COORDINATION OF CU- AN AB-INITIO DENSITY-FUNCTIONAL STUDY( IONS TO ZEOLITE FRAMEWORKS STRONGLY ENHANCES THEIR ABILITY TO BIND NO2 )

Comparison is made of the interaction of NO2 with Cu+ ions in the gas phase and inside zeolites using density functional theory (B3LYP funct ional). The zeolite is represented by a tritetrahedra model embedded i n the periodic structure of zeolite ZSM-5 and by a free space cluster model. Both models yield virtually the same results. Cu+ is coordinate d to two oxygen atoms of the zeolite framework only. For the complexes with NO2, several minima and transition structures on the potential e nergy surfaces are localized. The naked Cu+ ion preferentially binds N O2 in the eta(1)-O trans mode, while in zeolites the Cu+ site binds NO 2 in a (2) eta-O,O coordination. For the 2 eta-O,O structure the bindi ng is three to four times stronger in the zeolite (43 kcal/mol) than i n the gas phase which is due to a three-body zeolite framework-Cu+ ion -NO2 interaction. d(10)-s(1)d(9) promotion leads to a more favorable o rbital interaction between Cu+ and NO2 in the (2)A '' state and, due t o reduced repulsion, to a stronger electrostatic interaction between C u+ and the zeolite framework.