CN113277498B - 一种过渡金属基杂化材料纳米管及其制备方法和用途 - Google Patents
一种过渡金属基杂化材料纳米管及其制备方法和用途 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 97
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 76
- 239000002071 nanotube Substances 0.000 title claims abstract description 67
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000013110 organic ligand Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- -1 transition metal salt Chemical class 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 62
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 6
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 229960004543 anhydrous citric acid Drugs 0.000 description 12
- 238000004108 freeze drying Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 238000003917 TEM image Methods 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 4
- 229960004106 citric acid Drugs 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 3
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 3
- OWUGOENUEKACGV-UHFFFAOYSA-N [Fe].[Ni].[W] Chemical compound [Fe].[Ni].[W] OWUGOENUEKACGV-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 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 description 2
- VAWNDNOTGRTLLU-UHFFFAOYSA-N iron molybdenum nickel Chemical compound [Fe].[Ni].[Mo] VAWNDNOTGRTLLU-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- 229910002001 transition metal nitrate Inorganic materials 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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Abstract
本发明提供一种过渡金属基杂化材料纳米管及其制备方法和用途,属于纳米材料合成技术领域,尤其涉及杂化材料以及一维纳米材料合成方法。本发明通过使用有机配体,和过渡金属盐类水溶液提供的金属离子,通过简单的调节体系的酸碱性,在常温下持续搅拌,促使过渡金属离子与有机配体和碳源之间发生配合反应,再经过简单的离心处理得到目标产物。本发明所提供的制备方法具有的以下优点:(1)原料便宜易得,一步合成了过渡金属基杂化材料纳米管,成本低廉,有良好的应用前景;(2)反应在常温下就可以进行,相较于传统溶剂热法,效率更高、能量损失更低、并且具有更高的可重复性,对环境更友好,为过渡金属基杂化材料纳米管的制备提出了新的策略。
Description
技术领域
本发明涉及杂化材料以及纳米材料合成技术领域,更具体的涉及一种过渡金属基杂化材料纳米管及其制备方法和用途。
背景技术
