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铂族金属及合金纳米材料的制备及应用研究
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西北有色金属研究院

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国家自然科学基金资助(52103287),陕西省自然科学基础研究计划资助项目(2023-JC-QN-0570),陕西省留学人员科技活动择优资助项目(2022-026),陕西省重点研发计划项目资助(2023-YBGY-458),西安市科学技术协会青年人才托举计划项目(959202313040)


Preparation and application of platinum group metals and alloy nanomaterials
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1.Northwest Institute for Non-ferrous Metal Research,Xi’an 710016;2.China

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    摘要:

    随着催化领域的快速发展,对铂族金属纳米材料的需求也与日俱增,因此提供一种简单、高效、易产业化和通用制备铂族金属及合金纳米材料的新方法具有重要意义。本文以贵金属盐为原料,氯化铵为造孔剂,采用喷雾干燥法结合煅烧还原,成功制备了三维纳米骨架结构的Pd、Pt、Ir、Ru单金属粉末以及IrRu、PtNi和PtNiCo合金粉末。以铂族钯纳米材料为例,研究了NH4Cl浓度对雾化粉体微观形貌的影响规律,发现随NH4Cl浓度的增大,雾化(NH4)2PdCl4粉末的平均粒径呈现增大趋势,球形度逐渐降低,分散性变差;研究了不同煅烧温度对钯粉微观形貌的影响规律,发现在300℃煅烧还原的钯粉对前驱体形貌具有继承作用,由于煅烧过程气体溢出留下纳米孔洞,促使钯粉具有类球形三维纳米骨架结构,且具有较大的比表面积(28-40 m2/g);当煅烧温度升至400℃时,三维纳米骨架逐渐破碎,形成致密的Pd粉。因此,当NH4Cl浓度在5-10 g/L,煅烧温度控制在300℃时,有利于制备高比表面积类球形三维纳米骨架铂族金属粉体。此外,采用最优制备参数成功了三维纳米骨架结构的Pt、Ir、Ru、IrRu、PtNi和PtNiCo铂族金属及合金粉体,证明了该方法在制备其他铂族金属及合金上具有通用性。最后,为了证明合成材料的实用性,对本研究制备的 PtNiCo三维纳米骨架材料进行了燃料电池阳极甲醇催化氧化反应测试,结果表明PtNiCo纳米材料(1117 mA/mgPt)甲醇催化氧化性能是商用Pt黑(170 mA/mgPt)的6.5倍,并表现了优异的抗毒性和稳定性,证明采用本研究制备方法可制备出性能优异的铂族金属合金纳米催化剂。

    Abstract:

    With the rapid development of the catalysis field, the demand for platinum group metal nanomaterials is also increasing. So it is of great significance to provide a new method for preparing platinum group metal and alloy powders that is simple, efficient, easy to industrialization and universal. In this paper, Pd, Pt, Ir and Ru powders and IrRu, PtNi and PtNiCo alloy powders with 3D-nanoframeworks structure were successfully prepared by spray drying method combined with calcination and reduction using noble metal salt as raw material and ammonium chloride (NH4Cl) as pore making agent. The effect of NH4Cl concentration on the micromorphology of atomized powder was studied. It was found that with the increase of NH4Cl concentration, the average particle size of atomized (NH4)2PdCl4 powder showed an increasing trend, the sphericity gradually decreased, and the dispersion became worse. The effects of different calcination temperatures on the morphology of palladium powder were studied, and it was found that palladium powder reduced by calcination at 300℃ had an inherited effect on the precursor shape. Due to the nano-pores left by the gas spilling during calcination, palladium powder had a spheroidal 3D-nanoframeworks structure and a large specific surface area (28-40 m2/g). When the calcination temperature rises to 400℃, the 3D-nanoframeworks is gradually broken to form a dense Pd powders. Therefore, when the concentration of NH4Cl is 5-10 g/L and the calcination temperature is controlled at 300℃, it is conducive to the preparation of spherical 3D-nanoframeworks platinum group metal powders with high specific surface area. In addition, Pt, Ir, Ru, IrRu, PtNi and PtNiCo platinum group metals and alloy powders with 3D-nanoframeworks have been successfully prepared by using the optimal preparation parameters, which proves that the method is universal in the preparation of other platinum group metals and alloys. Finally, in order to prove the feasibility of the synthetic materials, the catalytic methanol oxidation reaction of the PtNiCo 3D-nanoframeworks materials prepared in this study was tested in fuel cell anode. The results showed that the catalytic methanol oxidation performance of PtNiCo nanomaterials (1117 mA/mgPt) was 6.5 times that of commercial Pt black (170 mA/mgPt), and it also has Excellent anti-toxicity and stability. It was proved that excellent performance of platinum group metal alloy nano-catalyst could be prepared by the preparation method in this study.

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陈相平,赵盘巢,皮和木,雷驰,王娇,周娜,张卜升,操齐高.铂族金属及合金纳米材料的制备及应用研究[J].稀有金属材料与工程,,().[Xiangping Chen, Panchao Zhao, Hemu Pi, Chi Lei, Jiao Wang, Na Zhou, Bosheng Zhang, Qigao Cao. Preparation and application of platinum group metals and alloy nanomaterials[J]. Rare Metal Materials and Engineering,,().]
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  • 收稿日期:2024-05-30
  • 最后修改日期:2024-11-29
  • 录用日期:2024-12-03
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