Greener and facile synthesis of Cu/ZnO catalysts for CO₂hydrogenation to methanol by urea hydrolysis of acetates

Cu/ZnO-based catalysts for methanol synthesis by COx hydrogenation are widely prepared via co-precipitation of sodium carbonates and nitrate salts, which eventually produces a large amount of wastewater from the washing step to remove sodium (Na+) and/or nitrate (NO3-) residues. The step is inevitable since the remaining Na+ acts as a catalyst poison whereas leftover NO3- induces metal agglomeration during the calcination. In this study, sodium- and nitrate-free hydroxy-carbonate precursors were prepared via urea hydrolysis co-precipitation of acetate salt and compared with the case using nitrate salts. The Cu/ZnO catalysts derived from calcination of the washed and unwashed precursors show catalytic performance comparable to the commercial Cu/ZnO/Al2O3 catalyst in CO2 hydrogenation at 240-280 °C and 331 bar. By the combination of urea hydrolysis and the nitrate-free precipitants, the catalyst preparation is simpler with fewer steps, even without the need for a washing step and pH control, rendering the synthesis more sustainable. This journal is ChemE/Catalysis Engineerin

Comprehensive Review on Two-Step Thermochemical Water Splitting for Hydrogen Production in a Redox Cycle

The interest in and need for carbon-free fuels that do not rely on fossil fuels are constantly growing from both environmental and energetic perspectives. Green hydrogen production is at the core of the transition away from conventional fuels. Along with popularly investigated pathways for hydrogen production, thermochemical water splitting using redox materials is an interesting option for utilizing thermal energy, as this approach makes use of temperature looping over the material to produce hydrogen from water. Herein, two-step thermochemical water splitting processes are discussed and the key aspects are analyzed using the most relevant information present in the literature. Redox materials and their compositions, which have been proven to be efficient for this reaction, are reported. Attention is focused on non-volatile redox oxides, as the quenching step required for volatile redox materials is unnecessary. Reactors that could be used to conduct the reduction and oxidation reaction are discussed. The most promising materials are compared to each other using a multi-criteria analysis, providing a direction for future research. As evident, ferrite supported on yttrium-stabilized zirconia, ceria doped with zirconia or samarium and ferrite doped with nickel as the core and an yttrium (III) oxide shell are promising choices. Isothermal cycling and lowering of the reduction temperature are outlined as future directions towards increasing hydrogen yields and improving the cyclability.ChemE/Catalysis Engineerin