Exploring the Electrochemistry of Iron Dithiolene and Its Potential for Electrochemical Homogeneous Carbon Dioxide Reduction.
Exploring the Electrochemistry of Iron Dithiolene and Its Potential for Electrochemical Homogeneous Carbon Dioxide Reduction.
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DOI：
10.1002/celc.202200610
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发表时间：
2022-09-13
期刊：
影响因子：
4
通讯作者：
Toghill, Kathryn E.
中科院分区：
文献类型：
--
作者：
Armstrong, Craig G.;Potter, Mark;Malcomson, Thomas;Hogue, Ross W.;Armstrong, Sapphire M.;Kerridge, Andrew;Toghill, Kathryn E.
在这项工作中，二硫茂铁(III)双马来腈二硫杂多烯[Fe(MNT)2]被表征和评价为均相CO2还原催化剂。在电化学上，Fe(Mnt)2被两次还原为三阴离子的Fe(Mnt)2 3−状态，相应地被发现对二氧化碳具有活性。有趣的是，第一个还原事件似乎包括重叠的可逆对，这归因于二硫杂物的二聚体和单体的存在。在乙腈中，Fe(MNT)2对CO2有催化作用，生成典型的双电子还原产物：H2、CO和CHOOH。产物的分布和产率受质子源的影响。以H2O为质子源时，仅生成H2和CO，而使用2，2，2-三氟乙醇时，CHOOH的法拉第效率为38 %，生成H2和CO。第一个铁基二硫烯络合物，铁(III)双顺丁二硫烯，具有二氧化碳还原活性和稳定性。在乙腈电解液中，以2，2，2-三氟乙醇为质子源运行，均相催化剂的CHOOH法拉第效率为38 %，生成少量的H2和CO。目前，催化剂的性能受到与电解液和催化剂分解的寄生副反应的限制。
In this work, the dithiolene complex iron(III) bis‐maleonitriledithiolene [Fe(mnt)2] is characterised and evaluated as a homogeneous CO2 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 CO2. 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 CO2 yielding typical two‐electron reduction products: H2, CO and CHOOH. The product distribution and yield were governed by the proton source. Operating with H2O as the proton source gave only H2 and CO as products, whereas using 2,2,2‐trifluoroethanol gave 38 % CHOOH faradaic efficiency with H2 and CO as minor products. The first iron‐based dithiolene complex, iron(III) bis‐maleonitriledithiolene, is characterised for carbon dioxide reduction activity and stability. Operating with 2,2,2‐trifluoroethanol proton source in acetonitrile electrolyte, the homogeneous catalyst gave 38 % CHOOH faradaic efficiency with H2 and CO minor products. The catalyst performance is presently limited by parasitic side‐reactions with the electrolyte and catalyst decomposition.
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DOI：
10.1073/pnas.1416697111
发表时间：
2014-10-21
影响因子：
11.1
作者：
Costentin, Cyrille;Passard, Guillaume;Saveant, Jean-Michel
通讯作者：
Saveant, Jean-Michel
DOI：
10.1002/prac.19983400311
发表时间：
1998-01-01
期刊：
JOURNAL FUR PRAKTISCHE CHEMIE-CHEMIKER-ZEITUNG
影响因子：
--
作者：
Hoepping, A;Mengel, R;Mayer, R
通讯作者：
Mayer, R
影响因子：
2.6
作者：
Jayarathne, Upul;Williams, Kia;Donahue, James P.
通讯作者：
Donahue, James P.
影响因子：
12.9
作者：
Das, Amit;Han, Zhiji;Eisenberg, Richard
通讯作者：
Eisenberg, Richard
影响因子：
4.6
作者：
Eisenberg, Richard;Gray, Harry B.
通讯作者：
Gray, Harry B.