Mechanistic studies on the conversion of NO gas on urea-iron and copper metal organic frameworks at low temperature conditions: in situ infrared spectroscopy and Monte Carlo investigations

Nitrogen oxide (NOx) emissions from high-temperature combustion processes under fuel-lean conditions continue to be a challenge for the energy industry. Selective catalytic reduction ( SCR) is possible using metal oxides and zeolites. There is still a need to identify catalytic materials that are efficient in reducing NOx to environmentally benign nitrogen gas at temperatures lower than 200 degrees C. Metal-organic frameworks (MOFs) have emerged as a class of highly porous materials with unique physical and chemical properties. This study is motivated by the lack of systematic investigations on SCR using MOFs under industrially relevant conditions. Here, we investigate the extent of NO conversion with two commercially available MOFs, Basolite F300 (Fe- BTC) and HKUST-1 (Cu-BTC), mixed with solid urea as a source for the reductant, ammonia gas. For comparison, experiments were also conducted using cobalt ferrite (CoFe2O4) as a non-porous counterpart to relate its reactivity to those obtained from MOFs. Fourier- transform infrared spectroscopy (FTIR) was utilized to identify the gas and surface species in the temperature range of 115-180 degrees C. Computational analysis was performed using Monte Carlo simulations to quantify the adsorption energies of different surface species. The results show that the rate of ammonia production from the in situ solid urea decomposition was higher using CoFe2O4 than Fe-BTC and Cu-BTC and that there was very limited conversion of NO on the mixed solid urea-MOF systems due to site blocking. The main conclusions from this study are that MOFs have limited ability to convert NO under low-temperature conditions and that surface regeneration requires additional experimental steps.