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... Show moreArtificial 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. Show less
To design the ideal water oxidation catalyst, understanding of the catalytic mechanism and decomposition pathways is essential. The aim of the research described in this thesis is to provide... Show moreTo design the ideal water oxidation catalyst, understanding of the catalytic mechanism and decomposition pathways is essential. The aim of the research described in this thesis is to provide mechanistic insight on the water oxidation reaction catalyzed by homogeneous electrocatalysts and topostulate design criteria for the ideal water oxidation catalyst. Show less
Oxygen vacancies (OVs) have been reported to significantly alter the photocatalytic properties of BiOCl nanosheets. However, their formation mechanism and their role in the enhancement of... Show moreOxygen vacancies (OVs) have been reported to significantly alter the photocatalytic properties of BiOCl nanosheets. However, their formation mechanism and their role in the enhancement of photoelectrochemical performance remain unclear. In this work, thermally induced oxygen vacancies are introduced in BiOCl nanosheets by annealing in He atmosphere at various temperatures and their formation mechanism is investigated by in-situ diffuse reflectance infrared (DRIFTS) measurements. The influence of OVs on band offset, carrier concentrations and photoelectrochemical performance are systematically studied. The results show that (1) the surface of BiOCl nanosheets is extremely sensitive to temperature and defects are formed at temperatures as low as 200 degrees C in inert atmosphere. (2) The formation of surface and bulk OVs in BiOCl is identified by a combination of XPS, in-situ DRIFTS, and EPR experiments. (3) The photocurrent of BiOCl is limited by the concentration of charge carriers and shallow defect states induced by bulk oxygen vacancies, while the modulation of these parameters can effectively increase light absorption and carrier concentration leading to an enhancement of photoelectrochemical performance of BiOCl. Show less
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... Show moreThe 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. Show less
The homogeneity of molecular Co-based wateroxidation catalysts (WOCs) has been a subject of debate over thelast 10 years as assumed various homogeneous Co-based WOCswere found to actually form... Show moreThe homogeneity of molecular Co-based wateroxidation catalysts (WOCs) has been a subject of debate over thelast 10 years as assumed various homogeneous Co-based WOCswere found to actually form CoOxunder operating conditions. Thehomogeneity of the Co(HL)(HL=N,N-bis(2,2 '-bipyrid-6-yl)amine) system was investigated with cyclic voltammetry,electrochemical quartz crystal microbalance, and X-ray photo-electron spectroscopy. The obtained experimental results werecompared with heterogeneous CoOx. Although it is shown thatCo(HL) interacts with the electrode during electrocatalysis, theformation of CoOxwas not observed. Instead, a molecular depositof Co(HL) was found to be formed on the electrode surface. Thisstudy shows that deposition of catalytic material is not necessarilylinked to the decomposition of homogeneous cobalt-based water oxidation catalysts. Show less
