Rights statement: 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
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Final published version
Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
}
TY - JOUR
T1 - Engendering Unprecedented Activation of Oxygen Evolution via Rational Pinning of Ni Oxidation State in Prototypical Perovskite
T2 - Close Juxtaposition of Synthetic Approach and Theoretical Conception
AU - Pittkowski, R.
AU - Divanis, S.
AU - Klementová, M.
AU - Nebel, R.
AU - Nikman, S.
AU - Hoster, H.
AU - Mukerjee, S.
AU - Rossmeisl, J.
AU - Krtil, P.
N1 - 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
PY - 2021/1/15
Y1 - 2021/1/15
N2 - 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.
AB - 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.
KW - DFT
KW - electrocatalysis
KW - oxygen evolution
KW - rational catalyst design
KW - Catalyst activity
KW - Chemical activation
KW - Lanthanum compounds
KW - Nanocrystalline materials
KW - Nanocrystals
KW - Nickel
KW - Oxidation
KW - Oxygen
KW - Perovskite
KW - Surface structure
KW - Freeze-drying synthesis
KW - Local coordination
KW - Oxygen evolution
KW - Perovskite structures
KW - Rational optimization
KW - Structural motifs
KW - Synthetic approach
KW - Synthetic procedures
KW - Nickel compounds
U2 - 10.1021/acscatal.0c04733
DO - 10.1021/acscatal.0c04733
M3 - Journal article
VL - 11
SP - 985
EP - 997
JO - ACS Catalysis
JF - ACS Catalysis
SN - 2155-5435
IS - 2
ER -