Co nanoparticles supported on mixed magnesium-lanthanum oxides: effect of calcium and barium addition on ammonia synthesis catalyst performance.

The synthesis of ammonia in the Haber-Bosch process produces millions of tons of ammonia annually needed for producing fertilisers required to feed the growing population. Although this process has been optimised extensively, it still accounts for about 2% of global energy consumption. It is, therefore, desirable to develop an efficient ammonia synthesis catalyst. Over the last decades, many attempts have been made to improve the ammonia synthesis catalyst efficiency under mild conditions. Here, we studied the effect of adding Ca and Ba to the cobalt ammonia synthesis catalyst. The combination of the different experimental results allows concluding that Ca served as an inactive additive, whereas Ba served as an electronic promoter. The Ca addition did not change the textural, structural, and chemisorptive properties of the Ca-doped Co catalyst. On the other hand, the Ba addition had a major effect on the nature of active Co sites. It contributed to the formation of new active sites for hydrogen and nitrogen adsorption and dissociation. Barium addition also contributed to the generation of new basic sites, particularly the strong ones. These unique characteristics were ascribed to the formation of Co(core)-BaO(shell) structures. It is likely that the donation of electrons from BaO to N2 via Co markedly promoted ammonia synthesis. This catalyst exhibited ammonia synthesis activity 4 times higher than that of the undoped Co catalyst and 2 times higher than that of the industrial Fe catalysts under identical conditions.

Influence of Magnesium Oxide on the Structure and Catalytic Activity of the Wustite Catalyst for Ammonia Synthesis.

The influence of a magnesium oxide admixture on the activation process and catalytic activity of the iron catalyst with a wustite structure was investigated during the ammonia synthesis reaction. The incorporation of magnesium oxide into wustite grains is considered to be a structure-forming and activating promoter. It stabilizes the α-Fe structure and increases the activity of the catalysts in the ammonia synthesis reaction. Moreover, magnesium oxide forms a solid solution with the wustite, which slows down the reduction of a catalyst precursor. Similar to calcium and potassium compounds, magnesium oxide is present on the α-Fe surface of the active form of the catalyst. The optimum MgO concentration in the catalyst structure was determined to be 1.2% wt.

On the effect of metal loading on the performance of Co catalysts supported on mixed MgO-La2O3 oxides for ammonia synthesis.

Synthesis of ammonia from nitrogen and hydrogen is one of the largest manmade chemical processes, with annual production reaching 170 million tons. The Haber-Bosch process is the main industrial method for producing ammonia, which proceeds at high temperatures (400-600 °C) and pressures (20-40 MPa) using an iron-based catalyst. It is thus highly desirable to develop new catalysts with sufficient activity and stability under mild conditions. In this work, we report cobalt catalysts supported on magnesium-lanthanum mixed oxide with different Co loading amounts synthesised via a simple wet impregnation method. We have found a clear relationship between the ammonia synthesis rate and the Co loading amount. Specifically, the NH3 synthesis rate increased on increasing cobalt loading and reached a maximum at 40 wt% Co deposition. A further increase in Co loading did not change the activity significantly. Interestingly, the surface-specific activity (TOF) remained almost unchanged regardless of the Co loading amount in the catalysts. It revealed that the resultant ammonia synthesis rate over the studied catalysts did not depend on the size and structure of Co nanoparticles but strongly on the Co loading amount. Finally, it is believed that the use of this type of catalyst will be a starting point toward energy-efficient ammonia production.

Nitriding and Denitriding of Nanocrystalline Iron System with Bimodal Crystallite Size Distribution.

An artificially prepared nanocrystalline iron sample with bimodal crystallite size distribution was nitrided and denitrided in the NH3/H2 atmosphere at 350 °C and 400 °C. The sample was a 1:1 mass ratio mixture of two iron samples with mean crystallite sizes of 48 nm and 21 nm. Phase transformations between α-Fe, γ'-Fe4N and ε-Fe3-2N were observed by the in situ X-ray powder diffraction method. At selected steps of nitriding or denitriding, phase transformations paused at 50% of mass conversion and resumed after prominent variation of the nitriding atmosphere. This effect was attributed to the separation of phase transformations occurring between sets of iron crystallites of 48 nm and 21 nm, respectively. This was due to the Gibbs-Thomson effect, which establishes the dependence of phase transformation conditions on crystallite sizes.

Ammonolysis of Cobalt Molybdenum Oxides - In Situ XRD Study.

The reduction of cobalt molybdenum oxide under an ammonia atmosphere resulting in the formation of ternary interstitial nitride Co3Mo3N was studied. Intermediate phases were identified by an in situ powder X-ray diffraction using a reaction chamber. It was supplemented by a thermogravimetric analysis of the process. The presence of intermediate phases, CoMoO4, Co2Mo3O8, Mo2N, metallic cobalt, and Co2Mo3N, was observed. A synthesis route of Co3Mo3N by an ammonolysis method was proposed.