High‐entropy alloys (HEAs) have attracted widespread attention in electrocatalysis due to their unique advantages (adjustable composition, complex surface, high tolerance, etc.). They allow for the formation of new and tailorable active sites in multiple elements adjacent to each other, and the interaction can be tailored by rational selection of element configuration and composition. However, it needs to be further explored in catalyst design, the interaction of elements, and the determination of active sites. This review article focuses on the important progress for multi‐sites electrocatalysis in HEAs. The classification is done on the basis of catalytic reaction, including hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, alcohol oxidation reaction, carbon dioxide reduction reaction, and nitrogen reduction reaction. Based on experiments and theories, a more in‐depth exploration of the high catalytic activity of HEAs will be conducted, including the selection of elements (the special role of each element in catalysis) and the multi‐sites effect. This review can provide the basis for the element selection and design of HEAs in some reactions, to adjust the compositions of HEAs to improve their intrinsic activity. Furthermore, the remaining challenges and future directions for promising research fields are also provided.
Direct ethanol fuel cells are among the most efficient and environmentally friendly energy-conversion devices and have been widely focused. The ethanol oxidation reaction (EOR) is a multielectron process with slow kinetics. The large amount of by-product generated by incomplete oxidation greatly reduces the efficiency of energy conversion through the EOR. In this study, a novel type of trimetallene called porous PdWM (M = Nb, Mo and Ta) is synthesized by a facile method. The mass activity (15.6 A mg Pd −1 ) and C1 selectivity (55.5%) of Pd 50 W 27 Nb 23 /C trimetallene, obtained after optimizing the compositions and proportions of porous PdWM, outperform those of commercial Pt/C (1.3 A mg Pt −1 , 5.9%), Pd/C (5.0 A mg Pd −1 , 7.2%), and Pd 97 W 3 /C bimetallene (9.5 A mg Pd −1 , 14.1%). The mechanism by which Pd 50 W 27 Nb 23 /C enhances the EOR performance is evaluated by in situ Fourier transform infrared spectroscopy and density functional theory calculations. It is found that W and Nb enhance the adsorption of CH 3 CH 2 OH and oxophilic high-valence Nb accelerates the subsequent oxidation of CO and -CH x species. Moreover, Nb promotes the cleavage of C-C bonds and increases the C1 selectivity. Pd 60 W 28 Mo 12 /C and Pd 64 W 27 Ta 9 /C trimetallene synthesized by the same method also exhibit excellent EOR performance.
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