ABSTRACT
The growing interest in green ammonia production has spurred the development of new catalysts with the potential to carry out the Haber-Bosch process under mild pressure and temperature conditions. While there is a wide experimental background on new catalysts involving transition metals, supports and additives, the fundamentals behind ammonia synthesis performance on these catalysts remained partially unsolved. Here, we review the most important works developed to date and analyze the traditional catalysts for ammonia synthesis, as well as the influence of the electron transfer properties of the so-called 3rd-generation catalysts. Finally, the importance of metal-support interactions is highlighted as an effective pathway for the design of new materials with potential to carry out ammonia synthesis at low temperatures and pressures.
ABSTRACT
The formose reaction is an autocatalytic series of aldol condensations that allows one to obtain monosaccharides from formaldehyde. The formose reaction suffers from a lack of selectivity, which hinders practical applications at the industrial level. Over the years, many attempts have been made to overcome this selectivity issue, with modest results. Heterogeneous porous catalysts with acid-base properties, such as Metal-Organic Frameworks (MOFs), can offer advantages compared to homogeneous strong bases (e.g., calcium hydroxide) for increasing the selectivity of this important reaction. For the very first time, four different Zeolite Imidazolate Frameworks are presented in this work as catalysts for the formose reaction in liquid phase, and their catalytic performances were compared with those of the typical homogeneous catalyst (i.e., calcium hydroxide). The heterogeneous nature of the catalysis, the possible contribution of leached metal or linkers to the solution, and the stability of the materials were investigated. The porous structure of these solids and their mild basicity make them suitable for obtaining enhanced selectivity at 30% formaldehyde conversion. Most of the MOFs tested showed low structural stability under reaction conditions, thereby indicating the need to search for new MOF families with higher robustness. However, this important result opens the path for future research on porous heterogeneous basic catalysts for the formose reaction.
ABSTRACT
In this study, a simple and scalable method to obtain heterogeneous indium nanoparticles and carbon-supported indium nanoparticles under mild conditions is described. Physicochemical characterization by X-ray diffraction (XRD), X-ray photoelectron microscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed heterogeneous morphologies for the In nanoparticles in all cases. Apart from In0, XPS revealed the presence of oxidized In species on the carbon-supported samples, whereas these species were not observed for the unsupported samples. The best-in-class catalyst (In50/C50) exhibited a high formate Faradaic efficiency (FE) near the unit (above 97%) at -1.6 V vs. Ag/AgCl, achieving a stable current density around -10 mA·cmgeo-2, in a common H-cell. While In0 sites are the main active sites for the reaction, the presence of oxidized In species could play a role in the improved performance of the supported samples.
