Pd Clusters Loaded with Multivalent Cu Foam for Superior Electrochemical Nitrate Reduction and Selective N≡N Bond Formation.

Abstract

The electrochemical denitrification of nitrate (NO3 - ) in actual wastewater to nitrogen (N2 ) is an effective approach to reversing the current imbalance of the nitrogen cycle and the eutrophication of water. However, electrostatic repulsion between NO3 - and the cathode results in the low efficiency of NO3 - reduction reaction (NO3 RR). Here, density functional theory (DFT) calculations are used as a theoretical guide to design a Pd cluster-loaded multivalent Cu foam (Pd/Cu2 O-CF) electrocatalyst, which achieves a splendid 97.8% NO3 - removal rate, 97.9% N2 selectivity, 695.5mg N g-1 Pd h-1 reduction efficiency, and 60.0% Faradaic efficiency at -1.3V versus SCE. The projected density of states (pDOS) indicates that NO3 - and Pd/Cu2 O-CF are bonded via strong complexation between the O 2p (in NO3 - ) and Cu 3d (in Cu2 O) with the input of voltage, which reduces the electrostatic repulsion and enhances the enrichment of NO3 - on the cathode. In-situ characterizations demonstrate that Pd[H] can reduce Cu2 O to Cu, and subsequently Cu reduces NO3 - to nitrite (NO2 - ) accompanied by in situ reconfiguration of multivalent Cu foam. NO2 - is then transferred to the surface of Pd clusters by the cascade catalysis and accelerates the breaking of N─O bonds to form Pd─N, and eventually achieves the N≡N bond formation.