Surface Defect Chemistry and Electronic Structure of Pr0.1Ce0.9O2-δ Revealed in Operando

Lu, Qiyang; Vardar, Gulin; Jansen, Maximilian; Bishop, Sean R.; Waluyo, Iradwikanari; Tuller, Harry L.; Yildiz, Bilge

doi:10.1021/acs.chemmater.7b05129

Title: Surface Defect Chemistry and Electronic Structure of Pr_0.1Ce_0.9O_2-δ Revealed in Operando

Journal Article · Tue Mar 27 00:00:00 EDT 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.7b05129· OSTI ID:1460703

^[1]; Vardar, Gulin ^[2]; Jansen, Maximilian ^[2]; Bishop, Sean R. ^[1];

^[3]; Tuller, Harry L. ^[4]; Yildiz, Bilge ^[5]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Lab. for Electrochemical Interfaces. Dept. of Materials Science and Engineering
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Lab. for Electrochemical Interfaces. Dept. of Nuclear Science and Engineering
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Materials Science and Engineering
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Lab. for Electrochemical Interfaces. Dept. of Materials Science and Engineering. Dept. of Nuclear Science and Engineering

Understanding the surface defect chemistry of oxides under functional operating conditions is important for providing guidelines for improving the kinetics of electrochemical reactions. Ceria-based oxides have applications in solid oxide fuel/electrolysis cells, thermo-chemical water splitting, catalytic convertors, and red-ox active memristive devices. The surface defect chemistry of doped ceria in the regime of high oxygen pressure, pO₂, approximating the operating conditions of fuel cell cathodes at elevated temperatures, has not yet been revealed. In this paper, we investigated the Pr_0.1Ce_0.9O_2-δ (PCO) surface by in operando X-ray photoelectron and absorption spectroscopic methods. We quantified the concentration of reduced Pr³⁺, at the near-surface region of PCO as a function of electrochemical potential, corresponding to a wide range of effective pO₂. We found that the Pr³⁺ concentration at the surface was significantly higher than the values predicted from bulk defect chemistry. This finding indicates a lower effective defect formation energy at the surface region compared with that in the bulk. Finally, in addition, the Pr³⁺ concentration has a weaker dependence on pO₂ compared to that in the bulk.

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Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0012704; DMR-1419807

OSTI ID:: 1460703

Report Number(s):: BNL-207841-2018-JAAM

Journal Information:: Chemistry of Materials, Vol. 30, Issue 8; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 14 works

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Constructing a pathway for mixed ion and electron transfer reactions for O2 incorporation in Pr0.1Ce0.9O2−x Chen, Di; Guan, Zixuan; Zhang, Dawei Nature Catalysis, Vol. 3, Issue 2 https://doi.org/10.1038/s41929-019-0401-9	journal	January 2020
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Figure 1(p. 7)

Figure 2(p. 8)

Figure 3(p. 12)

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Title: Surface Defect Chemistry and Electronic Structure of Pr0.1Ce0.9O2-δ Revealed in Operando

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