Cooperative Catalysis toward Oxygen Reduction Reaction under Dual Coordination Environments on Intrinsic AMnO3‐Type Perovskites via Regulating Stacking Configurations of Coordination Units
- 12 November 2020
- journal article
- research article
- Published by Wiley in Advanced Materials
- Vol. 32 (50), e2006145
- https://doi.org/10.1002/adma.202006145
Abstract
It remains challenging for pure‐phase catalysts to achieve high performance during the electrochemical oxygen reduction reaction to overcome the sluggish kinetics without the assistance of extrinsic conditions. Herein, a series of pristine perovskites, i.e., AMnO3 (A = Ca, Sr, and Ba), are proposed with various octahedron stacking configurations to demonstrate the cooperative catalysis over SrMnO3 jointly explored by experiments and first‐principles calculations. Comparing with the unitary stacking of coordination units in CaMnO3 or BaMnO3, the intrinsic SrMnO3 with a mixture of corner‐sharing and face‐sharing octahedron stacking configurations demonstrates superior activity (Ehalf‐wave = 0.81 V), and charge–discharge stability over 400 h without the voltage gap (≈0.8 V) increasing in zinc–air batteries. The theoretical study reveals that, on the SrMnO3(110) surface, the active sites switch from coordinatively unsaturated atop Mn (*OO, *OOH) to Mn–Mn bridge (*O, *OH). Therefore, the intrinsic dual coordination environments of Mn–Ocorner and Mn–Oface enable cooperative modulation of the interaction strength of the oxygen intermediates with the surface, inducing the decrease of the *OH desorption energy (rate‐limiting step) unrestricted by scaling relationships with the overpotential of ≈0.28 V. This finding provides insights into catalyst design through screening intrinsic structures with multiple coordination unit stacking configurations.Keywords
Funding Information
- National Basic Research Program of China (2016YFB0901600)
- National Natural Science Foundation of China (21975136, 21573117)
This publication has 32 references indexed in Scilit:
- Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteriesNature Chemistry, 2011
- Scaling Relationships for Adsorption Energies on Transition Metal Oxide, Sulfide, and Nitride SurfacesAngewandte Chemie, 2008
- Heat capacity and lattice dynamics of cubic and hexagonal: Calorimetry and density functional theory simulationsPhysical Review B, 2007
- Raman spectroscopy on cubic and hexagonal SrMnO3Journal of Raman Spectroscopy, 2006
- Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell CathodeThe Journal of Physical Chemistry B, 2004
- Raman spectroscopy ofMode assignment and relationship between Raman line intensities and structural distortionsPhysical Review B, 2002
- Electron-energy-loss core-edge structures in manganese oxidesPhysical Review B, 1993
- Oxygen 1sx-ray-absorption edges of transition-metal oxidesPhysical Review B, 1989
- Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenidesActa Crystallographica Section A, 1976
- Crystal field splitting diagramsJournal of Chemical Education, 1964