Given that the retention of nitrogen readily renders active site poisoning, designing versatile catalysts characterized by notable selectivity and even resistance to poisoning for alkyne semi‐hydrogenation under nitrogen‐containing conditions is considerably challenging. In this article, oxanilide‐decorated Pd/C (Pd/C‐oxa) catalyst is facilely synthesized by leveraging impregnation‐coordination, which exhibit remarkable performance in the semi‐hydrogenation of nitrogen‐containing alkynes, with ultrahigh turnover frequency (TOF) of 15,831 h−1 and selectivity of 97.2%. Strikingly, it still sustains TOF of 12,137 h−1 in a sulfur‐containing system, demonstrating distinguished tolerance to sulfur. Comprehensive studies corroborate that oxanilide tunes the electron density of Pd by constructing metal–ligand electronic interactions, facilitating hydrogen activation. Simultaneously, the reaction microenvironment is optimized, which effectively promotes the desorption of nitrogen‐containing olefins and attenuates the aggregation of nitrogen on the Pd surface. This strategy is universal and holds promising industrial applications, making it appropriate for use in commercial Pd/C catalysts as well.

中文翻译：

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增强对炔烃半氢化中金属-配体电子相互作用对 Pd 中毒的抵抗力


鉴于氮的保留很容易导致活性位点中毒，因此在含氮条件下设计具有显着选择性甚至抗炔烃半氢化中毒特性的多功能催化剂是相当具有挑战性的。本文利用浸渍配位法轻松合成了氧苯胺装饰的 Pd/C （Pd/C-oxa） 催化剂，在含氮炔烃的半氢化反应中表现出优异的性能，具有 15,831 h-1 的超高周转频率 （TOF） 和 97.2% 的选择性。引人注目的是，它在含硫系统中仍然维持着 12,137 h-1 的 TOF，显示出对硫的显着耐受性。综合研究证实，氧苯胺通过构建金属-配体电子相互作用来调节 Pd 的电子密度，促进氢活化。同时，优化反应微环境，有效促进含氮烯烃的解吸，减弱氮气在 Pd 表面的聚集。这种策略是通用的，并且具有广阔的工业应用前景，使其也适用于商业 Pd/C 催化剂。