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.

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.

A high performance barium-promoted cobalt catalyst supported on magnesium-lanthanum mixed oxide for ammonia synthesis.

Ammonia synthesis was performed over a barium-promoted cobalt catalyst supported on magnesium-lanthanum mixed oxide. The rate of NH3 formation over this catalyst was about 3.5 times higher than that over the unpromoted catalyst at 9 MPa and 400 °C. Furthermore, no sign of thermal deactivation was observed during long-term overheating at 600 °C for 360 h. The results of physicochemical studies, including XRPD, DRIFTS, H2-TPD, CO2-TPD, Nads + H2 TPSR and kinetic analysis, revealed that the addition of Ba promoter increased the surface basicity of the catalyst and modified the adsorption properties of the Co surface towards H2 and NH3. The decreased adsorption strength of the corresponding sites towards hydrogen and ammonia resulted in greater availability of active sites in the Ba-promoted cobalt catalyst. These characteristics are considered to have a profound effect on the performance of this catalyst in NH3 synthesis.

On the Sensitivity of the Ni-rich Layered Cathode Materials for Li-ion Batteries to the Different Calcination Conditions.

Ni-rich layered oxides, i.e., LiNi0.6Mn0.2Co0.2O2 (NMC622) and LiNiO2 (LNO), were prepared using the two-step calcination procedure. The samples obtained at different calcination temperatures (750-950 °C for the NMC622 and 650-850 °C for the LNO cathode materials) were characterized using nitrogen physisorption, PXRD, SEM and DLS methods. The correlation of the calcination temperature, structural properties and electrochemical performance of the studied Ni-rich layered cathode materials was thoroughly investigated and discussed. It was determined that the optimal calcination temperature is dependent on the chemical composition of the cathode materials. With increasing nickel content, the optimal calcination temperature shifts towards lower temperatures. The NMC-900 calcined at 900 °C and the LNO-700 calcined at 700 °C showed the most favorable electrochemical performances. Despite their well-ordered structure, the materials calcined at higher temperatures were characterized by a stronger sintering effect, adverse particle growth, and higher Ni2+/Li+ cation mixing, thus deteriorating their electrochemical properties. The importance of a careful selection of the heat treatment (calcination) temperature for each individual cathode material was emphasized.