CN113894288A - 一种超小、高分散金属纳米颗粒制备方法 - Google Patents
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Abstract
本发明属于纳米材料的制备领域，一种超小、高分散金属纳米颗粒的制备方法。将金属盐、结构导向剂和溶剂混合得混合液，将混合液置于水热釜中在120‑200℃下反应3‑10h，反应后冷却至室温，将悬浊液离心，即得超小、高分散金属纳米颗粒。本发明制备方法简单、易于操作、重复性好，可大规模生产，能均匀的分散到载体上，且制备出的金属颗粒具有粒径超小、颗粒大小均匀、分散度高、比表面积大等优势，在质子交换膜电池、传感器、超级电容器、工业催化等领域具有良好的应用前景。
Description
技术领域
本发明属于纳米材料的制备领域，一种超小、高分散金属纳米颗粒的制备方法。
背景技术
纳米材料，又被称为超细微材料，通常指在三维方向上至少存在一维方向处于纳米级(1-100nm)，或者是由纳米级别的材料作为基本单元而构成的材料。纳米材料的特殊结构使其作为一类新型材料具有重要的理化特性，通过调控其结构、形貌及尺寸等特征，可以有效地调节纳米材料的使用性能。目前，纳米材料在诸多技术领域中都展现出了重要的应用价值。
钌、铑、钯、铱、铂5个元素在地壳中的含量都非常少，化学性质稳定，对酸的化学稳定性极高，因此用途极广。在质子交换膜电池、传感器、超级电容器、工业催化等领域具有良好的应用前景。
但，这几类金属难还原，制备过程中容易团聚，制备其颗粒尺寸窄分布的超小纳米颗粒的常用方法是使用原子层沉积，化学气相沉积，脉冲激光沉积等。这些方法需要大量能量、对设备要求高、制作过程复杂，且制备出的颗粒在载体上分布不均匀。进而需要提供一种操作简单、所需设备简易、重复性好。而且能在载体上分布均匀，达到高分散性的金属纳米颗粒的制备方法。
发明内容
基于此，本发明的目的在于提供一种超小、高分散金属纳米颗粒的制备方法。
为实现上述目的，本发明所采用的技术方案为：
一种超小、高分散金属纳米颗粒的制备方法，其特征在于：将金属盐、结构导向剂和溶剂混合得混合液，将混合液置于水热釜中在120-200℃下反应3-10h，反应后冷却至室温，将悬浊液离心，即得超小、高分散金属纳米颗粒。
所述金属盐中的金属选自为钌、铑、钯、铱或铂。
所述金属盐为三氯化铱，溴化铱，醋酸铱，乙酰丙酮铱，乙酰丙酮铂，四氯化铂，醋酸铂，氯化钌，乙酰丙酮钌，醋酸钌，氯化钯，醋酸钯，乙酰丙酮钯，氯化铑，乙酰丙酮铑，醋酸铑中的一种或几种。
所述结构导向剂与溶剂的质量比为1:30-1:500；所述混合溶液中金属盐在溶剂的质量分数为0.1-5.0％。
所述溶剂为醇溶液；浓度为，醇溶液具体为乙二醇、苄醇、丙三醇、二乙二醇中的一种或几种；
所述混合液中金属盐的质量分数为0.1-5.0％；结构导向剂在混合溶液中的质量分数为0.1-3.0％。
所述结构导向剂为尿素，三乙醇胺，乌洛托品，三乙烯二胺，乙二胺，氨水中的一种或几种。
所述金属盐负载于载体上，而后与结构导向剂和溶剂混合得混合液；所述载体在混合溶液中的质量分数为0-3.0％(优选0.5-1.5％)。载体为Vulcan XC-72碳粉，BP2000碳粉，石墨，氧化石墨，石墨烯中的一种或几种
所述混合溶液置于聚四氟乙烯内衬的水热晶化釜中，密封反应，反应后降至室温，离心获得沉淀，并用有机溶剂洗涤沉淀3-5次，干燥，得黑色的催化剂颗粒；其中，清洗溶剂为无水甲醇、无水乙醇、异丙醇或叔丁醇中的一种或几种。
所述离心转速为9800-12000r/min，时间为5-10min；干燥温度为30-110℃，干燥时间为1-10h。
一种制备的超小高分散金属纳米颗粒，按所述制备方法获得纯度为99.999％、平均粒径大小<2nm的超小高分散金属。
相对于现有技术，本发明所提供的制备方法具有以下优势：
(1)本发明制备方法采用水热合成法，方法简单，所需的设备价格低廉，操作方便、重复性好、易于大规模生产，制备过程中也不会产生有害身体和污染空气的气体，制备过程绿色化，因此具有巨大的潜在应用价值。
(2)本发明方法制备出的超小高分散纳米颗粒尺寸小(<2nm)，粒径分布窄，在催化过程中可以暴露更多的高活性位点，从而大大提高催化活性。
(3)本发明方法在制备过程中加入结构导向剂，结构导向剂的存在一方面可以调控颗粒尺寸，另一方面保证了纳米颗粒在载体表面分散均匀，从而达到高分散的效果。
(4)本发明方法制备出的超小高分散纳米颗粒具有99.999％的高纯度优点，在质子交换膜电池、传感器、超级电容器、工业催化等领域具有良好的应用前景。
附图说明
图1为本发明实施例提供的实施例1合成的超小高分散铱纳米颗粒的TEM图。
图2为本发明实施例1获得纳米粒子的粒径分布图。
