CN108435202A - 一种高催化活性Pt基复合纳米枝晶及其制备方法 - Google Patents

一种高催化活性Pt基复合纳米枝晶及其制备方法 Download PDF

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CN108435202A
CN108435202A CN201810262084.4A CN201810262084A CN108435202A CN 108435202 A CN108435202 A CN 108435202A CN 201810262084 A CN201810262084 A CN 201810262084A CN 108435202 A CN108435202 A CN 108435202A
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曾宇乔
杨星梅
丁雪卉
肖敬才
郑云西
朱奎
季宝荣
张旭海
董岩
蒋建清
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Abstract

本发明公开了一种高催化活性Pt基复合纳米枝晶的制备方法，在K2PtCl4、NiSO4、CuSO4、(NH4)2SO4、Na3C6H5O7和H3BO3的混合溶液中,以铜片、镍片、石墨片或玻碳片为工作电极在溶液中以1.5‑3.0A/cm2恒流方式进行100‑300秒电化学沉积，可以获得Pt基复合材料。该材料具有纳米枝晶结构，一次枝晶长度约为300‑700纳米，二次枝晶尺寸在20‑50纳米之间。Pt分布于枝晶表面，并在枝晶尖端富集，形成大量原子级别的台阶。具有该种结构的Pt基复合纳米枝晶对甲醇和甲酸等有机物表现出优异的电化学催化效果。

