Engineering heterostaple in atomically precise palladium cluster for efficient hydrogen peroxide electrosynthesis.

Authors

Jiachun Li, Yan Sun, Min Du, Shuguang Wang, Baoliang Han, Jiacheng Wang, Xiaoyi Yang, Fangkai Wu, Fuling Liu, Xiaofeng Lei, Afang Dai, Zibao Gan, Xiuwen Zheng, Di Sun

Published in

Science bulletin. Sep 02, 2026. Epub Sep 02, 2026.

Abstract

The deliberate construction of well-defined heterostaples within atomically precise metal clusters offers a powerful route to heterometallic systems with unconventional functionalities and promising catalytic potential. However, realizing such precise interface engineering in palladium-based clusters remains highly challenging. Here, we report the first successful synthesis of well-defined Pd₅Au₂ and Pd₅Cu₂ architectures featuring heterometallic interfaces by customizing dual-atom site (Au-Au or Cu-Cu) in atomically precise palladium cluster. Their structures were unambiguously determined by single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS). Both heterometallic clusters share a similar architecture, comprising a slightly folded Pd₅S hexatomic ring encapsulating a central antimony atom from PhSb^2- ligand, a M₂S₃ (M=Au or Cu) staple and four bridging thiolate ligands. Incorporation of the Au-Au or Cu-Cu subunit modulates the geometric and electronic environments of the palladium core to varying extents, leading to markedly distinct two-electron oxygen reduction reaction performances. Notably, Pd₅Au₂ achieves a nearly 100% H₂O₂ Faradaic efficiency at 25 mA cm^-2 and an exceptional H₂O₂ production rate of 1366.4 mmol g_cat^-1 h^-1 at 125 mA cm^-2. Its efficacy was further demonstrated in practical Fenton-type pollutant degradation. Density functional theory (DFT) calculations, corroborated by operando infrared spectroscopy, reveal that the introduction of an Au-Au dual-atom site induces an electronic redistribution that weakens the *OOH adsorption, thereby facilitating its hydrogenation step. This study represents the first realization of atomically precise palladium-based clusters equipped with heterometallic interfaces, providing new mechanistic insights and design principles for cluster-based catalysts in small-molecule energy conversion.

PMID:
42686504
Bibliographic data and abstract were imported from PubMed on 03 Sep 2026.

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