图3为本发明实施例提供的实施例2合成的超小高分散铂纳米颗粒的TEM图。
图4为为本发明实施例2获得纳米粒子的粒径分布图。
图5为本发明实施例提供的实施例3合成的超小高分散钯纳米颗粒的TEM图。
图6为为本发明实施例3获得纳米粒子的粒径分布图。
具体实施方式
以下结合附图和实施例对本发明做进一步详细说明，但该实施例并不以任何形式限制本发明。
实施例1
0.5g乙酰丙酮铱溶解在150ml的丙三醇中，加入3g乌洛托品，充分搅拌均匀到全部溶解。加入1.5g的BP2000碳粉，搅拌30min。将上述溶液转移至250ml晶化釜中，密封，在200℃反应6h。反应结束后，将水热釜取出并自然冷却至室温。将所得沉淀用无水乙醇洗涤3次，在100℃下干燥5h，即可得纯度为99.999％的超小高分散负载型铱纳米颗粒(参见图1)。
由图1可见，通过实施例1可以获得高纯度超小高分散铱纳米颗粒子密集且均匀的地分散在BP2000载体上，未出现团聚现象，呈现高分散的特征，图2粒径分布可看出颗粒平均尺寸大小在1.3nm左右，并且颗粒尺寸分布在0.6-2.2nm之间，尺寸分布窄。
实施例2
0.65g乙酰丙酮铂溶解在150ml的苄醇中，加入1.3g三乙醇胺，充分搅拌均匀到全部溶解，形成透明溶液。加入1.5g的Vulcan XC-72碳粉，搅拌30min，。将上述溶液转移至250ml晶化釜中，密封，在120℃反应8h。反应结束后，将水热釜取出并自然冷却至室温。将所得沉淀用无水甲醇洗涤3次，在100℃下干燥5h，即可得纯度为99.999％的超小高分散铂纳米颗粒(参见图2)。
由图3可见，通过实施例2可以获得超小高分散铂纳米颗粒密集且均匀的地分散在Vulcan XC-72载体上，未出现团聚现象，呈现高分散的特征，图4粒径分布可看出颗粒尺寸在1.4nm左右，未发现有其它杂质残留。
实施例3
0.6g醋酸钯溶解在150ml的二乙二醇中，加入0.5g尿素，充分搅拌均匀到全部溶解。将上述溶液转移至250ml晶化釜中，密封，在140℃反应6h。反应结束后，将水热釜取出并自然冷却至室温。将所得沉淀用无水乙醇洗涤3次，在100℃下干燥5h，即可得纯度为99.999％的超小高分散钯纳米颗粒(参见图3)。
由图5可见，通过实施例3可以获得高纯度超小高分散钯纳米颗粒粉末，图6粒径分布可看出颗粒尺寸在1.5nm左右，并且颗粒尺寸分布在0.6-2.1nm之间，尺寸分布窄，且未发现有其它杂质残留。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无法对所有的实施方式予以穷举。凡是属于本发明的技术方案所隐身出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (9)
1.一种超小、高分散金属纳米颗粒的制备方法，其特征在于：将金属盐、结构导向剂和溶剂混合得混合液，将混合液置于水热釜中在120-200℃下反应3-10h，反应后冷却至室温，将悬浊液离心，即得超小、高分散金属纳米颗粒。
2.根据权利要求1所述的超小高分散金属纳米颗粒的制备方法，其特征在于：所述金属盐中的金属选自为钌、铑、钯、铱或铂。
3.根据权利要求2所述的超小高分散金属纳米颗粒的制备方法，其特征在于：所述金属盐为三氯化铱，溴化铱，醋酸铱，乙酰丙酮铱，乙酰丙酮铂，四氯化铂，醋酸铂，氯化钌，乙酰丙酮钌，醋酸钌，氯化钯，醋酸钯，乙酰丙酮钯，氯化铑，乙酰丙酮铑，醋酸铑中的一种或几种。
4.根据权利要求1所述的超小高分散金属纳米颗粒的制备方法，其特征在于：所述结构导向剂与溶剂的质量比为1:30-1:500；所述混合溶液中金属盐在溶剂中的质量分数为0.1-5.0％。
5.根据权利要求1-5任意一项所述的超小高分散金属纳米颗粒的制备方法，其特征在于：所述结构导向剂为尿素，三乙醇胺，乌洛托品，三乙烯二胺，乙二胺，氨水中的一种或几种。
6.根据权利要求1所述的超小高分散金属纳米颗粒的制备方法，其特征在于：所述金属盐负载于载体上，而后与结构导向剂和溶剂混合得混合液；所述载体在混合溶液中的质量分数为0-3.0％。
7.根据权利要求1或6所述的超小高分散金属纳米颗粒的制备方法，其特征在于：所述混合溶液置于聚四氟乙烯内衬的水热晶化釜中，密封反应，反应后降至室温，离心获得沉淀，并用有机溶剂洗涤沉淀3-5次，干燥，得黑色的催化剂颗粒；其中，溶剂为无水甲醇、无水乙醇、异丙醇或叔丁醇中的一种或几种。
8.根据权利要求7所述的超小高分散金属纳米颗粒的制备方法，其特征在于：所述离心转速为9800-12000r/min，时间为5-10min；干燥温度为30-110℃，干燥时间为1-10h。
9.一种权利要求1制备的超小高分散金属纳米颗粒，其特征在于：按所述权利要求1的制备方法获得纯度为99.999％、平均粒径大小<2nm的超小高分散金属。
