水氧稳定可分散黑磷烯/PEDOT复合材料的制备及其传感性能

Black phosphorene (BP) is a new material with graphene-like structure of a frontier of a novel two-dimensional semiconductor today. It has advantages such as optic/electric characteristics, mass-production techniques with sonication assisted liquid-phase exfoliation beyond graphene, which inspires prospective applications in photonic/electronic fields. The solution processability and environmental stability such as stability in water- or oxygen-rich environments have restricted the composite of BP, even the architecture and application of BP devices, which have become one of key scientific issues. In this project, we will plan to improve the solution processability and environmental stability of thin-layer BP via non-covalent (π-π interaction, electrostatic interaction, etc.) surface functionalization with monomer solutions or polymer dispersions of organic semiconductors PEDOT and their functionalized materials with extraordinary properties like high conductivity, flexibility, transparency in novel or traditional organic solvents, water and their mixed systems, then solve stability in water and/or oxygen of BP composites for the architecture and application of BP devices. Secondly, we will prepare BP composites, characterize their structures and morphology, and test their properties like conductivity, flexibility, and transparency. Thirdly, we will also fabricate BP film electrodes utilizing their various properties, then develop BP sensing devices in the combination with optical/electrical sensing characteristics of film electrodes towards analytes, optimize the preparative processes of sensing devices, and assess their sensing performance. Finally, we will explore their sensing application in agricultural fields. This project provides theoretical guidance and practical reference for the study of novel graphene-like composites and their architecture and application of sensing devices.

黑磷烯(BP)是当今新型二维半导体研究前沿的类石墨烯新材料，有超越石墨烯光/电特性、液相超声量产技术等优势，在光/电子学领域有潜在应用前景。水氧稳定性和溶液可加工性制约着薄层BP复合、器件构筑与应用并成为当前BP研究亟需解决的关键科学问题之一。本项目拟采用环境稳定、柔性透明、溶液可加工半导体PEDOT（包括其单体）及其功能材料通过π-π、静电等非共价键表面功能化改性薄层BP及其前驱体黑磷，改善它们在新型或传统有机溶剂、水及混合体系中的分散性和稳定性，解决薄层BP在复合、传感器件构筑与应用中的水氧稳定性；制备BP/PEDOT复合材料，表征其结构与形貌，测试其导电性、透明性、柔韧性等性能；结合复合材料性能构建膜电极，利用分析物对膜电极光/电传感特性构筑传感器件，优化其制备工艺并考察其性能，探索其在农业检测分析领域中的应用，为研究新型类石墨烯复合材料及其传感器件构筑与应用提供理论指导和实践参考。

黑磷是磷的同素异形体，BP具有可调直接带隙、高载流子迁移率、极大比表面积和各种液相剥离量产技术，这使得BP有望超越Gr成为新一代类石墨烯材料在纳米电子学领域的新宠。短短6年，BP在制备与修饰、器件性能与应用探索等方面备受关注并迅速得到各学科领域研究人员的青睐。尽管BP独特的结构特征和出色的性质在众多领域极具应用前景，但其制备与应用存在水氧稳定性和溶液可加工性问题，很难满足拥有高质量、高性能、高量BP制备对器件应用的需求。鉴于BP自身缺陷，其制备与表面修饰及应用探索现已成为多领域最热门的研究课题。.本项目主要通过液相超声剥离手段和非共价键表面功能化策略修饰BP获得对环境稳定可分散薄层BP复合材料，研究不同修饰材料对BP稳定性和可分散性的影响，表征其结构与形貌，建立高稳定可分散薄层BP复合材料的可复制方法，获得高质量、高性能和高稳定可分散薄层BP复合材料；本项目通过PEDOT改性黑磷溶液可加工性和BP环境稳定性，获得短期水氧稳定BP/PEDOT复合材料（3-5天）并成功应用于电化学领域；实现对农业有害物质和重要分子的电化学传感分析。本项目还扩展研究PEDOT改性其它类石墨烯解决环境稳定性和溶液可加工性问题及其电化学应用。此外，还发现金属盐和碳纳米材料混合超声剥离黑磷，磷烯可还原金属盐形成纳米金属修饰BP/碳纳米复合材料，其环境稳定性超过1周，并传感应用于生物分子和农药等电化学传感分析。.本项目掌握了π-π、静电等非共价键、有机溶剂、离子液体及混合体系对BP环境稳定性和溶液可加工性的影响规律；掌握了EDOT或PEDOT改性薄层BP的方法，制备了高稳定可分散薄层BP复合材料；发现了金属盐或碳材料等修饰BP可更好解决环境稳定性问题，实现薄层BP在复合、传感器件构筑与农业分析应用。该研究对解决薄层BP稳定性及其前驱体黑磷溶液可加工性问题具有重要参考意义。