Temperature-regulated synthesis of carbonate-pillared zinc-triazolate frameworks for precise molecular recognition

The efficient discrimination of industrially relevant gases, particularly those with closely analogous physicochemical properties, remains a formidable challenge within the realm of adsorptive separation technologies. Achieving satisfactory separation efficiency poses stringent requirements on the precise control over the pore structures of adsorbents. Here we introduce a strategy for the precise modulation of pore structures in a carbonate-pillared Zn-triazolate framework, Zn2(datrz)2CO3 (datrz = 3,5-diamino-1,2,4-triazolate), through the straightforward adjustment of the solvothermal synthesis temperature. Utilizing this approach, we have successfully fabricated a series of Zn2(datrz)2CO3 materials with tunable pore structures while maintaining the framework composition and overall connectivity. These materials demonstrate selective recognition for challenging gas mixtures, including C3H6/C3H8, CO2/CH4, and CO2/N2. Density functional theory (DFT) calculations confirm that the precisely engineered pore environment plays a decisive role on selective gas adsorption. Further, the high reproducibility and scalability of this temperature-controlled synthesis method underscore its immense potential for industrial-scale applications in gas purification and separation processes. This study demonstrates precise tuning of metal-organic framework pore structures by simply adjusting solvothermal temperature, enabling efficient gas separations (C3H6/C3H8, CO2/CH4 and CO2/N2) with good scalability and structural stability.