The direct electrochemical nitric oxide reduction reaction (NORR) is an attractive technique for converting NO into NH 3 with low power consumption under ambient conditions. Optimizing the electronic structure of the active sites can greatly improve the performance of electrocatalysts. Herein, we prepare body-centered cubic RuGa intermetallic compounds (i.e., bcc RuGa IMCs) via a substrate-anchored thermal annealing method. The electrocatalyst exhibits a remarkable NH 4+ yield rate of 320.6 μmol h À 1 mg À 1 Ru with the corresponding Faradaic efficiency of 72.3 % at very low potential of À 0.2 V vs. reversible hydrogen electrode (RHE) in neutral media. Theoretical calculations reveal that the electron-rich Ru atoms in bcc RuGa IMCs facilitate the adsorption and activation of *HNO intermediate. Hence, the energy barrier of the potentialdetermining step in NORR could be greatly reduced.
Benefiting from ordered atomic structures and strong d‐orbital interactions, intermetallic compounds (IMCs) are promising electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, the body‐centered cubic IrGa IMCs with atomic donor–acceptor architectures are synthesized and anchored on the nitrogen‐doped reduced graphene oxide (i.e., IrGa/N‐rGO). Structural characterizations and theoretical calculations reveal that the electron‐rich Ir sites are atomically dispersed in IrGa/N‐rGO, facilitating the electron transfer between Ir atoms and adsorbed species, which can efficiently decrease the energy barriers of the potential determining step for both HER and OER. Impressively, the IrGa/N‐rGO||IrGa/N‐rGO exhibits excellent performance for overall water splitting in alkaline medium, requiring a low cell voltage of 1.51 V to achieve 10 mA cm−2, meanwhile, exhibiting no significant degradation for 100 h. This work demonstrates that the rational design of noble metal electrocatalysts with donor–acceptor architectures is beneficial for catalytic reactions in energy conversion applications.
The electrocatalytic nitrate reduction reaction (NO3
–RR) to ammonia (NH3) under ambient
conditions not only has the benefit of lowering energy consumption,
but also helps remove nitrate contamination. Inspired by the unique
structure of nitrate/nitrite reductase with the active spheroproteins
encapsulated by larger enzymes, herein, we develop an in situ synthetic strategy for the construction of metal cluster–conductive
metal–organic framework (MOF) composite electrocatalysts. The
metallic Cu clusters are filled into the mesopores of a conductive
copper-based MOF (i.e., CuHHTP); meanwhile, CuHHTP
with a porous structure provides an internal environment to limit
the growth of metallic Cu clusters with an ultrasmall size (i.e., 1.5 ± 0.2 nm) and restrains their aggregation.
The obtained Cu@CuHHTP exhibits superb performance for NO3
–RR. In a neutral electrolyte with 500 ppm NO3
–, Cu@CuHHTP shows a high NO3
– conversion of 85.81% and a selectivity for NH3 of 96.84%. 15N isotope labeling experiments confirm
that the formation of NH3 originates from the process of
NO3
–RR. Theoretical calculations confirm
that Cu clusters are the active sites in the composite electrocatalysts,
in which the proper d-band center and the “accept–donate”
mechanism in charge transfer are the key factors for the improvement
of the electrocatalytic performance.
The direct electrochemical nitric oxide reduction reaction (NORR) is an attractive technique for converting NO into NH3 with low power consumption under ambient conditions. Optimizing the electronic structure of the active sites can greatly improve the performance of electrocatalysts. Herein, we prepare body‐centered cubic RuGa intermetallic compounds (i.e., bcc RuGa IMCs) via a substrate‐anchored thermal annealing method. The electrocatalyst exhibits a remarkable NH4+ yield rate of 320.6 μmol h−1 mg−1Ru with the corresponding Faradaic efficiency of 72.3 % at very low potential of −0.2 V vs. reversible hydrogen electrode (RHE) in neutral media. Theoretical calculations reveal that the electron‐rich Ru atoms in bcc RuGa IMCs facilitate the adsorption and activation of *HNO intermediate. Hence, the energy barrier of the potential‐determining step in NORR could be greatly reduced.
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