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

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.