Palladium-Catalyzed Electrocoupling of Acetylene to C4–C10 Hydrocarbons

IF 13.1 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-10-14 DOI:10.1021/acscatal.5c04413

Zhong Zheng, Wei Jie Teh, Ben Rowley, Alexander P. van Bavel, Boon Siang Yeo

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Abstract

Acetylene (C₂H₂) is a feedstock capable of undergoing C–C coupling to yield valuable long-chain hydrocarbons. Currently, only C₂ (ethylene) and C₄ hydrocarbon formation has been reported from the electrochemical C₂H₂ reduction reaction (C₂H₂RR). Herein, we demonstrate that C₂H₂ can be further coupled to form C₆, C₈, and C₁₀ hydrocarbons by using electrocatalysts with different binding strengths for carbon-containing molecules. Utilizing a palladium nanoparticle catalyst which binds to carbonaceous intermediates optimally, C₂H₂ was converted into hydrocarbons with total Faradaic efficiencies (FE) of up to 96%. Importantly, C₆ hydrocarbons were formed with a FE of 2.9% at −0.4 V vs reversible hydrogen electrode (RHE) and a partial current density (j_C6) of −3.3 mA·cm^–2 at −0.7 V vs RHE. C₈ and C₁₀ products were also formed with respective FEs up to 0.8 and 0.1% at −0.4 V vs RHE. A stronger adsorption of C₂H₂ on a catalyst surface also results in more hydrogenated products: strong-binding ruthenium favored more hydrogenated hexanes and hexenes (isomers), while weak-binding copper yielded less hydrogenated hexadienes and hexatriene. Interestingly, cyclic hydrocarbons were formed on copper, which we attribute to copper’s ability to facilitate rearrangement of C₂ intermediates into metallocycle moieties while preserving π-bond character, so that cyclization can occur.

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钯催化乙炔与C4-C10烃的电偶联

乙炔（C2H2）是一种能够进行C-C偶联以产生有价值的长链烃的原料。目前仅有C2H2电化学还原反应（C2H2RR）生成C2（乙烯）和C4烃的报道。在此，我们证明了C2H2可以通过使用不同结合强度的含碳分子电催化剂进一步偶联形成C6， C8和C10烃。利用钯纳米颗粒催化剂与碳质中间体结合最佳，C2H2转化为碳氢化合物，总法拉第效率（FE）高达96%。重要的是，在−0.4 V vs可逆氢电极（RHE）下，形成的C6碳氢化合物的FE为2.9%，在−0.7 V vs RHE下形成的分电流密度（jC6）为−3.3 mA·cm-2。在−0.4 V vs RHE下，C8和C10的FEs分别高达0.8和0.1%。催化剂表面对C2H2的强吸附也会产生更多的氢化产物：强结合的钌倾向于产生更多的氢化己烷和己烯（异构体），而弱结合的铜产生较少的氢化己二烯和己三烯。有趣的是，环烃在铜上形成，我们认为这是由于铜能促进C2中间体重排成金属环，同时保持π键特征，从而发生环化。

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.