Mechanosynthesis of Magnesium and Calcium Salt–Urea Ionic Cocrystal Fertilizer Materials for Improved Nitrogen Management

Abstract

Only 47% of the total fertilizer nitrogen applied to the environment is taken up by the plants whereas approximately 40% of the total fertilizer nitrogen lost to the environment reverts back into unreactive atmospheric dinitrogen that greatly affects the global nitrogen cycle including increased energy consumption for NH3 synthesis, as well as accumulation of nitrates in drinking water. In this letter, we provide a mechanochemical method of inorganic magnesium and calcium salt–urea ionic cocrystal synthesis to obtain enhanced stability nitrogen fertilizers. The solvent-free mechanochemical synthesis presented can result in a greater manufacturing process sustainability by reducing or eliminating the need for solution handling and evaporation. NH3 emission testing suggests that urea ionic cocrystals are capable of decreasing NH3 emissions to the environment when compared to pure urea, thus providing implications for a sustainable global solution to the management of the nitrogen cycle.

In situ monitoring of mechanochemical synthesis of calcium urea phosphate fertilizer cocrystal reveals highly effective water-based autocatalysis

“…1,2 Recently, co-crystallization has emerged as a powerful approach to develop new solid forms of fertilizers, which could maximize absorption by crops while minimizing runoff, which negatively impacts the environment and human health via eutrophication. [3][4][5] Urea phosphate is one of the most prevalent fertilizer components for the delivery of critical plant nutrients nitrogen and phosphorus, with the added benet of reducing ammonia losses by enzymatic degradation. 6 The loss of ammonia from urea fertilizers is further reduced by the presence of calcium, another key nutrient for plants, leading to improved formulations for simultaneous delivery of nitrogen, phosphorus and calcium.…”

“…12 Mechanochemistry has been shown to enable synthesis independent of the relative solubilities of reactants, providing an excellent opportunity to form agrochemical cocrystals that are typically based on inexpensive but poorly soluble ionic starting materials. 12 Mechanochemistry enables rapid reactions, such as the green synthesis of calcium urea phosphate, from very poorly soluble inorganic precursors, such as calcium carbonate or calcium hydroxide, 4,13,14 producing innocuous by-products of water and CO 2 ( Fig. 1).…”

Co‐crystal Prediction by Artificial Neural Networks**

“…[4][5][6][7][8][9] Multicomponent crystals therefore find their application in various fields (e.g. fertilizers, [10,11] pigments [12,13] and medicine [14][15][16] ), and play apivotal role in the effective formulation of pharmaceuticals.…”

Co‐crystal Prediction by Artificial Neural Networks**

“…Multicomponent crystals therefore find their application in various fields (e.g. fertilizers, [10, 11] pigments [12, 13] and medicine [14–16] ), and play a pivotal role in the effective formulation of pharmaceuticals.…”