4.7 Article

Finding the True Catalyst for Water Oxidation at Low Overpotential in the Presence of a Metal Complex

Journal

INORGANIC CHEMISTRY
Volume 61, Issue 8, Pages 3801-3810

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.2c00111

Keywords

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Funding

  1. Institute for Advanced Studies in Basic Sciences
  2. National Elite Foundation
  3. Slovenian Research Agency [P2-0348]

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This article presents the progress in molecular catalyst design for oxygen-evolution reaction (OER) and proposes a new method for detecting catalysts. Experimental results demonstrate the necessity of in-depth investigation to rule out heterogeneous catalysts formed in the presence of homogeneous OER (pre)catalysts, and have significant implications for the entire chemistry community.
The design of molecular-based catalysts for oxygen-evolution reaction (OER) requires more investigations for the true catalyst to be found. First-row transition metal complexes are extensively investigated for OER, but the role of these metal complexes as a true catalyst is doubtful. Some doubts have been expressed about the role of first-row transition metal complexes for OER at high overpotentials (eta > 450). Generally, the detection of the true catalyst has so far been focused on high overpotentials (eta > 450) because at low overpotentials (eta < 450), many methods are not sensitive enough to detect small amounts of heterogeneous catalysts on the electrode surface during the first seconds of the reaction. Ni(II) phthalocyanine-tetra sulfonate tetrasodium (1) is in moderate conditions (at 20-50 degrees C and pH 5-13) in the absence of electrochemical driving forces, which could make it noteworthy for OER, Herein, the results of OER in the presence of 1 at low overpotentials under alkaline conditions are presented. In addition, in the presence of Ni complexes, using an Fe ion is introduced as a new method for detecting Ni (hydr)oxide under OER. Our experiments indicate that in the presence of a homogeneous OER (pre)catalyst, a deep investigation is necessary to rule out the heterogeneous catalysts formed. Our approach is a roadmap in the field of catalysis to understand the OER mechanism in the presence of a molecular Ni-based catalyst design. Our results shown in this study are likely to open up new perspectives and discussion on many molecular catalysts in a considerable part of the chemistry community.

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