Interface Engineering of the Cu1.5Mn1.5O4/CeO2 Heterostructure for Highly Efficient Electrocatalytic Nitrate Reduction to Ammonia.

The electrochemical nitrate reduction reaction (NO3RR) is considered a sustainable technology to convert the nitrate pollutants to ammonia. However, developing highly efficient electrocatalysts is necessary and challenging given the slow kinetics of the NO3RR with an eight-electron transfer process. Here, a Cu1.5Mn1.5O4 (CMO)/CeO2 heterostructure with rich interfaces is designed and fabricated through an electrospinning and postprocessing technique. Benefiting from the strong coupling between CMO and CeO2, the optimized CMO/CeO2-2 catalyst presents excellent NO3RR performance, with NH3 Faraday efficiency (FE) up to 93.07 ± 1.45% at -0.481 V vs reversible hydrogen electrode (RHE) and NH3 yield rate up to 48.06 ± 1.32 mg cm-2 h-1 at -0.681 V vs RHE. Theoretical calculations demonstrate that the integration of CeO2 with CMO modulates the adsorption/desorption process of the reactants and intermediates, showing a reduced energy barrier in the rate determination step of NO* to N* and achieving an outstanding NO3RR performance.

Synergistic Integration of Amorphous Cobalt Phosphide with a Conductive Channel for Highly Efficient Electrocatalytic Nitrate Reduction to Ammonia.

Electrocatalytic nitrate reduction to ammonia (NO3 RR) is regarded as a viable alternative reaction to "Haber Bosch" process. Nevertheless, it remains a major challenge to explore economical and efficient electrocatalysts that deliver high NH3 yield rates and Faraday efficiencies (FE). Here, it demonstrates the fabrication of a 3D core-shell structured Co-carbon nanofibers (CNF)/ZIF-CoP for NO3 RR application. Benefitting from the distinct electron transport property of Co-CNF and desirable mass transfer ability from amorphous CoP framework, the as-prepared Co-CNF/ZIF-CoP exhibits large NH3 FE (96.8 ± 3.4% at -0.1 V vs reversible hydrogen electrode (RHE)) and high yield rate (38.44 ± 0.65 mg cm-2 h-1 at -0.6 V vs RHE), which are better than Co-CNF/ZIF-crystal CoP. Density functional theory (DFT) calculations further reveal that amorphous CoP presents a lower energy barrier in the rate determination step of the protonation of *NO to produce *NOH intermediates compared with crystal CoP, resulting in a superior NO3 RR performance. Eventually, an aqueous galvanic Zn-NO3 - battery is assembled by using Co-CNF/ZIF-CoP as cathode material to achieve efficient production of NH3 whilst simultaneously supplying electrical power. This work offers a reliable strategy to construct amorphous metal phosphide framework on conducting CNF as efficient electrocatalyst and enriches its promising application for NO3 RR.