Nano-ZrO<sub>2</sub>@C, Nano-(ZrC, ZrO<sub>2</sub>)@C and Nano-ZrC@C Composites Prepared by Plasma-Assisted Carbonization of Zr-Loaded Iminodiacetate-Functionalized Styrene-Divinylbenzene Copolymers

oleh: Alejandro Martiz, Zoltán Károly, Attila Domján, Miklós Mohai, Laura Bereczki, László Trif, Attila Farkas, Krisztina László, Alfréd Menyhárd, László Kótai

Format: Article
Diterbitkan: MDPI AG 2022-06-01

Deskripsi

We have developed an easy route to prepare (nano-ZrO<sub>2</sub>,nano-ZrC<sub>x</sub>)@C composites with varying ZrO<sub>2</sub>/ZrC<sub>x</sub> content. The process consists of preparing a zirconium-loaded, iminodiacetate-functionalized styrene-divinylbenzene (STY-DVB) copolymer, and its subsequent carbonization in a tube furnace and/or a thermal plasma reactor. Depending on the zirconium salt used (zirconyl chloride, zirconyl nitrate or zirconium (IV) sulfate) in the Zr loading, the Zr-loaded resins resulted in ZrO<sub>2</sub>@C pre-pyrolizates with C to Zr molar ratios of 5.8, 6.8 and 6.60. This carbon surplus is sufficient for the partial or even complete reduction of ZrO<sub>2</sub> into ZrC<sub>0.58</sub> at 1400 °C. The reaction products also contain 5 to 55 mass% residual free carbon. The plasma processing of the ZrO<sub>2</sub>@C composite formed at 1000 °C in a tube furnace led to ZrC<sub>0.94</sub>@C composites. The transformation of amorphous carbon content during the plasma treatment strongly depended on the atmosphere (He or H<sub>2</sub>) in the reactor and the anion type of the Zr salt. In the presence of He, amorphous carbon could be completely transformed into graphite. In the presence of H<sub>2</sub>, amorphous carbon and graphite were found at roughly the same ratio. No ZrO<sub>2</sub> could be detected in the plasma-treated samples, whilst different ZrO<sub>2</sub> polymorphs were found in the samples prepared in the tube furnace, depending on the synthesis conditions.