Hierarchical porous metal–organic frameworks (HP-MOFs) with tunable porosity are highly valuable for many applications. Here, we developed a versatile solvothermal method to synthesize various HP-MOFs, such as Cu–BTC and ZIF-8, by using an organic amine as the template. The resulting HP-MOF products were characterized by a complementary combination of X-ray powder diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption–desorption isotherms, pore size distributions analysis, thermogravimetric analysis, and density functional theory calculations. The results indicated that the obtained HP-MOF products had high thermal stability and contained multimodal hierarchically porous structures with mesopores or macropores interconnected with micropores. In addition, the porosities of the produced HP-MOFs could be easily tuned by controlling the amount of the template. The introduced organic amine served as the template to direct the formation of mesopores and macropores. Furthermore, the synthesis route is highly versatile as other organic amines (e.g., N,N-dimethylhexadecylamine and N,N-dimethyltetradecylamine) can also be used as templates to synthesize HP-MOFs. The method developed in this work may offer a new direction to synthesize various stable HP-MOFs with tunable porosities for a wide range of applications.

A simple, rapid and versatile method was developed to increase the pore sizes and pore volumes of microporous MOFs (HKUST-1, ZIF-8, ZIF-67, and ZIF-90) by employing organic amine as the template. The resultant hierarchically porous HKUST-1 exhibited significantly enhanced adsorption capacities and faster diffusion rates for CH ₄ and CO ₂ gas storage.

We report a facile, green, and versatile synthetic route that exploits hydroxy double salt (HDS)–template synergy to achieve hierarchically structured metal–organic frameworks (H-MOFs) with high space–time yields (STYs). Hierarchically structured HKUST-1 and ZIF-8 were synthesized using the cooperative template strategy within 30 min (crystallization time). The resulting MOF products exhibited multimodal, hierarchically porous structures with meso-/macropores interconnected with micropores, as revealed by scanning electron microscopy, transmission electron microscopy, N₂ adsorption–desorption isotherms, and pore size distributions. The porosities of the produced H-MOFs varied with the amount and type of template. The synergistic effect of the HDS and template on meso-/macropore generation was elucidated. The synergistic effect disclosed here dramatically extends the choice of templates for H-MOF synthesis at room temperature and pressure. Furthermore, the rapid synthetic method is readily scalable with an STY of up to 2366 kg m⁻³ d⁻¹, a new record for the synthesis of hierarchically structured HKUST-1. The green, versatile, and sustainable method developed in this work provides a new direction for the rapid synthesis of various H-MOFs with tuneable porosities and high STYs for a wide range of applications.