CN114471703A - 一类小尺寸双过渡金属氧化物纳米簇及其制备方法 - Google Patents
一类小尺寸双过渡金属氧化物纳米簇及其制备方法 Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B01J35/33—
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Abstract
本发明提供了一种小尺寸双过渡金属氧化物纳米簇及其制备方法,所述纳米簇结构式为M1 nM2 1‑nOm@IL;其中,M1和M2各自独立地选自Fe,Ni,Co,Zn和Cu中的一种;IL为咪唑型离子液体配体;n=0.01‑1,n和1‑n表示的是M2与M1的摩尔百分数占比;m=1‑1.5,m表示氧原子的个数;所述纳米簇的尺寸为1~2纳米。本发明所提供的小尺寸双过渡金属氧化物纳米簇的合成方法简单易行、产率高,相比于常用双过渡金属氧化物纳米颗粒,尺寸均一,同时具有稳定性优良,绿色环保等优点。
Description
技术领域
本发明属于纳米材料技术领域,特别涉及一类小尺寸1-2nm双过渡金属氧化物纳米簇的简单高效合成及制备。
背景技术
近年来,小尺寸双金属氧化物纳米簇由于其独特的化学物理特性引起了国内外研究者巨大的兴趣。双金属氧化物纳米簇的尺寸(1-2纳米)介于分子和传统纳米颗粒。双金属氧化物纳米簇超小的尺寸导致金属氧化物纳米簇具有非常高的表面原子占有率以及金属氧化物纳米簇表面的丰富缺陷,比如氧空位和金属空位。由于双金属氧化物纳米簇的尺寸与费米波长相当,所以具有独特的电子结构,在许多应用中表现优异,例如OER电催化。而传统的合成方法(例如共沉淀法和化学沉淀法)很难获得小尺寸双金属氧化物纳米簇(1-2纳米),往往合成大尺寸的双金属氧化物纳米颗粒。
目前,功能化有机配体在合成小尺寸贵金属纳米簇(Au,Pd,Pt等)得到广泛地应用(专利号:ZL 201510940346.4),此专利是利用贵金属的纳米团簇制备,贵金属的团簇合成目前是很成熟的技术,但该专利没有对过渡金属进行小尺寸制备。但是关于小尺寸过渡金属氧化物纳米簇,特别是关于小尺寸双金属氧化物纳米簇的合成方法鲜有报道。在一种小尺寸金属氧化物纳米簇/介孔SiO2纳米复合材料及其制备方法(CN106000391B)中提到MoO3和WO3纳米簇与SiO2复合材料的制备,所采用的合成方法是反相微乳法,但该专利得到的团簇尺寸较大,没有达到1-2nm尺度。在负载型过渡金属或过渡金属合金纳米簇催化剂及其制备方法与应用(CN101670286A)中提到利用“碱-多醇法”合成的过渡金属或合金纳米簇负载型催化剂,同样该专利尺寸也较大,我们的专利发明在纳米尺度上具有明显优势。同时基于对专利的搜索发现关于贵金属的团簇合成很多,但金属氧化物纳米簇的很少。
发明内容
针对以上技术问题,本发明的目的是提供一种小尺寸(1-2纳米)双过渡金属氧化物纳米簇的制备方法。该方法具有简单易行,经济适用,产率高等特点。
本发明技术方案如下:
一方面,本发明提供了一种被有机配体保护的双过渡金属氧化物纳米簇,结构式为M1 nM2 1-nOm@IL,M1和M2为过渡金属(Fe,Ni,Co,Zn和Cu中的一种),IL为咪唑型离子液体,n=0.01-1,n和1-n表示的是M2与M1的摩尔百分数占比,m=1-1.5,m表示氧原子的个数;双过渡金属原子簇粒径尺寸为1-2nm。
基于上述方案,优选地,双过渡金属原子簇为Fe,Ni,Co,Zn和Cu中的二种;咪唑型离子液体是1-乙基-3-甲基咪唑六氟磷酸盐,1-己基-3-甲基咪唑氯盐,1-胺丙基-3-甲基咪唑四氟硼酸盐,1-辛基-3-甲基咪唑四氟硼酸盐,1-丁基-3-甲基咪唑六氟磷酸盐中的一种,
基于上述方案,优选地,n=0.1~0.33;m=1.1~1.3。
基于上述方案,优选地,所述咪唑型离子液体配体与M2和M1的总摩尔比为2:1-5:1。
基于上述方案,优选地,所述双过渡金属原子簇是一种溶胶。
另一方面,本发明提供了一种上述小尺寸双过渡金属氧化物纳米簇的制备方法,所述方法包括以下步骤:
将M1和M2的金属前驱体溶于甲醇/水混合溶液体系,加入咪唑型离子液体配体,搅拌0.5~10小时后,加入无机碱,继续搅拌0.5~10小时,停止反应,得到所述纳米簇。
基于上述方案,优选地,所述过渡金属前驱体为相应过渡金属的硝酸盐或醋酸盐。
基于上述方案,优选地,所述溶剂为甲醇和水的混合溶剂,甲醇和水的比例为1:1~10:1。
