A Conceptual Approach for the Design of New Catalysts for Ammonia Synthesis: A Metal-Support Interactions Review.

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.

Metal-Organic Frameworks as Formose Reaction Catalysts with Enhanced Selectivity.

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.

Facile Synthesis of Heterogeneous Indium Nanoparticles for Formate Production via CO2 Electroreduction.

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.

Improved Thermochemical Energy Storage Behavior of Manganese Oxide by Molybdenum Doping.

To improve the thermochemical energy storage (TCS) behavior of Mn2O3, several Mn-Mo oxides with varying amounts of MoO3 (0-30 wt%) were prepared by a precipitation method. The physico-chemical properties of the solids were studied by N2 adsorption-desorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), and H2-temperature-programmed reduction (TPR), while their TCS behavior was determined by thermogravimetric analysis coupled with differential scanning calorimetry (TGA-DSC). Apart from Mn2O3 and MoO3 phases, XRD revealed a mixed MnMoO4 phase for MoO3 loadings equal or higher than 1.5 wt%. All samples showed a well-formed coral-like surface morphology, particularly those solids with low MoO3 contents. This coral morphology was progressively decorated with compact and Mo-enriched MnMoO4 particles as the MoO3 content increased. TPR revealed that the redox behavior of Mn2O3 was significantly altered upon addition of Mo. The TCS behavior of Mn2O3 (mostly oxidation kinetics and redox cyclability) was enhanced by addition of low amounts of Mo (0.6 and 1.5% MoO3) without significantly increasing the reduction temperature of the solids. The coral morphology (which facilitated oxygen diffusion) and a smoother transition from the reduced to oxidized phase were suggested to be responsible for this improved TCS behavior. The samples containing 0.6 and 1.5 wt% of MoO3 showed outstanding cyclability after 45 consecutive reduction-oxidation cycles at high temperatures (600-1000 °C). These materials could potentially reach absorption efficiencies higher than 90% at concentration capacity values typical of concentrated solar power plants.

Catalytic Production of Jet Fuels from Biomass.

Concerns about depleting fossil fuels and global warming effects are pushing our society to search for new renewable sources of energy with the potential to substitute coal, natural gas, and petroleum. In this sense, biomass, the only renewable source of carbon available on Earth, is the perfect replacement for petroleum in producing renewable fuels. The aviation sector is responsible for a significant fraction of greenhouse gas emissions, and two billion barrels of petroleum are being consumed annually to produce the jet fuels required to transport people and goods around the world. Governments are pushing directives to replace fossil fuel-derived jet fuels with those derived from biomass. The present mini review is aimed to summarize the main technologies available today for converting biomass into liquid hydrocarbon fuels with a molecular weight and structure suitable for being used as aviation fuels. Particular emphasis will be placed on those routes involving heterogeneous catalysts.

Interplay of Support Chemistry and Reaction Conditions on Copper Catalyzed Methanol Steam Reforming.

A series of Cu catalysts supported on SiO2, Al2O3-SiO2, TiO2 rutile, and Cu/TiO2 anatase metal oxides has been studied for methanol reforming in the vapor phase. The highest activity was obtained on Cu/SiO2 catalysts (5493 µmol H2 min-1·gcat -1) followed by Cu/TiO2 rutile, Cu/Al2O3-SiO2, and anatase. XRD and HRTEM characterization after reaction revealed that on Cu/SiO2 significant sintering occurred during reaction. In contrast, the particle size growth on Cu/TiO2 rutile and anatase was less pronounced, which could be associated with the interaction between Cu clusters and TiO2. Characterization by TGA showed that on Cu/Al2O3-SiO2 the main cause of deactivation was coke deposition.