In Situ Generation of Pseudorutile Oxide as the Cathode for Direct Electrolysis of CO 2 .

The conversion of CO 2 into CO in high-temperature solid oxide electrolysis cells (SOECs) is an attractive route for the CO 2 utilization using the intermittent renewables. The low-cost and highly catalytic cathode is important for the direct electrolysis of pure CO 2 . In this study, non-perovskite Fe 0.5 Mg 0.25+0.5 x Ti 0.25-0.5 x Nb 1- x Mo x O 4 oxides (denoted as Mo- x when x is equal to 0, 0.1, and 0.2) are evaluated as the cathode of an SOEC for the direct electrolysis of CO 2 . Mo 6+ doping converted the wolframite Mo-0 into an α -PbO 2 -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 2 as a large portion of the oxide converted into oxygen-deficient pseudorutile-type oxide with a nominal formula of M 5 O 9 (M = cation). The pseudorutile, a crystallographic shear phase of rutile, can be obtained after 60 h of direct electrolysis in CO 2 at a 1.3 V bias rather than a reduction under 5% H 2 . The SOEC with Mo-0.2 as the cathode imparted a stable current density of 0.45 A cm -2 , which could be related to the production of pseudorutile decorated with nanoparticles of MoO 2 . These results show that molybdenum doping is an effective strategy for developing oxygen-deficient rutile (pseudorutile) for the electrolysis of CO 2 .