Description

一种高催化活性Pt基复合纳米枝晶及其制备方法
技术领域
本发明涉及一种Pt基复合纳米枝晶材料的制备方法，特别是一种可用于电化学催化邻域的Pt基复合纳米材料制备方法，属于纳米材料制备领域。
背景技术
纳米化后的Pt具有优异的电化学活性和良好的导电性，对甲醇等有机物表现出极高的电化学催化性能，被广泛应用于能源、化工等领域。目前此类Pt纳米催化材料主要包括两种：一种是纳米颗粒，一种是纳米多孔。前者因容易团聚、缺乏自支撑性等缺陷需要与C粉等混合使用，一定程度上降低了催化效率。后者结构容易在催化过程中会发生结构粗化，循环寿命有待提高。枝晶状的纳米材料具有自支撑性，且兼具大比表面积、高结构稳定性等优势，在催化领域获得瞩目。目前，具有高催化活性的Pd、Cu、Au等纳米枝晶材料已被开发出来，也有大量研究者尝试在酸液中沉积Pt枝晶，但获得的材料为类枝晶的Pt簇，即由大量立方状的纳米颗粒堆积而成，无明显的分级尖锐枝晶结构，其对甲醇等有机物的催化效果与市售Pt纳米颗粒催化效果相当。具有更佳催化效果的Pt纳米枝晶材料尚未见任何报道。
发明内容
技术问题：本发明公开了一种本发明公开了一种具有高催化活性的Pt基复合纳米枝晶材料及其制备方法。该种材料对甲醇和甲酸等有机物具有优异的电化学催化效果。
技术方案：本发明的一种高催化活性Pt基复合纳米枝晶的制备方法，在含Ni2+、Cu2 +和PtCl4 -2的混合溶液中,以导电材料为工作电极在溶液中进行电化学沉积，可以获得Pt基复合纳米枝晶材料。
其中，该Pt基复合纳米枝晶材料的形态特点是由大量一次和二次枝晶构成，一次枝晶长度约为300-700纳米，二次枝晶尺寸在20-50纳米之间，Pt分布于枝晶表面，并在枝晶尖端富集，形成大量原子级别的台阶。
沉积Pt基复合纳米枝晶材料的混合溶液为：
K2PtCl4+NiSO4+CuSO4+(NH4)2SO4+Na3C6H5O7+H3BO3。
所述K2PtCl4的浓度为3-7mM，NiSO4浓度为5-15mM，CuSO4浓度为5-15mM，(NH4)2SO4浓度为2M Na3C6H5O7浓度为0.2-0.4M,H3BO3浓度为0.3-0.5M。
所述沉积Pt基复合纳米枝晶材料的工作电极为Cu、Ni、石墨或玻碳。
所述电化学沉积，工艺参数为：1.5-3.0A/cm2电流密度条件下沉积100-300秒。
有益效果：与现有类枝晶的Pt簇相比，本发明具有以下有益效果：
1.因本发明材料中Pt主要分布在枝晶表面，且枝晶分级结构显著，在相同比表面积条件下，本发明Pt载量更低，而催化活性位置更多，成本更低。
2.本发明中Pt显示出优于市售Pt纳米颗粒的催化活性，而形貌类似的类枝晶Pt簇催化效果与市售Pt纳米颗粒的催化活性相当。
具体实施方式
在含Ni2+、Cu2+和PtCl4 -2的混合溶液中,以导电材料为工作电极在溶液中进行电化学沉积，可以获得Pt基复合纳米枝晶材料。
沉积Pt基复合纳米枝晶材料的混合溶液为K2PtCl4+NiSO4+CuSO4+(NH4)2SO4+Na3C6H5O7+H3BO3。其中，K2PtCl4的浓度为3-7mM，NiSO4浓度为5-15mM，CuSO4浓度为5-15mM，(NH4)2SO4浓度为2M，Na3C6H5O7浓度为0.2-0.4M,H3BO3浓度为0.3-0.5M。
沉积Pt基复合纳米枝晶材料的工作电极为Cu、Ni、石墨或玻碳。
沉积Pt基复合纳米枝晶材料的工艺参数特征为：在1.5-3.0A/cm2电流密度条件下沉积100-300秒。
沉积得到的材料形态特征为:Pt基复合纳米枝晶材料的形态特点是由大量一次和二次枝晶构成，一次枝晶长度约为300-700纳米，二次枝晶尺寸在20-50纳米之间。Pt分布于枝晶表面，并在枝晶尖端富集，形成大量原子级别的台阶。
下面给出5个利用本发明的制备方法制备枝晶状三维石墨烯材料的具体实施例。
实施例1
在3mM K2PtCl4+15mM NiSO4+5mM CuSO4+2M(NH4)2SO4+0.2M Na3C6H5O7+0.3M H3BO3混合溶液中，以Cu为工作电极，1.5A/cm2电流密度条件下沉积100秒。获得的Pt基复合纳米枝晶材料由大量一次和二次枝晶构成，一次枝晶长度约为300纳米，二次枝晶尺寸在20-30纳米之间。Pt分布于枝晶表面，并在枝晶尖端富集，形成大量原子级别的台阶。枝晶中Pt平均含量约为10at％，Ni平均含量为45at％，Cu平均含量约为45at％。
实施例2
在7mM K2PtCl4+15mM NiSO4+5mM CuSO4+2M(NH4)2SO4+0.4M Na3C6H5O7+0.5M H3BO3混合溶液中，以Ni为工作电极，2.0A/cm2电流密度条件下沉积200秒。获得的Pt基复合纳米枝晶材料由大量一次和二次枝晶构成，一次枝晶长度约为400纳米，二次枝晶尺寸在20-50纳米之间。Pt分布于枝晶表面，并在枝晶尖端富集，形成大量原子级别的台阶。枝晶中Pt平均含量约为20at％，Ni平均含量为45at％，Cu平均含量约为35at％。
实施例3
在7mM K2PtCl4+5mM NiSO4+15mM CuSO4+2M(NH4)2SO4+0.4M Na3C6H5O7+0.5M H3BO3混合溶液中，以石墨片为工作电极，3.0A/cm2电流密度条件下沉积200秒。获得的Pt基复合纳米枝晶材料由大量一次和二次枝晶构成，一次枝晶长度约为700纳米，二次枝晶尺寸在40-50纳米之间。Pt分布于枝晶表面，并在枝晶尖端富集，形成大量原子级别的台阶。枝晶中Pt平均含量约为10at％，Ni平均含量为20at％，Cu平均含量约为70at％。
实施例4
在7mM K2PtCl4+15mM NiSO4+5mM CuSO4+2M(NH4)2SO4+0.4M Na3C6H5O7+0.5M H3BO3混合溶液中，以玻碳为工作电极，2.0A/cm2电流密度条件下沉积300秒。获得的Pt基复合纳米枝晶材料由大量一次和二次枝晶构成，一次枝晶长度约为300纳米，二次枝晶尺寸在20-40纳米之间。Pt分布于枝晶表面，并在枝晶尖端富集，形成大量原子级别的台阶。枝晶中Pt平均含量约为20at％，Ni平均含量为45at％，Cu平均含量约为35at％。
实施例5
在5mM K2PtCl4+12.5mM NiSO4+5mM CuSO4+2M(NH4)2SO4+0.4M Na3C6H5O7+0.5MH3BO3混合溶液中，以Cu为工作电极，2.0A/cm2电流密度条件下沉积200秒。获得的Pt基复合纳米枝晶材料由大量一次和二次枝晶构成，一次枝晶长度约为400纳米，二次枝晶尺寸在20-30纳米之间。Pt分布于枝晶表面，并在枝晶尖端富集，形成大量原子级别的台阶。枝晶中Pt平均含量约为20at％，Ni平均含量为40at％，Cu平均含量约为40at％。该材料对甲醇的电催化氧化峰值电位相较市售Pt纳米颗粒负移了30mV,循环寿命提高了20％。

