Using the Alkynyl-Substituted Rhenium(I) Complex (4,4'-Bisphenyl-Ethynyl-2,2'-Bipyridyl)Re(CO)(3)Cl as Catalyst for CO2 Reduction-Synthesis, Characterization, and Application

摘要

The synthesis, structure, photophysics, and spectroscopic characterization of an organometallic rhenium multichromophore compound carrying a central 2,2'-bipyridyl acceptor moiety with additional phenylethynyl substituents conjugated at the 4,4'-positions of the acceptor ligands and its effect on the electron density of the central rhenium atom as metal center for CO2 reduction is reported. The results were compared to fac-(2,2'-bipyridyl)Re(CO)(3)Cl and fac-(5,5'-bisphenylethynyl-2,2'-bipyridyl)Re(CO)(3)Cl. Cyclovoltammetric studies and rotating disk electrochemistry were performed for electrochemical characterization. Ultraviolet and visible (UV-vis) absorption, Fourier transform infrared (FTIR), and luminescence measurements were carried out for a spectroscopic characterization and compared to theoretical calculations at the density functional theory (DFT) level. In addition, the rhenium complex fac-(4,4'-bisphenyl-ethynyl-2,2'-bipyridyl)-Re(CO)(3)Cl was used as a novel catalyst for the electrochemical reduction of CO2 in homogeneous solution. Results showed an 11-fold increase in the current density under CO2 saturation and a catalytic second-order rate constant for CO formation of about 560 M-1 s(-1) on a Pt working electrode. For further characterization of the CO2 reduction capabilities, bulk controlled potential electrolysis experiments were performed using a CO2-saturated acetonitrile electrolyte solution. The headspace product gas analysis yields CO as main reduction product with faradaic efficiencies of about 12 % over 5-h electrolysis time.