面向综合管廊环境中抗“中毒”H2S气体传感器的研究

综合管廊环境中剧毒、易燃易爆H2S气体的快速准确检测对巡廊人员和廊道安全保护至关重要。与大型分析化学仪器相比，金属氧化物半导体传感器更易应用于智能化、便携式在线检测。但目前用于H2S气体检测的氧化物敏感材料存在易硫化中毒和受湿度干扰大的瓶颈问题。申请人提出铜铁矿、钙钛矿和尖晶石结构的铜基多元金属氧化物构筑策略，通过调控晶体结构、离子配位环境和化学计量比等实现H2S气体吸附模式和强度的优化及可逆恢复；分别通过稀土元素掺杂、疏水聚合物包覆和生物质材料复合等改性手段提高材料抗湿性；设计“共平面直热式”传感器，获得面向综合管廊H2S气体检测的微型化、稳定的传感器；通过原位表征技术和第一性原理计算系统分析H2S气体在铜基多元金属氧化物表面的吸附-反应-脱附机制，构建载流子传输模型，深化多元金属氧化物气体传感器感知机理。本项目的实施为H2S气体传感器的研究和应用提供有力的科学依据和技术支撑。

The fast and accurate detection of highly toxic, flammable and explosive hydrogen sulfide (H2S) gases in the utility tunnel is very important for the protection of patrol personnels and the safety of the underground tunnel environment. Compared with the large analytical chemical instruments, gas sensors based on metal oxide semiconductors are easier to be used for the intelligent on-line detection and portable application. However, the H2S gas sensors based on metal oxide semiconductors have the bottleneck problems of poisoning and humidity interference. The applicant proposed a construction strategy of copper-based multi-element metal oxide semiconductors with delafossite, perovskite and spinel structures. The adsorption mode and strength of H2S gas sensors with the reversible resistance recovery property are optimized by adjusting the crystal structure, ion coordination environment and stoichiometric ratio. The moisture resistance of the sensing materials will be improved by rare earth element doping, hydrophobic polymer coating and biomass material modifying, respectively. A plane structured gas sensor is designed to obtain a miniaturized and stable H2S gas sensor. The adsorption, reaction and desorption mechanisms of H2S gas on copper-based multi-element metal oxides are comprehensively analyzed through in-situ characterization technology and first-principles calculation. A carrier transport model will be established to deepen the sensing mechanism of gas sensor based on multi-element metal oxides. The implementation of this project provides a great scientific basis and technical support for the research and application of H2S gas sensors.