Direct Electrochemical CO(2) Capture Using Substituted Anthraquinones in Homogeneous Solutions: A Joint Experimental and Theoretical Study

[Image: see text] Electrochemical capture of carbon dioxide (CO(2)) using organic quinones is a promising and intensively studied alternative to the industrially established scrubbing processes. While recent studies focused only on the influence of substituents having a simple mesomeric or nucleophilicity effect, we have systematically selected six anthraquinone (AQ) derivatives (X-AQ) with amino and hydroxy substituents in order to thoroughly study the influence thereof on the properties of electrochemical CO(2) capture. Experimental data from cyclic voltammetry (CV) and UV–Vis spectroelectrochemistry of solutions in acetonitrile were analyzed and compared with innovative density functional tight binding computational results. Our experimental and theoretical results provide a coherent explanation of the influence of CO(2) on the CV data in terms of weak and strong binding nomenclature of the dianions. In addition to this terminology, we have identified the dihydroxy substituted AQ as a new class of molecules forming rather unstable [X-AQ-(CO(2))(n)](2–) adducts. In contrast to the commonly used dianion consideration, the results presented herein reveal opposite trends in stability for the X-AQ-CO(2)(•–) radical species for the first time. To the best of our knowledge, this study presents theoretically calculated UV–Vis spectra for the various CO(2)-AQ reduction products for the first time, enabling a detailed decomposition of the spectroelectrochemical data. Thus, this work provides an extension of the existing classification with proof of the existence of X-AQ-CO(2) species, which will be the basis of future studies focusing on improved materials for electrochemical CO(2) capture.