Claims (6)

1.一种高催化活性Pt基复合纳米枝晶的制备方法，其特征在于在含Ni2+、Cu2+和PtCl4 -2的混合溶液中,以导电材料为工作电极在溶液中进行电化学沉积，可以获得Pt基复合纳米枝晶材料。
2.根据权利要求1所述的一种高催化活性Pt基复合纳米枝晶的制备方法，其特征在于该Pt基复合纳米枝晶材料的形态特点是由大量一次和二次枝晶构成，一次枝晶长度约为300-700纳米，二次枝晶尺寸在20-50纳米之间，Pt分布于枝晶表面，并在枝晶尖端富集，形成大量原子级别的台阶。
3.根据权利要求1所述的一种高催化活性Pt基复合纳米枝晶的制备方法，其特征在于，沉积Pt基复合纳米枝晶材料的混合溶液为：
K2PtCl4+NiSO4+CuSO4+(NH4)2SO4+Na3C6H5O7+H3BO3。
4.根据权利要求3所述的一种高催化活性Pt基复合纳米枝晶的制备方法，其特征在于，所述K2PtCl4的浓度为3-7mM，NiSO4浓度为5-15mM，CuSO4浓度为5-15mM，(NH4)2SO4浓度为2MNa3C6H5O7浓度为0.2-0.4M,H3BO3浓度为0.3-0.5M。
5.根据权利要求1所述的一种高催化活性Pt基复合纳米枝晶的制备方法，其特征在于，所述沉积Pt基复合纳米枝晶材料的工作电极为Cu、Ni、石墨或玻碳。
6.根据权利要求1所述的一种高催化活性Pt基复合纳米枝晶的制备方法，其特征在于，所述电化学沉积，工艺参数为：1.5-3.0A/cm2电流密度条件下沉积100-300秒。
CN201810262084.4A 2018-03-28 2018-03-28 一种高催化活性Pt基复合纳米枝晶及其制备方法 Withdrawn CN108435202A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113241447A (zh) * 2021-04-06 2021-08-10 华南理工大学 一种低铂核壳结构催化剂及其制备方法与其掺杂改性方法
CN114836780A (zh) * 2022-05-07 2022-08-02 东南大学 一种水解制氢用六元高熵泡沫及其制备方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113241447A (zh) * 2021-04-06 2021-08-10 华南理工大学 一种低铂核壳结构催化剂及其制备方法与其掺杂改性方法
CN114836780A (zh) * 2022-05-07 2022-08-02 东南大学 一种水解制氢用六元高熵泡沫及其制备方法
CN114836780B (zh) * 2022-05-07 2023-11-03 东南大学 一种水解制氢用六元高熵泡沫及其制备方法

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