Li Weixin, Sun Jikai, Wang Mingda, Xu Jiajia, Wang Yanjie, Yang Li, Yan Ran, He Haoxian, Wang Shuai, Deng Wei-Qiao, Tian Zhong-Qun, Fan Feng Ru
State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, College of Chemistry and Chemical Engineering, Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen University, Xiamen, 361005, China.
Institute of Frontier Chemistry, School of Chemistry and Chemical Engineering, Shandong University, Qingdao, 266237, China.
Angew Chem Int Ed Engl. 2024 May 13;63(20):e202403114. doi: 10.1002/anie.202403114. Epub 2024 Apr 5.
The conversion of methane under ambient conditions has attracted significant attention. Although advancements have been made using active oxygen species from photo- and electro- chemical processes, challenges such as complex catalyst design, costly oxidants, and unwanted byproducts remain. This study exploits the concept of contact-electro-catalysis, initiating chemical reactions through charge exchange at a solid-liquid interface, to report a novel process for directly converting methane under ambient conditions. Utilizing the electrification of commercially available Fluorinated Ethylene Propylene (FEP) with water under ultrasound, we demonstrate how this interaction promote the activation of methane and oxygen molecules. Our results show that the yield of HCHO and CHOH can reach 467.5 and 151.2 μmol ⋅ g , respectively. We utilized electron paramagnetic resonance (EPR) to confirm the evolution of hydroxyl radicals (⋅OH) and superoxide radicals (⋅OOH). Isotope mass spectrometry (MS) was employed to analyze the elemental origin of CHOH, which can be further oxidized to HCHO. Additionally, we conducted density functional theory (DFT) simulations to assess the reaction energies of FEP with HO, O, and CH under these conditions. The implications of this methodology, with its potential applicability to a wider array of gas-phase catalytic reactions, underscore a significant advance in catalysis.
在环境条件下甲烷的转化已引起了广泛关注。尽管利用光化学和电化学过程中产生的活性氧物种已取得了进展，但仍存在诸如复杂的催化剂设计、昂贵的氧化剂以及不需要的副产物等挑战。本研究利用接触电催化的概念，通过固液界面的电荷交换引发化学反应，报道了一种在环境条件下直接转化甲烷的新方法。利用超声作用下市售的氟化乙丙烯（FEP）与水的带电作用，我们展示了这种相互作用如何促进甲烷和氧分子的活化。我们的结果表明，HCHO和CHOH的产率分别可达467.5和151.2 μmol ⋅ g 。我们利用电子顺磁共振（EPR）证实了羟基自由基（⋅OH）和超氧自由基（⋅OOH）的产生。采用同位素质谱（MS）分析了可进一步氧化为HCHO的CHOH的元素来源。此外，我们进行了密度泛函理论（DFT）模拟，以评估在这些条件下FEP与HO、O和CH的反应能量。这种方法的意义在于其潜在适用于更广泛的气相催化反应，突显了催化领域的一项重大进展。
