Ternary and quaternary Cr or Ga-containing ex-LDH catalysts—Influence of the additional oxides onto the microstructure and activity of Cu/ZnAl2O4 catalysts

• Cr and Ga can be introduced into Cu,Zn,Al-LDH precursors.
• Substitution series allow studying the effect of the quaternary promoter.
• The microstructure of the resulting Cu/Al2−xMxO4 (M = Ga, Cr) was characterized.
• The Cu-oxide interactions are gradually affected by Ga and Cr.
• Improved methanol synthesis activity was found for intermediate Ga contents.

The stepwise substitution of Al by Cr and Ga leads to quaternary LDH precursors for Cu/ZnM2O4 (M = Al, Ga, Cr) catalysts. With the substitution of Al by Cr the interaction of the Cu phase with the oxide matrix is gradually weakened, which is caused by the participation of the chromium oxide phase in the redox processes during catalyst preparation. Such reactive Cr oxide matrix is less efficient than the inert Al oxide matrix in stabilizing the special microstructure of Cu/ZnM2O4 catalysts. These weakened interactions led to a lowering of the Cu particle embedment, coinciding with a pronounced Cu crystallite growth during reduction. Both effects partially compensate each other and a maximum in Cu surface area is observed for intermediate Cr contents. In the Ga-substituted catalysts, two distinct Cu species were found for high Ga contents. This is attributed to the presence of partially crystalline spinel and the resulting different strength of interface interaction of the CuO phase with the crystalline and the amorphous oxide. After reduction Cu catalysts with similar average Cu particle sizes as well as Cu surface areas were obtained. In both sample series, the catalytic activity in methanol synthesis does not scale with the Cu surface area and the experiments show that a strong interaction to the oxide is necessary to gain stability and activity of the Cu phase. Al substitution thus confirms that interface interactions between Cu and the oxide seem to beneficially affect the activity of the Cu particles and the optimal catalyst requires a compromise of exposed surface and interface.

Figure optionsDownload high-quality image (259 K)Download as PowerPoint slide