Cuδ+位置增强吸附和冠醚重构界面D2O促进电催化脱卤氘化

IF 15.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2025-01-28 DOI:10.1021/jacs.4c17432

Meng He, Haotian Wang, Chuanqi Cheng, Rui Li, Cuibo Liu, Ying Gao, Bin Zhang

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引用次数: 0

摘要

电催化脱卤脱氘是一种可持续的精确脱氘方法，但其法拉第效率（FE）受高过电位和严重的D2演化反应（DER）的限制。据报道，Cuδ+位置调整吸附和冠醚重新配置的界面D2O共同提高了- 100 mA cm-2下脱卤氘化的FE高达84%。Cuδ+位点加强了芳基碘化物的吸附，促进了界面传质，从而加速了脱卤氘化动力学。冠醚破坏了K·D2O的水化作用，重构了与界面D2O的氢键，降低了双电层中K·D2O的含量，阻碍了D2O与阴极的相互作用，从而抑制了竞争DER的动力学。证明了冠醚与碱金属阳离子的匹配尺寸之间存在线性关系，从而普遍提高了FEs。该方法也适用于在−100 mA cm-2下具有高易还原性官能团相容性和改善的FEs的各种卤化物的氘化。

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Cuδ+ Site-Enhanced Adsorption and Crown Ether-Reconfigured Interfacial D2O Promote Electrocatalytic Dehalogenative Deuteration

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Cuδ+ Site-Enhanced Adsorption and Crown Ether-Reconfigured Interfacial D2O Promote Electrocatalytic Dehalogenative Deuteration

Electrocatalytic dehalogenative deuteration is a sustainable method for precise deuteration, whereas its Faradaic efficiency (FE) is limited by a high overpotential and severe D₂ evolution reaction (DER). Here, Cu^δ+ site-adjusted adsorption and crown ether-reconfigured interfacial D₂O are reported to cooperatively increase the FE of dehalogenative deuteration up to 84% at −100 mA cm^–2. Cu^δ+ sites strengthen the adsorption of aryl iodides, promoting interfacial mass transfer and thus accelerating the kinetics toward dehalogenative deuteration. The crown ethers disrupt the hydration effect of K·D₂O and reconstruct the hydrogen bond with the interfacial D₂O, lowering the content K·D₂O of the electric double layer and hindering the interaction between D₂O and the cathode, thus inhibiting the kinetics of the competitive DER. A linear relationship between the matched sizes of crown ethers and alkali metal cations is demonstrated for universally increasing FEs. This method is also suitable for the deuteration of various halides with high easily reducible functional group compatibility and improved FEs at −100 mA cm^–2.

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来源期刊

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.