Oxygen-Bridged Long-Range Dual Sites Boost Ethanol Electrooxidation by Facilitating C–C Bond Cleavage

Abstract

Optimizing the interatomic distance of dual sites to realize C–C bond breaking of ethanol is critical for the commercialization of direct ethanol fuel cells. Herein, the concept of holding long-range dual sites is proposed to weaken the reaction barrier of C–C cleavage during the ethanol oxidation reaction (EOR). The obtained long-range Rh–O–Pt dual sites achieve a high current density of 7.43 mA/cm2 toward EOR, which is 13.3 times that of Pt/C, as well as remarkable stability. Electrochemical in situ Fourier transform infrared spectroscopy indicates that long-range Rh–O–Pt dual sites can increase the selectivity of C1 products and suppress the generation of a CO intermediate. Theoretical calculations further disclose that redistribution of the surface-localized electron around Rh–O–Pt can promote direct oxidation of −OH, accelerating C–C bond cleavage. This work provides a promising strategy for designing oxygen-bridged long-range dual sites to tune the activity and selectivity of complicated catalytic reactions.

Atomic Diffusion Engineered PtSnCu Nanoframes with High‐Index Facets Boost Ethanol Oxidation

“…As shown in Figures 3c and Figure S36 (Supporting Information), Pt 47 Sn 12 Cu 41 achieves a record‐high peak mass activity of 3.10 A mg −1 Pt, which is 6.3, 2.2, 1.3, 1.4, and 2.7 times higher than Pt/C, Pt 41 Cu 59 , Pt 45 Sn 5 Cu 50 , Pt 48 Sn 19 Cu 33 , and Pt 49 Sn 45 Cu 6 , outperforming the state‐of‐the‐art EOR electrocatalysts previously reported in the literature (Figure 3e; Table S2, Supporting Information). [ 2–7,9,21,31,32 ] These results illustrate the extraordinary effects of sophisticated structure (octopod nanoframes enclosed by high‐index facets) and composition (a high content of trimetallic fcc PtSnCu) engineering in boosting EOR.…”

Electronic state regulation induced by the strong metal–support interactions boosts the performance of alcohol oxidation reactions

“…As incomplete oxidation occurs, CO on the surface of the catalyst will occupy the active sites leading to a poisoning effect that significantly reduces catalytic performance by preventing the adsorption of substrate and reaction intermediates. 41 CO-stripping experiments were performed to assess the anti-CO poisoning ability of the as-synthesized catalysts. As shown in Fig.…”

Recent Approaches for Cleaving the C─C Bond During Ethanol Electro‐Oxidation Reaction

“…constructed oxygen‐bridged long‐range Rh–O–Pt dual sites to accelerate C─C cleavage through redistributing the surface‐localized electron around Rh–O–Pt (Figure 6E ). [ 71 ] Theoretical calculations disclosed that the redistribution of the surface‐localized electron around Rh–O–Pt could lower the energy of C─C bond cleavage (0.59 eV, Figure 6F ), accelerating C─C bond cleavage.…”

“…F) Scheme and computed energetics of ethanol being oxidized to the major product acetaldehyde and reaction energy barriers of CH 3 CO* oxidation and cleavage on Rh-O-Pt models. Reproduced with permission [71]. Copyright 2023, American Chemical Society.…”