Sulphur vs NH Group: Effects on the CO₂ Electroreduction Capability of Phenylenediamine-Cp Cobalt Complexes.

ABSTRACT: The cobalt complex (I) with cyclopentadienyl and 2-aminothiophenolate ligands was investigated as a homogeneous catalyst for electrochemical CO₂ reduction. By comparing its behavior with an analogous complex with the phenylenediamine (II), the effect of sulfur atom as a substituent has been evaluated. As a result, a positive shift of the reduction potential and the reversibility of the corresponding redox process have been observed, also suggesting a higher stability of the compound with sulfur. Under anhydrous conditions, complex I showed a higher current enhancement in the presence of CO₂ (9.41) in comparison with II (4.12). Moreover, the presence of only one -NH group in I explained the difference in the observed increases on the catalytic activity toward CO₂ due to the presence of water, with current enhancements of 22.73 and 24.40 for I and II, respectively. DFT calculations confirmed the effect of sulfur on the lowering of the energy of the frontier orbitals of I, highlighted by electrochemical measurements. Furthermore, the condensed Fukui function f ^- values agreed very well with the current enhancement observed in the absence of water.

SUBMITTER: Melis N 

PROVIDER: S-EPMC10005266 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature