Preparation and Investigation of Pd and Bimetallic Pd-Sn Nanocrystals on γ-Al₂O₃

• Main Authors: Ivan Bondarchuk, Francisco José Cadete Santos Aires, Grigoriy Mamontov, Irina Kurzina
• Format: Article
• Language: English
• Published: MDPI AG 2021-04-01
• Series: Crystals
• Subjects: bimetallic nanoparticles; palladium-tin; palladium acetylacetonate; Pd(acac)₂; tin(IV) bis(acetylacetonate) dichloride; Sn(acac)₂Cl₂
• Online Access: https://www.mdpi.com/2073-4352/11/4/444

One of the key factors for producing highly dispersed controlled nanoparticles is the method used for metal deposition. The decomposition of metal-organic precursors is a good method for deposition of metal nanoparticles with very small sizes and narrow size distributions on the surface of various supports. The preparation process of Pd and bimetallic Pd-Sn nanoparticles supported onto γ‑Al₂O₃ is considered. The samples were prepared by diffusional co-impregnation of the γ‑Al₂O₃ support by using organometallic Pd(acac)₂ and Sn(acac)₂Cl₂ precursors. To achieve the formation of Pd and bimetallic Pd-Sn nanoparticles on the support surface, the synthesized samples were then subjected to thermal decomposition under Ar (to decompose the organometallic bound to the surface while keeping the formed nanoparticles small) followed by an oxidation in O₂ (to eliminate the organic compounds remaining on the surface) and a reduction in H₂ (to reduce the nanoparticles oxidized during the previous step). A combination of methods (ICP-OES, TPR-H₂, XPS, TEM/EDX) was used to compare the physical-chemical properties of the synthesized Pd and bimetallic Pd-Sn nanoparticles supported on the γ‑Al₂O₃. The three samples exhibit narrow size distribution with a majority on nanoparticles between 3 and 5 nm. Local EDX measurements clearly showed that the nanoparticles are bimetallic with the expected chemical composition and the measured global composition by ICP-OES. The surface composition and electronic properties of Pd and Sn on the γ-Al₂O₃ support were investigated by XPS, in particular the chemical state of palladium and tin after each step of thermal decomposition treatments (oxidation, reduction) by the XPS method has been carried out. The reducibility of the prepared bimetallic nanoparticles was measured by hydrogen temperature programmed reduction (TPR-H₂). The temperature programmed reduction TPR-H₂ experiments have confirmed the existence of strong surface interactions between Pd and Sn, as evidenced by hydrogen spillover of Pd to Sn (Pd-assisted reduction of oxygen precovered Sn). These results lead us to propose a mechanism for the formation of the bimetallic nanoparticles.