In situ formation of oxygen vacancy in perovskite Sr(0.95)Ti(0.8)Nb(0.1)M(0.1)O3 (M = Mn, Cr) toward efficient carbon dioxide electrolysis.

In this work, redox-active Mn or Cr is introduced to the B site of redox stable perovskite Sr(0.95)Ti(0.9)Nb(0.1)O3.00 to create oxygen vacancies in situ after reduction for high-temperature CO2 electrolysis. Combined analysis using X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis confirms the change of the chemical formula from oxidized Sr(0.95)Ti(0.9)Nb(0.1)O3.00 to reduced Sr(0.95)Ti(0.9)Nb(0.1)O2.90 for the bare sample. By contrast, a significant concentration of oxygen vacancy is additionally formed in situ for Mn- or Cr-doped samples by reducing the oxidized Sr(0.95)Ti(0.8)Nb(0.1)M(0.1)O3.00 (M = Mn, Cr) to Sr(0.95)Ti(0.8)Nb(0.1)M0.1O2.85. The ionic conductivities of the Mn- and Cr-doped titanate improve by approximately 2 times higher than bare titanate in an oxidizing atmosphere and 3-6 times higher in a reducing atmosphere at intermediate temperatures. A remarkable chemical accommodation of CO2 molecules is achieved on the surface of the reduced and doped titanate, and the chemical desorption temperature reaches a common carbonate decomposition temperature. The electrical properties of the cathode materials are investigated and correlated with the electrochemical performance of the composite electrodes. Direct CO2 electrolysis at composite cathodes is investigated in solid-oxide electrolyzers. The electrode polarizations and current efficiencies are observed to be significantly improved with the Mn- or Cr-doped titanate cathodes.