近年来,杂化材料由于其温和的合成方法、纳米结构合成可控性以及后续应用优异的性能,被广泛应用在能量储存、催化、电学、光学以及传感等方面。其中,金属无机-有机杂化材料由于其优越的电化学性能在近几年来也备受关注,由于是不同组分相互结合成复杂多样的复合材料,经过后续简单的工艺处理可以形成不同性能的高性能材料。
另一方面,Iijima课题组在1991年对碳纳米管的首次报道,突破了在纳米尺度上对物质结构的传统认知,于是开启了对具有一维(1D)纳米结构材料的广泛研究,如纳米线、纳米棒和纳米管等,其以过渡金属族为代表的一维纳米材料具有优秀的物理性能和化学性能,从而被广泛应用在能量转换和储存领域。而目前过渡金属基一维材料的合成方法为溶剂热合成法,危险性较高、能量利用率低、反应条件较苛刻、重复率不高等特点,很难大规模生产。因此,寻找一种反应温和,效率高,成本低且符合绿色化学要求的一维过渡金属基杂化材料的制备方法成为了研究者关注的目标。
发明内容
针对上述问题,本发明的目的在于提供一种过渡金属基杂化材料纳米管及其制备方法和用途,所述制备方法反应具备条件温和、效率高、重复性好和节约成本的特点。
本发明的第一个目的是提供了一种过渡金属基杂化材料纳米管及其制备方法,技术方案如下,包括以下步骤:
S1、称取过渡金属盐溶于去离子水中得到0.125~0.375mol/mL的溶液,在溶液中加入有机配体混合后,再加入柠檬酸使溶液pH值为5~6,搅拌使其形成均匀混合液,并持续搅拌2-8h,得到浑浊液,之后离心收集浑浊液中的沉淀物;
S2、将S1中的沉淀物洗涤使体系呈中性后干燥处理,得到过渡金属基杂化材料纳米管。
优选的,过渡金属盐为Fe、Cu、Zn、Mn、Co、Mo、W的硝酸盐或氯化物,有机配体为三聚氰胺、三聚氰酸,过渡金属盐类与有机配体的质量比为0.48~1.34:1。
优选的,过渡金属盐为Fe、Cu、Zn、Mn、Co、Mo、W的硝酸盐或氯化物的1~3种;
优选的,当过渡金属盐的种类为2种或3种时,各个金属盐类物质的量比值为1。
优选的,S1中柠檬酸与有机配体的质量比为1.5~3:1。
优选的,S1中离心的转速为3000-5000rpm,时间为3~5min;
优选的,还包括,S3、碳化工序,碳化条件为:将S2中的过渡金属基杂化材料纳米管置于氩气氛围下,于400~500℃煅烧2~3h。
本发明的第二个目的是根据上述的方法提供一种过渡金属基杂化材料纳米管。
本发明的第三个目的是提供上述过渡金属基杂化材料纳米管在制备催化剂、电池中的用途。
与现有技术相比,本发明具有以下有益效果:
本发明使用常见的过渡金属硝酸盐或氯化物、简单易得的有机配体和碳源,通过调节酸碱性,在常温下,安全无害的水溶液体系中,通过搅拌反应,促使过渡金属离子与有机配体和碳源之间发生配合反应;同时,过渡金属离子,如Fe、Ni、Cu、Zn、Mn、Co、Mo、W等对应的金属离子与有机配体,如三聚氰胺或三聚氰酸等,再加上柠檬酸,三者发生反应,过渡金属离子固定在羧基的位置上,单个聚合物分子链可以高度有序自组装成一维纳米材料结构,形成的一维纳米材料沉积降低了配合物的浓度,使其继续微溶于水中,不断地为过渡金属基一维纳米材料提供原料。
本发明合成方法简便高效,能量利用率提高,比现在公开的传统方法效率更高,重复性好、可控性高,具备突出的优势,为过渡金属基杂化材料纳米管的制备提出新策略。
附图说明
图1为本发明实施例1中所得材料的SEM图;
图2为本发明实施例2中所得材料的SEM图;
图3为本发明实施例3中所得材料的SEM图;
图4为本发明实施例4中所得材料的SEM图;
图5为本发明实施例5中所得材料的SEM图;
图6为本发明实施例8中所得材料的TEM图;
图7为本发明实施例9中所得材料的TEM图;
图8为本发明实施例10中所得材料的TEM图,图8a为15000倍数下的TEM图,图8b为40000倍数下的TEM图;
图9为本发明实施例1、实施例2、实施例3、实施例5、实施例6、实施例7、实施例8、实施例9中所得材料的XRD图;
图10为本发明实施例13与实施例14中所得材料后的XRD图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明实施例中的技术方案进行清楚、完整的描述。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
下述实验方法和检测方法,如没有特殊说明,均为常规方法;下述试剂和原料,如没有特殊说明,均为市售试剂和原料。
