Zn/Co ZIF derived synthesis of Co-doped ZnO nanoparticles and application as high-performance trimethylamine sensors

$Zn_{1-x}Co_x$ Zeolitic Imidazolate Framework (ZIF) (x = 0~0.05) were prepared by the co-precipitation of $Zn^{2+}$ and $Co^{2+}$ using 2-methylimidazole, which were converted into pure and Co-doped ZnO nanoparticles by heat treatment at $600^{\circ}C$ for 2 h. Homogeneous Zn/Co ZIFs were achieved at x < 0.05 owing to the strong coordination of the imidazole linker to $Zn^{2+}$ and $Co^{2+}$, facilitating atomic-scale doping of Co into ZnO via annealing. By contrast, heterogeneous Zn/Co ZIFs were formed at $x{\geq}0.05$, resulting in the formation of $Co_3O_4$ second phase. To investigate the potential as high-performance gas sensors, the gas sensing characteristics of pure and Co-doped ZnO nanoparticles were evaluated. The sensor using 3 at% Co-doped ZnO exhibited an unprecedentedly high response and selectivity to trimethylamine, whereas pure ZnO nanoparticles did not. The facile, bimetallic ZIF derived synthesis of doped-metal oxide nanoparticles can be used to design high-performance gas sensors.

Co가 도핑된 ZnO 나노입자의 Zn/Co ZIF 유도 합성 및 고성능 트리메틸아민 센서로의 응용

$Zn_{1-x}Co_x$ Zeolitic Imidazolate Framework-8(ZIF)(x = 0~0.05)를 2-methylimidazole을 사용하여 $Zn^{2+}$와 $Co^{2+}$를 공침시켜 합성하고, 이를 $600^{\circ}C$에서 2시간 열처리하여 순수한 ZnO 나노입자와 Co가 도핑된 ZnO 나노입자를 합성했다. x가 < 0.05일 경우, 2-methylimidazole 링커가 $Zn^{2+}$ 및 $Co^{2+}$ 모두에 강하게 배향되어 균질한 Zn/Co ZIFs가 합성되었으며, 열처리를 통해 Co가 균일하게 도핑된 ZnO를 합성할 수 있었다. 반면, $x{\geq}0.05$일 때는 불균질한 Zn/Co ZIFs가 합성되었으며, 열처리 이후 $Co_3O_4$ 이차상이 형성되었다. 합성된 나노입자들에 대한 가스감응특성 평가 결과, 3 at%의 Co가 도핑된 ZnO 센서는 순수한 ZnO와는 달리 trimethylamine에 대해 고감도, 고선택적 가스감응특성을 나타냈다. 본 연구의 bimetallic ZIF 유도 산화물 나노복합체 합성방법은 고성능 가스센서를 설계하는데 활용될 수 있을 것으로 기대된다.