Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 125, Issue 7, Pages 3758-3763Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.0c10882
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Zirconium phosphate has been studied for its ammonia absorption properties, with calculations showing different standard enthalpy changes for ZrP-NH3 and ZrP-2NH3. P-31 MAS NMR and FT-IR analysis indicated distinct local structures for the absorbed ammonia on ZrP. The study suggests a reaction between nitrogen in ammonia and hydrogen in the phosphate group forming different local structures.
Zirconium phosphate is insoluble in water and has a large ammonia storage capacity with a low ammonia plateau concentration in water. In this study, the thermodynamics of ammonia on zirconium phosphate (ZrP) and the local structure such as the interaction between ammonia and ZrP have been investigated using the temperature dependence of ammonia concentration composition isotherm (CCI) measurements, P-31 magic angle spinning nuclear magnetic resonance (P-31 MAS NMR), and Fourier transform infrared (FT-IR) spectroscopy. The standard enthalpy changes Delta H-0 of ZrP-absorbed ammonia (1 mol(NH3) mol(-1) (ZrP):ZrP-NH3 and 2 mol(NH3) mol(-1) (ZrP):ZrP-2NH(3)) were calculated to be <= -111 and -64 kJ mol(-1)(NH3), respectively. P-31 MAS NMR and FT-IR indicated that the local structures of ZrP-NH3 and ZrP-2NH(3) were different. It was suggested that nitrogen in ammonia reacts with hydrogen in the phosphate group to form a N-H covalent bond in NH4+ having hydrogen bonds, although the number of hydrogen bonds in ZrP-NH3 was smaller than that in ZrP-2NH(3).
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