甲烷化学势对其在铜交换丝光沸石上转化为甲醇的重要性。

Zheng Jian, Lee Insu, Khramenkova Elena, Wang Meng, Peng Bo, Gutiérrez Oliver Y, Fulton John L, Camaioni Donald M, Khare Rachit, Jentys Andreas, Haller Gary L, Pidko Evgeny A, Sanchez-Sanchez Maricruz, Lercher Johannes A

Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA, 99352, USA.

Department of Chemistry and Catalysis Research Institute, TU München, Lichtenbergstrasse 4, 85748, Garching, Germany.

Chemistry. 2020 Jun 18;26(34):7563-7567. doi: 10.1002/chem.202000772. Epub 2020 May 11.

Copper-oxo clusters exchanged in zeolite mordenite are active in the stoichiometric conversion of methane to methanol at low temperatures. Here, we show an unprecedented methanol yield per Cu of 0.6, with a 90-95 % selectivity, on a MOR solely containing [Cu (μ-O) ] active sites. DFT calculations, spectroscopic characterization and kinetic analysis show that increasing the chemical potential of methane enables the utilization of two μ-oxo bridge oxygen out of the three available in the tricopper-oxo cluster structure. Methanol and methoxy groups are stabilized in parallel, leading to methanol desorption in the presence of water.

在丝光沸石中交换的铜氧簇在低温下将甲烷化学计量转化为甲醇的反应中具有活性。在此，我们展示了在仅含有[Cu(μ-O)]活性位点的丝光沸石上，每铜的甲醇产率达到了前所未有的0.6，选择性为90-95%。密度泛函理论计算、光谱表征和动力学分析表明，提高甲烷的化学势能够利用三核铜氧簇结构中三个可用的μ-氧桥氧中的两个。甲醇和甲氧基平行稳定存在，导致在有水存在的情况下甲醇解吸。