借鉴自然界中生物材料的独特结构和功能，探索和开发具有新特性和功能的人工材料具有重要的研究意义和应用价值。本论文采用多维多尺度的调控与组装策略，围绕受自然启发的先进功能材料，通过调控二维石墨烯（2D-G）与一维纤维素（1D-Cs）衍生物，构建高度有序的三维（3D）结构，实现了独特的各向异性。本研究的创新之处在于有效利用了石墨烯与纤维素（GC）之间的异质界面，进而创制出具有独特特异性和功能性的3D结构。借助自上而下合成和自下而上组装技术，实现了对材料结构和功能特性的精确控制。论文重点解决了原始单分散2D-G纳米片和1D-Cs纳米链的制备问题，深入理解了分子间和分子内界面复杂的相互作用，实现了亲水性和疏水性之间的平衡。同时，本研究精准地考虑了中心、基面和边缘的2D/1D-GC单层悬挂π键和反应性质，揭示了双层、三层和多层结构的π-π堆叠相互作用机制。通过原位和非原位方案的结合，在保持其原始结构的基础上实现了均匀分散。阐明了范德华（vdW）相互作用在上述纳米结构组装中以及在定义2D/1D-GC异质界面上的载荷传递和热传递过程中的关键作用，为不同条件下结构的变形行为以及vdW相互作用和原子级驱动力之间的相互作用提供了新见解。在此基础上，检测了多尺度3D结构中的平面内和平面外热导率。此外，开发了双模板策略，包括无模板、模板辅助和模板导向的方法，用于制备和模拟复杂的3D形状、3D连续和3D双连续石墨烯纤维素（3D2GC）结构。采用定量和定性分析技术（如扫描电子显微镜、透射电子显微镜、原子力显微镜等）对2D/1D-GC异质界面及3D结构进行了全面表征、可视化分析和模拟。综上所述，本论文工作为纳米宏观组装技术提供了重要见解，不仅揭示了基于vdW相互作用的功能化的基本原理，还提供了将二维石墨烯和一维纤维素转化为新型三维结构的实用方法，为其后续应用奠定的实验基础。
This doctoral dissertation delves into the development of next-generation, advanced functional materials, drawing inspiration from the hierarchical architectures found in nature. Central to this exploration is the strategic manipulation of 2D-graphene (2D-G) and 1D-cellulose (1D-Cs) derivatives, which are assembled to generate bio-inspired and highly ordered 3D-structures. These structures are distinguished by their unique anisotropic features, aspects that have previously been ignored, neglected, or insufficiently explored within the domain of interfacial nanoarchitectonics. The novelty of this research stems from leveraging the anisotropic properties of graphene-cellulose heterointerfaces in 2D/1D configurations, yielding sophisticated 3D-architectures characterized by their superior specificity and functionality. Utilizing both top-down synthesis and bottom-up assembly techniques, the research achieves precise control over the structural and functional properties of these advanced materials. A significant focus of the dissertation is on overcoming the challenges of fabricating pristine, monodispersed 2D-G nanosheets and 1D-Cs nanochains, challenges that stem from their complex intermolecular and intramolecular interfacial interactions, and the equilibrium between hydrophilicity and hydrophobicity. The research precisely considers the dangling π-bonds and the reactive nature of the 2D/1D-GC monolayers at the central, basal planes, and edges. It also addresses the tendency of bi-, tri-, and multilayered structures to undergo π?π stacking interactions. Through a combination of in-situ and ex-situ protocols, the research endeavors to retain their pristine structures and achieve uniform dispersion. Additionally, the dissertation highlights the pivotal role of van der Waals (vdW) forces in the assembly of these nanostructures and in defining the mechanisms of load transfer (LT) and heat transfer (HT) across 2D/1D-GC heterointerfaces. It offers new insights into the deformation behavior under diverse conditions and the interplay between vdW forces and atomic-level driving forces. Furthermore, the study probes the in-plane and out-of-plane thermal conductivities within these multi-scale 3D-architectures, identifying areas that require further exploration. The dissertation also explores dual-templating strategies, including template-free, template-assisted, and template-directed approaches, for the fabrication and simulation of complex 3D-shaped, 3D-continuously, and 3D-bicontinuously graphene-cellulose (3D2GC) architectures. A wide range of quantitative and qualitative analytical techniques, including OM, SEM, TEM, AFM, μ-CT, Raman, Zeta, UV-visible, FTIR, TGA, DTA, BET, BJH, PPMS, TMA, TPS, and computational software, is employed to comprehensively characterize, visualize, analyze, and simulate these 2D/1D-GC heterointerfaces and resultant 3D-architectures. In conclusion, this doctoral dissertation significantly advances the field of interfacial nanoarchitectonics, offering a forward-looking roadmap for future research aimed at optimizing the efficiency and unlocking the full potential of these multi-scale 2D/1D-GC heterointerfaces structures. The dissertation not only demonstrates a profound understanding of the fundamental principles of vdW forces and anisotropic characteristics, but also presents feasible approaches for transforming 2D-G and 1D-Cs derivatives into intricate 3D2GC architectures. Eventually, we aim to inspire further research in this dynamic domain and shed light on its wide-ranging implications throughout multiple disciplines.
