暨南大学高庆生团队报道了Li⁺原位插层到纳米Chevrel相Mo₆S₈中，实现高效电化学硝基芳烃还原。相关论文发表在2025年3月11日出版的《美国化学会杂志》上。

电化学硝基arene还原可以通过控制电位和电流来操纵多个电子和质子的转移，从而在环境条件下实现苯胺的绿色生产，但在PH中性电解中仍然存在挑战，特别是非精细催化剂。具有高导电性和可插入框架的Chevrel相Mo₆S₈首次被提出，作为一种具有突出性能的低成本候选物，更重要的是，作为一个新的平台来揭示阳离子对硝基芳烃电还原的影响。在0.1M LiClO₄中，在- 0.45V （vs RHE）条件下，由聚合物限制硫化得到的纳米Mo₆S₈在将4-硝基苯乙烯还原为4-氨基苯乙烯方面具有较高的产率（~95%）和法拉第效率（~99%），优于一系列金属硫化物甚至贵金属。结合实验和理论分析，确定了插层相关的阳离子效应，扩展了目前仅限于电极外亥姆霍兹平面的知识。在电解过程中，原位Li⁺插入到Mo₆S₈腔中改善了电子构型，从而通过质子耦合电子转移机制促进硝基在低配位Mo位点上的吸附进行氢化。

此外，从广泛的底物中高效地电合成具有保守还原基的苯胺衍生物，突出了Mo₆S₈在电化学精炼方面的前景。

附：英文原文

Title: In Situ Li+ Intercalation into Nanosized Chevrel Phase Mo6S8 toward Efficient Electrochemical Nitroarene Reduction

Author: Jingwen Tan, Lei Feng, Junjie Shao, Wenbiao Zhang, Haoran Qin, Hongxi Liu, Yijin Shu, Lichun Yang, Yuying Meng, Yi Tang, Qingsheng Gao

Issue&Volume: March 11, 2025

Abstract: Electrochemical nitroarene reduction enables the green production of anilines at ambient conditions thanks to the manipulated transfer of multiple electrons and protons via controlling potentials and currents, but challenges remain in pH-neutral electrolysis using nonprecious catalysts. Here, Chevrel phase Mo6S8 with high conductivity and insertable frameworks is proposed for the first time as a cost-efficient candidate with prominent performance and, more importantly, as a new platform to unravel cation effects on nitroarene electroreduction. Nanosized Mo6S8 derived from polymer-confined sulfidation affords a high yield (～95%) and Faradaic efficiency (～99%) for reducing 4-nitrostyrene to 4-aminostyrene at 0.45 V (vs RHE) in 0.1 M LiClO4, outperforming a series of counterparts of metal sulfides and even noble metals. The combination of experimental and theoretical analyses identifies an intercalation-correlated cation effect, expanding the current knowledge limited to the outer Helmholtz plane of electrodes. In situ Li+ intercalation into Mo6S8 cavities during electrolysis ameliorates the electronic configurations and thereby promotes the adsorption of the nitro group on low-coordinated Mo sites for  hydrogenation via a proton-coupled electron transfer mechanism. Furthermore, the efficient electrosynthesis of aniline derivatives with conserved reducing groups from a wide range of substrates highlights the promise of Mo6S8 for electrochemical refinery.

DOI: 10.1021/jacs.4c14111

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c14111