Metal–organic framework effects on tricalcium silicate hydration: Experimental and density functional theory study

Abstract The interaction between metal–organic frameworks (MOFs) and cement hydration remains poorly understood. This study investigates the effects of UiO‐66 and amino‐functionalized UiO‐66‐NH 2 on tricalcium silicate (C 3 S) hydration, the dominant phase in Portland cement. Controlled hydration experiments, combined with inductively coupled plasma atomic emission spectroscopy, X‐ray diffraction, Fourier transform infrared, thermogravimetric analysis, Brunaue–Emmett–Teller (BET), scanning electron microscopy coupled with energy‐dispersive spectroscopy, and density functional theory (DFT) calculations, reveal that carboxyl and amino groups in UiO‐66/UiO‐66‐NH 2 adsorb Ca 2+ , accelerating C 3 S dissolution and enhancing calcium–silicate–hydrate (C–S–H) nucleation while inhibiting portlandite (CH) crystal growth. UiO‐66‐NH 2 exhibits superior promotion due to higher hydrophilicity and stronger Ca 2+ adsorption, supported by DFT adsorption energy and orbital interaction analysis. Quantitative phase analysis and BET results confirm increased C–S–H content and specific surface area with higher MOF dosage. These findings elucidate the mechanistic pathways through which MOF chemistry tailors ion transport, phase composition, and microstructure in cement hydration, offering a strategy for designing functional nanomaterial additives to improve cement‐based materials.