超薄钯铜纳米片组装纳米花的构建及其氧还原性能

doi:10.16085/j.issn.1000-6613.2020-2265

摘要/Abstract

摘要：

在原子水平上精确调控电催化剂的组成是增强其氧还原（ORR）性能的有效途径。本文采用简单的一步溶剂热还原法制备了由不同PdCu组成的超薄双金属纳米片自组装而成的三维（3D）合金纳米花（Pd₁Cu_x NCFs）。利用透射电子显微镜（TEM）、扫描透射电子显微镜-能谱仪（STEM-EDS）、X射线粉末衍射（XRD）和X射线光电子能谱（XPS）等手段系统表征了Pd₁Cu_x NCFs的形貌、晶体结构及成分。相比于传统二维（2D）纳米材料，Pd₁Cu_x NCFs丰富的快速传质路径、较高的Pd原子利用效率和更强的PdCu双金属间协同作用使得其在碱性介质中表现出增强的ORR性能。另外，本文还研究了Pd、Cu前体用量对ORR性能的影响。结果显示，Pd、Cu前体摩尔比为1∶0.5时，催化剂（Pd₁Cu_0.5NCFs）在碱性介质中ORR活性和电化学稳定性最佳。其半波电位E_1/2（0.937V）远高于商业Pt/C（0.851V）；在加速循环1000次扫描后，E_1/2几乎没有变化，说明其稳定性优异；0.90V电势下，Pd₁Cu_0.5 NCFs的质量比活性为1.09A/mg，是商业Pt/C的14.5倍。

关键词: 氧还原反应, 钯铜, 催化剂, 电化学, 燃料电池, 纳米材料

Abstract:

Rationally controlling the composition of electrocatalysts at the atomic level is proved to be an effective way to improve their catalytic performance towards oxygen reduction reaction (ORR). Here, PdCu ultrathin nanosheets-composed three-dimensional (3D) nanoflowers (Pd₁Cu_x NCFs) with different compositions were prepared by a facile one-pot solvothermal reduction. The morphology, crystal structure and composition of catalysts were characterized by TEM,STEM-EDS,XRD,XPS,etc. Compared with traditional two-dimensional nanomaterials, their abundant routes for fast mass transport, high Pd atom utilization efficiency as well as the synergistic effect of PdCu bimetal endowed Pd₁Cu_x NCFs with enhanced ORR performance under alkaline condition. In addition, the effect of the dosage of Pd and Cu precursors on the ORR performance was studied. Electrochemical measurement results indicated that the optimal catalyst (Pd₁Cu_0.5NCFs, the molar ratio of Pd/Cu precursor was 1∶0.5) exhibited the best ORR performance. A half-wave potential (E_1/2) of 0.937V in alkaline medium was obtained, which was higher than that of commercial Pt/C (0.851V). Electrochemical accelerated durability test results showed that the Pd₁Cu_0.5 NCFs could endure at least 1000 cycles with negligible activity decay, suggesting their excellent stability. At 0.90V, the mass activity of Pd₁Cu_0.5NCFs could achieve 1.09A/mg, which was 14.5 times higher than that of commercial Pt/C.

Key words: oxygen reduction reaction, PdCu, catalyst, electrochemistry, fuel cells, nanomaterials

中图分类号:

刘文栋, 张成会, 陈传霞, 倪朋娟, 姜媛媛, 王波, 逯一中. 超薄钯铜纳米片组装纳米花的构建及其氧还原性能[J]. 化工进展, 2021, 40(11): 6246-6253.

LIU Wendong, ZHANG Chenghui, CHEN Chuanxia, NI Pengjuan, JIANG Yuanyuan, WANG Bo, LU Yizhong. Engineering ultrathin PdCu nanosheets-composed nanoflowers with high catalytic activity for oxygen reduction reaction[J]. Chemical Industry and Engineering Progress, 2021, 40(11): 6246-6253.

图/表 10

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实验材料与试剂	参数	商家
Na₂PdCl₄	98%	阿拉丁
CuCl₂·2H₂O	99.99%	Sigma-Aldrich
W(CO)₆	97%	Sigma-Aldrich
N，N-二甲基甲酰胺（DMF）	分析纯	Sigma-Aldrich
乙酸	97%	阿拉丁
Nafion	5%	阿拉丁
Vulcan XC-72（导电炭黑）	—	美国卡博特公司
无水乙醇	分析纯	Sigma-Aldrich
异丙醇	分析纯	Sigma-Aldrich
商业Pt/C	20%	Sigma-Aldrich
氢氧化钾	分析纯	阿拉丁

实验材料与试剂	参数	商家
Na₂PdCl₄	98%	阿拉丁
CuCl₂·2H₂O	99.99%	Sigma-Aldrich
W(CO)₆	97%	Sigma-Aldrich
N，N-二甲基甲酰胺（DMF）	分析纯	Sigma-Aldrich
乙酸	97%	阿拉丁
Nafion	5%	阿拉丁
Vulcan XC-72（导电炭黑）	—	美国卡博特公司
无水乙醇	分析纯	Sigma-Aldrich
异丙醇	分析纯	Sigma-Aldrich
商业Pt/C	20%	Sigma-Aldrich
氢氧化钾	分析纯	阿拉丁

催化剂	半波电位（E_1/2）/V	质量活性/A·mg^-1	参考文献
Pd₆Ni	0.89	0.22	［30］
B-Pd	—	0.97	［31］
PdMo	0.95	16.37	［32］
Pd/W₁₈O₄₉	0.875	0.216	［33］
PdAuCu	—	1.781	［34］
Pd-Cu	0.90	0.59	［35］
Pd₂FeCo@Pt	0.880	2.5	［36］
Pd@PdFe	—	0.31	［37］
Pd₁Cu_0.5 NCFs	0.937	1.09	本工作

催化剂	半波电位（E_1/2）/V	质量活性/A·mg^-1	参考文献
Pd₆Ni	0.89	0.22	［30］
B-Pd	—	0.97	［31］
PdMo	0.95	16.37	［32］
Pd/W₁₈O₄₉	0.875	0.216	［33］
PdAuCu	—	1.781	［34］
Pd-Cu	0.90	0.59	［35］
Pd₂FeCo@Pt	0.880	2.5	［36］
Pd@PdFe	—	0.31	［37］
Pd₁Cu_0.5 NCFs	0.937	1.09	本工作

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