Rh-MnO Interface Sites Formed by Atomic Layer Deposition Promote Syngas Conversion to Higher Oxygenates

Rhodium (Rh) catalysts are among the major candidates for syngas conversion to higher oxygenates (C₂₊oxy), with manganese (Mn) as a commonly used promoter for enhancing the activity and selectivity toward C₂₊oxy. In this study, we use atomic layer deposition (ALD) to controllably modify Rh catalysts with MnO, by depositing manganese oxide as a support layer or an overlayer, in order to identify the function of the Mn promoter. We also compare the ALD-modified catalysts with those prepared by coimpregnation. An ultrathin MnO support layer shows the most effective enhancement for C₂₊oxy production. Transmission electron microscopy, temperature-programmed reduction, and diffuse reflectance infrared Fourier transform spectroscopy characterization indicates that formation of Rh-MnO interface sites is responsible for the observed activity and selectivity improvements, while ruling out Rh nanoparticle size and alloy or mixed oxide formation as significant contributors. MnO overlayers on Rh appear to suffer from poor stability upon CO adsorption and are less effective than a MnO support layer. Density functional theory (DFT) calculations show that MnO species on the Rh(111) surface lower the transition state energy for CO bond dissociation and stabilize the key transition state for C₂₊oxy synthesis more significantly than that for methane synthesis, leading to enhanced activity and C₂₊oxy selectivity.