Spontaneous Atomic Ruthenium Doping in Mo₂CT_X MXene Defects Enhances Electrocatalytic Activity for the Nitrogen Reduction Reaction

Abstract

The electrochemical nitrogen reduction reaction (NRR) process usually suffers extremely low Faradaic efficiency and ammonia yields due to sluggish NN dissociation. Herein, single‐atomic ruthenium modified Mo2CTX MXene nanosheets as an efficient electrocatalyst for nitrogen fixation at ambient conditions are reported. The catalyst achieves a Faradaic efficiency of 25.77% and ammonia yield rate of 40.57 µg h−1 mg−1 at ‐0.3 V versus the reversible hydrogen electrode in 0.5 m K2SO4 solution. Operando X‐ray absorption spectroscopy studies and density functional theory calculations reveal that single‐atomic Ru anchored on MXene nanosheets act as important electron back‐donation centers for N2 activation, which can not only promote nitrogen adsorption and activation behavior of the catalyst, but also lower the thermodynamic energy barrier of the first hydrogenation step. This work opens up a promising avenue to manipulate catalytic performance of electrocatalysts utilizing an atomic‐level engineering strategy.

Rational strain engineering of single-atom ruthenium on nanoporous MoS2 for highly efficient hydrogen evolution

“…6 , 7 ) 30 , 31 . Then, SVs were created with the introduction of isolated Ru atoms in the basal plane of MoS 2 , forming the desired catalyst (Ru/np-MoS 2 ) through a spontaneous reduction strategy 23 , 32 . Representative scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images emphasize the three-dimensional bicontinuous nanoporous morphology of the as-prepared Ru/np-MoS 2 (Fig.…”

Atomic-level-designed copper atoms on hierarchically porous gold architectures for high-efficiency electrochemical CO2 reduction

“…To elucidate the structure and chemical state of the active sites of np-Cu 1 Au SAA during CO 2 reduction, operando XAS spectra were recorded under real working conditions with a homemade operando cell [45,46]. Fig.…”

Nanoporous Intermetallic Pd3Bi for Efficient Electrochemical Nitrogen Reduction

“…[ 20 ] Meanwhile, the intensity of the white line peaks of the Bi L 3 ‐edge XANES spectra (Figure 4b) shows obvious enhancement, which is attributed to the delocalization of the unpaired electron from Bi due to the interaction with N species during NRR. [ 21 ] According to molecular orbital theory, the interaction between the Bi atomic orbital and the N 2p orbital of the same main group would lead to the formation of a NN π antibonding orbital and a decrease of the bond order. [ 22 ] With voltage bias, the voltage‐driven electron transfer from the Bi atom to the N 2p orbital leads to the formation of N 2 δ− adsorption species, and the electron backdonation could effectively weaken the NN molecular bond, resulting in the activation of N 2 and formation of NH species.…”