Electronic Structure Optimization and Proton-Transfer Enhancement on Titanium Oxide-Supported Copper Nanoparticles for Enhanced Nitrogen Recycling from Nitrate-Contaminated Water.

Electrocatalytic reduction of nitrate to NH 3 (NO3RR) on Cu offers sustainable NH 3 production and nitrogen recycling from nitrate-contaminated water. However, Cu affords limited NO3RR activity owing to its unfavorable electronic state and the slow proton transfer on its surface, especially in neutral/alkaline media. Furthermore, although a synchronous "NO3RR and NH 3 collection" system has been developed for nitrogen recycling from nitrate-laden water, no system is designed for natural water that generally contains low-concentration nitrate. Herein, we demonstrate that depositing Cu nanoparticles on a TiO 2 support enables the formation of electron-deficient Cu δ+ species (0 < δ ≤ 2), which are more active than Cu 0 in NO3RR. Furthermore, TiO 2 -Cu coupling induces local electric-field enhancement that intensifies water adsorption/dissociation at the interface, accelerating proton transfer for NO3RR on Cu. With the dual enhancements, TiO 2 -Cu delivers an NH 3 -N selectivity of 90.5%, mass activity of 41.4 mg-N h g Cu -1 , specific activity of 377.8 mg-N h -1 m -2 , and minimal Cu leaching (<25.4 μg L -1 ) when treating 22.5 mg L -1 of NO 3 - -N at -0.40 V, outperforming most of the reported Cu-based catalysts. A sequential NO3RR and NH 3 collection system based on TiO 2 -Cu was then proposed, which could recycle nitrogen from nitrate-contaminated water under a wide concentration window of 22.5-112.5 mg L -1 at a rate of 209-630 mg N m -2 h -1 . We also demonstrated this system could collect 83.9% of nitrogen from NO 3 - -N (19.3 mg L -1 ) in natural lake water.