实施例1
一种过渡金属基杂化材料纳米管及其制备方法,包括以下步骤:
S1、称取404mg硝酸铁Fe(NO3)3·9H2O溶于8mL去离子水中搅拌1min后,形成均一溶液;取300mg三聚氰胺均匀分散在上述溶液中;加入900mg无水柠檬酸,搅拌5min形成均一相混合液,测试溶液PH为5~6,随后连续搅拌2h,得到黄色浑浊液,之后将黄色浑浊液进行离心处理,离心转速为3000rpm,时间为5min,得到沉淀物;
S2、将S1的沉淀物用去离子水洗涤至体系呈中性,冷冻干燥过夜,得到黄色粉末状的过渡金属铁基杂化材料纳米管。
实施例2
一种过渡金属基杂化材料纳米管及其制备方法,包括以下步骤:
S1、称取240mg硝酸铜Cu(NO3)2·3H2O溶于8mL去离子水中搅拌1min后,形成均一溶液;取300mg三聚氰胺均匀分散在上述溶液中;加入900mg无水柠檬酸,搅拌5min形成均一相混合液,测试溶液PH为5~6,随后连续搅拌2h,得到蓝色浑浊液,之后将蓝色浑浊液进行离心处理,离心转速为5000rpm,时间为3min,得到沉淀物;
S2、将S1的沉淀物用去离子水洗涤至体系呈中性,冷冻干燥过夜,得到蓝色粉末状的过渡金属铜基杂化材料纳米管。
实施例3
一种过渡金属基杂化材料纳米管及其制备方法,包括以下步骤:
S1、称取404mg硝酸铁Fe(NO3)3·9H2O和290mg硝酸镍Ni(NO3)2·6H2O溶于8mL去离子水中搅拌1min后,形成均一溶液;取300mg三聚氰胺均匀分散在上述溶液中;加入900mg无水柠檬酸,搅拌5min形成均一相混合液,测试溶液PH为5~6,随后连续搅拌2h,得到黄色浑浊液,之后将黄色浑浊液进行离心处理,离心转速为4000rpm,时间为4min,得到沉淀物;
S2、将S1的沉淀物用去离子水洗涤至体系呈中性,冷冻干燥过夜,得到黄色粉末状的过渡金属铁-镍基杂化材料纳米管。
实施例4
一种过渡金属基杂化材料纳米管及其制备方法,包括以下步骤:
S1、称取404mg硝酸铁Fe(NO3)3·9H2O和290mg硝酸钴Co(NO3)2·6H2O溶于8mL去离子水搅拌1min后,形成均一溶液;300mg三聚氰胺均匀分散上述溶液;加入900mg无水柠檬酸,搅拌5min形成均一相混合液,测试溶液pH为5~6,随后连续搅拌2h,得到橘红色浑浊液,之后将橘红色浑浊液进行离心处理,离心转速为3000rpm,时间为5min,得到沉淀物;
S2、将S1的沉淀物用去离子水洗涤至体系呈中性,冷冻干燥过夜,得到橘红色粉末状的过渡金属铁-钴基杂化材料纳米管。
实施例5
一种过渡金属基杂化材料纳米管及其制备方法,包括以下步骤:
S1、称取404mg硝酸铁Fe(NO3)3·9H2O和240mg硝酸铜Cu(NO3)2·3H2O溶于8mL去离子水搅拌1min后,形成均一溶液;300mg三聚氰胺均匀分散上述溶液;加入900mg无水柠檬酸,搅拌5min形成均一相混合液,测试溶液pH为5~6,随后连续搅拌2h,得到淡蓝色浑浊液;之后将淡蓝色浑浊液进行离心处理,离心转速为5000rpm,时间为3min,得到沉淀物;
S2、将S1的沉淀物用去离子水洗涤至体系呈中性,冷冻干燥过夜,得到淡蓝色粉末状的过渡金属铁-铜基杂化材料纳米管。
实施例6
一种过渡金属基杂化材料纳米管及其制备方法,包括以下步骤:
S1、称取404mg硝酸铁Fe(NO3)3·9H2O和135mg氯化锌ZnCl3溶于8mL去离子水搅拌1min后,形成均一溶液;300mg三聚氰胺均匀分散上述溶液;加入900mg无水柠檬酸,搅拌5min形成均一相混合液,测试溶液pH为5~6,随后连续搅拌2h,得到白色浑浊液;之后将白色浑浊液进行离心处理离心转速为4500rpm,时间为4min,得到沉淀物;
S2、将S1的沉淀物用去离子水洗涤至体系呈中性,冷冻干燥过夜,得到白色粉末状的过渡金属铁-锌基杂化材料纳米管。
实施例7
一种过渡金属基杂化材料纳米管及其制备方法,包括以下步骤:
S1、称取404mg硝酸铁Fe(NO3)3·9H2O和200mg氯化锰MnCl2·4H2O溶于8mL去离子水搅拌1min后,形成均一溶液;300mg三聚氰胺均匀分散上述溶液;加入900mg无水柠檬酸,搅拌5min形成均一相混合液,测试溶液PH为5~6,随后连续搅拌8h,得到橙黄色浑浊液;之后将橙黄色浑浊液进行离心处理,离心转速为5000rpm,时间为3min,得到沉淀物;
S2、将S1的沉淀物用去离子水洗涤至体系呈中性,冷冻干燥过夜,得到橙黄色粉末状的过渡金属铁-锰基杂化材料纳米管。
