基于 TA-Fe₃O₄@MXene 自引发聚合的室温快速制备丝素蛋白复合水凝胶及其柔性传感应用

Rapid Room-Temperature Fabrication of Silk Fibroin Composite Hydrogels Based on TA-Fe ₃O ₄@MXene Self-Initiated Polymerization for Flexible Sensing Applications

摘要

通过将单宁酸（TA）和四氧化三铁（Fe₃O₄）纳米颗粒负载于导电二维过渡金属碳化物/氮化物（MXene）纳米片上作为催化剂，在水/甘油二元溶剂中引发丙烯酸（AA）、丙烯酰胺（AM）与丝素蛋白（SF）进行室温“一锅法”自由基聚合，制备了 P(AA-co-AM)/SF/TA-Fe₃O₄@MXene 水凝胶，该过程无需外部能量输入。用 X 射线衍射、X 射线光电子能谱、扫描电镜和透射电镜对材料的组成、化学态及微观结构进行了表征；用电子万能试验机测试了水凝胶的拉伸、压缩力学性能及抗疲劳性能；用差示扫描量热法评估了其宽温域稳定性；结合数字万用表与拉伸装置对水凝胶的导电性及应变传感性能进行了测试。结果表明，该水凝胶具有超高拉伸性（1 640%）、高拉伸强度（282 kPa）、高电导率（206.8 μS/cm）及优异的宽温域（−40～60 ℃）稳定性。作为柔性应变传感器，该水凝胶表现出高灵敏度（应变因子（GF）为 5.92）、良好的循环稳定性及对微弱生理信号（如关节运动、喉部振动）的实时响应能力，适用于柔性可穿戴电子器件。

Abstract

Acrylic acid (AA), acrylamide (AM), silk fibroin (SF), tannic acid (TA), iron oxide (Fe₃O₄) nanoparticles, and two-dimensional MXene nanosheets were used as raw materials. A conductive hydrogel marked as P(AA-co-AM)/SF/TA-Fe₃O₄@MXene was fabricated via one-pot free radical polymerization in a water/glycerol binary solvent at room temperature. TA-modified Fe₃O₄ nanoparticles anchored on MXene nanosheets (TA-Fe₃O₄@MXene) were employed as functional fillers in a system requiring no external energy supply. The composition, chemical states, and microstructure of the material were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The tensile and compressive mechanical properties and anti-fatigue performance of the hydrogel were evaluated using an electronic universal testing machine. Its wide-temperature stability was assessed by differential scanning calorimetry (DSC). The electrical conductivity and strain-sensing performance were investigated using a digital multimeter combined with a tensile apparatus. The hydrogel exhibits ultrahigh stretchability (1 640%), high tensile strength (282 kPa), high electrical conductivity (206.8 μS/cm), and excellent wide-temperature (−40 ℃ to 60 ℃) stability. As a flexible strain sensor, it demonstrates high sensitivity (gauge factor (GF) of 5.92), good cycling stability, and real-time response to weak physiological signals such as joint motion and throat vibration, showing great potential for flexible wearable electronics.

关键词

丝素蛋白 / 二维过渡金属碳化物/氮化物 / 快速凝胶化 / 水凝胶 / 自引发聚合 / 柔性传感器

Key words

silk fibroin / MXene / rapid gelation / hydrogel / self-initiated polymerization / flexible sensor

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基金资助

国家自然科学基金(52303067)