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Breaking the activity-stability trade-off in ammonia borane hydrolysis via atomically engineered platinum single
Jiankang Zhang1, Panzhe Qiao2, Jinlong Hu3
1Interdisciplinary Research Center of Biology & Catalysis, School of Life Sciences, Northwestern Polytechnical University, Xi'an 710072, China.
Abstract:
Atomically dispersed heterometal catalysts offer ultrahigh atomic utilization and defined heterointerfaces for superior catalytic performance compared to single-metal-site analogues, yet their precise atomic-level construction remains challenging. Herein, a structure-defined atomic-cluster catalyst (PtSANiC/CNT) is synthesized via sequential atomic layer deposition (ALD). This strategy enables atomic-scale engineering of Pt surface exposure and electronic properties through controlled ALD cycles. The optimized PtSANiC/CNT exhibits exceptional activity and durability for ammonia borane (AB) hydrolytic dehydrogenation, breaking the activity-stability trade-off with 9.6-fold and 1.4-fold higher activity than PtSA/CNT (single-atom) and PtSANiSA/CNT (dual-atom) catalysts, respectively. Through in situ X-ray absorption spectroscopy, kinetic and dynamic analysis, and DFT calculations, we elucidate that PtSANiC interfacial sites synergistically promote concurrent H2O adsorption-dissociation and H2 desorption. Mechanistic studies reveal that nickel clusters facilitate H2O activation while Pt single atoms favor B-H bond cleavage due to an upshifted d-band center. This interfacial synergy also enhances selective hydrogenation and O2/H2O2-involved oxidation. The ALD-based atomic engineering approach provides a generalizable route to construct efficient and durable heterometal catalysts with defined active sites.
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