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792432A (zh) * | 2005-11-17 | 2006-06-28 | 上海交通大学 | 负载贵金属的碳纳米材料的制备方法 |
| CN101773853A (zh) * | 2009-01-14 | 2010-07-14 | 中国科学院大连化学物理研究所 | 一种非担载型催化剂浆料及其制备和应用 |
| CN102205420A (zh) * | 2010-03-31 | 2011-10-05 | 中国科学院福建物质结构研究所 | 一种水相贵金属纳米颗粒的制备方法 |
| CN102974365A (zh) * | 2012-12-12 | 2013-03-20 | 天津工业大学 | 负载型高分散多组份贵金属纳米颗粒催化剂的制备方法 |
| US20150183028A1 (en) * | 2012-08-11 | 2015-07-02 | Council Of Scientific & Industrial Research | One pot process for the preparation of ultra-small size transition metal nonoparticles |
| CN105032449A (zh) * | 2015-07-11 | 2015-11-11 | 哈尔滨工业大学 | 一种多元梯度金属基纳米颗粒催化剂及其制备方法 |
| CN109841856A (zh) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | 一种燃料电池用单分散核壳纳米催化剂的制备方法 |
| CN110841631A (zh) * | 2019-10-18 | 2020-02-28 | 东北大学 | 一种高活性钯碳催化剂的制备方法 |
-
2020
- 2020-07-06 CN CN202010639923.7A patent/CN113894288B/zh active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792432A (zh) * | 2005-11-17 | 2006-06-28 | 上海交通大学 | 负载贵金属的碳纳米材料的制备方法 |
| CN101773853A (zh) * | 2009-01-14 | 2010-07-14 | 中国科学院大连化学物理研究所 | 一种非担载型催化剂浆料及其制备和应用 |
| CN102205420A (zh) * | 2010-03-31 | 2011-10-05 | 中国科学院福建物质结构研究所 | 一种水相贵金属纳米颗粒的制备方法 |
| US20150183028A1 (en) * | 2012-08-11 | 2015-07-02 | Council Of Scientific & Industrial Research | One pot process for the preparation of ultra-small size transition metal nonoparticles |
| CN102974365A (zh) * | 2012-12-12 | 2013-03-20 | 天津工业大学 | 负载型高分散多组份贵金属纳米颗粒催化剂的制备方法 |
| CN105032449A (zh) * | 2015-07-11 | 2015-11-11 | 哈尔滨工业大学 | 一种多元梯度金属基纳米颗粒催化剂及其制备方法 |
| CN109841856A (zh) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | 一种燃料电池用单分散核壳纳米催化剂的制备方法 |
| CN110841631A (zh) * | 2019-10-18 | 2020-02-28 | 东北大学 | 一种高活性钯碳催化剂的制备方法 |
Non-Patent Citations (2)
| Title |
|---|
| 赵鹏,姚燕燕,田晓珍,许启明,A.GEDANKEN: "醇热还原法制备纳米金属钌颗粒", 中国有色金属学报, no. 11, pages 1953 - 1957 * |
| 黄涛;于明;刁香菊;刘汉范;: "金属钌纳米颗粒的形貌控制合成", 中南民族大学学报(自然科学版), no. 01, pages 1 - 4 * |
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