Abstract
Detecting methanol is of great importance in the organic synthesis industry. Herein, the effective utilization of ZnSnO3-based microstructures for room-temperature methanol monitoring was realized through a template-free approach. ZnSnO3-based heterojunctions with different structures and morphologies were successfully synthesized via regulating the molar ratio of Zn2+ and Sn4+ sources. And room-temperature sensing properties towards methanol were investigated. Among them, ZnO/ZnSnO3 hollow microcubes exhibited an outstanding sensing performance including a high sensitivity (10.16) and a response/recovery time (14/75 s) and a limit of detection (490 × 10–9) towards 5 × 10–6 methanol. Additionally, the synergistic effects of hollow structure with larger specific surface areas (42.277 m2·g−1), the construction of n–n heterojunctions formed at ZnSnO3 and ZnO interfaces, the high percentage of dissociative and chemisorbed oxygen are the main causes of the elevated sensing characteristics. Besides, the practical experiment demonstrated that ZnO/ZnSnO3 was capable of on-field monitoring methanol in the chemical reaction utilizing H2 and CO2 as raw materials. Moreover, with the help of density functional theory calculations, the enhanced sensing properties of ZnO/ZnSnO3 are due to the special tuning effects of Zn ionic sites on methanol adsorption.
Graphical abstract
摘要
甲醇的检测在有机合成工业中具有重要意义。在此, 通过无模板方法实现了基于ZnSnO3的气敏材料在室温甲醇检测中的有效利用。通过调节Zn2+和Sn4+的摩尔比, 成功合成了具有不同结构和形貌的ZnSnO3基异质结。本文研究了该气敏材料对甲醇气体的室温传感特性。其中, ZnO/ZnSnO3中空立方体表现出优异的气敏性能, 包括对5 × 10–6 甲醇的高灵敏度 (10.16) 和快速响应/恢复速度 (14/75 s) 以及低检测限(490 × 10–9) 。此外, 中空结构具有较大比表面积(42.277 m2·g−1) 、在 ZnSnO3和ZnO界面形成的n-n异质结和高缺陷氧和表面吸附氧含量的协同作用是气敏特性提升的主要原因。此外, 实测结果表明ZnO/ZnSnO3能够检测以H2和CO2为原料的化学反应中的甲醇。此外, 借助密度泛函理论计算, ZnO/ZnSnO3增强的气敏性能是由于Zn离子位点对甲醇吸附的特殊调节作用。
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Acknowledgements
This study was financially supported by the Outstanding Youth of Jiangsu Province of China (No. BK20211548), the China Scholarship Council (No. 202108320264) and the Excellent Doctoral Dissertation Fund of Yangzhou University (2022).
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Xu, JY., Xu, KC., He, XX. et al. Interface engineering of ZnSnO3-based heterojunctions for room-temperature methanol monitoring. Rare Met. 42, 4153–4166 (2023). https://doi.org/10.1007/s12598-023-02344-7
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DOI: https://doi.org/10.1007/s12598-023-02344-7