Pairing d-Band Center of Metal Sites with π-Orbital of Alkynes for Efficient Electrocatalytic Alkyne Semi-Hydrogenation

Jinjin Li, Ying Guo, Siyu Chang, Jin Lin, You Wang, Zhenpeng Liu, Yafei Wu, Jian Zhang

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摘要

Electrocatalytic alkyne semi-hydrogenation has attracted ever-growing attention as a promising alternative to traditional thermocatalytic hydrogenation. However, the correlation between the structure of active sites and electrocatalytic performance still remains elusive. Herein, the energy difference (∆ε) between the d-band center of metal sites and π orbital of alkynes as a key descriptor for correlating the intrinsic electrocatalytic activity is reported. With two-dimensional conductive metal organic frameworks as the model electrocatalysts, theoretical and experimental investigations reveal that the decreased ∆ε induces the strengthened d–π orbitals interaction, which thus enhances acetylene π-adsorption and accelerates subsequent hydrogenation kinetics. As a result, Cu3(HITP)2 featuring the smallest ∆ε (0.10 eV) delivers the highest turnover frequency of 0.36 s−1, which is about 124 times higher than 2.9 × 10−3 s−1 for Co3(HITP)2 with the largest ∆ε of 2.71 eV. Meanwhile, Cu3(HITP)2 presents a high ethylene partial current density of −124 mA cm−2 and a large ethylene Faradaic efficiency of 99.3% at −0.9 V versus RHE. This work will spark the rapid exploration of high-activity alkyne semi-hydrogenation catalysts.

源语言英语
文章编号2205845
期刊Small
19
5
DOI
出版状态已出版 - 1 2月 2023

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