The Golden Atomic Ratio in Binary Nanoalloys for Enhanced CO 2 Electroreduction: Dual-Metal Synergy of AgPd

作者：Guoqiang Lü, Shuo Liu, Shuo Liu, Yufeng Tang, Mulin Yu, Zhiyuan Wang, Peng‐Fei Sui, Xian‐Zhu Fu, Yifei Sun, Subiao Liu, Subiao Liu, Jing‐Li Luo · 发表于：ACS Catalysis · 年份：2025 · DOI：10.1021/acscatal.5c04933 · 被引用次数：4 · 研究领域：CO2 Reduction Techniques and Catalysts、Nanocluster Synthesis and Applications、Advanced Thermoelectric Materials and Devices

An intriguing phenomenon has been observed in various binary nanoalloys for the electrochemical CO 2 reduction reaction (CO 2 RR), where an atomic ratio close to 1:3 mostly yields the optimal activity, but its origin remains poorly understood. Here, we synthesized a series of size-uniform Ag x Pd 1– x nanoclusters (NCs) with precisely controlled atomic ratios as a model system to verify its universality and intrinsic derivation since Ag offers a high intrinsic CO selectivity but requires a large overpotential (η) due to weak intermediate binding, while Pd forms CO at a small η but suffers from CO poisoning due to an overly strong CO adsorption. Indeed, Ag 0.25 Pd 0.75 NCs with an atomic ratio of 1:3 possessed optimal CO 2 RR activity, delivering a nearly 100% CO Faraday efficiency and a maximum energy efficiency of 71.8%. Computational calculations demonstrated that the Ag/Pd atomic ratio of 1:3 induced an optimal electronic structure characterized by a d -band center positioned favorably relative to the Fermi level. This configuration synergistically lowered the energy barrier for *COOH formation and promoted *CO desorption kinetics, as corroborated by in situ spectroscopic analysis, where Ag 0.25 Pd 0.75 NCs exhibited attenuated *CO adsorption signals compared with other stoichiometries, indicating enhanced CO desorption capability. This study provides in-depth mechanistic insights into the “golden ratio” in nanoalloys for the CO 2 RR and reveals a universal paradigm of des...