Title: Manipulating Surface Termination of Perovskite Manganate for Oxygen Activation

Abstract

Abstract For ABO ₃ perovskite oxides, one of the key issues limiting their utilization in heterogeneous catalysis is the dominant presence of catalytically inactive A‐site cations at the surface. The engineering of B‐site terminated perovskites is considered as an effective method to address this issue, especially when dealing with Mn/Co‐based perovskite catalysts. However, to date, such a strategy has not been fully successful and remains a major challenge in the field. Herein, a Mn‐terminated La _0.45 Sr _0.45 MnO ₃ (B‐LSM) is successfully synthesized via a one‐pot hydrothermal method, in which low‐valence Mn ions partially occupy the A site to form the active Mn‐excess phase. Experimental results and theoretical calculations reveal that the presence of the surface Mn termination in B‐LSM optimizes the hybrid orbitals of Mn 3d‐O 2p and promotes the activation of surface lattice oxygen, where the pristine inert lattice O ²⁻ is evolved into active and stable lattice O ^{2− x} . Such structural optimization significantly reduces the activation energy barriers on going from O ₂ ⁻ species to important intermediate O ⁻ species during O ₂ activation. Moreover, this results in good stability and Pt‐like activity for the B‐LSM during CO oxidation. This work offers amore » new chemical route for the design of advanced perovskite‐type oxides possessing novel functions.« less

Authors:

Wang, Xiyang ^[1]; Li, Xinbo ^[1]; Chu, Xuefeng ^[2]; Cao, Rui ^[3]; Qian, Jingyu ^[1]; Cong, Yingge ^[1]; Huang, Keke ^[1]; Wang, Jiaao ^[4]; Redshaw, Carl ^[5]; Sarangi, Ritimukta ^[3]; Li, Guangshe ^[1]; Feng, Shouhua  ^[1]

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• Search DOE PAGES for ORCID "0000-0001-6888-068X"

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+ Show Author Affiliations

1. Jilin Univ., Changchun (China). State Key Lab. of Inorganic Synthesis and Preparative Chemistry
2. Jianzhu Univ., Changchun (China). Jilin Provincial Key Lab. of Architectural Electricity & Comprehensive Energy Saving
3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
4. Univ. of Jinan (China)
5. University of Hull (United Kingdom). Plastics Collaboratory

Publication Date:

Wed Jan 27 00:00:00 EST 2021

Research Org.:

SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); Natural Science Foundation of Jilin Province; Fundamental Research Funds for the Central Universities; Chinese Academy of Sciences (CAS); China Postdoctoral Science Foundation

OSTI Identifier:

1768207

Alternate Identifier(s):

OSTI ID: 1804174

Grant/Contract Number:  

AC02-76SF00515; 21621001; 21671076; 21831003; 21801090; 20191004020TC; 3102018bzc007; 2020HSC‐UE002; 2019M661203

Resource Type:

Accepted Manuscript

Journal Name:

Advanced Functional Materials

Additional Journal Information:

Journal Volume: 31; Journal Issue: 14; Journal ID: ISSN 1616-301X

Publisher:

Wiley

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; electron structure; oxygen activation; perovskite oxides; surface active site; surface segregation