实施例8
一种过渡金属基杂化材料纳米管及其制备方法,包括以下步骤:
S1、称取404mg硝酸铁Fe(NO3)3·9H2O、290mg硝酸镍Ni(NO3)2·6H2O和177mg钼酸铵(NH4)6Mo7O24·4H2O溶于8mL去离子水搅拌1min后,形成均一溶液;300mg三聚氰胺均匀分散上述溶液;加入900mg无水柠檬酸,搅拌5min形成均一相混合液,测试溶液PH为5~6,随后连续搅拌5h,得到淡黄色浑浊液;之后将淡黄色浑浊液进行离心处理,离心转速为5000rpm,时间为3min,得到沉淀物;
S2、将S1的沉淀物用去离子水洗涤至体系呈中性,冷冻干燥过夜,得到淡黄色粉末状的过渡金属铁-镍-钼基杂化材料纳米管。
实施例9
一种过渡金属基杂化材料纳米管及其制备方法,包括以下步骤:
S1、称取404mg硝酸铁Fe(NO3)3·9H2O、290mg硝酸镍Ni(NO3)2·6H2O和329mg钨酸钠Na2WO4·2H2O溶于8mL去离子水搅拌1min后,形成均一溶液;300mg三聚氰胺均匀分散上述溶液;加入900mg无水柠檬酸,搅拌5min形成均一相混合液,测试溶液PH为5~6,随后连续搅拌2h,得到淡黄色浑浊液;之后将淡黄色浑浊液进行离心处理,离心转速为3500rpm,时间为4min,得到沉淀物;
S2、将S1的沉淀物用去离子水洗涤至体系呈中性,冷冻干燥过夜,得到淡黄色粉末状的过渡金属铁-镍-钨基杂化材料纳米管。
实施例10
一种过渡金属基杂化材料纳米管及其制备方法,包括以下步骤:
S1、称取404mg硝酸铁Fe(NO3)3·9H2O和290mg硝酸镍Ni(NO3)2·6H2O溶于8mL去离子水搅拌1min后,形成均一溶液;600mg三聚氰酸均匀分散上述溶液;加入900mg无水柠檬酸,搅拌5min形成均一相混合液,测试溶液PH为5~6,随后连续搅拌2h,得到淡黄色浑浊液;之后将淡黄色浑浊液进行离心处理,离心转速为5000rpm,时间为3min,得到沉淀物;
S2、将S1的沉淀物用去离子水洗涤至体系呈中性,冷冻干燥过夜,得到淡黄色粉末状的过渡金属铁-镍基杂化材料纳米管。
实施例11
一种过渡金属基杂化材料纳米管及其制备方法,包括以下步骤:
S1、称取404mg硝酸铁Fe(NO3)3·9H2O、290mg硝酸镍Ni(NO3)2·6H2O和177mg钼酸铵(NH4)6Mo7O24·4H2O溶于8mL去离子水搅拌1min后,形成均一溶液;600mg三聚氰酸均匀分散上述溶液;加入900mg无水柠檬酸,搅拌5min形成均一相混合液,测试溶液PH为5~6,随后连续搅拌2h,得到淡黄色浑浊液;之后将淡黄色浑浊液进行离心处理,离心转速为3000rpm,时间为5min,得到沉淀物;
S2、将S1的沉淀物用去离子水洗涤至体系呈中性,冷冻干燥过夜,得到淡黄色粉末状的过渡金属铁-镍-钼基杂化材料纳米管。
实施例12
一种过渡金属基杂化材料纳米管及其制备方法,包括以下步骤:
S1、称取404mg硝酸铁Fe(NO3)3·9H2O、290mg硝酸镍Ni(NO3)2·6H2O和329mg钨酸钠Na2WO4·2H2O溶于8mL去离子水搅拌1min后,形成均一溶液;600mg三聚氰酸均匀分散上述溶液;加入900mg无水柠檬酸,搅拌5min形成均一相混合液,测试溶液PH为5~6,随后连续搅拌2h,得到淡黄色浑浊液;得到淡黄色浑浊液;之后将淡黄色浑浊液进行离心处理,离心转速为3000rpm,时间为5min,得到沉淀物;
S2、将S1的沉淀物用去离子水洗涤至体系呈中性,冷冻干燥过夜,得到淡黄色粉末状的过渡金属铁-镍-钨基杂化材料纳米管。
实施例13
一种过渡金属基杂化材料纳米管及其制备方法,与实施例2的操作基本相同,区别在于,本实施例还包括,S3、碳化工序,碳化条件为:将S2中干燥后的过渡金属铜基杂化材料纳米管置于氩气氛围的管式炉中,于500℃煅烧2h,得到煅烧后的过渡金属铜基杂化材料纳米管。
实施例14
一种过渡金属基杂化材料纳米管及其制备方法,与实施42的操作基本相同,区别在于,本实施例还包括,S3、碳化工序,碳化条件为:将S2中干燥后的过渡金属铁-钴基杂化材料纳米管置于氩气氛围的管式炉中,于400℃煅烧3h,得到煅烧后的过渡金属铁-钴基杂化材料纳米管。
采用本发明所提供的一种过渡金属基杂化材料纳米管制备方法,各实施例中制备的材料的扫描电镜(SEM)图如图1~图8所示,其对应关系分别为:
