Heat-Up Colloidal Synthesis of Shape-Controlled Cu-Se-S Nanostructures—Role of Precursor and Surfactant Reactivity and Performance in N<sub>2</sub> Electroreduction
Stefanos Mourdikoudis,
George Antonaropoulos,
Nikolas Antonatos,
Marcos Rosado,
Liudmyla Storozhuk,
Mari Takahashi,
Shinya Maenosono,
Jan Luxa,
Zdeněk Sofer,
Belén Ballesteros,
Nguyen Thi Kim Thanh,
Alexandros Lappas
Affiliations
Stefanos Mourdikoudis
Biophysics Group, Department of Physics and Astronomy, University College London, London WC1E 6BT, UK
George Antonaropoulos
Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas, Vassilika Vouton, 71110 Heraklion, Greece
Nikolas Antonatos
Department of Inorganic Chemistry, University of Chemistry and Technology Prague, Technicka 5, 16628 Prague, Czech Republic
Marcos Rosado
Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and the Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona, Spain
Liudmyla Storozhuk
Biophysics Group, Department of Physics and Astronomy, University College London, London WC1E 6BT, UK
Mari Takahashi
School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi 923-1292, Ishikawa, Japan
Shinya Maenosono
School of Materials Science, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi 923-1292, Ishikawa, Japan
Jan Luxa
Department of Inorganic Chemistry, University of Chemistry and Technology Prague, Technicka 5, 16628 Prague, Czech Republic
Zdeněk Sofer
Department of Inorganic Chemistry, University of Chemistry and Technology Prague, Technicka 5, 16628 Prague, Czech Republic
Belén Ballesteros
Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and the Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, 08193 Barcelona, Spain
Nguyen Thi Kim Thanh
Biophysics Group, Department of Physics and Astronomy, University College London, London WC1E 6BT, UK
Alexandros Lappas
Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas, Vassilika Vouton, 71110 Heraklion, Greece
Copper selenide-sulfide nanostructures were synthesized using metal-organic chemical routes in the presence of Cu- and Se-precursors as well as S-containing compounds. Our goal was first to examine if the initial Cu/Se 1:1 molar proportion in the starting reagents would always lead to equiatomic composition in the final product, depending on other synthesis parameters which affect the reagents reactivity. Such reaction conditions were the types of precursors, surfactants and other reagents, as well as the synthesis temperature. The use of ‘hot-injection’ processes was avoided, focusing on ‘non-injection’ ones; that is, only heat-up protocols were employed, which have the advantage of simple operation and scalability. All reagents were mixed at room temperature followed by further heating to a selected high temperature. It was found that for samples with particles of bigger size and anisotropic shape the CuSe composition was favored, whereas particles with smaller size and spherical shape possessed a Cu2−xSe phase, especially when no sulfur was present. Apart from elemental Se, Al2Se3 was used as an efficient selenium source for the first time for the acquisition of copper selenide nanostructures. The use of dodecanethiol in the presence of trioctylphosphine and elemental Se promoted the incorporation of sulfur in the materials crystal lattice, leading to Cu-Se-S compositions. A variety of techniques were used to characterize the formed nanomaterials such as XRD, TEM, HRTEM, STEM-EDX, AFM and UV-Vis-NIR. Promising results, especially for thin anisotropic nanoplates for use as electrocatalysts in nitrogen reduction reaction (NRR), were obtained.
