ABSTRACT
Palladium hydrides (PdHx) are pivotal in both fundamental research and practical applications across a wide spectrum. PdHx nanocrystals, synthesized by heating in dimethylformamide (DMF), exhibit remarkable stability, granting them widespread applications in the field of electrocatalysis. However, this stability appears inconsistent with their metastable nature. The substantial challenges in characterizing nanoscale structures contribute to the limited understanding of this anomalous phenomenon. Here, through a series of well-conceived experimental designs and advanced characterization techniques, including aberration-corrected scanning transmission electron microscopy (AC-STEM), in situ X-ray diffraction (XRD), and time-of-flight secondary ion mass spectrometry (TOF-SIMS), we have uncovered evidence that indicates the presence of C and N within the lattice of Pd (PdCxNy), rather than H (PdHx). By combining theoretical calculations, we have thoroughly studied the potential configurations and thermodynamic stability of PdCxNy, demonstrating a 2.5:1 ratio of C to N infiltration into the Pd lattice. Furthermore, we successfully modulated the electronic structure of Pd nanocrystals through C and N doping, enhancing their catalytic activity in methanol oxidation reactions. This breakthrough provides a new perspective on the structure and composition of Pd-based nanocrystals infused with light elements, paving the way for the development of advanced catalytic materials in the future.
ABSTRACT
The activity-stability trade-off relationship of oxygen reduction reaction (ORR) is a tricky issue that strikes the electrocatalyst population and hinders the widespread application of fuel cells. Here neoteric biphase Pd nanosheets that are structured with ultrathin two-dimensional crystalline Pd inner cores and ≈1 nm thin atomic-hybrid RhOx/Pd amorphous skins, named c/a-Pd@PdRh NSs, for disentangling this trade-off dilemma for alkaline ORR are developed. The superthin amorphous skins significantly amplify the quantity of flexibly low-coordinated atoms for electrocatalysis. An in situ selected oxidation of the top-surface Rh dopants creates atomically hybrid RhOx/Pd disorder surfaces. Detailed energy spectra and theoretical simulation confirm that these RhOx/Pd interfaces can arouse a surface charge redistribution, causing significant electron deficiency and lowered d-band center for surface Pd. Meanwhile, anticorrosive Rh/RhOx species can thermodynamically passivate the neighboring Pd atoms from oxidative dissolution. Thanks to these amplified interfacial effects, the biphase c/a-Pd@PdRh NSs simultaneously exhibit a superhigh ORR activity (5.92 A mg-1, 22.8 times that of Pt/C) and an outstanding long-lasting stability after 100k cycles of accelerated durability test, showcasing unprecedented electrocatalysts for breaking the activity-stability trade-off relationship of ORR. This work paves a bran-new strategy for designing high-performance electrocatalysts through creating modulated amorphous skins on low-dimensional nanomaterials.