Abstract
The energy deficiency and environmental problems have motivated researchers to develop energy conversion systems into a sustainable pathway, and the development of catalysts holds the center of the research endeavors. Natural catalysts such as metalloenzymes have maintained energy cycles on Earth, thus proving themselves the optimal catalysts. In the previous research results, the structural and functional analogs of enzymes and nano-sized electrocatalysts have shown promising activities in energy conversion reactions. Mo ion plays essential roles in natural and artificial catalysts, and the unique electrochemical properties render its versatile utilization as an electrocatalyst. In this review paper, we show the current understandings of the Mo-enzyme active sites and the recent advances in the synthesis of Mo-catalysts aiming for high-performing catalysts.
Highlights
Fixation of atmospheric nitrogen to ammonia has been promoted by the Haber–Bosch process, and the capacitated mass production of foods accelerated the increase of the world population [1,2]
This review summarizes Mo-containing metalloenzymes and their model complexes, homogeneous and heterogeneous catalysts under categories of reactivities with CO2, N2, H2, and O2
Compared to the Mo enzymes, catalytic activities of synthetic systems remain at a low-efficiency level
Summary
Fixation of atmospheric nitrogen to ammonia has been promoted by the Haber–Bosch process, and the capacitated mass production of foods accelerated the increase of the world population [1,2]. In 2006, Raaijmakers and coworkers reinterpreted the crystal structure and proposed a reaction pathway of the FDH active site (Scheme 1) [25]. Complex 2 generated by hydrolysis of [WIV(OPh)(S2C2Ph2)2]− (1) Catalysts 2021, 11, [23177,38] showed the CO2 reactivity at mild condition, and it was suggested that a nucleophilic attack of –OH to CO2 formed a W-(bi)carbonate intermediate. An enhanced surface electron transfer to MoS2 edge could lower the energy barrier for the formation of CO2 reduction intermediates on the catalytic site [66]. N-MoS2@NCDs loaded on glassy carbon electrode exhibited high catalytic activity for the CO2 reduction to CO as recording 36 mA/cm at −0.9 V vs RHE (90% FE). −65 mA/cm at −0.76 V vs. RHE −237 mA/cm at −0.8 V vs. RHE −98~68 mA/cm at −0.8 V vs. RHE −12.1 mA/cm at −0.7 V vs. SHE −43 mA/cm at −1.15 V vs. RHE
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