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Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - Exploring the Electrochemistry of Iron Dithiolene and Its Potential for Electrochemical Homogeneous Carbon Dioxide Reduction
AU - Armstrong, Craig G.
AU - Potter, Mark
AU - Malcomson, Thomas
AU - Hogue, Ross W.
AU - Armstrong, Sapphire McNeil
AU - Kerridge, Andrew
AU - Toghill, Kathryn
PY - 2022/9/1
Y1 - 2022/9/1
N2 - In this work, the dithiolene complex iron(III) bis-maleonitriledithiolene [Fe(mnt) 2 ] is characterised and evaluated as a homogeneous CO 2 reduction catalyst. Electrochemically the Fe(mnt) 2 is reduced twice to the trianionic Fe(mnt) 2 3- state, which is correspondingly found to be active towards CO 2 . Interestingly, the first reduction event appears to comprise overlapping reversible couples, attributed to the presence of both a dimeric and monomeric form of the dithiolene complex. In acetonitrile Fe(mnt) 2 demonstrates a catalytic response to CO 2 yielding typical two-electron reduction products; H 2 , CO and CHOOH. The product distribution and yield were governed by the proton source. Operating with H 2 O as the proton source gave only H 2 and CO as products, whereas using 2,2,2-trifluoroethanol gave 38% CHOOH faradaic efficiency with H 2 and CO as minor products.
AB - In this work, the dithiolene complex iron(III) bis-maleonitriledithiolene [Fe(mnt) 2 ] is characterised and evaluated as a homogeneous CO 2 reduction catalyst. Electrochemically the Fe(mnt) 2 is reduced twice to the trianionic Fe(mnt) 2 3- state, which is correspondingly found to be active towards CO 2 . Interestingly, the first reduction event appears to comprise overlapping reversible couples, attributed to the presence of both a dimeric and monomeric form of the dithiolene complex. In acetonitrile Fe(mnt) 2 demonstrates a catalytic response to CO 2 yielding typical two-electron reduction products; H 2 , CO and CHOOH. The product distribution and yield were governed by the proton source. Operating with H 2 O as the proton source gave only H 2 and CO as products, whereas using 2,2,2-trifluoroethanol gave 38% CHOOH faradaic efficiency with H 2 and CO as minor products.
KW - carbon dioxide reduction
KW - iron dithiolene
KW - homogeneous catalysis
KW - density funtional theory
KW - mechanistic insights
U2 - 10.1002/celc.202200610
DO - 10.1002/celc.202200610
M3 - Journal article
C2 - 36246849
VL - 9
SP - e202200610
JO - ChemElectroChem
JF - ChemElectroChem
SN - 2196-0216
IS - 17
M1 - e202200610
ER -