Copper-exchanged zeolites with mordenite structure mimic the nuclearity and reactivity of active sites in particulate methane monooxygenase, which are enzymes able to selectively oxidize methane to methanol. Here we show that the mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon-hydrogen bonds in methane and its subsequent transformation to methanol. The similarity with the enzymatic systems is also implied from the similarity of the reversible rearrangements of the trinuclear clusters occurring during the selective transformations of methane along the reaction path towards methanol, in both the enzyme system and copper-exchanged mordenite.
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http://dx.doi.org/10.1038/ncomms8546 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
South China University of Technology, School of Chemistry and Chemical Engineering, Wushan St., 510640, Guangzhou, CHINA.
An inevitable overoxidation process is considered as one of the most challenging problems in the direct conversion of methane (CH4) to methanol (CH3OH), which is limited by the uncontrollable cracking of key intermediates. Herein, we have successfully constructed a photocatalyst, the Fe-doped ZnO hollow polyhedron (Fe/ZnOHP), for the highly selective photoconversion of CH4 to CH3OH under mild conditions. In-situ experiments and density functional theory calculations confirmed that the introduction of Fe was able to decrease the energy level of the O 2p orbital, which passivated the activity of lattice oxygen in ZnO nanocrystals.
View Article and Find Full Text PDFPhys Chem Chem Phys
January 2025
Department of Chemical Engineering, Northeastern University, Boston, Massachusetts, 02115, USA.
Discovering electrocatalysts that can efficiently convert carbon dioxide (CO) to valuable fuels and feedstocks using excess renewable electricity is an emergent carbon-neutral technology. A single metal atom embedded in doped graphene, , single-atom catalyst (SAC), possesses high activity and selectivity for electrochemical CO reduction (COR) to CO, yet further reduction to hydrocarbons is challenging. Here, using density functional theory calculations, we investigate stability and reactivity of a broad SAC chemical space with various metal centers (3d transition metals) and dopants (2p dopants of B, N, O; 3p dopants of P, S) as electrocatalysts for COR to methane and methanol.
View Article and Find Full Text PDFJ Colloid Interface Sci
January 2025
Institute of Applied Electrochemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029 PR China. Electronic address:
The electrochemical activation and partial oxidation of methane are highly attractive to enable the direct conversion in a sustainable and decentralized way. Herein, we report an electrochemical system in a non-diaphragm electrochemical bath to convert CH to CHOH and CHCHOH at room temperature, in which VO·HO as the anodic catalyst to activate CH and an aprotic ionic liquid [BMIM]BF as supporting electrolyte to control superoxide radicals (O) as the main active oxygen species generated on cathode. As a result, methanol and ethanol were identified as the liquid products, and the superior methanol Faraday efficiency (FE) of 32.
View Article and Find Full Text PDFJ Phys Chem B
January 2025
Centre for Lasers & Photonics, Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh 208016, India.
Nonideality in a binary solvent mixture is manifested through anomalies in various physical properties like viscosity, dielectric constant, polarity, freezing point, boiling point, and so forth. Sometimes, such anomalies become much more prominent, leading to a synergistic behavior, where the physical property of the mixture is way different from its bulk counterparts. Various alcohols/chlorinated methane binary solvent mixtures show such a synergistic behavior.
View Article and Find Full Text PDFChemistry
January 2025
Boreskov Institute of Catalysis SB RAS, Siberian Branch of Russian Academy of Sciences, RUSSIAN FEDERATION.
Cu-modified zeolites provide methane conversion to methanol with high selectivity under mild conditions. The activity of different possible Cu-sites for methane transformation is still under discussion. Herein, ZSM-5 zeolite has been loaded with Cu2+ cations (1.
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