Light-driven oxidation of CH4 to C1 chemicals catalysed by an organometallic Ru complex with O2

Developing highly efficient catalysts for chemoselective oxidation of methane to methanol under mild conditions is a grand challenge. We report the successful design and synthesis of a heterogeneous single-site cobalt hydroxide catalyst [Ce-UiO-Co(OH)] supported by the nodes of a cerium metal–organic framework (Ce-UiO-66 MOF), which is efficient in partial methane oxidation using hydrogen peroxide at 80 °C, giving an extraordinarily high methanol yield of 2166 mmol gcat –1 in 99% selectivity with a turnover number of 3250. The Ce-UiO-Co catalyst is significantly more active and selective than its iso-structural zirconium analogue Zr-UiO-Co in methane to methanol conversion. Experimental and computational studies suggest the formation of the CoIII(η2-hydroperoxide) intermediate coordinating with one μ4-O– and two neutral carboxylate oxygens of Ce4+ oxo nodes within the pores of Ce-UiO-66, which undergoes σ-bond metathesis with the methane C–H bond in the turnover limiting step of the catalytic cycle. The significantly lower activation energy of Ce-UiO-Co than Zr-UiO-Co is due to the highly electron-deficient nature of the cobalt ion of the Co(η2-O2H) species supported by the Ce-UiO nodes, which promotes facile C–H activation of methane via σ-bond metathesis. This MOF-based catalyst design holds promise in developing molecular electrophilic abundant metal catalysts for chemoselective functionalization of saturated hydrocarbons.

show abstract

Smart Design of Organometallic Catalysts to Induce Innovative Material Transformations

Matsumoto

2022

J. Jpn. Petrol. Inst.

View full text Add to dashboard Cite

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Light-driven oxidation of CH₄ to C₁ chemicals catalysed by an organometallic Ru complex with O₂

Abstract: We have achieved aerobic transformation of methane to C1 chemicals catalysed by a homogeneous organometallic catalyst with light energy input.

Cited by 3 publications

References 62 publications

Conversion of methane to methyl trifluoroacetate by NHC ruthenium complexes under mild conditions

Conversion of methane to methyl trifluoroacetate by NHC ruthenium complexes under mild conditions

Metal–Organic Framework-Encaged Monomeric Cobalt(III) Hydroperoxides Enable Chemoselective Methane Oxidation to Methanol

Smart Design of Organometallic Catalysts to Induce Innovative Material Transformations

Contact Info

Product

Resources

About