Mechanism Investigations on Water Gas Shift Reaction over Cu(111), Cu(100), and Cu(211) Surfaces

Cu-based catalysts are commonly applied in low-temperature water gas shift (WGS) reactions, owing to their low cost and high catalytic activity. The influence of different Cu surfaces on catalytic activity and mechanism over the WGS reaction remains unclear. In this work, the effect of different structures of surfaces on the WGS mechanism is studied using density functional theory (DFT). Three surface terminations (Cu(100), Cu(111), and Cu(211)) of Cu are considered, and the coordination number (CN) of the active Cu site is in the range from 7 to 9. The most stable surface is Cu(211). Then, d-band center values are calculated, which decrease in the following sequence: Cu(211) > Cu(100) > Cu(111). This shows that d-band center values decrease with increasing coordination number. The increase in the centers of the d-band leads to an increase in the adsorption strength of CO and H₂O adsorbates, which is in line with the theory of the d-band center. In addition, the further calculated mechanism for WGS reaction over three different Cu surfaces illustrates that the carboxyl path is the most favorable mechanism, and the rate-determining step is H₂O dissociation. Cu(211) shows excellent WGS catalytic performance, better than the Cu(100) and Cu(111) surfaces. This work provides theoretical insights into the rational design of highly active Cu-based catalysts toward WGS reaction.