Pappas Dimitrios K, Martini Andrea, Dyballa Michael, Kvande Karoline, Teketel Shewangizaw, Lomachenko Kirill A, Baran Rafal, Glatzel Pieter, Arstad Bjørnar, Berlier Gloria, Lamberti Carlo, Bordiga Silvia, Olsbye Unni, Svelle Stian, Beato Pablo, Borfecchia Elisa
Center for Materials Science and Nanotechnology, Department of Chemistry , University of Oslo , 1033 Blindern , 0315 Oslo , Norway.
IRC "Smart Materials" , Southern Federal University , Zorge Street 5 , 344090 Rostov-on-Don , Russia.
J Am Chem Soc. 2018 Nov 14;140(45):15270-15278. doi: 10.1021/jacs.8b08071. Epub 2018 Nov 2.
The direct conversion of methane to methanol (MTM) is a reaction that has the potential to disrupt a great part of the synthesis gas-derived chemical industry. However, despite many decades of research, active enough catalysts and suitable processes for industrial application are still not available. Recently, several copper-exchanged zeolites have shown considerable activity and selectivity in the direct MTM reaction. Understanding the nature of the active site in these materials is essential for any further development in the field. Herein, we apply multivariate curve resolution analysis of X-ray absorption spectroscopy data to accurately quantify the fraction of active Cu in Cu-MOR (MOR = mordenite), allowing an unambiguous determination of the active site nuclearity as a dicopper site. By rationalizing the compositional parameters and reaction conditions, we achieve the highest methanol yield per Cu yet reported for MTM over Cu-zeolites, of 0.47 mol/mol.
甲烷直接转化为甲醇（MTM）是一个有可能撼动很大一部分合成气衍生化学工业的反应。然而，尽管经过了数十年的研究，仍未获得活性足够高的催化剂以及适用于工业应用的工艺。最近，几种铜交换沸石在MTM直接反应中表现出了相当高的活性和选择性。了解这些材料中活性位点的性质对于该领域的任何进一步发展都至关重要。在此，我们应用X射线吸收光谱数据的多元曲线分辨分析来准确量化Cu-MOR（MOR = 丝光沸石）中活性铜的比例，从而明确确定活性位点核为双铜位点。通过对组成参数和反应条件进行合理化处理，我们实现了Cu-沸石上MTM反应中每铜的甲醇产量达到迄今报道的最高值，即0.47 mol/mol。
