CN112589090B - 一种单质态和氧化态共混的金属纳米粉末的制备方法 - Google Patents

一种单质态和氧化态共混的金属纳米粉末的制备方法 Download PDF

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CN112589090B
CN112589090B CN202011226968.8A CN202011226968A CN112589090B CN 112589090 B CN112589090 B CN 112589090B CN 202011226968 A CN202011226968 A CN 202011226968A CN 112589090 B CN112589090 B CN 112589090B
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朱正旺
赵博文
张海峰
张宏伟
李宏
付华萌
王爱民
李正坤
张龙
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Abstract

本发明提供了一种利用非晶合金为前驱体制备成分可控的金属单质态和氧化态共混纳米粉末的方法，具体为：分别以二元、三元和四元Zr基非晶合金粉末为前驱体，在空气气氛下燃烧并进行高能球磨处理，制备得到金属单质和氧化态共混的纳米粉末；按原子百分比计，Zr基非晶合金化学成分为：二元Zr基非晶合金：ZrxM100‑x，50≤x≤80，M代表Ni或Pd；三元Zr基非晶合金：ZrxCuyM’100‑x‑y，40≤x≤75，15≤y≤35，M’代表Ag或Al；四元Zr基非晶合金：ZrxCuyAlzM”100‑x‑y‑z，40≤x≤65，30≤y≤65，2≤z≤10，M”代表Ag、Ni、Ti、Gd或Y中的一种。本发明采用空气气氛燃烧和机械球磨相结合的方法，制备出金属单质态和金属氧化态共混的纳米粉末，合成路线简单可靠，可得到纯度高、尺寸小、分散度好、形貌优良、成分可控、活性高、选择性好的纳米粉末。

Description

一种单质态和氧化态共混的金属纳米粉末的制备方法
技术领域
本发明属于金属氧化物的制备技术领域，具体涉及一种单质态和氧化态共混的金属纳米粉末的制备方法。该纳米粉末可应用于二氧化碳加氢制甲醇、析氢或析氧反应、有机物合成与转化以及有机废水降解等多种化学反应过程。
背景技术
金属氧化物在物理、化学和材料科学等众多领域中起着至关重要的作用。金属氧化物一直是功能材料研究领域的热点，由于具有氧化物特有的物理化学性质，被广泛应用于光学、催化、电子及生物医学等行业。同时，金属氧化物拥有较好的热稳定性和化学稳定性，易于制备和进一步功能化，通常被用作氧化催化剂或者还原催化剂，在化学催化反应中有着重要作用。由于纳米材料具有表面与界面效应、小尺寸效应、量子尺寸效应和宏观隧道效应等独特性能，将金属氧化物催化剂纳米化处理或者合成金属氧化物纳米材料，可以明显减小催化剂的尺寸，进而增大其比表面积，提高催化剂的催化活性和选择性。此外，催化剂中形成的金属氧化物的种类和形态在催化反应中尤为重要，因此，迫切需要开发一种成分可控的金属氧化物纳米材料的制备方法。本发明所述的燃烧法为金属氧化物纳米粉末的制备提供了一条简单、绿色、有效的合成路线，能够实现金属单质态和金属氧化态混合的纳米粉末催化剂的高效制备。
发明内容
为了克服金属纳米粉末制备过程中存在的问题，本发明提供了一种利用非晶合金为前驱体制备成分可控且分布均匀、颗粒尺寸均一、稳定性高以及比表面积大的金属单质态和氧化态共混纳米粉末的有效方法。
为了实现上述目的，本发明可以通过以下措施完成：
一种单质态和氧化态共混的金属纳米粉末的制备方法，其特征在于：分别以二元、三元和四元Zr基非晶合金粉末为前驱体，在空气气氛下燃烧并进行高能球磨处理，制备得到金属单质和氧化态共混的纳米粉末；
按原子百分比计，Zr基非晶合金化学成分为：
二元Zr基非晶合金：ZrxM100-x
其中：50≤x≤80，M代表Ni或Pd；
三元Zr基非晶合金：ZrxCuyM’100-x-y
其中：40≤x≤75，15≤y≤50，M’代表Ag或Al；
四元Zr基非晶合金：ZrxCuyAlzM”100-x-y-z
其中：40≤x≤65，30≤y≤65，2≤z≤10，M”代表Ag、Ni、Ti、Gd或Y中的一种。
本发明所述单质态和氧化态共混的金属纳米粉末的制备方法，其特征在于：将不同成分的合金通过气雾化法制备成非晶粉末，并使其在空气气氛下发生燃烧反应，然后将燃烧所得氧化产物研磨至200目以下置于行星式球磨机中进行高能球磨得到混合粉体；
气雾化制粉参数：喷粉气体流量：0.4～0.8m3/h；球磨参数：球料比：10:1～30:1，转速：100～400rpm/min，球磨时间：0.5～12h。
进一步优选为：气雾化制粉参数：喷粉气体流量：0.45～0.65m3/h；球磨参数：球料比：15:1～30:1，转速：250～350rpm/min，球磨时间：2～4h。
本发明选用纯度≥99.5wt％的纯金属单质原材料锆、铜、镍、钯、铝、银、钛、钆或钇制备Zr基非晶合金粉末。
采用本发明所述方法制备的单质态和氧化态共混的金属纳米粉末，其特征在于，所述纳米粉末为以下任一组合：一种金属单质和一种金属氧化物，一种金属单质和多种金属氧化物，两种金属单质和多种金属氧化物以及多种金属单质和多种金属氧化物；该粉末具有良好催化反应活性和高选择性等优势。
本发明的有益效果为：
本发明采用空气气氛燃烧和机械球磨相结合的方法，制备出金属单质态和金属氧化态共混的纳米粉末，合成路线简单可靠，可得到纯度高、尺寸小、分散度好、形貌优良、成分可控、活性高、选择性好的纳米粉末。可广泛应用于二氧化碳加氢制甲醇、析氢或析氧反应、有机物合成与转化以及有机废水降解等多种化学反应过程。
附图说明
图1是分别由实施例1-2实验过程中得到的OP和NP实物图。
图2是由实施例1所制金属单质态和氧化态共混的纳米粉末NP的TEM照片。
图3是由实施例1中研磨工艺后所制氧化物粉末OP的XRD曲线。
图4是由实施例2中研磨工艺后所制氧化物粉末OP的XRD曲线。
图5是由实施例3中研磨工艺后所制氧化物粉末OP的XRD曲线。
具体实施方式
为使本发明的目的、技术方案和优势更加清楚，下面将结合各实施方式进行详细的阐述，可以实现本发明各权利要求所要求保护的技术方案。
实施例1-7
由非晶合金粉末制备金属单质和金属氧化态共混纳米粉末的方法包括如下步骤：
1、非晶粉末及氧化产物的制备
(1)将按照化学成分原子百分比配制好的合金成分(纯度大于99.5％)放入到非自耗真空电弧熔炼炉内，预抽真空至3.0×10-3Pa后，充入高纯氩气作为保护气，利用电弧加热熔炼金属原料，多次反复熔炼以致完全均匀得到母合金锭。
(2)将步骤(1)熔炼均匀的母合金切割成大小适中的小块合金锭放入气雾化坩埚内，控制气体流量为0.1m3/h，保护母合金融化过程中不被氧化，同时通过气压阀控制体系的气压达到气雾化压力值0.15MPa，然后利用感应加热将合金锭融化，迅速加大进入气雾化坩埚气体流量至0.45～0.65m3/h进而得到非晶粉末，所得非晶粉末通过连续加热反应器使非晶粉末发生类燃烧反应得到金属氧化复合物粉末并研磨至200目以下，记为OP。
2、金属单质和氧化态共混纳米粉末的制备
将上述所得的金属氧化物复合粉末置于行星式球磨机中进行高能球磨处理进而得到纳米粉末，记为NP。球磨参数：球料比：15:1～25:1，转速：250～350rpm/min，球磨时间：2～4h。
实施例1-7的Zr基非晶合金的化学成分元素比例详见表1。
实施例1-7的由Zr基非晶合金制备的纳米粉末中氧化物的种类详见表2。
表1Zr基非晶合金的化学成分元素比例
Figure BDA0002763884590000051
表2纳米粉末中氧化物的种类
Figure BDA0002763884590000052
Figure BDA0002763884590000061
本发明未尽事宜为公知技术。
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。

