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
收稿日期: 2021-03-27
修回日期: 2021-05-08
网络出版日期: 2021-06-09
DFT Study of Nim@Pt1Aun-m-1 (n=19, 38, 55, 79; m = 1, 6, 13, 19) Core-Shell ORR Catalyst
Received date: 2021-03-27
Revised date: 2021-05-08
Online published: 2021-06-09
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。
李文杰 , 田东旭 , 杜红 , 燕希强 . 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[J]. 电化学, 2021 , 27(4) : 357 -365 . DOI: 10.13208/j.electrochem.210329
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.
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