Highly Efficient Photo-/Electrocatalytic Reduction of Nitrogen into Ammonia by Dual-Metal Sites

Abstract

The photo-/electrocatalytic nitrogen reduction reaction (NRR) is an up and coming method for sustainable NH 3 production; however, its practical application is impeded by poor Faradaic efficiency originating from the competing hydrogen evolution reaction (HER) and the inert N≡N triple bond activation. In this work, we put forth a method to boost NRR through construction of donor–acceptor couples of dual-metal sites. The synergistic effect of dual active sites can potentially break the metal-based activity benchmark toward efficient NRR. By systematically evaluating the stability, activity, and selectivity of 28 heteronuclear dual-atom catalysts (DACs) of M1M2/g-C 3 N 4 candidates, FeMo/g-C 3 N 4 is screened out as an effective electrocatalyst for NRR with a particularly low limiting potential of −0.23 V for NRR and a rather high potential of −0.79 V for HER. Meanwhile, TiMo/g-C 3 N 4 , NiMo/g-C 3 N 4 , and MoW/g-C 3 N 4 with suitable band edge positions and visible light absorption can be applied to NRR as photocatalysts. The excellent catalytic activity is attributed to the tunable composition of metal dimers, which play an important role in modulating the binding strength of the target intermediates. This work may pave a new way for the rational design of heteronuclear DACs with high activity and stability for NRR, which may also apply to other reactions.

Electrochemical C–N coupling with perovskite hybrids toward efficient urea synthesis

“…[18][19][20][21][22] In comparison, energy-saving and environmentally benign electrocatalysis technologies such as the nitrogen reduction reaction (NRR) and the carbon dioxide reduction reaction (CO 2 RR) are drawing growing attention. [23][24][25][26][27][28][29][30] Besides, the emerged electrochemical C-N coupling reaction may provide a new possibility of enhancing the spectrum of products of CO 2 by using CO 2 and amine derivatives/nitrogen sources (nitrate, nitrite, NO, and even N 2 ) as feedstock. 9,31,32 The desired product urea [CO(NH 2 ) 2 ] will be produced when the electrochemical C-N bond formation occurs by employing both N 2 and CO 2 as the feeding gas.…”

Cooperative Single-Atom Active Centers for Attenuating the Linear Scaling Effect in the Nitrogen Reduction Reaction

“…Importantly, the bridge-on pattern relies on the proximity of two metal active sites, which could well explain other reported promising NRR catalytic systems invoking bridge-on-like activation of N2 by multiple active centers. [59][60][61] Based on the survey, we then identified VN4 duo and ReN4 duo as promising NRR catalysts through associative mechanisms and dissociative mechanisms, respectively. For VN4 duo, the remarkably low onset potential (0.17 eV) indicates the level of excellent activity of NRR that can be achieved by high-density SACs.…”

Cooperative Single-Atom Active Centers for Attenuating Linear Scaling Effect in Nitrogen Reduction Reaction

“…Importantly, the bridge-on pattern relies on the proximity of two metal active sites, which could well explain other reported promising NRR catalytic systems invoking bridge-on like activation of N2 by multiple active centers. [59][60][61] Based on the survey, we then identified VN4 duo and ReN4 duo as promising NRR catalysts through associative mechanisms and dissociative mechanisms, respectively. For VN4 duo, the remarkably low onset potential (0.18 eV) indicates the level of excellent activity of NRR that can be achieved by high-density SACs.…”