Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal–Organic Framework Jian Zheng Jingyun Ye Manuel A. Ortuño John L. Fulton Oliver Y. Gutiérrez Donald M. Camaioni Radha Kishan Motkuri Zhanyong Li Thomas E. Webber B. Layla Mehdi Nigel D. Browning R. Lee Penn Omar K. Farha Joseph T. Hupp Donald G. Truhlar Christopher J. Cramer Johannes A. Lercher 10.1021/jacs.9b02902.s001 https://acs.figshare.com/articles/journal_contribution/Selective_Methane_Oxidation_to_Methanol_on_Cu-Oxo_Dimers_Stabilized_by_Zirconia_Nodes_of_an_NU-1000_Metal_Organic_Framework/8210795 Mononuclear and dinuclear copper species were synthesized at the nodes of an NU-1000 metal–organic framework (MOF) via cation exchange and subsequent oxidation at 200 °C in oxygen. Copper-exchanged MOFs are active for selectively converting methane to methanol at 150–200 °C. At 150 °C and 1 bar methane, approximately a third of the copper centers are involved in converting methane to methanol. Methanol productivity increased by 3–4-fold and selectivity increased from 70% to 90% by increasing the methane pressure from 1 to 40 bar. Density functional theory showed that reaction pathways on various copper sites are able to convert methane to methanol, the copper oxyl sites with much lower free energies of activation. Combining studies of the stoichiometric activity with characterization by <i>in situ</i> X-ray absorption spectroscopy and density functional theory, we conclude that dehydrated dinuclear copper oxyl sites formed after activation at 200 °C are responsible for the activity. 2019-05-22 00:00:00 cation exchange copper oxyl sites X-ray absorption spectroscopy dinuclear copper oxyl sites Selective Methane Oxidation Copper-exchanged MOFs dinuclear copper species Zirconia Nodes stoichiometric activity reaction pathways NU methane pressure activation copper sites 40 bar 1 bar methane Cu-Oxo Dimers Stabilized -1000 methanol Methanol productivity copper centers