Engendering Unprecedented Activation of Oxygen Evolution via Rational Pinning of Ni Oxidation State in Prototypical Perovskite:Close Juxtaposition of Synthetic Approach and Theoretical Conception

Pittkowski, R. and Divanis, S. and Klementová, M. and Nebel, R. and Nikman, S. and Hoster, H. and Mukerjee, S. and Rossmeisl, J. and Krtil, P. (2021) Engendering Unprecedented Activation of Oxygen Evolution via Rational Pinning of Ni Oxidation State in Prototypical Perovskite:Close Juxtaposition of Synthetic Approach and Theoretical Conception. ACS Catalysis, 11 (2). pp. 985-997. ISSN 2155-5435

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Abstract

Rational optimization of the OER activity of catalysts based on LaNiO3 oxide is achieved by maximizing the presence of trivalent Ni in the surface structure. DFT investigations of the LaNiO3 catalyst and surface structures related to it predict an improvement in the OER activity for these materials to levels comparable with the top of the OER volcano if the La content is minimized while the oxidation state of Ni is maintained. These theoretically predicted structures of high intrinsic OER activity can be prepared by a templated spray-freeze freeze-drying synthesis followed by a simple postsynthesis exfoliation-like treatment in acidic media. These nanocrystalline LaNiO3-related materials confirm the theoretical predictions, showing a dramatic improvement in OER activity. The exfoliated surfaces remain stable in OER catalysis, as shown by an in-operando ICP-OES study. The unprecedented OER activation of the synthesized LaNiO3-based materials is related to a close juxtaposition of the theoretical conception of ideal structural motifs and the ability to engender such motifs using a unique synthetic procedure, both principally related to stabilization and pinning of the Ni oxidation state within the local coordination environment of the perovskite structure. © 2021 American Chemical Society. All rights reserved.

Item Type:
Journal Article
Journal or Publication Title:
ACS Catalysis
Additional Information:
This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acscatal.0c04733
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/1500/1503
Subjects:
ID Code:
151927
Deposited By:
Deposited On:
19 Feb 2021 14:10
Refereed?:
Yes
Published?:
Published
Last Modified:
21 Jul 2021 04:28