Solid-State NMR Demonstrates Urea Entrapment in Biochar Composites for Slow-Release Nitrogen Fertilizers

In recent years, biochar loaded with urea has been proposed as a promising N-rich fertilizer with both high-N capacity and slow release. Understanding the interaction between urea and biochar at the molecular level is key to product design. Solid-state NMR (SSNMR) spectroscopy is a particularly powerful method to probe molecular composition and interactions within the bulk of materials. The objective of this work was to identify molecular structures and interactions when urea is loaded into and released from biochar. To do so, we carried out SSNMR investigations of biochar loaded with 13C and 15N isotopically enriched urea. Biochar-urea composites were prepared both with a saturated aqueous urea solution (BUs) and with molten urea (BUm). SSNMR analysis revealed that urea is predominantly in a paracrystalline form on the biochar surface or physically entrapped within biochar pores. In BUm, products of the thermal degradation of urea were also detected, mainly in the form of biuret. Water-immersion experiments showed that 78 and 64% of the urea contained in BUs and BUm is released, respectively, after 24 h, demonstrating substantial retention of urea. The residual urea is mainly physically confined in the biochar pores. In the case of BUm, urea thermal degradation species are also partially retained.