Generation of Pseudorutile Oxide as the Cathode for Direct Electrolysis of CO.

The conversion of CO into CO in high-temperature solid oxide electrolysis cells (SOECs) is an attractive route for the CO utilization using the intermittent renewables. The low-cost and highly catalytic cathode is important for the direct electrolysis of pure CO. In this study, non-perovskite FeMgTiNbMoO oxides (denoted as Mo- when is equal to 0, 0.1, and 0.2) are evaluated as the cathode of an SOEC for the direct electrolysis of CO. Mo doping converted the wolframite Mo-0 into an -PbO-type with cation disordering, while further doping to Mo-0.2 showed a wolframite with cation ordering again. The SOEC with Mo-0.2 as the cathode exhibits the best electrochemical performance for the direct electrolysis of CO as a large portion of the oxide converted into oxygen-deficient pseudorutile-type oxide with a nominal formula of MO (M = cation). The pseudorutile, a crystallographic shear phase of rutile, can be obtained after 60 h of direct electrolysis in CO at a 1.3 V bias rather than a reduction under 5% H. The SOEC with Mo-0.2 as the cathode imparted a stable current density of 0.45 A cm, which could be related to the production of pseudorutile decorated with nanoparticles of MoO. These results show that molybdenum doping is an effective strategy for developing oxygen-deficient rutile (pseudorutile) for the electrolysis of CO.