TiO2/CeO2 Frame with Enriched Oxygen Vacancies and Hetero‐Interfaces for Efficient Electrochemical N2 Reduction

Abstract Electrochemical nitrogen reduction reaction (NRR) under ambient conditions offers an environmentally benign and sustainable alternative for NH 3 synthesis. Exploring highly active and robust NRR electrocatalysts is one of the prerequisites for developing sustainable N 2 /NH 3 cycle systems. In this work, a surface chemistry rich TiO 2 /CeO 2 frame is developed for electrochemical NRR, which is composed of ultrathin TiO 2 nanosheets supported with CeO 2 nanoparticles. Its unique porous framework as well as formed plentiful oxygen vacancies (OVs) and hetero‐interfaces collectively facilitate the adsorption/activation of N 2 and transfer of electrons and protons. The catalyst can attain a high NH 3 yield rate of 8.8 μg h −1 mg −1 cat. and a Faradaic efficiency of 6.8 % at −0.25 V versus reversible hydrogen electrode, comparable with other reported Ti‐based and OVs‐contained catalysts. Moreover, the TiO 2 /CeO 2 can maintain high durability over repeated 20 cycles. Therefore, this work heralds a new paradigm of fabricating framework‐structured catalyst with enriched hetero‐interfaces and defects toward effective and sustainable NH 3 synthesis.