Exploring the Electrochemistry of Iron Dithiolene and Its Potential for Electrochemical Homogeneous Carbon Dioxide Reduction

被引:1
作者
Armstrong, Craig G. [1 ]
Potter, Mark [1 ]
Malcomson, Thomas [1 ,2 ]
Hogue, Ross W. [1 ,3 ]
Armstrong, Sapphire M. [1 ]
Kerridge, Andrew [1 ]
Toghill, Kathryn E. [1 ]
机构
[1] Univ Lancaster, Dept Chem, Lancaster LA1 4YB, England
[2] Univ Manchester, Sch Nat Sci, Dept Chem, Manchester M13 9PL, Lancs, England
[3] Leiden Inst Chem, LIC Energy & Sustainabil, Gorlaeus Labs, Einsteinweg 55, NL-2333 CC Leiden, Netherlands
基金
欧洲研究理事会; 英国工程与自然科学研究理事会;
关键词
CO2; reduction; density functional theory; homogeneous catalysis; iron dithiolene; mechanistic insights; CORRELATED MOLECULAR CALCULATIONS; GAUSSIAN-BASIS SETS; ELECTROCATALYTIC REDUCTION; CO2; REDUCTION; HYDROGEN EVOLUTION; ELECTRON-TRANSFER; COMPLEXES; CATALYST; ENERGY; WATER;
D O I
10.1002/celc.202200610
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
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: H-2, CO and CHOOH. The product distribution and yield were governed by the proton source. Operating with H2O 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.
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页数:11
相关论文
共 58 条
[1]  
[Anonymous], 2015, ANGEW CHEM, V127, P14296
[2]  
[Anonymous], 2017, ANGEW CHEM, V129, P4311
[3]   Characterisation of the ferrocene/ferrocenium ion redox couple as a model chemistry for non-aqueous redox flow battery research [J].
Armstrong, Craig G. ;
Hogue, Ross W. ;
Toghill, Kathryn E. .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 2020, 872 (872)
[4]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[5]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[6]   Ultraefficient homogeneous catalyst for the CO2-to-CO electrochemical conversion [J].
Costentin, Cyrille ;
Passard, Guillaume ;
Robert, Marc ;
Saveant, Jean-Michel .
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2014, 111 (42) :14990-14994
[7]   Multielectron, Multistep Molecular Catalysis of Electrochemical Reactions: Benchmarking of Homogeneous Catalysts [J].
Costentin, Cyrille ;
Saveant, Jean-Michel .
CHEMELECTROCHEM, 2014, 1 (07) :1226-1236
[8]   Electrocatalytic reduction of CO2 to CO in the presence of a mononuclear polypyridyl ruthenium(II) complex [J].
Daryanavard, Marzieh ;
Hadadzadeh, Hassan ;
Weil, Matthias ;
Farrokhpour, Hossein .
JOURNAL OF CO2 UTILIZATION, 2017, 17 :80-89
[9]   Nickel Complexes for Robust Light-Driven and Electrocatalytic Hydrogen Production from Water [J].
Das, Amit ;
Han, Zhiji ;
Brennessel, William W. ;
Holland, Patrick L. ;
Eisenberg, Richard .
ACS CATALYSIS, 2015, 5 (03) :1397-1406
[10]  
Davison A.H., 1967, INORG SYN <D>, V10, P8, DOI DOI 10.1002/9780470132418.CH3