基于上述方案,优选地,所述无机碱为氢氧化钠,氢氧化钾中的一种。
基于上述方案,优选地,控制咪唑型离子液体配体与总过渡金属盐的摩尔比为2:1-5:1;控制无机碱与总过渡金属盐的摩尔比为100:1-300:1。
基于上述方案,优选地,反应在常温15-40℃下进行。
一类小尺寸(1-2纳米)双过渡金属氧化物纳米簇的制备方法,具体包括以下实验步骤:
以二种过渡金属盐为反应原料,按一定的比例,将其置于50ml的三口圆底烧瓶中,溶于一定量的甲醇/水混合溶液体系中,加入适量的咪唑型离子液体配体,搅拌一定的时间,加入适量的无机碱,再搅拌一定的时间,停止反应。
本发明提供的小尺寸双过渡金属氧化物纳米簇可用于电催化领域。
有益效果
(1)本发明所提供的小尺寸双过渡金属氧化物纳米簇的合成方法简单易行、产率高。
(2)本发明所提供的小尺寸双过渡金属氧化物纳米簇具有丰富氧空位缺陷,有利于催化活性的提高。
(3)本发明所提供的小尺寸双过渡金属氧化物纳米簇相比于常用双过渡金属氧化物纳米颗粒,尺寸均一。
(4)本发明提供的小尺寸双过渡金属氧化物纳米簇是一种非晶态水溶性溶胶,有利于负载于其他材料使用。
(5)本发明提供的小尺寸双过渡金属氧化物纳米簇,稳定性优良,图2的TEM衍射图和图4的XRD图可说明结晶稳定,绿色环保。
附图说明
图1为实施例1制备的Fe0.5Ni0.5O1.25@1-乙基-3-甲基咪唑纳米簇的透射电子显微镜图(TEM),表明金属团簇尺寸小,在1-2nm范围;
图2为实施例1制备的Fe0.5Ni0.5O1.25@1-乙基-3-甲基咪唑纳米簇的电子衍射图,说明金属纳米簇形成微晶,有利于稳定性;
图3为实施例2制备的Fe0.5Ni0.5O1.25@1-乙基-3-甲基咪唑纳米簇的光电子能谱图(O1s XPS),中间的峰突出表明缺陷氧含量高,有利于提高催化活性;
图4为实施例3制备的Cu0.33Ni0.67O1@1-胺丙基-3-甲基咪唑纳米簇的粉末衍射图,同样说明形成的纳米簇形成微晶有利于稳定性;
图5为实施例4制备的Fe0.5Co0.5O1.25@1-辛基-3-甲基咪唑纳米簇的Tyndall效应图,说明得到的纳米簇尺寸很小对光有折射作用。
图6为对比例1的Fe0.5Ni0.5O1.25透射电镜照片,其中显示常规方法制备的铁镍氧化物微观尺寸很大。
具体实施方式
下面结合附图及具体实施案例来对本发明作进一步的详细说明。
实施例1合成产物为Fe0.5Ni0.5O1.25@1-乙基-3-甲基咪唑
以~40.4mg Fe(NO3)3 9H2O和29.1mg Ni(NO3)2 6H2O为反应原料,将其置于50ml的三口圆底烧瓶中,溶于30ml的甲醇/水溶液体系中,加入~204mg 1-乙基-3-甲基咪唑六氟磷酸盐,在室温下搅拌30分钟,加入160mg NaOH,在室温下再搅拌4小时,停止反应,得到产物Fe0.5Ni0.5O1.25@1-乙基-3-甲基咪唑。
实施例2合成产物为Co0.5Ni0.5O1@1-丁基-3-甲基咪唑
以~29.1mg Co(NO3)2 6H2O和29.1mg Ni(NO3)2 6H2O为反应原料,将其置于50ml的三口圆底烧瓶中,溶于30ml的甲醇/水溶液体系中,加入~213mg 1-丁基-3-甲基咪唑六氟磷酸盐,在室温下搅拌30分钟,加入160mg NaOH,在室温下再搅拌4小时,停止反应,得到产物Co0.5Ni0.5O1@1-丁基-3-甲基咪唑。实施例2所得小尺寸纳米簇的高分辨透射电镜图与实施例1相似。
实施例3合成产物为Cu0.33Ni0.67O1@1-胺丙基-3-甲基咪唑
以~16.1mg Cu(NO3)2 3H2O和43.5mg Ni(NO3)2 6H2O为反应原料,将其置于50ml的三口圆底烧瓶中,溶于30ml的甲醇/水溶液体系中,加入~138mg 1-胺丙基-3-甲基咪唑四氟硼酸盐,在室温下搅拌30分钟,加入214mg KOH,在室温下再搅拌4小时,停止反应,得到产物Cu0.33Ni0.67O1@1-胺丙基-3-甲基咪唑。实施例3所得纳米簇的高分辨透射电镜图与实施例1相似。
实施例4合成产物为Fe0.5Co0.5O1.25@1-辛基-3-甲基咪唑
以~24.9mg Co(OAc)2 6H2O和~40.4mg Fe(NO3)3 9H2O为反应原料,将其置于50ml的三口圆底烧瓶中,溶于30ml的甲醇/水溶液体系中,加入~247mg 1-辛基-3-甲基咪唑四氟硼酸盐,在室温下搅拌30分钟,加入160mg NaOH,在室温下再搅拌4小时,停止反应,得到Fe0.5Co0.5O1.25@1-辛基-3-甲基咪唑。实施例4所得纳米簇的高分辨透射电镜图与实施例2相似。
