中国石油大学（华东） 控制科学与工程学院，山东 青岛 266580
周兰娟，牛昶，王家乐，等. 基于 MXene与还原氧化石墨烯的石英晶体微天平氨气传感器［J］. 中国粉体技术，2026，32（1）：14-22.
ZHOU Lanjuan， NIU Chang， WANG Jiale， et al. Quartz crystal microbalance ammonia sensor based on MXene and reduced graphene oxide［J］. China Powder Science and Technology，2026，32（1）：14−22.
DOI：10.13732/j.issn.1008-5548.2026.01.003
收稿日期：2025-02-18，修回日期：2025-11-22，上线日期：2025-12-12。
基金项目：国家自然科学基金项目，编号：52475580；山东省泰山学者人才计划项目，编号： tsqn202211077。
第一作者：周兰娟（1978—），女，副教授，硕士，硕士生导师，研究方向为气敏传感器研制和测试计量技术。E-mail：zhlj@upc.edu.cn。
通信作者：张冬至（1981—），男，教授，博士，博士生导师，山东省泰山学者特聘专家，研究方向为先进传感器技术。E-mail：dzzhang@upc.edu.cn。
摘要：【目的】为了实现对食物腐败产生氨气的快速、高响应检测。【方法】设计并制备基于MXene与还原氧化石墨烯（reduced Graphene Oxide，rGO）复合薄膜的石英晶体微天平（Quartz Crystal Microbalance，QCM）传感器，采用扫描电子显微镜对MXene-rGO复合敏感膜的表面形貌与微观结构进行分析；使用石英晶体微天平传感平台测试技术对该传感器对氨气的灵敏度、线性度、长期稳定性等动态响应特性进行测试分析，并进一步研究其在实际食物腐败检测中的应用效能。【结果】MXene-rGO 复合薄膜表征显示MXene与rGO复合良好，MXene-rGO复合薄膜传感器灵敏度高，线性度好，长期稳定性优异。【结论】MXene-rGO复合薄膜对氨气吸附性强，具有良好的重复性和长期稳定性，能够应用于食物腐败检测中。
关键词：食物腐败；石英晶体微天平；氨气；还原氧化石墨烯
Objective Food spoilage is a significant cause of food waste. To address this issue， the study designs a quartz crystal microbalance (QCM) sensor using a MXene-reduced graphene oxide (MXene-rGO) composite as the sensitive film. This sensor is employed to detect ammonia gas released during food spoilage， facilitating the monitoring of food spoilage levels.
Methods A MXene-rGO solution was synthesized by mixing the prepared MXene solution with rGO. Scanning electron microscopy (SEM) was employed to characterize the surface morphology of the composite material. Subsequently, a QCM experimental setup was established to systematically investigate the sensor's dynamic response characteristics, linearity, sensitivity, stability, repeatability, and selectivity toward ammonia gas. Finally, experiments were conducted to validate the sensor's applicability for food spoilage detection.
Results and Discussion In dynamic response tests, QCM sensors modified with MXene, rGO, and MXene-rGO were sequentially exposed to ammonia concentrations of 1×10-6, 5×10-6, 1×10-5, 2×10-5, 5×10-5, and 7×10-5, with air used as a reference environment. Among the three, the MXene-rGO modified QCM sensor exhibited the largest frequency shift at all concentrations, indicating superior sensing performance. Its frequency responses reached 18.336，59.692，78.36，107.856，252.174, and 343. 992 Hz at respective ammonia concentrations. Linear fitting of the sensor output showed that the MXene-rGO modified QCM sensor exhibited the steepest linear regression slope， demonstrating excellent sensitivity. For the repeatability analysis, the MXene-rGO modified QCM sensor was tested for its response characteristics to 2×10-5 ammonia gas under room-temperature conditions. The frequency shift remained consistent across multiple repeated cycles, indicating good repeatability. Long-term stability testing conducted at ammonia concentrations of 1×10-5, 2×10-5, and 5×10-5 over one month further confirmed its excellent stability. Overall, the experimental results validate the superior performance of the MXene-rGO modified QCM sensor in ammonia gas sensing applications, highlighting its potential for practical application in food spoilage monitoring systems.
Conclusion This paper presents a novel ammonia gas sensor designed for monitoring food spoilage levels, employing MXene-rGO composite as the sensitive film. The sensor exhibits excellent capability in detecting ammonia gas, with a frequency shift of up to 252.174 Hz at 5×10-5 ammonia. Additionally, it demonstrates good stability and repeatability. These findings highlight its strong practical value, offering a promising sensing technology for detecting gases associated with food spoilage.
Keywords：food spoilage; quartz crystal microbalance; ammonia gas; reduced graphene oxide
［1］LEI Z J， LIN M H， ZHOU Y， et al. Glucose-modulated defect-enriched Sv-SnS2 sensor for rapid detection of NH3 at room temperature［J］. Journal of Alloys and Compounds，2025，1026：180379.
［2］周兰娟，杜宸，张冬至. 基于MoSe2 纳米结构的乙醇气体检测系统［J］. 实验室研究与探索，2021，40（9）：87-90.
ZHOU L J， DU C， ZHANG D Z. Molybdenum diselenide nanoflower based ethanol gas sensor and its detection system［J］. Research and Exploration in Laboratory，2021，40（9）：87-90.
