Highly Stable and Efficient Catalyst with In Situ Exsolved Fe–Ni Alloy Nanospheres Socketed on an Oxygen Deficient Perovskite for Direct CO2 Electrolysis

The massive emission of carbon dioxide (CO2), the major portion of greenhouse gases, has negatively affected our ecosystem. Developing new technologies to effectively reduce CO2 emission or convert CO2 to useful products has never been more imperative. In response to this challenge, we herein developed novel in situ exsolved Fe–Ni alloy nanospheres uniformly socketed on an oxygen-deficient perovskite [La(Sr)Fe(Ni)] as a highly stable and efficient catalyst for the effective conversion of CO2 to carbon monoxide (CO) in a high-temperature solid oxide electrolysis cell (HT-SOEC). The symmetry between the reduction and reoxidation cycles of this catalyst indicates its good redox reversibility. The cathodic reaction kinetics for CO2 electrolysis is significantly improved with a polarization resistance as low as 0.272 Ω cm2. In addition, a remarkably enhanced current density of 1.78 A cm–2, along with a high Faraday efficiency (∼98.8%), was achieved at 1.6 V and 850 °C. Moreover, the potentiostatic stability test of up to 100 h showed that the cell was stable without any noticeable coking in a CO2/CO (70:30) flow at an applied potential of 0.6 V (vs OCV) and 850 °C. The increased oxygen vacancies together with the in situ exsolved nanospheres on the perovskite backbone ensures sufficiently active sites and consequently improves the electrochemical performance for the efficient CO2 conversion. Therefore, this newly developed perovskite can be a promising cathode material for HT-SOEC. More generally, this study points to a new direction to develop highly efficient catalysts in the form of the perovskite oxides with perfectly in situ exsolved metal/bimetal nanospheres.