Promotion of binary nitride catalysts: Isothermal N-2 adsorption, microkinetic model, and catalytic ammonia synthesis activity

作者：Boisen A; Dahl S; Jacobsen CJH^*

来源：Journal of Catalysis, 2002, 208(1): 180-186.

DOI：10.1006/jcat.2002.3571

• ammonia synthesis
• microkinetic analysis
• dinitrogen adsorption
• promotion
• nitride catalyst

The kinetics of ammonia synthesis and N-2 dissociation over cesium-promoted Co3Mo3N are studied. The results support recent DFT calculations and explain why Co3Mo3N shows a higher ammonia synthesis activity than either constituting metal. The ammonia synthesis activity of cesium-promoted Co3Mo3N is reported for a series of conditions, with H-2 : N-2 ratios of both 3 : 1 and 1 : 1, total pressures of 50, 25, and 10 bar, and temperatures from 593 to 713 K. Isothermal N2 adsorption experiments were carried out and the results were well described by a simple model. The total number of surface sites on the catalyst capable of binding nitrogen was found to be approximately 30 mumol/g of catalyst. When only 1% of these surface sites is active for N-2 dissociation, the initial sticking coefficient, s(0), of dinitrogen on the active sites was found to be s(0) = 0.1727 (.) exp((-42.8 +/- 5 kJ/mol)/RT). This result was used as input to a microkinetic model for ammonia synthesis where it was assumed that N* and H* are the only surface intermediates. In this way it was possible to obtain a good fit to the ammonia synthesis activity data with the nitrogen-binding energy as the only adjustable parameter.

• 出版日期2002-5-15