RESUMO
A multi-component coordination compound, in which ruthenium antenna complexes are connected to a polyoxotungstate core is presented. This hybrid cluster effectively promotes the electrochemical conversion of CO2 to C1 feedstocks, the selectivity of which can be controlled by the acidity of the media.
RESUMO
The supramolecular photocatalysts in which a Ru(II) complex as a molecular redox photosensitizer unit and a Re(I) complex as a molecular catalyst unit are connected with a various alkyl or ether chain have attracted attention because they can efficiently photocatalyze CO2 reduction with high durability and high selectivity of CO formation, especially on various solid materials such as semiconductor electrodes and mesoporous organosilica. The intramolecular electron transfer from the one-electron reduced photosensitizer unit to the catalyst unit, which follows excitation of the photosensitizer unit and subsequent reductive quenching of the excited photosensitizer unit by a reductant, is one of the most important processes in the photocatalytic reduction of CO2. We succeeded in determining the rate constants of this intramolecular electron transfer process by using subnanosecond time-resolved IR spectroscopy. The logarithm of rate constants shows a linear relationship with the lengths of the bridging chain in the supramolecular photocatalysts with one bridging alkyl or ether chain. In conformity with the exponential decay of the wave function and the coupling element in the long-distance electron transfer, the apparent decay coefficient factor (ß) in the supramolecular photocatalysts with one bridging chain was determined to be 0.74 Å-1. In the supramolecular photocatalyst with two ethylene chains connecting between the photosensitizer and catalyst units, on the other hand, the intramolecular electron transfer rate is much faster than that with only one ethylene chain. These results strongly indicate that the intramolecular electron transfer from the one-electron reduced species of the Ru photosensitizer unit to the Re catalyst unit proceeds by the through-bond mechanism.
RESUMO
Utilization of low concentration CO2 contained in the exhaust gases from various industries and thermal power stations without the need for energy-consuming concentration processes should be an important technology for solving global warming and the shortage of fossil resources. Here we report the direct electrocatalytic reduction of low concentration CO2 by a Re(i)-complex catalyst that possesses CO2-capturing ability in the presence of triethanolamine. The reaction rate and faradaic efficiency of CO2 reduction were almost the same when using Ar gas containing 10% CO2 or when using pure CO2 gas, and the selectivity of CO formation was very high (98% at 10% CO2). At a concentration of 1% CO2, the Re(i) complex still behaved as a good electrocatalyst; 94% selectivity of CO formation and 85% faradaic efficiency were achieved, and the rate of CO formation was 67% compared to that when using pure CO2 gas. The electrocatalysis was due to the efficient insertion of CO2 into the Re(i)-O bond in fac-[Re(dmb)(CO)3{OC2H4N(C2H4OH)2}] (dmb = 4,4'-dimethyl-2,2'-bipyridine).
