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电化学(中英文) ›› 2021, Vol. 27 ›› Issue (4): 357-365.  doi: 10.13208/j.electrochem.210329

• 论文 • 上一篇    下一篇

ORR催化剂Nim@Pt1Aun-m-1 (n = 19, 38, 55, 79; m = 1, 6, 13, 19)的密度泛函研究

李文杰1, 田东旭1,*(), 杜红1, 燕希强2,*()   

  1. 1.大连理工大学化工学院,精细化工国家重点实验室,辽宁 大连 116024
    2.佛山(云浮)氢能产业与新材料发展研究院,广东省氢能技术重点实验室,广东 佛山 528000
  • 收稿日期:2021-03-27 修回日期:2021-05-08 出版日期:2021-08-28 发布日期:2021-06-09
  • 通讯作者: 田东旭,燕希强 E-mail:tiandx@dlut.edu.cn;965664856@qq.com

DFT Study of Nim@Pt1Aun-m-1 (n=19, 38, 55, 79; m = 1, 6, 13, 19) Core-Shell ORR Catalyst

Wen-Jie Li1, Dong-Xu Tian1,*(), Hong Du1, Xi-Qiang Yan2,*()   

  1. 1. State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
    2. Guangdong Key Laboratory for Hydrogen Energy Technologies, Foshan University, Foshan 528000, Guangdong, China
  • Received:2021-03-27 Revised:2021-05-08 Published:2021-08-28 Online:2021-06-09
  • Contact: Dong-Xu Tian,Xi-Qiang Yan E-mail:tiandx@dlut.edu.cn;965664856@qq.com

摘要:

燃料电池的阴极反应的反应动力学速率非常慢,限制了燃料电池技术的发展。因此,寻找低成本、高活性的氧还原催化剂具有重要的意义。多元金属核壳团簇表现出优良的氧还原活性。在本文中,以原子个数为19、38、55和79的八面体团簇作催化剂模型,采用密度泛函理论(GGA-PBE-PAW)方法,研究了一系列不同尺寸核壳Nim@Mn-m (n = 19, 38, 55, 79;m = 1, 6, 13, 19; M = Pt, Pd, Cu, Au, Ag)团簇催化剂的活性规律。优化*O、*OH和*OOH吸附中间体结构,计算了吸附自由能和反应吉布斯自由能,以超电势为催化活性的描述符,研究了单原子Pt嵌入Nim@Aun-m团簇的活性规律。结果表明,Ni6@Pt1Au31具有最好的ORR活性,并且Ni1@Pt1Au17、Ni6@Pt1Au31、Ni13@Pt1Au41、Ni19@Pt1Au5表现出比Pt38团簇以及Pt(111)表面更高的催化活性。Bader电荷和态密度分析表面,核壳之间的电荷转移以及单原子Pt嵌入Nim@Aun-m表面,改变了吸附位的电子性质,降低了*OH的吸附强度,提高了ORR活性。单原子Pt嵌入Nim@Aun-m表面可能是一种合适的多元金属核壳ORR催化剂设计策略。

关键词: 核壳金属团簇, 氧还原反应, 密度泛函理论, 超电势, 单原子催化

Abstract:

The slow kinetics of oxygen reduction reaction (ORR) limits the performance of low temperature fuel cells. Thus, it needs to design effective catalysts with low cost. Core-shell clusters (CSNCs) show promising activity because of their size-dependent geometric and electronic effects. The ORR activity trend of Nim@Pt1Aun-m-1(n = 19, 38, 55, 79; m = 1, 6, 13, 19) was studied using the GGA-PBE-PAW methods. The adsorption configurations of *O, *OH and *OOH were optimized and the reaction free energies of four proton electron (H+ + e-) transfer steps were calculated. Using overpotential as a descriptor for the catalytic activity, Ni6@Pt1Au31 was found to be the most active ORR catalyst. Ni1@Pt1Au17, Ni13@Pt1Au41, and Ni19@Pt1Au59 had better activity than pure Pt clusters and Pt(111). Bader charge and DOS data indicate that the single Pt atom embedded on Nim@Aun-m can tune the electronic property of active site, and thus, significantly improve the activity. The present study showed that the single Pt atom embedded on Nim@Aun-m is a rational strategy to design effective core-shell ORR catalysts.

Key words: core-shell metal clusters, oxygen reduction reaction, density functional theory, overpotential, single atom catalysis