双金属纳米粒子修饰的单/几层MoS2片的制备及其用于葡萄糖检测的研究

As one of the graphene-like two-dimensional (2D) layered materials, the preparation and applications of MoS2 have become a hot research topic currently in many fields including physics, chemistry, material science. Especially, the modification of the single/few-layer MoS2 sheets with metal nanoparticles (NPs) might not only enhance the intrinsic performance of the material but also bring about some new properties and functionalities. To design and develop the single/few-layer MoS2 sheets modified with metal NPs, hence, is of theoretical significance and high practical value. Glucose as a biochemical indicator in the diagnosis of diabetes is important. As one of the methods widely applied for glucose detection, the colorimetric method provides a simple and convenient platform for glucose detection and is established in the combination of the specific glucose oxidase-catalyzed oxidation reaction of glucose with the peroxidase-catalyzed oxidation of the chromogenic substrate. However, the applications of natural enzymes are limited with the sensitivity of catalytic activity to experimental conditions, low stability due to denaturation as well as high cost in purification. Therefore, it is highly desirable to develop the enzyme mimics with high stability possess the characteristics of natural enzymes. The aim of this research is to synthesize and characterize a series of single/few-layer MoS2 sheets modified with bimetallic NPs MN (M = Pt, Pd, Rh; N = Au, Ag, Cu), which could be served as a kind of promising candidates for the natural enzymes for glucose detection based on the colorimetric method, and provide a new system for glucose detection with high sensitivity, good selectivity and strong anti-interference capability.

二维层状类石墨烯材料MoS2的制备与应用，已成为当前物理、化学和材料科学等领域研究的热点。特别地，用金属纳米粒子修饰单/几层MoS2片，不仅可能增强材料固有的性能，还能产生新的性能与功能。因此，设计和开发金属纳米粒子修饰的单/几层MoS2片具有重要的理论意义和较高的实际价值。葡萄糖是糖尿病诊断的一项重要生化指标。作为一种简单、方便且应用较多的葡萄糖检测法，比色法是基于葡萄糖氧化酶对葡萄糖的特异性催化氧化反应并结合过氧化物酶催化氧化显色底物的方法。然而，酶的应用因其活性易受实验条件的影响、易变性不稳定且纯化成本高而受限，因而有必要开发更稳定且具酶性特征的模拟酶。本项目试图合成与表征一系列双金属纳米粒子MN(M = Pt, Pd, Rh; N = Au, Ag, Cu)修饰的单/几层MoS2片，作为一类多功能纳米模拟酶用于葡萄糖检测，提供一种灵敏度高、选择性好、抗干扰能力强的葡萄糖检测新体系。

二维类石墨烯层状化合物，由于其独特的理化性质，近年来在催化等领域引起了广泛关注。基于MoS2片等层状材料负载双金属纳米粒子的制备、催化性质及其用于生化检测，研究内容如下：.一、铂基合金（铂钴、多孔铂银八面体）的可控制备及其用于癌细胞检测与抗菌。铂钴有较好的氧化物酶模拟酶性质，克服了过氧化物酶需要双氧水的缺点；以其超顺磁性增强癌细胞分离，提高了检测灵敏度。脱合金法制备多孔铂银，得到表面富铂的结构，增强了材料稳定性、毒性，提高了贵金属铂原子的利用率。铂银作为多功能模拟酶，比天然酶表现出更高的活性，表现出极好的抗菌效果，比文献极大减少了材料和双氧水用量。.二、开发了MoS2片的新制法，负载了不同形貌的铂基合金（铂银八面体、铂铜纳米花、铂金纳米粒子）。载体和合金之间的协同作用，使材料表现出了增强的氧化物酶/过氧化物酶模拟酶活性。用于葡萄糖、癌细胞、苯酚等比色检测，材料比载体有更高的灵敏度，比色方法表现出较高的选择性。.三、其它薄层纳米片或其负载金属纳米粒子的新制法与生化检测。包括：.（1）单层铑片作为多功能模拟酶。阐释了其催化机理、动力学，并构建出了黄嘌呤、双氧水、抗坏血酸等检测用的液相及纸基小分子高灵敏度、高选择性传感器。对提高铑原子利用率，延伸单层材料新颖的催化性质，提高现有纳米酶活性有一定意义。.（2）一锅合成其它薄层材料负载金属纳米粒子。有别于制备负载型材料的传统两步法，一锅制备出薄层镍基材料负载钯纳米粒子，提出了还原-氧化-组装的成核与生长机理。揭示了载体与金属之间协同催化机理，提供了一类结构新颖的高效过氧化物酶模拟酶。此外，一锅制备了铑片负载铂铑合金，实现铂种优先生成、铂种催化铑前驱体还原生成铂铑合金及载体铑片生长三步过程，构建出一种新型铂铑/铑结构，揭示了其生长、成核机理，作为氧化物酶模拟酶表现出了协同增强的活性。