A common challenge in electrochemical processes is developing high performance, stable catalysts for specific chemical reactions. In this work, a Pd‐Sn intermetallic compound with Pd site deficiency (Pd1.9−xSn) (x = 0.06) and trace amount of SnOx was synthesised by controlled process. Under the electrochemical conditions, the deficient Pd site is filled by metallic Sn, which generates a highly active and stable (Pd1.84Sn0.06)Sn catalyst for ethanol oxidation reaction (EOR). The crystal structure and atomic arrangements for synthesized and in situ generated compound are comprehensively characterized by various spectroscopic techniques. The in situ generated catalyst exhibits excellent performance toward EOR (anodic reaction in fuel cell), which outperforms the state‐of‐the‐art Pd/C catalyst by three times in terms of activity. Furthermore, it is observed that the catalyst preferentially cleaves the CC bond in ethanol, which is a crucial process that enhances the efficiency of the fuel cells. The catalyst retains its superlative activity even after 1500 cycles of continuous operation. The mechanism for EOR and CC bond cleavage is evidenced by operando Infra Red spectroscopy and Differential Electrochemical Mass Spectroscopy (DEMS), and the driving force toward excellent performance has been proposed via theoretical calculations.

中文翻译：

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在稳定的 Pd-Sn 金属间化合物催化剂中原位填充金属空位以增强乙醇氧化中 CC 键的裂解


电化学过程中的一个常见挑战是为特定化学反应开发高性能、稳定的催化剂。在本工作中，通过受控过程合成了一种具有 Pd 位点缺陷 （Pd1.9−xSn） （x = 0.06） 和痕量 SnOx 的 Pd-Sn 金属间化合物。在电化学条件下，缺乏的 Pd 位点被金属 Sn 填充，生成高活性和稳定的 （Pd1.84Sn0.06）Sn 催化剂，用于乙醇氧化反应 （EOR）。通过各种光谱技术对合成和原位生成化合物的晶体结构和原子排列进行全面表征。原位生成的催化剂对 EOR（燃料电池中的阳极反应）表现出优异的性能，其活性是最先进的 Pd/C 催化剂的三倍。此外，据观察，催化剂优先裂解乙醇中的 CC 键，这是提高燃料电池效率的关键过程。该催化剂即使在连续运行1500次循环后仍能保持其最高活性。原位红外光谱和差分电化学质谱 （DEMS） 证明了 EOR 和 CC 键裂解的机制，并通过理论计算提出了优异性能的驱动力。