CN103769600B - 一种表面高分散贵金属高指数晶面纳米颗粒的制备方法 - Google Patents
一种表面高分散贵金属高指数晶面纳米颗粒的制备方法 Download PDFInfo
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 38
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000003223 protective agent Substances 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- 239000004332 silver Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000010931 gold Substances 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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Abstract
一种表面高分散贵金属高指数晶面纳米颗粒的制备方法，是将合成体系组分中的铜或银纳米颗粒加入至2M浓度的KCl溶液中，再加入保护剂PVP和贵金属前体溶液，常温下搅拌2小时后静置30个小时，制得样品。本发明由于贵金属分布于基底金属颗粒表面，保证了贵金属的高分散度和高利用率，对于三种贵金属，在常温下通过较简单工艺即在合成过程中将实验条件控制为本申请所筛选出的体系组成、配比及制备步骤都可以构建出高分散度的高指数晶面，体现了本发明的体系和方法具有较好的普适性，为其推广应用奠定了基础。
Description
技术领域
本发明涉及一种在相对便宜的金属纳米颗粒表面构建贵金属高指数晶面的可控合成新方法，特别是使贵金属以具有特殊性能的高指数晶面形态存在的同时兼具高分散度或高利用率的突出优点。
背景技术
贵金属如金、铂、钯等对于很多工业生产过程特别是一些重要的多相化学化工过程如石油精制、精细化工品合成、氢能转化等方面仍是不可缺少或重要的催化材料，这些重要应用依赖于贵金属材料的表面性质。研究表明，以高指数晶面形态存在的贵金属表面具有显著优于一般晶面的特殊物理化学性质，因而其合成与应用备受关注。但是从目前的制备方法看来，所得具有高指数贵金属晶面的样品都是尺寸较大如50nm的纯贵金属颗粒，虽然其表面是具有特殊优点的高指数晶面，但从颗粒整体尺寸看来，大部分贵金属原子处于体相中不可被利用，其分散度或利用率非常低，导致这些颗粒难以真正实际应用。因此，开发能使贵金属以高指数晶面形态存在兼具高分散度或高利用率的合成体系和方法是一项充满挑战性而意义重大的工作。从目前研究现状看来，合成具有高指数晶面纯贵金属颗粒并提高贵金属分散度的努力方向在于尽量合成小尺寸的颗粒，但是这方面的进展非常困难，因为控制贵金属颗粒的高指数晶面分布与减小其尺寸在实际合成中表现为一对相互对立的方面，针对这一情况，本发明突破合成此类材料的常规，以相对便宜的金属(铜，银等)纳米颗粒为基底，引入贵金属氯代化合物，在贵金属盐与基底金属颗粒表面之间进行氧化还原过程即基底金属颗粒表面氧化蚀刻同时还原沉积贵金属的过程中，辅以PVP作为形貌保护剂，通过精细调控体系中的组分组成及其配比发现确定了将贵金属以高指数晶面形态高度分散于纳米颗粒表面的可控合成条件和方法。
发明内容
本发明的目的是针对难以获得兼具高指数晶面和高分散度贵金属颗粒这一问题，通过独特的控制合成体系即以相对便宜的金属(铜，银等)纳米颗粒为基底，在其表面氧化还原置换沉积贵金属提供了一种在便宜金属纳米颗粒表面构建贵金属高指数晶面的新方法，由此为解决贵金属高指数晶面样品利用率低以及支持其相关应用研究提供了新参考。
所采取的技术方案是：
本发明在含有事先合成的具有一定形貌特征的相对便宜金属如铜、银纳米颗粒的水分散体系中，于常温下直接将贵金属(Au,Pd,Pt)的氯代化合物前体引入，并辅以一定量的表面活性剂如PVP，通过精细调控体系中的组分组成及其配比实现了由贵金属原子置换基底金属颗粒的表层原子并以高指数晶面形态存在，由此获得了贵金属以高指数晶面存在且其分散度显著提高的样品。
制备方法：
(1)合成体系的组分为：
贵金属前体溶液：HAuCl4、Na2PdCl4或K2PtCl4水溶液，取10-20mL水溶液，每mL溶液中含贵金属0.01-0.1mg；
基底颗粒：粒径为5-50nm的Ag纳米颗粒或粒径为20-100nm的Cu纳米颗粒，5.0-20.0mg
保护剂：PVP0.2-1.0g
(2)制备步骤：
将合成体系组分中的铜或银纳米颗粒加入至20mL2M浓度的KCl溶液中，再加入保护剂PVP和贵金属前体溶液，常温下搅拌2小时后静置30个小时，制得样品。
合成体系的控制因素：
通过透射电子显微镜(TEM)和X射线衍射谱图(XRD)分析表明，控制贵金属前体与基底金属的原子比是将贵金属以高指数形态置换于基底金属颗粒表面的关键因素，而体系中的阴离子以及保护剂也是影响样品形貌的重要影响因素，总之，通过控制这些因素，可以将Au、Pd、Pt在基底金属颗粒表面构建为高度分散的高指数晶面。(具体见实施范例)。
本发明的有益效果：
(1)在相对便宜的金属颗粒表面构建出了贵金属的高指数晶面。
(2)由于贵金属分布于基底金属颗粒表面，保证了贵金属的高分散度和高利用率。
(3)对于三种贵金属，在常温下通过较简单工艺都可以构建出高分散度的高指数晶面，体现了本发明的体系和方法具有较好的普适性，为其推广应用奠定了基础。
具体实施方式
实施例一：表层为Au晶面的凹面(高指数晶面)Ag纳米立方颗粒之合成
3mL含有7mgAg纳米立方颗粒的水分散液加入至20mL2MKCl溶液中，而后加入600mgPVP和10mL0.5mMHAuCl4溶液，室温下搅拌2小时候避光静置，30小时后得到样品，形貌如图1TEM照片显示，HAuCl4引入后，Ag纳米立方颗粒变化成为了表层为Au晶面的凹面(高指数晶面)Ag纳米立方颗粒。
实施例二：表层为Pd晶面的凹面(高指数晶面)Ag纳米立方颗粒之合成
3mL含有7mgAg纳米立方颗粒的水分散液加入至20mL2MKCl溶液中，而后加入600mgPVP和10mL0.5mMNa2PdCl4溶液，室温下搅拌2小时候后避光静置，30小时后得到样品，形貌如图2TEM照片显示，Na2PdCl4引入后，Ag纳米立方颗粒变化成为了表层为Pd晶面的凹面(高指数晶面)Ag纳米立方颗粒。
Claims (1)
1.一种表面高分散贵金属高指数晶面纳米颗粒的制备方法，其特征是：
(1)合成体系的组分为：贵金属前体溶液：HAuCl4、Na2PdCl4或K2PtCl4水溶液，取10-20mL水溶液，每mL溶液中含贵金属0.01-0.1mg；
基底颗粒：粒径为5-50nm的Ag纳米颗粒或粒径为20-100nm的Cu纳米颗粒5.0-20.0mg；
保护剂：PVP0.2-1.0g
(2)制备步骤：
将合成体系组分中的铜或银纳米颗粒加入至20mL2M浓度的KCl溶液中，再加入保护剂PVP和贵金属前体溶液，常温下搅拌2小时后静置30个小时，制得样品。
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| CN114073713B (zh) * | 2020-08-21 | 2023-07-11 | 中国科学技术大学 | 一种钯银纳米颗粒以及其应用和制备方法 |
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