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

doi:10.13208/j.electrochem.210329

摘要/Abstract

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Ni_m@M_n_-_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Ni_m@Au_n_-_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Ni_m@Au_n_-_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Ni_m@Au_n_-_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 Ni_m@Pt₁Au_n_-_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 Ni_m@Au_n_-_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 Ni_m@Au_n_-_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

李文杰, 田东旭, 杜红, 燕希强. ORR催化剂Ni_m@Pt₁Au_n_-_m_-1(n = 19, 38, 55, 79; m = 1, 6, 13, 19)的密度泛函研究[J]. 电化学（中英文）, 2021, 27(4): 357-365.

Wen-Jie Li, Dong-Xu Tian, Hong Du, Xi-Qiang Yan. DFT Study of Ni_m@Pt₁Au_n_-_m_-1(n=19, 38, 55, 79; m = 1, 6, 13, 19) Core-Shell ORR Catalyst[J]. Journal of Electrochemistry, 2021, 27(4): 357-365.

图/表 10

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System	ΔG₁/eV	ΔG₂/eV	ΔG₃/eV	ΔG₄/eV
Pt₁₉	-3.09	-0.95	-1.89	1.01
Pt₃₈	-2.47	-1.74	-1.14	0.42
Pt₅₅	-2.57	-1.67	-1.17	0.49
Pt₇₉	-2.23	-1.85	-1.08	0.24
Pt(111)	-1.80	-1.96	-0.96	-0.20

System	ΔG₁/eV	ΔG₂/eV	ΔG₃/eV	ΔG₄/eV
Pt₃₈	-2.47	-1.74	-1.14	0.42
Ni₆@Pd₃₂	-1.93	-1.91	-1.11	0.03
Ni₆@Pt₃₂	-2.10	-1.79	-1.02	0.01
Ni₆@Cu₃₂	-2.70	-1.63	-1.50	0.91
Ni₆@Au₃₂	-1.66	-1.58	-2.13	0.45
Ni₆@Ag₃₂	-2.58	-1.17	-1.96	0.79
Pt(111)	-1.80	-1.96	-0.96	-0.2

System	ΔG₁/eV	ΔG₂/eV	ΔG₃/eV	ΔG₄/eV
Pt₃₈	-2.47	-1.74	-1.14	0.42
Ni₆@Pt₁Pd₃₁	-1.81	-1.76	-1.34	-0.01
Ni₆@Pt₁Cu₃₁	-2.05	-2.01	-0.49	-0.38
Ni₆@Pt₁Au₃₁	-1.52	-1.01	-1.61	-0.77
Ni₆@Pt₁Ag₃₁	-2.92	-0.23	-1.56	-0.21
Pt(111)	-1.80	-1.96	-0.96	-0.20

ORR催化剂Ni_m@Pt₁Au_n_-_m_-1(n = 19, 38, 55, 79; m = 1, 6, 13, 19)的密度泛函研究

DFT Study of Ni_m@Pt₁Au_n_-_m_-1(n=19, 38, 55, 79; m = 1, 6, 13, 19) Core-Shell ORR Catalyst

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