Structure sensitivity of supported ruthenium catalysts for ammonia synthesis

The catalytic ammonia synthesis activities of four supported ruthenium catalysts are reported. It is seen that Ru/MgAl2O4 is more active than two similar Ru/C catalysts, which are significantly more active than Ru/Si3N4. The activity differences cannot be satisfactorily explained solely by the differences in dispersion. Recent results from single crystal studies and DFT calculations have shown that ammonia synthesis over ruthenium catalysts is a very structure sensitive reaction, more so than on iron catalysts. It is suggested that special B5-type sites are primarily responsible for the catalytic activity of the present supported Ru catalysts. It is shown how the number of such B5-type sites depends on the Ru crystal size for a given crystal morphology. We have found that the activity of the Ru/MgAl2O4 catalyst increases significantly during the initial part of a test run. This activity increase is paralleled by the disappearance of crystals smaller than ca. 1.0 nm due to sintering and a resulting formation of larger crystals. We conclude that there exists a lower limit to the desired crystal size of Ru in supported ammonia synthesis catalysts. This is in agreement with a low number of B5-type sites expected for such crystal sizes. Furthermore, we suggest that the support plays a decisive role in controlling the morphology of the Ru crystals and the resulting change in abundance of B5-type sites is the main cause for the significant activity variations observed for Ru catalysts with different supports. Finally, the support may also influence the electronic and catalytic properties of neighboring B5-type sites.