胺、十二胺、十四胺、十六胺或十八胺或者它们的混合物。
上述制法得到的磷酸钴纳米管用于光解水制氧气,具体的做法如下:将磷酸钴纳米管分散于纯水中,在可见光或紫外光的照射之下,即可产生氧气。
本发明的有益效果在于:
1、磷酸钴纳米管材料的合成属于首次报道。
2、利用廉价易得的磷源、钴源和有机胺为反应物,通过化学液相共沉淀法和水热合成法就可以制备磷酸钴纳米管材料。
3、本发明方法工艺简单、适用于工业化大量生产、且成本低、基本没有环境污染。
4、本发明中所得到的磷酸钴纳米管材料用于光解水制氧气,过程简单、环保、高效,有较大的经济价值。
附图说明:
图1 是本发明实施例1制备的磷酸钴纳米管材料的X射线粉末衍射图;
图2 是本发明实施例1制备的磷酸钴纳米管材料的TEM透射电镜照片;
图3 是本发明实施例2制备的磷酸钴纳米管材料的TEM透射电镜照片;
图4 是本发明实施例3制备的磷酸钴纳米管材料的TEM透射电镜照片;
图5 是本发明实施例4制备的磷酸钴纳米管材料的TEM透射电镜照片;
图6 是本发明实施例5制备的磷酸钴纳米管材料的TEM透射电镜照片;
图7 是本发明实施例6制备的磷酸钴纳米管材料的TEM透射电镜照片。
具体实施方式:
以下结合实施例进一步说明本发明。
实施例1:
将0.025 mol的磷酸二氢钠和0.020 mol的氯化钴溶于100 ml水中,然后加入50 ml 含有0.050 mol的乙二胺的乙醇溶液,搅拌600分钟。将上述悬浊液转移到有聚四氟乙烯内衬的水热釜中,密封后,150 °C下水热72小时。之后,冷却至室温,打开水热釜,得到蓝色的悬浊液。将此蓝色的悬浊液抽滤,并用乙醇多次洗涤,80 °C下干燥,得到的蓝色粉末即为磷酸钴纳米管材料。产物经X射线粉末衍射鉴定为磷酸钴(见图1),TEM电镜检测产品形貌(见图2)。
实施例2:
将0.150 mol的磷酸二氢铵和0.120 mol的氯化钴溶于100 ml水中,然后加入100 ml含有1.2 mol的环己胺的乙醇溶液,搅拌120分钟。将上述悬浊液转移到有聚四氟乙烯内衬的水热釜中,密封后,160 °C下水热48小时。之后,冷却至室温,打开水热釜,得到红色的悬浊液。将此红色的悬浊液抽滤,并用乙醇多次洗涤,80 °C下干燥,得到的红色粉末即为磷酸钴纳米管材料。产物经X射线粉末衍射鉴定为磷酸钴,TEM电镜检测产品形貌(见图3)。
实施例3:
将0.100 mol的磷酸二氢钾和0.080 mol的硫酸钴溶于100 ml水中,然后加入30 ml 含有0.060 mol的四甲基氢氧化铵的乙醇溶液,搅拌300分钟。将上述悬浊液转移到有聚四氟乙烯内衬的水热釜中,密封后,170 °C下水热36小时。之后,冷却至室温,打开水热釜,得到红色的悬浊液。将此红色的悬浊液抽滤,并用乙醇多次洗涤,80 °C下干燥,得到的红色粉末即为磷酸钴纳米管材料。产物经X射线粉末衍射鉴定为磷酸钴,TEM电镜检测产品形貌(见图4)。
实施例4:
将0.05 mol的磷酸和0.060 mol的醋酸钴溶于100 ml水中,然后加入50 ml 含有0.300mol的乙二胺和0.100 mol的十二胺的乙醇溶液,搅拌720分钟。将上述悬浊液转移到有聚四氟乙烯内衬的水热釜中,密封后,180 °C下水热72小时。之后,冷却至室温,打开水热釜,得到紫色的悬浊液。将此紫色的悬浊液抽滤,并用乙醇多次洗涤,80 °C下干燥,得到的紫粉末即为磷酸钴纳米管材料。产物经X射线粉末衍射鉴定为磷酸钴,TEM电镜检测产品形貌(见图5)。
