基于类石墨炔多孔聚合物的湿气发电研究

As a promising clean energy conversion technology, hygroelectric generation devices based on hygroscopic materials enable capture gaseous water molecules in the air, and the asymmetrically distributed ions achieve the conversion of chemical energy of water molecules to electric power by moving in a directional manner. Hygroscopic materials are the key components in hygroelectric generation devices, and the performance of devices can be effectively improved by adjusting their proton activity and concentration, but there is currently a lack of efficient method. The characteristics of nanopore and easy-modification of graphdiyne-like materials contribute to the longitudinal diffusion of water molecules and ions, which provides a novel way for the study of hygroscopic materials. Based on these issues, this project proposes a two-step synthesis route including the dehydrogenation coupling reaction of terminal alkyne groups and the post-modification method of thiol-yne click reaction, to prepare a graphdiyne-like porous polymer film with a gradient functional carboxyl structure for constructing hygroelectric generation devices with high output voltage. The effect of the gradient distribution of carboxyl groups in the film on its water adsorption, proton concentration and distribution will be systematically investigated. Meanwhile, the effects of surface charge density and porous characteristics on proton dissociation and diffusion will be seriously studied. Eventually, the essential connection between the energy conversion performance of hygroelectric generation devices and the material structure and proton activity will be revealed. On the basis of the rational design and regulation of interaction at the gas-solid interface, this project will provide a novel insight for the development of high-performance energy conversion devices, and has great scientific significance and practical prospect in the fields of self-powered sensors and wearable devices.

作为一项极具潜力的清洁能源转换技术，湿气发电器件能够捕获空气中的气态水分子，并利用不对称性分布的离子定向传输，将湿气的化学能转换为电能。吸湿材料是湿气发电器件的核心部件，调节其质子活性与扩散可有效提升发电性能，但目前尚缺乏相关手段。类石墨炔材料的纳米孔道与易修饰特征有助于水分子与离子的纵向扩散，为吸湿材料研究提供了新途径。为此，本项目提出通过端炔基脱氢偶联与巯基-炔点击化学后修饰两步法，制备含梯度功能羧基结构的类石墨炔多孔聚合物薄膜，用于构筑高输出电压的湿气发电器件。探究薄膜内部梯度分布羧基对水吸附、质子浓度与分布的调控规律，研究其表面电荷密度与多孔特征对质子解离、扩散的影响，进而揭示发电器件的能源转换性能与材料结构、质子活性之间的关联性。本项目从气-固界面相互作用的设计与调控出发，将为发展高性能的能源转换器件提供新的思路，同时在自驱动传感器与可穿戴设备等领域有着重要的科学意义与实用前景。

纳米材料的表界面特性在电化学基础研究与应用领域起着关键作用，尤其是能源转化与生物传感。然而，现有调控方式往往存在操作复杂、工作模式单一、稳定性不足等难题。基于此，申请人提出从分子层次出发，调控并优化纳米材料的表界面性质与工作模式，发展高效、简单的新型水诱导产电器件与高灵敏、均相的单颗粒碰撞分析方法以及高稳定性、快动力学的流动电催化模式。首先，我们分别构建了基于两种纳米材料（类石墨炔多孔聚合物与掺杂氧化锌薄膜）的水诱导产电器件，实现持续、稳定的化学/热能转化与电能输出，成功应用于驱动小型电子产品与实时监测人体呼出信号。同时，基于单颗粒碰撞电化学原理，我们调控纳米表面与疾病标志物的相互作用，发展了高灵敏、高选择性的均相电化学传感器，实现人体实际样品中标志物的可靠检测。此外，我们首次证明了纳米颗粒在流动工作模式下可以有效提升电催化反应的动力学与稳定性。这些研究发现不仅论证了纳米表界面调控对电化学能源转化与生物传感领域的重要影响，同时为探索气-固-液界面的复杂相互作用研究提供了新的思路。