实施例5合成Fe0.67Zn0.33O1.33@1-丁基-3-甲基咪唑
以~14.5mg Zn(OAc)2 6H2O和~60.5mg Fe(NO3)3 9H2O为反应原料,将其置于50ml的三口圆底烧瓶中,溶于30ml的甲醇/水溶液体系中,加入~199mg 1-丁基-3-甲基咪唑六氟磷酸盐,在室温下搅拌30分钟,加入233mg KOH,在室温下再搅拌4小时,停止反应,得到Fe0.67Zn0.33O1.33@1-丁基-3-甲基咪唑。实施例5所得纳米簇的高分辨透射电镜图与实施例2一致。
对比例合成产物为Fe0.5Ni0.5O1.25
以~40.4mg Fe(NO3)3 9H2O和29.1mg Ni(NO3)2 6H2O为反应原料,将其置于50ml的三口圆底烧瓶中,溶于30ml的水溶液体系中,在室温下搅拌30分钟,加入160mg NaOH,在室温下再搅拌4小时,停止反应,得到产物Fe0.5Ni0.5O1.25。图6位对比例的样品透射电镜图。
Claims (9)
1.一种小尺寸双过渡金属氧化物纳米簇,其特征在于,所述纳米簇结构式为M1 nM2 1-nOm@IL;
其中,M1和M2各自独立地选自Fe,Ni,Co,Zn和Cu中的一种;
IL为咪唑型离子液体配体;
n=0.01-1,n和1-n表示的是M2与M1的摩尔百分数占比;
m=1-1.5,m表示氧原子的个数;所述纳米簇的尺寸为1~2纳米。
2.根据权利要求1所述的小尺寸双过渡金属氧化物纳米簇,其特征在于,所述M1和M2选自Fe,Ni,Co,Zn和Cu中的两种。
3.根据权利要求1所述的小尺寸双过渡金属氧化物纳米簇,其特征在于,所述咪唑型离子液体为1-乙基-3-甲基咪唑六氟磷酸盐,1-己基-3-甲基咪唑氯盐,1-胺丙基-3-甲基咪唑四氟硼酸盐,1-辛基-3-甲基咪唑四氟硼酸盐及1-丁基-3-甲基咪唑六氟磷酸盐中的一种。
4.根据权利要求1所述的小尺寸双过渡金属氧化物纳米簇,其特征在于:所述咪唑型离子液体配体与M2和M1的总摩尔比为2:1-5:1。
5.根据权利要求1所述的小尺寸双过渡金属氧化物纳米簇,其特征在于:所述纳米簇以溶胶形式存在。
6.一种权利要求1~5任一所述的小尺寸双过渡金属氧化物纳米簇的制备方法,其特征在于,所述方法包括以下步骤:
将M1和M2的金属前驱体溶于甲醇/水混合溶液体系,加入咪唑型离子液体配体,搅拌0.5~10小时后,加入无机碱,继续搅拌0.5~10小时,停止反应,得到所述纳米簇。
7.根据权利要求6所述的制备方法,其特征在于:所述无机碱为氢氧化钠或氢氧化钾;所述金属前驱体为M1和M2的硝酸盐或醋酸盐;所述甲醇和水的比例为1:1~10:1;所述反应在15-40℃下进行。
8.根据权利要求6所述的制备方法,其特征在于:所述无机碱与M1和M2的总摩尔比为100:1-300:1。
9.一种权利要求1所述的小尺寸双过渡金属氧化物纳米簇在电催化中的应用。
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CN106800315A (zh) * | 2017-01-17 | 2017-06-06 | 上海交通大学 | 一种离子液体辅助微波辐射法合成超小磁性纳米簇的方法 |
CN107537517A (zh) * | 2016-06-29 | 2018-01-05 | 北京大学 | 一种合金胶体及其制备方法与应用 |
CN110706944A (zh) * | 2019-09-12 | 2020-01-17 | 陕西国防工业职业技术学院 | 一步电沉积法制备3d针状镍钴双金属氧化物纳米簇的方法 |
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CN107537517A (zh) * | 2016-06-29 | 2018-01-05 | 北京大学 | 一种合金胶体及其制备方法与应用 |
CN106800315A (zh) * | 2017-01-17 | 2017-06-06 | 上海交通大学 | 一种离子液体辅助微波辐射法合成超小磁性纳米簇的方法 |
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