In operando studies on the electrochemical oxidation of water mediated by molecular catalysts

Catalysis and Surface Chemistr

Evaluation of iron-based electrocatalysts for water oxidation: an on-line mass spectrometry approach

Metals in Catalysis, Biomimetics & Inorganic MaterialsCatalysis and Surface Chemistr

Periodate as an oxidant for catalytic water oxidation: oxidation via electron transfer or O-atom transfer?

Metals in Catalysis, Biomimetics & Inorganic MaterialsCatalysis and Surface Chemistr

Design principles for homogeneous water oxidation catalysts based on first–row transition metals

The development of homogeneous first-row transition metal (FRTM) catalysts for the water oxidation reaction is considerably more challenging than for second and third-row catalysts. Given that FRTM catalysts are, in general, more labile, additional design principles must be considered to develop robust and stable catalysts for the water oxidation reaction. In this review, we highlight important design criteria and summarize important lessons learned for FRTM water oxidation catalysts.Catalysis and Surface Chemistr

Challenges in reduction of dinitrogen by proton and electron transfer

Catalysis and Surface ChemistryMetals in Catalysis, Biomimetics & Inorganic Material

Elucidation of the electrocatalytic nitrite reduction mechanism by bio-inspired copper complexes

Metals in Catalysis, Biomimetics & Inorganic MaterialsSolid state NMR/Biophysical Organic Chemistr

Catalytic water splitting with an iridium carbene complex: a theoretical study

Metals in Catalysis, Biomimetics & Inorganic MaterialsCatalysis and Surface Chemistr

Unusual water oxidation mechanism via a redox-active copper polypyridyl complex

Metals in Catalysis, Biomimetics & Inorganic Material

Challenges in elucidating the free energy scheme of the laccase catalyzed reduction of oxygen

Artificial redox catalysts are typically limited by unfavorable scaling relations of reaction intermediates leading to a significant overpotential in multi-electron redox reactions such as for example the oxygen reduction reaction (ORR). The multicopper oxidase laccase is able to catalyze the ORR in nature. In particular the high-potential variants show a remarkably low overpotential for the ORR and apparently do not suffer from such unfavorable scaling relations. Although laccases are intensively studied, it is presently unknown why the overpotential for ORR is so low and a clear description regarding the thermodynamics of the catalytic cycle and the underlying design principles is lacking. In order to understand the laccase catalyzed ORR from an electrochemical perspective, elucidation of the free energy scheme would be of high value. This article reviews the energetics of the proposed laccase catalyzed ORR mechanisms based on experimental and computational studies. However, there are still remaining challenges to overcome to elucidate the free energy scheme of laccase. Obtaining thermodynamic data on intermediates is hard or even impossible with analytical techniques. On the other hand, several computational studies have been performed with significantly different parameters and conditions, thus making a direct comparison difficult. For these reasons, a consensus on a clear free energy scheme is still lacking. We anticipate that ultimately conquering these challenges will result in a better understanding of laccase catalyzed ORR and will allow for the design of low overpotential redox catalysts.Metals in Catalysis, Biomimetics & Inorganic MaterialsSolid state NMR/Biophysical Organic Chemistr