Heterointercalation in Chevrel-Phase Sulfides: A Model Periodic Solid for the Investigation of Chain Electron Transfer
Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Modulation of electron density localization on periodic crystal solids through electron transfer from interstitial cations can directly influence the bonding configurations of small-molecule intermediates at the catalyst binding site. This study presents the microwave-assisted solid-state synthesis of four heterointercalant Chevrel-phase (CP) sulfides with varying metal cation intercalants with compositional and electronic structure investigations of the electron density redistribution as a result of intercalation. The heterointercalant CP sulfides, with the general formula Cu x M y Mo 6 S 8 (where M = Cr, Mn, Fe, Ni; x, y = 1.5–2.5), are presented here for the probe reaction of electrochemical CO 2 reduction. A change in product selectivity is observed toward the production of methanol at low overpotentials of −0.5 V vs reversible hydrogen electrode (RHE), as a result of the intercalant combination present within the CP interstitial cavity. Structural confirmation of all materials was examined through Rietveld refinement of the powder X-ray diffraction (PXRD) data, high-resolution transmission electron microscopy (HR-TEM), and selected-area electron diffraction (SAED). Electron transfer from the intercalated metal cations to the Mo 6 S 8 cluster was investigated via X-ray photoelectron spectroscopy (XPS) of the intercalated metal cations and the chalcogenide cluster. Electron transfer was further confirmed through X-ray absorption analysis (XAS) of the K-edges of Mo and intercalants. Intermediate studies of electrochemical reduction of formaldehyde to methanol resulted in a faradaic efficiency of ∼78% methanol production on Cu x Ni y Mo 6 S 8 . The results presented herein identify distinct principles for materials design that can be utilized in other compositional spaces within the broad families of periodic crystal solids.
DOI: 10.1021/jacs.5c04404
Language: English
Field: Energy
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Funders: National Science Foundation, U.S. Department of Energy, Alfred P. Sloan Foundation, Camille and Henry Dreyfus Foundation, Research Corporation for Science Advancement, Office of Science, University of California, Davis, Office of the President, University of California, Division of Materials Research, Division of Chemistry, Basic Energy Sciences, SLAC National Accelerator Laboratory
Awards: G2250076308, Direct Production of Renewable Fuels and Chemicals from Captured CO2, G3401394235, G3703756441, G4015655581, G4209771228, G4483995681, MRI: Acquisition of an X-ray Photoelectron Spectrometer for Characterization of Next-Generation Materials, G5102453286, G517489566, G5815300442, G6231004316, CAREER: Blueprint for Unlocking New Energy Conversion Functionality in Chalcogenide Frameworks through Precisely Designed Composition, Electronic Structure and Surface Coordination, G8930668236
OpenAlex ID: W4410386002