Energy-Efficient Hydrogen Evolution by Fe-S Electrocatalysts: Mechanistic Investigations

被引:5
|
作者
Chu, Kai-Ti [1 ]
Liu, Yu-Chiao [1 ]
Chung, Min-Wen [1 ]
Poerwoprajitno, Agus Riyanto [1 ]
Lee, Gene-Hsiang [2 ]
Chiang, Ming-Hsi [1 ]
机构
[1] Acad Sinica, Inst Chem, Taipei 115, Taiwan
[2] Natl Taiwan Univ, Instrumentat Ctr, Taipei 106, Taiwan
关键词
COUPLED ELECTRON-TRANSFER; CONCERTED PROTON; ACTIVE-SITE; ELECTROCHEMICAL APPROACH; NICKEL ELECTROCATALYST; IRON HYDROGENASES; H-2; PRODUCTION; WATER; REDUCTION; COMPLEXES;
D O I
10.1021/acs.inorgchem.8b00543
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The intrinsic catalytic property of a Fe-S complex toward H-2 evolution was investigated in a wide range of acids. The title complex exhibited catalytic events at -1.16 and -1.57 V (vs Fc(+)/Fc) in the presence of trifluoromethanesulfonic acid (HOTf) and trifluoroacetic acid (TFA), respectively. The processes corresponded to the single reduction of the Fe-hydride-S-proton and Fe-hydride species, respectively. When anilinium acid was used, the catalysis occurred at -1.16 V, identical with the working potential of the HOTf catalysis, although the employment of anilinium acid was only capable of achieving the Fe-hydride state on the basis of the spectral and calculated results. The thermodynamics and kinetics of individual steps of the catalysis were analyzed by density functional theory (DFT) calculations and electroanalytical simulations. The stepwise CCE or CE (C, chemical; E, electrochemical) mechanism was operative from the HOTf or TFA source, respectively. In contrast, the involvement of anilinium acid most likely initiated a proton-coupled electron transfer (PCET) pathway that avoided the disfavored intermediate after the initial protonation. Via the PCET pathway, the heterogeneous electron transfer rate was increased and the overpotential was decreased by 0.4 V in comparison with the stepwise pathways. The results showed that the PCET-involved catalysis exhibited substantial kinetic and thermodynamic advantages in comparison to the stepwise pathway; thus, an efficient catalytic system for proton reduction was established.
引用
收藏
页码:7620 / 7630
页数:11
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