Challenges and Opportunities of Transition Metal Oxides as Electrocatalysts.

As a sustainable energy technology, electrocatalytic energy conversion and storage has become increasingly prominent. The oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), nitrogen reduction reaction (NRR), and carbon dioxide reduction reaction (CO2 RR) are the key steps in the industrial applications of energy conversion and storage. Compared to the widely used precious metal catalysts, less-noble transition metal oxides (TMOs) and TMO-like materials have attracted broad attention as electrocatalysts in the above reactions. In this concept, we summarize the challenges and opportunities of some typical TMOs in electrocatalysis, and modification strategies of TMOs as electrocatalysts are discussed.

A simple hydrothermal synthesis of an oxygen vacancy-rich MnMoO4 rod-like material and its highly efficient electrocatalytic nitrogen reduction.

Electrocatalytic nitrogen reduction (NRR) for artificial ammonia synthesis under ambient conditions is considered a promising alternative to the traditional Haber-Bosch process. However, it still faces multiple challenges such as the difficulty of N2 adsorption and activation and limited Faraday efficiency. In this work, a bimetallic oxide MnMoO4 was prepared by a hydrothermal method and low temperature calcination. The influence of the sintering temperature on the microstructure (crystallinity and oxygen vacancies) of the oxide and its NRR properties were systematically explored. The results showed that MnMoO4 sintered at 500 °C had the highest concentration of OVs and showed excellent NRR performance, with the highest NH3 yield (up to 12.28 µg h-1 mgcat-1), high Faraday efficiency (23.04% at -0.30 V vs. RHE), and good stability at -0.40 V vs. RHE, and the catalytic performance was about two times higher than that of Mn2O3 and MoO3. It is also superior to other bimetallic oxide NRR electrocatalysts reported in some cases. In addition, we also explored the ratio between Mn and Mo metals, and the catalytic effect was the best when Mn : Mo = 1 : 1. Due to the synergistic effect between Mn and Mo metals and the large number of OVs present internally, the catalytic activity for the NRR was largely improved. This study suggests that the bimetallic oxide MnMoO4 may be a promising NRR electrocatalyst.