Two-dimensional (2D) heterostructures hold great promise in designing integrated materials, while the current synthesis strategies still confront challenges for multilayer heterostructure construction and scale-up production. Here we report a generalized host-guest strategy based on non-exfoliated layered graphene oxide (LGO) to construct graphene-based heterostructures that consist of multilayered, alternately aligned graphene and metal oxide nanosheets. The 2D-aligned GOs and open interlayer spaces make LGO an ideal platform to create periodic 2D host frameworks. Polyetheramine oligomers covalently bond the adjacent GOs. The extended chain conformation endows the resulting accordionlike GO frameworks with high structural stability, periodicity and enlarged interlayer space. Owing to the high affinity of the open and well-arranged 2D channels toward guest precursors, a variety of high-quality heterostructures can be synthesized. Furthermore, a variety of exfoliated, ultrathin metal oxide nanosheets can also be prepared by removing the graphene skeleton. The flexible interlayer chemistry presented in this study paves a way toward the synthesis of a large family of graphene-inorganic/organic 2D heterostructures.

二维（2D）异质结构在设计集成材料方面具有广阔的前景，而当前的合成策略仍面临多层异质结构构建和规模生产的挑战。在这里，我们报告了一种基于非剥离层状氧化石墨烯（LGO）的通用主宾策略，以构建由多层交替排列的石墨烯和金属氧化物纳米片组成的基于石墨烯的异质结构。2D对齐的GO和开放的层间空间使LGO成为创建定期2D宿主框架的理想平台。聚醚胺低聚物共价键合相邻的GO。延伸的链构象赋予所得的手风琴状GO框架高度的结构稳定性，周期性和更大的层间空间。由于开放和排列合理的2D通道对客体前体的高度亲和力，可以合成各种高质量的异质结构。此外，还可以通过去除石墨烯骨架来制备各种剥离的超薄金属氧化物纳米片。这项研究中提出的柔性中间层化学为大系列石墨烯-无机/有机2D异质结构的合成铺平了道路。