Hou Liwei, Xu Xinyue, Zhong Zhoujun, Tian Fengchun, Wang Li, Xu Yi
Key Disciplines Lab of Novel Micro-Nano Devices and System Technology, Key Laboratory of Optoelectronic Technology and Systems, Ministry of Education, Chongqing University, Shapingba, Chongqing 400044, China.
School of Chemistry and Chemical Engineering, Chongqing University, Shapingba, Chongqing 400044, China.
ACS Appl Mater Interfaces. 2024 Mar 13;16(10):13191-13201. doi: 10.1021/acsami.3c16745. Epub 2024 Feb 28.
The demand for the detection of ultralow concentrations of ammonia gas is growing. A bimetallic metal-organic framework (MOF) comprising Prussian blue analogs (PBAs) was used to achieve highly sensitive and stable detection of ammonia gas at room temperature in this study. First, PB was enriched by using ammonia for improved gas sensing properties. Second, a sensitive membrane with more vacancies was formed by partially replacing Fe with Cu through a cation-exchange strategy. Finally, a capacitive sensor was developed for ultralow-concentration ammonia detection using a Cu-Fe PBA sensitive membrane and interdigitated electrodes (IDEs). To investigate the adsorption efficiency of the designed composite sensitive film for ammonia, PBAs nanoparticles were deposited on a quartz microcrystal balance (QCM) via cyclic voltammetry and a hydrothermal method. Approximately 10 ppm of ammonia was adsorbed under 1 atm by the Cu-Fe PBA film prepared using a reaction time of 36 h, and the adsorption efficiency was measured to be 2.2 mmol g using the QCM frequency response. The Cu-Fe PBAs were also tested using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Brunauer-Emmett-Teller theory. The introduction of Cu ions significantly increased the specific surface area of Cu-Fe PBAs MOF, and the number of adsorption sites for ammonia also increased; however, its skeleton structure remained similar to that of PB. Then, the capacitive sensor based on Cu-Fe PBA sensitive membrane and IDE was fabricated and the gas sensing detection device was established for ammonia detection. Overall, the developed capacitive sensor exhibits a linear response of 75-1000 ppb and a detection limit of 3.8 ppb for ultralow ammonia concentrations, which makes it superior to traditional detection methods and thus allows excellent application prospects.
对超痕量氨气检测的需求日益增长。本研究中,一种由普鲁士蓝类似物(PBAs)组成的双金属金属有机框架(MOF)被用于在室温下实现对氨气的高灵敏度和稳定检测。首先,利用氨气对PB进行富集以改善气敏性能。其次,通过阳离子交换策略用铜部分替代铁,形成了具有更多空位的敏感膜。最后,使用铜铁PBA敏感膜和叉指电极(IDE)开发了一种用于超痕量氨气检测的电容式传感器。为了研究设计的复合敏感膜对氨气的吸附效率,通过循环伏安法和水热法将PBAs纳米颗粒沉积在石英晶体微天平(QCM)上。使用反应时间为36小时制备的铜铁PBA膜在1个大气压下吸附了约10 ppm的氨气,通过QCM频率响应测得吸附效率为2.2 mmol/g。还使用扫描电子显微镜、透射电子显微镜、X射线衍射和布鲁诺尔-埃米特-泰勒理论对铜铁PBAs进行了测试。铜离子的引入显著增加了铜铁PBAs MOF的比表面积,氨气的吸附位点数量也增加了;然而,其骨架结构与PB的骨架结构相似。然后,制备了基于铜铁PBA敏感膜和IDE的电容式传感器,并建立了用于氨气检测的气敏检测装置。总体而言,所开发的电容式传感器对超痕量氨气浓度呈现出75 - 1000 ppb的线性响应和3.8 ppb的检测限,这使其优于传统检测方法,具有出色的应用前景。