Stable amorphous georgeite as a precursor to a high-activity catalyst .

Copper and zinc form an important group of hydroxycarbonate minerals that include zincian malachite, aurichalcite, rosasite and the exceptionally rare and unstable—and hence little known and largely ignored1—georgeite. The first three of these minerals are widely used as catalyst precursors2, 3, 4 for the industrially important methanol-synthesis and low-temperature water–gas shift (LTS) reactions5, 6, 7, with the choice of precursor phase strongly influencing the activity of the final catalyst. The preferred phase2, 3, 8, 9, 10 is usually zincian malachite. This is prepared by a co-precipitation method that involves the transient formation of georgeite11; with few exceptions12 it uses sodium carbonate as the carbonate source, but this also introduces sodium ions—a potential catalyst poison. Here we show that supercritical antisolvent (SAS) precipitation using carbon dioxide (refs 13, 14), a process that exploits the high diffusion rates and solvation power of supercritical carbon dioxide to rapidly expand and supersaturate solutions, can be used to prepare copper/zinc hydroxycarbonate precursors with low sodium content. These include stable georgeite, which we find to be a precursor to highly active methanol-synthesis and superior LTS catalysts. Our findings highlight the value of advanced synthesis methods in accessing unusual mineral phases, and show that there is room for exploring improvements to established industrial catalysts

Structure sensitivity of Cu and CuZn catalysts relevant to industrial methanol synthesis

For decades it has been debated whether the conversion of synthesis gas to methanol over copper catalysts is sensitive or insensitive to the structure of the copper surface. Here we have systematically investigated the effect of the copper particle size in the range where changes in surface structure occur, that is, below 10 nm, for catalysts with and without zinc promotor at industrially relevant conditions for methanol synthesis. Regardless of the presence or absence of a zinc promotor in the form of zinc oxide or zinc silicate, the surface-specific activity decreases significantly for copper particles smaller than 8 nm, thus revealing structure sensitivity. In view of recent theoretical studies we propose that the methanol synthesis reaction takes place at copper surface sites with a unique configuration of atoms such as step-edge sites, which smaller particles cannot accommodate.