The efficiency of electrochemical nitrogen reduction reaction (eNRR) can be enhanced by modulating the nitrogen adsorption pattern and microenvironment at the active site. The research team developed an efficient electrocatalyst consisting of ultrafine ruthenium nanoclusters with a hydrophobic molecular layer on the surface of two-dimensionalTi3C2TxMXene. This structure not only forms low-energy activated ligand active sites favorable forN2chemisorption, but the hydrophobic molecular layer can modulate the local microenvironment around the catalytic active sites, effectively promoting N2 accumulation and inhibiting the competitive hydrogen-extraction reaction (HER). At a potential of -0.25 V (relative to the reversible hydrogen electrode), the catalyst achieved an ammonia yield of up to 33.5ugh-1mg-1catand a Faraday efficiency of 65.3%, which outperformed previously reportedTi3C2Tx-basedelectrocatalysts. In addition, the research team also gained an in-depth understanding of the thermodynamic and kinetic processes of the catalytic mechanism through density-functional theory (DFT) calculations, which provide important theoretical support for understanding the adsorption and activation processes of nitrogen on the active sites, as well as the kinetics of hydrogen transfer, and further confirm the validity of the experimental observations. This work provides a valuable strategy to enhance the electrochemical catalytic performance by rationally designing the active site and local microenvironment. The related results are published inSmall.
Link to original article:https://doi.org/10.1002/smll.202408111
