Boosting Electrocatalytic Ammonia Production through Mimicking “π Back-Donation”

Abstract

Mimicking ''p back-donation'' is proposed as a facile, feasible, and generalizable approach to boost electrocatalytic ammonia production from dinitrogen on pblock-element catalysts, which lack d-orbitals. Such behavior is realized by providing sufficient empty orbitals on the surface of Bi 4 O 5 I 2 . The integrated modification of oxygen vacancy with hydroxyl achieves the generation of empty orbitals to reduce the energy barrier for N 2 protonation. The intriguing strategy that takes advantage of the electronic structure modulation endows this p-blockelement catalyst with a relatively high ammonia synthesis of 20.44 mg h À1 mg À1 cat . in neutral media at a high faradic efficiency of 32.4%.

Regulating Fe2(MoO4)3 by Au Nanoparticles for Efficient N2 Electroreduction under Ambient Conditions

“…And then the electron redistribution with the difference of electron density (Δρ = ρ total − ρ N2 − ρ catalyst ) of N 2 * adsorption configuration is plotted in Figure S28, Supporting Information, it is clear that the electrons can transfer from σ to d xy and to π*, which actives the NN bond and decreases the reaction energy of the RDS for eNRR successfully. [ 39–41 ]…”

Gel‐Derived Amorphous Bismuth–Nickel Alloy Promotes Electrocatalytic Nitrogen Fixation via Optimizing Nitrogen Adsorption and Activation

“…Furthermore, in terms of the binding capability with N 2 , despite the stronger bonding between *NNH intermediate and Bi, Bi cannot absorb N 2 in the first step, which significantly increases the NRR energy barrier [7b,d] . Substitution of Bi with heteroatoms can modulate the electronic configuration of Bi, and thus optimize the surface properties and N adsorption energy of electrocatalysts [12] …”

Recent Advances in the Application of Structural‐Phase Engineering Strategies in Electrochemical Nitrogen Reduction Reaction

“…In neutral media, the Faradaic efficiency of this catalyst is as high as 32.4%. [ 20 ] In addition, the intermetallic compound Mo 3 Fe 3 C yields an NH 3 production rate of 72.5 µg h −1 mg cat. −1 at −0.05 V versus RHE.…”

“…Therefore, it is necessary to concisely analyze and comment on the recently reported electrocatalysts. Here, we summarize the principles and related research on the construction of NRR electrocatalyst based on nano‐to‐atomic structure phase engineering strategy using strain engineering (Au@SnO 2 ), [ 22 ] defect engineering (VO‐Bi 4 O 5 I 2 ‐OH), [ 20 ] interface engineering (TiO 2 /Ti 3 C 2 T x ), [ 23 ] atomic arrangement engineering (Mo 3 Fe 3 C), [ 21 ] and single atom, to promote this uprising research field moving toward further development. Figure is a schematic diagram of a design strategy based on phase structure engineering.…”