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

0539024 - ÚFCH JH 2022 RIV US eng J - Journal Article
Pittkowski, Rebecca - Divanis, S. - Klementová, Mariana - Nebel, Roman - Nikman, S. - Hoster, H. - Mukerjee, S. - Rossmeisl, J. - Krtil, Petr
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. Roč. 11, č. 2 (2021), s. 985-997. ISSN 2155-5435. E-ISSN 2155-5435
R&D Projects: GA MŠMT LM2018110
EU Projects: European Commission(XE) 722614 - ELCOREL
Institutional support: RVO:61388955 ; RVO:68378271
Keywords : dft * electrocatalysis * oxygen evolution * rational catalyst design
OECD category: Physical chemistry; Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) (FZU-D)
Impact factor: 13.700, year: 2021
Method of publishing: Limited access

All rights reserved. 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.
Permanent Link: http://hdl.handle.net/11104/0316770