Tuning the Selective Ethanol Oxidation on Tensile‐Trained Pt(110) Surface by Ir Single Atoms

Abstract

Development of efficient and robust electrocatalysts for complete oxidation of ethanol is critical for the commercialization of direct ethanol fuel cells. However, the complete oxidation of ethanol suffers from poor efficiency due to the low C1 pathway selectivity. Herein, single‐atomic Ir (Ir1) on hcp‐PtPb/fcc‐Pt core–shell hexagonal nanoplates (PtPb@PtIr1 HNPs) enclosed by Pt(110) surface with a 7.2% tensile strain is constructed to drive complete electro‐oxidation of ethanol. Benefiting from the construction of Ir1 sites, the PtPb@PtIr1 HNPs exhibit a Faraday efficiency of 57.93% for the C1 pathway, which is ≈8.3 times higher than that of the commercial Pt/C‐JM. Furthermore, the PtPb@PtIr1 HNPs show a top‐ranked electro‐activity achieving 45.1‐fold and 56.3‐fold higher than the specific and mass activities of Pt/C‐JM, respectively. Meanwhile, the durability can be significantly enhanced by the construction of Ir1 sites. Density functional theory calculations indicate that the strong synergy on the PtPb@PtIr1 HNPs surface significantly promotes the breaking of CC bond of CH2CO* and facilitates CO oxidation and suppresses the deactivation of the catalyst. This work offers a unique single‐atom approach using low‐coordination active sites on shape‐controlled nanocrystals to tune the selectivity and activity toward complicated catalytic reactions.

CoFe-Layered Double Hydroxide Coupled with Pd Particles for Electrocatalytic Ethanol Oxidation

“…The oxidation current of Pd/Co 1 Fe 3 –LDH/NF (7505 mA·mg Pd –1 ) was much higher than that of Pd/NF (3267 mA·mg Pd –1 ), demonstrating that Pd/Co 1 Fe 3 –LDH/NF displayed much higher catalytic activity for EOR than Pd/NF. In addition, 1 H nuclear magnetic resonance ( 1 H NMR) and high-performance liquid chromatography (HPLC) were carried out for the qualitative and quantitative analysis of the products over Pd/Co 1 Fe 3 –LDH/NF. , The 1 H NMR results showed that acetate (CH 3 COOH) was the main product, and the peak intensity of CH 3 COOH in the Pd/Co 1 Fe 3 –LDH/NF-catalyzed system was much lower than that in the Pd/NF-catalyzed system (Figure S19a). As shown in Figure S19b–d, the concentration of CH 3 COOH in the Pd/Co 1 Fe 3 –LDH/NF-catalyzed system (7.4 mM) was ∼2 times lower than that in the Pd/NF-catalyzed system (14.5 mM), indicating that Pd/Co 1 Fe 3 –LDH/NF could usefully break the C–C bond and promote the complete oxidation of ethanol.…”

Design strategies of Pt-based electrocatalysts and tolerance strategies in fuel cells: a review

“…PtPd@PtIr1 HNPs show a top-ranked activity and a Faraday efficiency of 57.93% for C1 pathway for ethanol oxidation reaction (EOR). 83 DFT results conrm that the strong synergy between Ir1 sites and tensile strain contributes to breaking the C-C bond of CH 2 CO* and facilitating oxidative removal of CO. As a result, it can be seen that shape-controlled multielement nanocrystals with low-coordination active sites could effectively tune their catalytic properties.…”

Plate-Like Colloidal Metal Nanoparticles

“…Recent advances in synthesis allow for modulating catalytic performance at the atomic level . Atomically flat nanoplates are ideal substrates for the precise study of single-atom catalysis, owing to their well-defined crystalline facets that simplify the growth environment of the single-atom catalysts. ,, Gao et al developed a ligand-mediated self-terminating strategy to realize a progressive growth of Pt single atoms, ensembles, and eventually a full monolayer of Pt on Ag@Au nanoplates, enabling the formation of isolated Pt single atoms up to 26% coverage . The resulting Ag@Au@Pt nanoplates with rich Pt single atoms show record-high catalytic activities in the electrocatalytic FAOR without involving poisoning of CO intermediates (Figure E,F).…”

“…Quan et al developed an atomic galvanic replacement strategy to generate isolated Rh atoms on PtBi nanoplates, and subsequent electrochemical transformation into a tensile-strained alloy consisting of atomic fcc -Pt layers and Rh single atoms, which remarkably boosts the ethanol oxidation reaction (EOR) . Very recently, Cui et al introduced single-atomic Ir sites on the surface of hcp -PtPb/ fcc -Pt core–shell nanoplates to tune the selectivity and activity of EOR, offering another strategy for tuning the activity and selectivity toward other electrocatalytic reactions …”

“…431 Very recently, Cui et al introduced single-atomic Ir sites on the surface of hcp-PtPb/fcc-Pt core−shell nanoplates to tune the selectivity and activity of EOR, offering another strategy for tuning the activity and selectivity toward other electrocatalytic reactions. 519…”