Interfacial Engineering of Porous Pd/M (M = Au, Cu, Mn) Sponge-like Nanocrystals with a Clean Surface for Enhanced Alkaline Electrochemical Oxidation of Ethanol

The interfacial engineering of Pd-based alloys (i.e., PdM with distinct morphologies, compositions, and strain defects) is an efficient way for enhanced catalytic activity; however, it remains a grand challenge to fabricate such alloys in aqueous solutions without heating, organic solvents, and multiple reaction steps. Herein, we present a simple, aqueous-phase, one-step, and ultrafast approach for the interfacial engineering of surfactant-free porous PdM (M = Cu, Au, and Mn) nanocrystals with well-controlled spongy-like morphology and compositions. The electronic interaction in PdM nanocrystals and their effect on the alkaline electrochemical ethanol oxidation reaction (EOR) are investigated using XRD, XPS, and electrochemical tests. Notably, integrating M metals into Pd atoms results in upshifting the d-band center of Pd and subsequently modulating the EOR activity and stability substantially. The EOR mass activity (10.78 A/mg(Pd )(6.93 A/mg(PdCu))) of PdCu was 1.83, 3.09, 4.51, and 53.90 times higher than those of AuPd (5.90 A/mg(Pd) (3.27 A/mg(AuPd))), PdMn (3.48 A/mg(Pd) (3.19 A/mg(PdMn))), Pd (2.39 A/mg(Pd)), and Pd/C (0.20 A/mg(Pd)), respectively, besides substantial durability after 1000 cycles. This is due to the porous two-dimensional morphology, a low synergetic effect, higher interfacial interaction, and greater active surface area of PdCu, besides a high Cu content with more oxophilicity that facilitates activation/dissociation of H2O to generate -OH species needed for quick EOR electrocatalysis. The electrochemical impedance spectroscopy (EIS) reveals better electrolyte/electrode interfacial interaction and lower charge transfer resistance on PdCu. The EOR activity of PdCu porous sponge-like nanocrystals was superior to all previously reported Pd-based alloys for electrochemical EOR. This study indicates that binary Pd-based catalysts with less synergetic effect are preferred for boosting the EOR activity, which could help in manipulating the surface properties of Pd-based alloys to optimize EOR performance.

Automated summary

This study presents a simple, aqueous-phase, one-step, and ultrafast approach for the interfacial engineering of surfactant-free porous PdM (M = Cu, Au, and Mn) nanocrystals. The PdCu nanocrystals exhibit excellent alkaline electrochemical ethanol oxidation reaction (EOR) activity and stability, providing a new direction for improving the EOR performance of palladium-based catalysts.