Because of their good performance in diffusion‐limited processes, ordered macro‐microporous single‐crystalline metal‐organic frameworks (MOFs) have potential for use in various fields. However, there are still very few reports of the synthesis of such MOFs. A general synthesis methodology for ordered macro‐microporous single‐crystalline MOFs is highly desired. Here, a novel strategy is reported for synthesizing single‐crystalline ordered macro‐microporous MOFs by monodentate‐ligand‐induced in situ crystallization within a 3D ordered hard template in a double‐solvent system. A space‐confined growth model is proposed to clarify the shaping effect of the template; the role of the monodentate ligand is also analyzed. Moreover, a carbon material derived from the macro‐microporous MOF inherits the ordered interconnected macroporous structure. The improved diffusion and lower resistance, as well as the structural robustness, endow the derivative carbon material with superior rate performance and excellent cycling stability when prepared as electrodes for a supercapacitor. It is anticipated that the method will provide new paths to the synthesis of such macro‐microporous materials for applications in energy‐related fields and beyond.

The ability to detect linearly polarized light is essential in the field of angle‐dependent optoelectronics and polarization optical applications. To date, most polarization‐sensitive photodetectors are mainly based on single 2D anisotropic materials, which still suffer from the large dark current, from being external bias driven, and from low anisotropy ratio. To address these obstacles, we fabricated a van der Waals (vdW) GeAs/InSe heterojunction with type‐II band alignment achieving a high‐performance self‐driven polarization‐sensitive photodetector. The heterojunction exhibits excellent rectifying characteristics with a current rectification ratio exceeding 103. By operating in photovoltaic mode at zero bias, the device shows a very low dark current of ∼0.1 picoampere, high photoresponsivity of 357 mA/W, and large photo‐switching ratio of 103, yielding a high specific detectivity of 2 × 1011 Jones and photoelectric conversion efficiency (PCE) up to 8%. Benefiting from the anisotropic structure of the GeAs components, the heterojunctions also exhibit self‐driven polarization‐sensitive photodetection with superior anisotropic photocurrent ratio of ∼18 which surpasses state‐of‐the‐art 2D based polarization‐dependent detectors. This work proposes an effective strategy utilizing the anisotropic/isotropic vdW heterojunctions to enable self‐powered and high‐performance polarization‐sensitive photodetectors, opening a new avenue towards the promising potential applications in polarization‐resolved electronics and photonics.

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