Effect of titanium, antimony, and ruthenium doping on tin dioxide adsorption properties. Quantum‐chemical modeling

• Published in: Journal of the Chinese Chemical Society (Taipei) 2023-03, Vol.70 (3), p.432-438
• Main Authors: Zyubina, Tatyana S., Zyubin, Alexander S., Frolova, Lyubov A., Pisarev, Rostislav V., Pisareva, Anna V., Dobrovolsky, Yury A.
• Format: Article
• Language: English
• Subjects: Antimony; Boundary conditions; Catalysts; Clusters; Crystal defects; Crystal structure; Density functional theory; Dioxides; Doping; Electrolytic cells; material science; Nanoparticles; physical chemistry; Platinum; Proton exchange membrane fuel cells; quantum chemistry; Ruthenium; Tin dioxide; Titanium
• ISSN: 0009-4536; 2192-6549
• DOI: 10.1002/jccs.202200448

The influence of the composition of oxides supports on the specific electroactive surface area of Pt in the catalysts, the platinum nanoparticles dispersion, and Pt contents in the catalysts was studied. The Sb‐doped SnO2 oxides with various Sb‐doping levels were prepared as a supports of platinum catalysts in polymer electrolyte membrane fuel cells. Density functional theory simulation of Ti, Sb, and Ru doping of tin dioxide and interaction of the doped surfaces with platinum cluster Pt19 have been carried out. All calculations were performed in PBE exchange–correlation functional, with periodic boundary conditions and projector‐augmented waves (PAW) basis set. The calculation results were compared with the experimental data X‐ray diffraction and transmission electron microscopy (TEM). It was shown that Sb doping of tin dioxide (in quantity of less than 10%, that is, the quantity which cannot provoke significant defects of crystal structure of the supports) leads to a significant increase in a number of platinum clusters adsorbed from the colloidal solution onto the supports surface which results to an increase of the platinum cluster interaction with the supports. The calculated and experimental results are in close fit. The interaction energy (E) of the platinum cluster with the A‐doped SnO2(110) surface (A= Ti, Sb, Ru) increases by 0.4–0.6 eV for Sb and Ru compared to undoped surface. The position of platinum cluster above the doping atom with coordination number (K) equal to 5 is energetically the most preferable.