Claims (6)

1.一种单质态和氧化态共混的金属纳米粉末的制备方法，其特征在于：分别以二元、三元和四元Zr基非晶合金粉末为前驱体，在空气气氛下燃烧并进行高能球磨处理，制备得到金属单质和氧化态共混的纳米粉末；
按原子百分比计，Zr基非晶合金化学成分为：
二元Zr基非晶合金：ZrxM100-x
其中：50≤x≤80，M代表Ni或Pd；
三元Zr基非晶合金：ZrxCuyM’100-x-y
其中：40≤x≤75，15≤y≤50，M’代表Ag或Al；
四元Zr基非晶合金：ZrxCuyAlzM”100-x-y-z
其中：40≤x≤65，30≤y≤65，2≤z≤10，M”代表Ag、Ni、Ti、Gd或Y中的一种；
所述纳米粉末为以下任一组合：一种金属单质和一种金属氧化物，一种金属单质和多种金属氧化物，两种金属单质和多种金属氧化物以及多种金属单质和多种金属氧化物。
2.按照权利要求1所述单质态和氧化态共混的金属纳米粉末的制备方法，其特征在于：将不同成分的合金通过气雾化法制备成非晶粉末，并使其在空气气氛下发生燃烧反应，然后将燃烧所得氧化产物研磨至200目以下置于行星式球磨机中进行高能球磨得到混合粉体；
气雾化制粉参数：喷粉气体流量：0.4～0.8m3/h；球磨参数：球料比：10：1～30：1，转速：100～400rpm/min，球磨时间：0.5～12h。
3.按照权利要求1或2所述单质态和氧化态共混的金属纳米粉末的制备方法，其特征在于：喷粉气体流量：0.45～0.65m3/h；球磨参数：球料比：15：1～30：1，转速：250～350rpm/min，球磨时间：2～4h。
4.按照权利要求1所述单质态和氧化态共混的金属纳米粉末的制备方法，其特征在于：选用纯度≥99.5wt％的纯金属单质原材料锆、铜、镍、钯、铝、银、钛、钆或钇制备Zr基非晶合金粉末。
5.一种采用权利要求1所述方法制备的单质态和氧化态共混的金属纳米粉末，其特征在于，所述纳米粉末为以下任一组合：一种金属单质和一种金属氧化物，一种金属单质和多种金属氧化物，两种金属单质和多种金属氧化物以及多种金属单质和多种金属氧化物。
6.一种权利要求5所述单质态和氧化态共混的金属纳米粉末的应用，其特征在于：所述单质态和氧化态共混的金属纳米粉末用于二氧化碳加氢制甲醇、析氢或析氧反应、有机物合成与转化以及有机废水降解化学反应过程。
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