［3］GUO X Z， DING Y Q， LIANG C Y， et al. Humidity-activated H2S sensor based on SnSe2/WO3 composite for evaluating the spoilage of eggs at room temperature［J］. Sensors and Actuators B： Chemical，2022，357：131424.
［4］MATINDOUST S， FARZI G， NEJAD M B， et al. Polymer-based gas sensors to detect meat spoilage: a review［J］. Reactive and Functional Polymers，2021，165：104962.
［5］ALEV O， SARICA N， ÖZDEMIR O， et al. Cu-doped ZnO nanorods based QCM sensor for hazardous gases［J］. Journal of Alloys and Compounds，2020，826：154177.
［6］KANG Z J， ZHANG D Z， LI T T， et al. Polydopamine-modified SnO2 nanofiber composite coated QCM gas sensor for high-performance formaldehyde sensing［J］. Sensors and Actuators B： Chemical，2021，345：130299.
［7］CHEN S H， QI G Y， ZHANG L， et al. Detection of salmon meat freshness using QCM gas sensor array combined with physicochemical method［J］. Microchemical Journal，2023，194：109353.
［8］王艳，曾禹，吕天奕，等. 基于石英晶体微天平的油液铁离子检测技术研究［J］.传感器与微系统，2023，42（7）：40-42，47.
WANG Y， ZENG Y， LÜ T Y， et al. Detection technology research on iron ion in oil based on quartz crystal microbalance［J］. Transducer and Microsystem Technologies，2023，42（7）：40-42，47.
［9］SU H Y， LI H， LIN H， et al. Highly sensitive formaldehyde sensors based on CuO/ZnO composite nanofibrous mats using porous cellulose acetate fibers as templates［J］. International Journal of Biological Macromolecules，2022，206：653-660.
［10］TRAJCHEVA A， POLITAKOS N， PÉREZ B T， et al. QCM nanocomposite gas sensors：expanding the application of waterborne polymer composites based on graphene nanoribbon［J］. Polymer，2021，213：123335.
［11］沈兵，徐甲强，王炉煜，等. 基于羟基磷灰石的QCM湿度传感器研究［J］. 电子元件与材料，2022，41（1）：53-58.
SHEN B， XU J Q， WANG L Y， et al. Research on QCM humidity sensor based on hydroxyapatite［J］. Electronic Components & Materials，2022，41（1）：53-58.
［12］CAI J F， YAN Y， WANG W W， et al. Detection of formic acid and acetic acid gases by a QCM sensor coated with an acidified multi-walled carbon nanotube membrane［J］. Environmental Technology，2023，44（6）：751-761.
［13］FENG L H， FENG L Y， LI Q， et al. Sensitive formaldehyde detection with QCM sensor based on PAAm/MWCNTs and PVAm/MWCNTs［J］. ACS Omega，2021，6（22）：14004-14014.
［14］ZHANG B H， LI Z Q， LI C， et al. High-sensitive ppb-level ammonia QCM sensor based on sulfur doped Ti3C2Tx MXene［J］. Sensors and Actuators A： Physical，2023，350：114138.
［15］LIU X， WANG J J， HOU J C. Repeatability and sensitivity of quartz crystal microbalance （QCM） sensor array modified with four sensitive materials［J］. Materials Science in Semiconductor Processing，2022，147：106764.
［16］ISHIGURO Y， NISHITANI T， LI C， et al. A graphitic carbon nitride-coated quartz crystal microbalance gas sensor for H2 detection［J］. Journal of Materials Chemistry C，2023，11（30）：10178-10184.
［17］XU X Y， HE L W， CAO S， et al. Humidity-mediated QCM sensor based on COF-5 for carbon dioxide detection［J］. IEEE Electron Device Letters，2023，44（7）：1188-1191.
［18］MA Z H， YUAN T W， FAN Y， et al. Mesoporous-structure MOF-14-based QCM p-xylene gas sensor［J］. Nanomaterials，2023，13（11）：1743.
［19］LIU C， CHEN S H， LIU S Q， et al. Highly sensitive QCM gas sensor based on ZIF-8-derived porous carbon and multi-walled carbon nanotubes decorated nanocomposite for salmon meat freshness detection［J］. Journal of Food Composition and Analysis，2024，133：106392.
［20］SU P G， ZHENG Y X. A room temperature NH3 gas sensor based on a quartz crystal microbalance coated with a rGO-SnO2 composite film［J］. Analytical Methods，2022，14（14）：1454-1461.
［21］WANG L Y， WU Y L， GAO J K， et al. La doped AlPO-5: enhenced NH3 sensing properties, thermodynamic investigation and humidity-enhanced effect［J］. Journal of Solid State Chemistry，2019，277：54-60.
［22］GASSO S， SOHAL M K， MAHAJAN A. MXene modulated SnO2 gas sensor for ultra-responsive room-temperature detection of NO2［ J］. Sensors and Actuators B： Chemical，2022，357：131427.
［23］MENG F L， LI X Z， YUAN Z Y， et al. Ppb-level xylene gas sensors based on Co3O4 nanoparticle-coated reduced graphene oxide（rGO） nanosheets operating at low temperature［J］. IEEE Transactions on Instrumentation and Measurement，2021, 70：9511510.
［24］ROTO R， RIANJANU A， RAHMAWATI A， et al. Quartz crystal microbalances functionalized with citric acid-doped polyvinyl acetate nanofibers for ammonia sensing［J］. ACS Applied Nano Materials，2020，3（6）：5687-5697.
