Hierarchically Porous Metal–Organic Frameworks-Based Controlled-Release Fertilizer: Improved Nutrient Loading and Rice Growth

Nitrogen (N) and phosphorus (P) play vital roles in crop growth. However, conventional fertilizers exhibit low utilization efficiency, making them prone to causing resource wastage and water eutrophication. Although metal–organic frameworks (MOFs) have shown great potential for application in controlled-release fertilizers (CRFs), currently reported MOF-based CRFs suffer from low nutrient content, which limits their further application. To address this issue, this study synthesized a series of hierarchically porous MOFs, denoted as MIL-156(X), using sodium acetate as a modulator under hydrothermal conditions. These materials were subsequently loaded with urea and phosphate from aqueous solution to form MOFs-based CRFs (N-P-MIL-156(X)). Results indicate that MIL-156(X) retain microporous integrity while incorporating abundant mesopores. Increasing modulator content reduced particle size and average pore diameter but increased specific surface area and adsorption capacity for urea and phosphate. MIL-156-H (with a high modulator content addition) exhibited the highest adsorption capacity, conforming to Langmuir isotherm and pseudo-second-order kinetics. The adsorption mechanisms of urea and phosphate involved hydrogen bonding and the formation of Ca intra-spherical complexes, respectively. N-P-MIL-156-H contained 10.8% N and 16.3% P2O5, with sustained release durations exceeding 42 days (N) and 56 days (P2O5) in an aqueous solution. Pot trials demonstrated significantly higher nutrient use efficiency (N-44.8%, P2O5-16.56%) and a 12.22% yield increase compared to conventional fertilization (N-35.6%, P2O5-13.32%). Thus, N-P-MIL-156-H-based fertilization significantly promotes rice growth and N/P utilization efficiency, offering a promising strategy for developing controlled-release fertilizers and improving nutrient management.