Pivotal role of Ce3+ polarons on promoting oxygen reduction reaction activity of Pt1/CeO2 catalysts

被引：0

作者：

Yan, Jiasi ^{[1
,2
,3
,4
,5
]}

Xiao, Wei ^{[1
,2
,3
,4
]}

Zeng, Rong ^{[1
,2
,3
,4
]}

Hong, Qijun ^{[6
]}

Li, Xiaowu ^{[5
]}

Wang, Ligen ^{[1
,2
,3
,4
]}

机构：

[1] China GRINM Grp Co Ltd, State Key Lab Nonferrous Met & Proc, Beijing 100088, Peoples R China

[2] China GRINM Grp Co Ltd, Natl Engn Res Ctr Nonferrous Met Mat & Prod New En, Beijing 100088, Peoples R China

[3] GRIMAT Engn Inst Co Ltd, Beijing 101407, Peoples R China

[4] Gen Res Inst Nonferrous Met, Beijing 100088, Peoples R China

[5] Northeastern Univ, Sch Mat Sci & Engn, Dept Mat Phys & Chem, Key Lab Anisotropy & Texture Mat,Minist Educ, Shenyang 110819, Peoples R China

[6] Arizona State Univ, Sch Engn Transport Energy & Matter, Tempe, AZ 85287 USA

来源：

JOURNAL OF POWER SOURCES | 2024年 / 603卷

关键词：

Pt1(/)CeO(2) catalysts; Ce3+ polaron; Oxygen reduction reaction; First-principles calculations; TOTAL-ENERGY CALCULATIONS; PLATINUM SINGLE ATOMS; ELECTROCATALYSTS; PERFORMANCE; UNIVERSALITY; CHALLENGES; MECHANISM; EFFICIENT; INSIGHT; DOPINGS;

D O I：

10.1016/j.jpowsour.2024.234393

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The Pt-1/CeO2 single-atom catalyst excels across catalytic fields, promising applications in the oxygen reduction reactions (ORRs). Here, we employ first-principles calculations to systematically investigate the ORR mechanism catalyzed by Pt-1/CeO2 systems and the activity regulated by Ce3+ polarons. We determine the reaction pathways of different Pt-1/CeO2 systems by evaluating four critical factors: O-2 adsorption energy, O-2 dissociation Gibbs barrier, Gibbs free energy change for O-2 -> OOH*, and H2O2 adsorption structure. Notably, most P(t)1/CeO2 systems tend to react through the 4e(-) associative path. Theoretical activity calculations reveal that Pt-OH/CeO2(110) system show low overpotential of 0.47 V comparable to pure Pt. The excellent ORR activity is attributed to the synergistic mechanism of Pt and surrounding Ce3+ polarons, where the polaron regulation mechanism dominates the reaction. The quantity of Ce3+ polarons not only affects the reaction active sites but also regulates the radical adsorption state. With an elevated Ce3+ polarons concentration, the ORR overpotential in Pt-1/CeO2 system can decrease from 0.47 to 0.16 V, leading to a substantial enhancement in activity. This work first underscores the crucial involvement of Ce3+ polarons in catalyzing the ORR, reducing the significance of Pt in catalysis, inspiring a new way to design active non-platinum electrocatalysts for ORR in experiments.

引用

页数：11