Graphene-based mixed-dimensional materials hybridization is important for a myriad of applications. However, conventional manufacturing techniques face critical challenges in producing arbitrary geometries with programmable features, continuous interior networks, and multimaterials homogeneity. Here we propose a generalized three-dimensional (3D) printing methodology for graphene aerogels and graphene-based mixed-dimensional (2D + nD, where n is 0, 1, or 2) hybrid aerogels with complex architectures, by the development of hybrid inks and printing schemes to enable mix-dimensional hybrids printability, overcoming the limitations of multicomponents inhomogeneity and harsh post-treatments for additives removal. Importantly, nonplanar designed geometries are also demonstrated by shape-conformable printing on curved surfaces. We further demonstrate the 3D-printed hybrid aerogels as ultrathick electrodes in a symmetric compression tolerant microsupercapacitor, exhibiting quasi-proportionally enhanced areal capacitances at high levels of mass loading. The excellent performance is attributed to the sufficient ion- and electron-transport paths provided by the 3D-printed highly interconnected networks. The encouraging finding indicates tremendous potentials for practical energy storage applications. As a proof of concept, this general strategy provides avenues for various next-generation complex-shaped hybrid architectures from microscale to macroscale, for example, seawater desalination devices, electromagnetic shielding systems, and so forth.

Controlled scalable assembly of 2D building blocks into macroscopic 3D architectures is highly significant. However, the assembly of g‐C3N4 into tailored, 3D architectures is not yet reported. Here, a 3D printing methodology to enable the programmable construction of carbon nitride–based hybrid aerogel membranes with patterned macroscopic architectures is proposed. g‐C3N4 nanosheets (CNNS) are used as the building block, and sodium alginate (SA) increases the viscosity of the ink to obtain the desired rheological properties. Three printing routes, including printing directly in air and in the supporting reservoirs composed of CaCl2/glycerol solution or Pluronic F127, are demonstrated for printing versatility. The printed Au nanobipyramid–CNNS–SA hybrid aerogels exhibit broadband visible‐light absorption and superior solar wastewater remediation performance with excellent cyclic stability and easy manipulation features. Remarkably, the activity of the 3D‐printed aerogel is about 2.5 times of that of the contrast sample, attributing to the enhanced liquid velocity and solution diffusion efficiency because of the 3D‐printed structure, which is demonstrated by experimental and theoretical simulations. This approach can be extended to the macroscopic assembly of other 2D materials for myriad applications.

We report a facile sacrificial casting–etching method to synthesize nanoporous carbon nanotube/polymer composites for ultra-sensitive and low-cost piezoresistive pressure sensors.