Reaction intermediate-mediated electrocatalyst synthesis favors specified facet and defect exposure for efficient nitrate-ammonia conversion

The electrochemical nitrate (NO3-) reduction reaction (NO3-RR), with much faster kinetics than the nitrogen (N-2) reduction, provides new opportunities to harvest ammonia (NH3) under ambient conditions. However, the NH3 production rate of NO3-RR is still much inferior to that of the industrial Haber-Bosch route due to the lack of robust electrocatalysts for suppressing the hydrogen evolution reaction (HER) at large current densities. Herein, we demonstrate an electrocatalyst synthesis strategy based on the in situ electrochemical reduction of ultrathin copper-oxide nanobelts under NO3-RR conditions, which favorably exposes Cu(100) facets and abundant surface defects, thereby markedly facilitating the NO3-RR yet hindering the HER. We discover that the intermediates of NO3-RR (i.e., N*) can serve as capping agents for controlling the exposed facets during the reduction. Impressively, in alkaline media, the NO3-RR catalyzed by defective Cu(100) facets gives a NH3 yield rate which is 2.3-fold higher than that of the Haber-Bosch process. The synergy of Cu(100) facets and defects, which upshifts the d band center of Cu, is the key to excellent performance. The reaction intermediate-mediated strategy demonstrated in this study offers a fresh concept and robust methodology for directional electrocatalyst synthesis to achieve markedly enhanced performance.

Automated summary

The study demonstrates that in alkaline media, the NH3 yield rate catalyzed by defective Cu(100) facets in NO3-RR is 2.3 times higher than that of the Haber-Bosch process. It is discovered that the intermediates of NO3-RR, N*, can serve as capping agents for controlling the exposed facets during the reduction.