Investigating Cu-Site Doped Cu-Sb-S Nanoparticles Using Photoelectron and Electron Paramagnetic Resonance Spectroscopy.

Autor: Daniel JE; Department of Chemistry, Furman University, Greenville, South Carolina 29613, United States., Weaver SI; Department of Chemistry, Furman University, Greenville, South Carolina 29613, United States., Matthias BR; Department of Chemistry, Furman University, Greenville, South Carolina 29613, United States., Golden R; Department of Chemistry, Furman University, Greenville, South Carolina 29613, United States., George GM; Department of Chemistry, Furman University, Greenville, South Carolina 29613, United States., Kerpal C; Department of Physics and Astronomy, UNC Asheville, Asheville, North Carolina 28804, United States., Donley CL; Chapel Hill Analytical and Nanofabrication Lab, Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599, United States., Jarocha LE; Department of Chemistry, Furman University, Greenville, South Carolina 29613, United States., Anderson ME; Department of Chemistry, Furman University, Greenville, South Carolina 29613, United States.
Jazyk: angličtina
Zdroj: The journal of physical chemistry. C, Nanomaterials and interfaces [J Phys Chem C Nanomater Interfaces] 2024 Aug 08; Vol. 128 (33), pp. 13888-13899. Date of Electronic Publication: 2024 Aug 08 (Print Publication: 2024).
DOI: 10.1021/acs.jpcc.4c02602
Abstrakt: Tetrahedrite (Cu 12 Sb 4 S 13 ) and famatinite (Cu 3 SbS 4 ) are good candidates for green energy applications because they possess promising thermoelectric and photovoltaic properties as well as contain earth-abundant and nontoxic constituents. Herein, X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and electron paramagnetic resonance spectroscopy (EPR) methods examined inherent electronic properties and interatomic magnetic interactions of Cu-site doped tetrahedrite and famatinite nanomaterials. An energy-efficient modified polyol method was utilized for the synthesis of tetrahedrite and famatinite nanoparticles doped on the Cu-site with Zn, Fe, Ni, Mn, and Co. This is the first parallel study of tetrahedrite and famatinite nanomaterials with XPS, UPS, and EPR methods alongside a systematic analysis of dopant-dependent effects on the electronic structure and magnetic interactions for each material. XPS showed that the Cu and Sb species in tetrahedrite and famatinite possess different oxidation states, while UPS characterization reveals larger dopant-dependent shifts in the work function for tetrahedrite nanoparticles (4.21 to 4.79 eV) than for famatinite nanoparticles (4.57 to 4.77 eV). Finally, all famatinite nanoparticles display an EPR signal, indicating trace amounts of paramagnetic Cu(II) present below the detection limit of XPS. For tetrahedrite, EPR signatures were observed only for the Zn-doped and Mn-doped nanoparticles, suggesting signal broadening from Cu-Cu spin exchange or spin-lattice relaxation. This study demonstrates the complementary nature of XPS and EPR techniques for studying the oxidation states of metals in solid-state nanomaterials. Comparing the electronic and magnetic properties of tetrahedrite and famatinite while studying the impact of dopant incorporation will guide future endeavors in designing sustainable, high-performance materials for renewable energy applications.
Competing Interests: The authors declare no competing financial interest.
(© 2024 The Authors. Published by American Chemical Society.)
Databáze: MEDLINE
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