Aluminum Nitride Hydrolysis Enabled by Hydroxyl-Mediated Surface Proton Hopping

Aluminum nitride (AIN) is used extensively in the semiconductor industry as a high-thermal-conductivity insulator, but its manufacture is encumbered by a tendency to degrade in the presence of water. The propensity for AIN to hydrolyze has led to its consideration as a redox material for solar thermochemical ammonia (NH3) synthesis applications where AIN would be intentionally hydrolyzed to produce NH3 and aluminum oxide (Al2O3), which could be subsequently reduced in nitrogen (N-2) to reform AIN and reinitiate the NH3 synthesis cycle. No quantitative, atomistic mechanism by which AlN, and more generally, metal nitrides react with water to become oxidized and generate NH3 yet exists. In this work, we used density-functional theory (DFT) to examine the reaction mechanisms of the initial stages of AIN hydrolysis, which include: water adsorption, hydroxyl-mediated proton diffusion to form NH3, and NH3 desorption. We found activation barriers (E-a) for hydrolysis of 330 and 359 kJ/mol for the cases of minimal adsorbed water and additional adsorbed water, respectively, corroborating the high observed temperatures for the onset of steam AIN hydrolysis. We predict AlN hydrolysis to be kinetically limited by the dissociation of strong Al-N bonds required to accumulate protons on surface N atoms to form NH3. The hydrolysis mechanism we elucidate is enabled by the diffusion of protons across the AlN surface by a hydroxyl-mediated Grotthuss mechanism. A comparison between intrinsic (E-a = 331 kJ/mol) and mediated proton diffusion (E-a = 89 kJ/mol) shows that hydroxyl-mediated proton diffusion is the predominant mechanism in AIN hydrolysis. The large activation barrier for NH3 generation from AIN (E-a = 330 or 359 kJ/mol, depending on water coverage) suggests that in the design of materials for solar thermochemical ammonia synthesis, emphasis should be placed on metal nitrides with less covalent metal nitrogen bonds and, thus, more-facile NH3 liberation.