Non-rigid metal–oxygen bonding empowered nitrate reduction on ruthenium catalysts

Abstract

Electrocatalytic nitrate reduction (NitRR) offers exciting potential for mass production of ammonia (NH3) from renewables. However, the rigidity of metal−ligand bonds in most electrocatalysts renders them unable to survive the structural transformations required for NitRR. Herein, we establish a type of non-rigid metal−oxygen bonds by employing graphene oxide (GO) sheets as a 'micron-scale' ligand for transition metals (TM). Because of being confined to the interfaces between GO and TM, the oxygenated groups in GO can associate with and dissociate from the TM in response to reaction dynamics. As a proof-of-concept demonstration, an electrocatalyst was developed by dispersing nanoscale ruthenium (Ru) on graphene oxide (GO) and utilizing two-dimensional MXene to compensate for the low electrical conductivity of GO. This electrocatalyst exhibits a maximum NH3 yield of over 5 mg cm−2 h−1, with almost 100 % current-to-NH3 efficiency, far outperforming the performance of most reported Ru-based materials. What's even more remarkable is the achievement of a record-breaking performance: a 200-hour stable electrolysis with a NH3 yield of 40.2 mg cm−2 h−1, using a membrane electrode reactor. Our experimental and theoretical investigations further reveal the non-rigidity of the Ru–O bonds and how they self-regulate to adapt to diverse intermediates involved in NitRR. This work provides an approach to fabricate a high-performance electrocatalyst featuring reversible and non-rigid metal−oxygen bonds, opening new possibilities for practical nitrate electrolysis.