实施例5:
将0.009 mol的磷酸二氢铵和0.008 mol的硝酸钴溶于100 ml水中,然后加入25 ml 含有0.027 mol的十二胺和0.003十六胺的乙醇溶液,搅拌480分钟。将上述悬浊液转移到有聚四氟乙烯内衬的水热釜中,密封后,180 °C下水热48小时。之后,冷却至室温,打开水热釜,得到紫色的悬浊液。将此紫色的悬浊液抽滤,并用乙醇多次洗涤,80 °C下干燥,得到的紫色粉末即为磷酸钴纳米管材料。产物经X射线粉末衍射鉴定为磷酸钴,TEM电镜检测产品形貌(见图6)。
实施例6:
将0.120 mol的磷酸二氢铵和0.100 mol的硝酸钴溶于100 ml水中,然后加入40 ml 含有0.036 mol的十二胺的乙醇溶液,搅拌240分钟。将上述悬浊液转移到有聚四氟乙烯内衬的水热釜中,密封后,200 °C下水热12小时。之后,冷却至室温,打开水热釜,得到红色的悬浊液。将此红色的悬浊液抽滤,并用乙醇多次洗涤,80 °C下干燥,得到的红色粉末即为磷酸钴纳米管材料。产物经X射线粉末衍射鉴定为磷酸钴,TEM电镜检测产品形貌(见图7)。
实施例7:
磷酸钴纳米管用于光解水制氧气,具体的做法如下:取0.100 g磷酸钴纳米管材料,分散于50 ml纯水中,在300 W的氙灯光源照射下(已滤掉波长420纳米以下的可见光),或者100 W的紫外光的照射之下,即可产生氧气。其产生的氧气利用气相色谱检测。其产生氧气的速率为33 mmol/g/h。
Claims (6)
1.一种磷酸钴纳米管材料,其特征在于:直径为5~50纳米,长度为100~2000纳米的中空管状结构。
2.一种制备权利要求1所述的磷酸钴纳米管材料的方法,其特征在于,包括以下步骤:
步骤1. 在含有浓度为0.025-1.5 mol/L的磷酸二氢根离子和0.02-1.2 mol/L的钴离子溶液中,加入磷酸二氢根离子物质的量0.6-8倍的有机胺作为模板剂,混合均匀;
步骤2. 将步骤1中的悬浊液转移到有聚四氟乙烯内衬的水热釜中,密封后,150~200 °C下水热12~72小时;之后,冷却至室温,打开水热釜,得到紫色、红色或蓝色的悬浊液;
步骤3. 将步骤2中的悬浊液抽滤,并用乙醇多次洗涤,80 °C下干燥,得到的紫色、红色或蓝色的粉末即为磷酸钴纳米管材料。
3.根据权利要求2所述的制法,其特征在于:步骤1所述的磷酸二氢根离子和钴离子的溶液是磷酸、磷酸二氢铵、磷酸二氢钠、磷酸二氢钾、硝酸钴、氯化钴、硫酸钴和醋酸钴的水溶液。
4.根据权利要求2所述的制法,其特征在于:步骤1所述的有机胺是乙二胺、丁二胺、戊二胺、四甲基氢氧化铵、苯胺、环己胺、己胺、辛胺、癸胺、十二胺、十四胺、十六胺或十八胺或者它们的混合物。
5.根据权利要求1所述的磷酸钴纳米管材料,其特征在于,其用于光解水制氧气。
6.根据权利要求5所述的磷酸钴纳米管材料用于光解水制氧气,其特征在于,光解水中所述的光源为太阳光、模拟太阳光的氙灯或者紫外灯。
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