An FeIII dinuclear metallacycle complex as a size-selective adsorbent for nitrogenous compounds and a potentially effective ammonia storage material

Abstract

Ammonia has a large volume energy density and consequently high potential for application as a fuel and energy reservoir in the future. In this study, the dinuclear Fe^III metallacycle complex [Fe₂(H₂opba)₂Cl₂(dmso)₂]·2CH₂Cl₂·2dmso (1) with excellent capacity to selectively adsorb ammonia (11.3 mmol g⁻¹) was investigated, demonstrating a strong preference for nitrogenous compounds, especially short-chain amines. The adsorption results suggest that the cavity in the structure of 1 has an essential role in the adsorption mechanism i.e. it is the responsible for size selectivity of 1 during the adsorption process. To better understand the adsorption mechanism of ammonia, 1 was fully characterized before and after adsorption. Thermogravimetric-mass spectrometry (TG-MS) and ammonia isotherm experiments revealed that 8 ammonia molecules were physisorbed by the complex cavity (free ammonia) and 4 ammonia molecules were chemisorbed (coordinated ammonia) per dinuclear metallacycle unit. Further characterization also confirmed the proposed adsorption mechanism, corroborating the structural modification of the compound after its interaction with ammonia; in addition, reuse tests showed that despite a small loss of efficiency, the compound was capable of desorbing most of the ammonia and could be used consecutively for at least three cycles. Thus, 1 is a potential ammonia storage material and adsorbent for the removal of ammonia from effluents.