Abstract
A lot of effort is nowadays put into the development of novel water oxidation catalysts. In this context, mechanistic studies are crucial in order to elucidate the reaction mechanisms governing this complex process, new design paradigms and strategies how to improve the stability and efficiency of those catalysts. This review is focused on recent theoretical mechanistic studies in the field of homogeneous cobalt-based water oxidation catalysts. In the first part, computational methodologies and protocols are summarized and evaluated on the basis of their applicability toward real catalytic or smaller model systems, whereby special emphasis is laid on the choice of an appropriate model system. In the second part, an overview of mechanistic studies is presented, from which conceptual guidelines are drawn on how to approach novel studies of catalysts and how to further develop the field of computational modeling of water oxidation reactions.
Highlights
In the past decade, artificial water splitting has become a hot topic in research on renewable energy sources
While metadynamics simulations give a more realistic picture of the reaction than static approaches and might allow further insight on how the solvent molecules participate in the O−O bond formation, they are still depended on the choice of the observables, the bias potential, and the quality of the sampling, all of which make such simulations computationally very demanding and de facto limit their application to small systems
The development of multiconfigurational pair-density functional theory (DFT) (Li Manni et al, 2014; Ghosh et al, 2015), heat bath configuration interaction (Holmes et al, 2016; Sharma et al, 2017), CAS-quantum Monte Carlo (QMC) (Li Manni et al, 2016), as well as the application of domain-based local pair natural orbital methods such as DLPNO-CCSD(T) (Sparta and Neese, 2014; Liakos et al, 2015; Saitow et al, 2017) highlight the fact that those methods and methodologies are subject to active research - an in depth overview of which is beyond the scope of this review
Summary
Artificial water splitting has become a hot topic in research on renewable energy sources. Even though some of them show outstanding catalytic performance, we still lack fundamental understanding of the catalytic process The latter is crucial in order to systematically improve those catalysts in terms of their catalytic performance and long term stability. The complexity of such systems often makes experimental investigations of catalytic intermediates a very tedious task. We will review some of the recent theoretical studies based on homogeneous transition metals complexes used for water oxidation with emphasis on cobalt-based catalysts. The latter has not been the most commonly used metal for artificial water oxidation catalysts (WOCs).
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