Université Lille, CNRS, Centrale Lille, ENSCL, Université Artois, UMR 8181 - UCCS - Unité de Catalyse et Chimie du Solide, 59000, Lille, France.
Université Lille, CNRS, UMR 8516, LASIR, Laboratoire de Spectrochimie Infrarouge et Raman, 59000, Lille, France.
Nat Commun. 2019 Feb 11;10(1):700. doi: 10.1038/s41467-019-08525-2.
Chemical utilization of vast fossil and renewable feedstocks of methane remains one of the most important challenges of modern chemistry. Herein, we report direct and selective methane photocatalytic oxidation at ambient conditions into carbon monoxide, which is an important chemical intermediate and a platform molecule. The composite catalysts on the basis of zinc, tungstophosphoric acid and titania exhibit exceptional performance in this reaction, high carbon monoxide selectivity and quantum efficiency of 7.1% at 362 nm. In-situ Fourier transform infrared and X-ray photoelectron spectroscopy suggest that the catalytic performance can be attributed to zinc species highly dispersed on tungstophosphoric acid /titania, which undergo reduction and oxidation cycles during the reaction according to the Mars-van Krevelen sequence. The reaction proceeds via intermediate formation of surface methyl carbonates.
将大量的甲烷化石和可再生原料进行化学利用仍然是现代化学面临的最重要的挑战之一。在此，我们报告了在环境条件下直接、选择性地用光催化甲烷氧化为一氧化碳，这是一种重要的化学中间体和平台分子。基于锌、磷钨酸和二氧化钛的复合催化剂在该反应中表现出优异的性能，在 362nm 时具有高的一氧化碳选择性和 7.1%的量子效率。原位傅里叶变换红外和 X 射线光电子能谱表明，催化性能可归因于高度分散在磷钨酸/二氧化钛上的锌物种，根据马尔斯-范克雷维伦序列，它们在反应过程中经历还原和氧化循环。反应通过表面碳酸甲酯的中间形成进行。