实施例1得到铁基杂化材料纳米管的SEM图如图1所示,可以看出明显的管状结构,材料的长径比较大;实施例2得到铜基杂化材料纳米管的SEM图如图2所示,可以看出明显的管状结构,材料的长径比较大;
实施例3得到铁-镍基杂化材料纳米管的SEM图如图3所示,实施例4得到的铁-钴基杂化材料纳米管的SEM图如图4所示,实施例5得到铁-铜基杂化材料纳米管的SEM图如图5所示,从图3-5中均可以看出明显的管状结构,相较于单金属基杂化材料而言,材料的长径比较小,且管壁更薄;
实施例8得到铁-镍-钼基杂化材料纳米管的透射电镜(TEM)图如图6所示,实施例9得到铁-镍-钨基杂化材料纳米管的TEM图如图7所示,从图6和图7中均可以看出明显的管状结构,相较于单金属基杂化材料而言,材料的长径比较小,且管壁更薄,与双金属基杂化材料相比,表面上出现多孔结构;
实施例10得到铁-镍基杂化材料纳米管的TEM图如图8所示,在明显管状结构下,表面的多孔结构更为明显,可能归因于不同有机配体的作用。
图9为本发明实施例1、实施例2、实施例3、实施例5、实施例6、实施例7、实施例8、实施例9中所得材料的X-射线衍射图(XRD)。从图中可以看到其中杂化材料没有明显的特征峰,且出峰位置均在较小角度范围内,即代表合成材料为过渡金属基杂化材料。
图10为本发明实施例2与实施例4中所得材料碳化后的XRD图。对比铜基杂化材料纳米管与铁-铜基杂化材料纳米管,在400℃碳化2h后所的材料的XRD图像,可以看到仅出现碳的特征峰,证实材料中含有碳基质,并没有出现金属的特征峰,进一步证明制备材料为杂化材料。
本发明中过渡金属盐溶于去离子水提供了相对应的过渡金属离子,在弱酸性环境下,有机配体与过渡金属离子发生配位反应,同时体系中含有柠檬酸,柠檬酸不仅在体系中可提供碳源,还可以调节溶液为弱酸性,三者反应生成有机配体与过渡金属配合物,之后经过洗涤和干燥处理得到过渡金属基杂化材料纳米管。本发明的制备方法简便高效,能量利用率提高,比现在公开的传统方法效率更高,重复性好、可控性高。
尽管已描述了本发明的优选实施例,但本领域内的技术人员一旦得知了基本创造性概念,则可对这些实施例作出另外的变更和修改。所以,所附权利要求意欲解释为包括优选实施例以及落入本发明范围的所有变更和修改。
显然,本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样,倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内,则本发明也意图包含这些改动和变型在内。
Claims (9)
1.一种过渡金属基杂化材料纳米管的制备方法,其特征在于,包括以下步骤:
S1、称取过渡金属盐溶于去离子水中得到0.125-0.375mol/mL的溶液,在溶液中加入有机配体混合后,再加入柠檬酸使溶液pH值为5~6,搅拌使其形成均匀混合液,并持续搅拌2-8h,得到浑浊液,之后离心收集浑浊液中的沉淀物;有机配体为三聚氰胺、三聚氰酸,过渡金属盐类与有机配体的质量比为0.48~1.34:1;柠檬酸与有机配体的质量比为1.5~3:1;
S2、将S1中的沉淀物洗涤使体系呈中性后干燥处理,得到过渡金属基杂化材料纳米管。
2.根据权利要求1所述的一种过渡金属基杂化材料纳米管的制备方法,其特征在于,过渡金属盐为Fe、Cu、Zn、Mn、Co、Mo、W的硝酸盐或氯化物。
3.根据权利要求2所述的一种过渡金属基杂化材料纳米管的制备方法,其特征在于,过渡金属盐为Fe、Cu、Zn、Mn、Co、Mo、W的硝酸盐或氯化物的1~3种。
4.根据权利要求3所述的一种过渡金属基杂化材料纳米管的制备方法,其特征在于,当过渡金属盐的种类为2种或3种时,各个金属盐类物质的量比值为1。
5.根据权利要求1所述的一种过渡金属基杂化材料纳米管的制备方法,其特征在于,S1中离心的转速为3000-5000rpm,时间为3~5min。
6.根据权利要求1所述的一种过渡金属基杂化材料纳米管的制备方法,其特征在于,还包括,S3、碳化工序,碳化条件为:将S2中的过渡金属基杂化材料纳米管置于氩气氛围下,于400~500℃煅烧2~3h。
7.根据权利要求6所述的一种过渡金属基杂化材料纳米管的制备方法,其特征在于,S3的碳化工序是在管式炉中进行。
8.根据权利要求1-7任一项所述的方法制备的过渡金属基杂化材料纳米管。
9.根据权利要求8所述的一种过渡金属基杂化材料纳米管在制备催化剂、电池中的用途。
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