CN110787796B - 一种具有规则表面纳米多孔金属的制备方法 - Google Patents

一种具有规则表面纳米多孔金属的制备方法 Download PDF

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CN110787796B
CN110787796B CN201911078879.0A CN201911078879A CN110787796B CN 110787796 B CN110787796 B CN 110787796B CN 201911078879 A CN201911078879 A CN 201911078879A CN 110787796 B CN110787796 B CN 110787796B
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习卫
侯新刚
罗俊
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Tianjin University of Technology
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Abstract

本发明公开了一种具有规则表面纳米多孔金属(NPM)的制备方法。先用脱合金法制备纳米多孔金属，此时NPM表面复杂无规则。然后将NPM作为催化剂，通入气体进行加热催化使其表面发生重构，表面逐渐变得规则有序，从而制备出具有规则表面的NPM。所述纳米多孔金属包括纳米多孔金、纳米多孔铜、纳米多孔银、以及纳米多孔钯。所述通入的气体包括CO、CO2、甲醇或者NO。本发明的制备工艺简单、普适性高，开创了具有大量规则表面NPM制备方法的先河，为纳米多孔材料暴露晶面的靶向调控提供了依据，同时有望扩大NPM的应用范围。

Description

一种具有规则表面纳米多孔金属的制备方法
技术领域
本发明是一种关于纳米多孔金属(NPM)的，特别涉及一种在催化反应过程中、表面原子重组而产生更稳定的高配位结构、制备出具有规则表面的纳米多孔金属。
背景技术
具有一定晶面的金属纳米催化材料在许多领域有广泛的应用，通过物理和化学方法使其具有规则晶面这种方式可以调节催化剂的催化活性和选择性。与传统的低维材料如纳米粒子，纳米线，纳米片和纳米薄膜相比，纳米多孔金属(NPM)的表面原子分布高度随机，表面形貌十分复杂，导致难以通过暴露特定的晶面来提高其催化活性和选择性。到目前为止，只有极少量的工作发现部分NPG的{111}晶面可以在低温CO氧化过程中形成，或通过优化脱合金条件可控制。所以怎样有效简单地制备具有规则表面的NPM是一个难题。
纳米多孔金属作为一类应用广泛的高活性催化剂，在催化反应过程中由于反应物的影响表面形貌会发生一定程度的变化。如果能利用催化反应制备出具有规则表面的NPM，那么对于提高NPM的高催化活性和选择性是重要的，并可以为NPM暴露晶面的靶向调控提供了依据。基于这种需求，开发一种制备具有规则表面纳米多孔金属的方法，是本专利申请的核心思想。
发明内容
本发明的目的，是为了克服现有技术的纳米多孔金属表面原子分布高度随机的缺陷，制备出一种具有规则表面的纳米多孔金属，为精确合成具有高选择性和稳定性的常规三维孔催化剂提供一种新的可行途径。
本发明通过如下技术方案予以实现：
本发明采用将合金薄膜通过脱合金法制备出NPM片，之后将NPM通入气体进行加热催化反应。催化过程中NPM表面原子重组从而获得具备规则表面的NPM。
一种具有规则表面纳米多孔金属的制备方法，具体步骤如下：
(1)采用脱合金法制备纳米多孔金属——纳米多孔金，缩写为NPG；
(2)将步骤(1)的NPG作为催化剂，通入甲烷气体进行热解反应；
整个气体系统先在常压下用氩气冲洗30分钟，然后引入纯甲烷气体，随后以30℃min–1的加热速率加热升高至300-500℃，发生明显的催化现象，反应后得到具有规则晶面的NPG；
催化过程中，NPG表面原子重组以产生更稳定的结构，使得NPG的韧带尺度在反应过程中逐渐变得更加规则，导致NPG形成规则表面。
所述步骤(1)的纳米多孔金属还包括纳米多孔铜、纳米多孔银、以及纳米多孔钯；
所述步骤(1)的纳米多孔金属也可以是通过电化学法或模板法获得。
所述步骤(2)中通入的气体还可以是CO、CO2、甲醇或者NO。
所述步骤(2)的加热设备为气相加热芯片，及其它在加热的同时可以引入气体的设备。
本发明开创了大量规则表面纳米多孔金属制备方法的先河，为精确合成具有高选择性和稳定性的常规三维孔催化剂提供新的可行途径。本发明的制备工艺简单、普适性高。
附图说明
图1是实施例1脱合金方法制备得到的纳米多孔金(NPG)的低倍TEM明场像；
图2是实施例1催化反应后得到的NPG的低倍TEM明场像；
图3是实施例1脱合金方法制备得到的NPG的SAED选区电子衍射图；
图4是实施例1催化反应后得到的NPG的SAED选区电子衍射图；
图5是实施例1脱合金方法制备得到的NPG的单个韧带的高倍TEM明场像；
图6是实施例1催化反应后得到的NPG的单个韧带的TEM明场像。
具体实施方式
下面通过以下具体实施例来进一步说明本发明。
实施例1
NPG催化甲烷热解反应获得具有规则晶面的NPG。
(1)使用脱合金法制备NPG。
将厚度为100nm的12Ka Au-Ag合金薄膜在恒温水浴30℃下的浓HNO3中进行去合金化30分钟，然后将脱合金薄膜浸入超纯水中35分钟。所得到的材料即为纳米多孔金，参见图1、图3和图5。图1为NPG的低倍TEM明场像，从图中可以看出其表面形貌比较复杂，没有规则表面的暴露；图3是其对应的SAED选区电子衍射，由图中可以看出微观结构为多晶；图5为单个韧带的高分辨TEM明场像，可以看出韧带表面原子分布高度随机，是既有正曲率又有负曲率的不规则表面。
(2)将步骤(1)中的NPG进行催化甲烷(CH4)热解反应。
使用加热芯片收集超纯水中的NPG片，将该芯片组装到原位TEM(这里所用加速电压为200kv)气相系统中进行原位观察。整个气体系统先在常压下用氩气冲洗30分钟，然后引入纯CH4气体。随后以30℃min–1的加热速率加热升高至346℃(发生明显的催化现象)。反应后得到的NPG因其韧带表面原子重组而形成具有规则晶面的NPG，参见图2、图4和图6。图2为反应过后NPG的低倍TEM明场像，从图中可以看出其表面形貌较为有序，暴露的表面也比较规则；图4是其对应的SAED选区电子衍射，由图中可以看出微观结构暴露大量{111}和{100}的规则表面；图6为反应过后NPG单个韧带的高分辨TEM明场像，可以看出韧带表面原子分布有序，从既有正曲率又有负曲率的不规则表面变为具有规则晶面的平整表面。

Claims (2)

1.一种具有规则表面纳米多孔金属的制备方法，具体步骤如下：
(1)采用脱合金法制备纳米多孔金属——纳米多孔金，缩写为NPG；
(2)将步骤(1)的NPG作为催化剂，通入甲烷气体进行热解反应；
整个气体系统先在常压下用氩气冲洗30分钟，然后引入纯甲烷气体，随后以30℃min–1的加热速率加热升高至300-500℃，发生明显的催化现象，反应后得到具有规则晶面的NPG；
催化过程中，NPG表面原子重组以产生更稳定的结构，使得NPG的韧带尺度在反应过程中逐渐变得更加规则，导致NPG形成规则表面。
2.根据权利要求1所述的一种具有规则表面纳米多孔金属的制备方法，其特征在于，所述步骤(2)的加热设备为气相加热芯片，及其它在加热的同时可以引入气体的设备。
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