Reaction sites optimization mediated by ligand coverage for semi‐hydrogenation of different alkynes

IF 3.5 3区工程技术 Q2 ENGINEERING, CHEMICAL

AIChE Journal Pub Date : 2025-04-09 DOI:10.1002/aic.18752

Zhongzhe Wei, Songtao Huang, Jiayuan Li, Yao Lv, Zihao Yao, Guanglu Dong, Molin Xia, Zhixiang Yang, Ming Jiang, Sheng Dai, Jianguo Wang

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引用次数: 0

Abstract

Precise regulation of catalysts active sites is the key to optimizing activity. In this work, a strategy for modulating alkyne adsorption sites by modifying the support is proposed. A series of Pd/ZSM‐5@PPh3‐X with different coverage of triphenylphosphine (PPh3) were synthesized. Pd/ZSM‐5@PPh3‐X enable efficient semi‐hydrogenation of alkynes under mild conditions. Specifically, the catalyst with lower surface ligand coverage (Pd/ZSM‐5@PPh3‐2) exhibits a preference for the hydrogenation of 2‐methyl‐3‐butyn‐2‐ol, while the catalyst with higher ligand coverage (Pd/ZSM‐5@PPh3‐10) favors the conversion of phenylacetylene. Both catalysts maintain an alkene selectivity exceeding 94%. Comprehensive experimental, characterization, and computational analyses revealed that for 2‐methyl‐3‐butyn‐2‐ol, which adsorbs on the palladium surface, the PPh3 inhibits the strong adsorption of alkynes, thereby preventing catalyst self‐poisoning. Conversely, the high PPh3 coverage redirects the adsorption site of phenylacetylene to the support surface, and the enhanced hydrogen spillover accelerates the reaction. This ligand‐modulated strategy offers guidance for the rational design of chemoselective catalysts.

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以配体覆盖率为媒介优化不同炔烃半氢化反应位点

催化剂活性位点的精确调控是优化活性的关键。在这项工作中，提出了一种通过修饰载体来调节炔吸附位点的策略。合成了一系列具有不同覆盖度的三苯基膦（PPh3）的Pd/ZSM‐5@PPh3‐X。Pd/ZSM‐5@PPh3‐X在温和条件下实现了炔的高效半加氢。具体来说，配体覆盖率较低的催化剂（Pd/ZSM‐5@PPh3‐2）更倾向于2‐甲基‐3‐丁醇的加氢，而配体覆盖率较高的催化剂（Pd/ZSM‐5@PPh3‐10）更倾向于苯乙炔的转化。两种催化剂的烯烃选择性均超过94%。综合实验、表征和计算分析表明，对于吸附在钯表面的2‐甲基‐3‐丁醇，PPh3抑制了炔烃的强吸附，从而防止了催化剂的自中毒。相反，高PPh3覆盖率使苯乙炔的吸附位点重定向到载体表面，增强的氢气溢出加速了反应。这种配体调节策略为化学选择性催化剂的合理设计提供了指导。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

AIChE Journal 工程技术-工程：化工

CiteScore

7.10

自引率

10.80%

发文量

411

审稿时长

3.6 months

期刊介绍： The AIChE Journal is the premier research monthly in chemical engineering and related fields. This peer-reviewed and broad-based journal reports on the most important and latest technological advances in core areas of chemical engineering as well as in other relevant engineering disciplines. To keep abreast with the progressive outlook of the profession, the Journal has been expanding the scope of its editorial contents to include such fast developing areas as biotechnology, electrochemical engineering, and environmental engineering. The AIChE Journal is indeed the global communications vehicle for the world-renowned researchers to exchange top-notch research findings with one another. Subscribing to the AIChE Journal is like having immediate access to nine topical journals in the field. Articles are categorized according to the following topical areas: Biomolecular Engineering, Bioengineering, Biochemicals, Biofuels, and Food Inorganic Materials: Synthesis and Processing Particle Technology and Fluidization Process Systems Engineering Reaction Engineering, Kinetics and Catalysis Separations: Materials, Devices and Processes Soft Materials: Synthesis, Processing and Products Thermodynamics and Molecular-Scale Phenomena Transport Phenomena and Fluid Mechanics.