The Active Site of Methanol Synthesis over Cu/ZnO/Al2O3 Industrial Catalysts

Mechanisms in Methanol Catalysis The industrial production of methanol from hydrogen and carbon monoxide depends on the use of copper and zinc oxide nanoparticles on alumina oxide supports. This catalyst is “structure sensitive”; its activity can vary by orders of magnitude, depending on how it is prepared. Behrens et al. (p. 893, published online 19 April; see the Perspective by Greeley) used a combination of bulk and surface-sensitive analysis and imaging methods—along with insights from density functional theory calculations—to study several catalysts, including the one similar to that used industrially. High activity depended on the presence of steps on the copper nanoparticles stabilized by defects such as stacking faults. Partial coverage of the copper nanoparticles with zinc oxide was critical for stabilizing surface intermediates such as HCO and lowering energetic barriers to the methanol product. Catalysis is favored by stepped copper nanoparticles decorated with zinc oxide, which promotes stronger intermediate binding. One of the main stumbling blocks in developing rational design strategies for heterogeneous catalysis is that the complexity of the catalysts impairs efforts to characterize their active sites. We show how to identify the crucial atomic structure motif for the industrial Cu/ZnO/Al2O3 methanol synthesis catalyst by using a combination of experimental evidence from bulk, surface-sensitive, and imaging methods collected on real high-performance catalytic systems in combination with density functional theory calculations. The active site consists of Cu steps decorated with Zn atoms, all stabilized by a series of well-defined bulk defects and surface species that need to be present jointly for the system to work.