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用于四氢萘电化学氧化的疏水性铜/氧化铜电极的合理设计:一种策略性方法。

Rational Design of Hydrophobic Cu/CuO Electrodes for Electrochemical Oxygenation of Tetralin: A Strategic Approach.

作者信息

Cherukuthota Sri Vidya, Mathew Elizabeth, Verma Tushar Singh, Joshi Krati, Selvaraj Kaliaperumal

机构信息

Nano and Computational Materials Lab, Catalysis and Inorganic Chemistry Division, CSIR-National Chemical Laboratory, Pune, 411008, India.

Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, Uttar Pradesh, 201 002, India.

出版信息

ChemSusChem. 2025 Aug 6;18(16):e202501184. doi: 10.1002/cssc.202501184. Epub 2025 Jul 16.

DOI:10.1002/cssc.202501184
PMID:40580083
Abstract

Electro-organic synthesis presents a sustainable and practical alternative to traditional organic synthesis methods, which typically utilize harsh reagents and require energy-intensive conditions. Nevertheless, the challenge of achieving satisfactory conversion and selectivity rates in electrocatalytic oxidation using a non-platinum group metal (PGM) catalyst pair still needs to be addressed. This study demonstrates the application of a non-PGM-based catalyst pair for the electrocatalytic oxidation of tetralin to 1-tetralone, a highly demanded raw material in the pharma industry. Copper electrodeposited on teflonated carbon paper combined with copper foam as the electrocatalyst pair has demonstrated impressive conversion and selectivity ratios to electro-synthesize 1-tetralone at room temperature and atmospheric pressure. The optimal choice of a non-PGM catalyst, ideal mass loading, and a unique electrode configuration resulted in an ultimate conversion of about 99% of tetralin and 1-tetralone selectivity -93.7%, yield -92.6%. The reaction pathway associated with the electrochemical phenomena is supported by first principles-based density functional theory calculations and X-ray photoelectron spectroscopy of the electrocatalyst. This process has exceptional performance that can be adapted for a wide range of substrates and is straightforward, ambient, reagent-free, scalable, and therefore beneficial for industrial use. Therefore, initiatives have been taken in this direction.

摘要

有机电合成是传统有机合成方法的一种可持续且实用的替代方案,传统方法通常使用苛刻的试剂且需要高能耗条件。然而,使用非铂族金属(PGM)催化剂对实现电催化氧化中令人满意的转化率和选择性仍然是一个需要解决的挑战。本研究展示了一种基于非PGM的催化剂对在将四氢萘电催化氧化为1-四氢萘醌方面的应用,1-四氢萘醌是制药行业中一种急需的原材料。沉积在氟化碳纸上的铜与泡沫铜作为电催化剂对,在室温和大气压下电合成1-四氢萘醌时表现出了令人印象深刻的转化率和选择性。非PGM催化剂的最佳选择、理想的质量负载以及独特的电极配置,最终实现了约99%的四氢萘转化率、93.7%的1-四氢萘醌选择性和92.6%的产率。基于第一性原理的密度泛函理论计算和电催化剂的X射线光电子能谱支持了与电化学现象相关的反应途径。该过程具有卓越的性能,可适用于广泛的底物,且操作简单、环境友好、无需试剂、可扩展,因此有利于工业应用。因此,已朝着这个方向采取了一些举措。

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