Tuning the atomic configuration environment of MnN_(4) sites by Co cooperation for efficient oxygen reduction

Carbon-based N-coordinated Mn(Mn-N_(x)/C)single-atom electrocatalysts are considered as one of the most desirable non-precious oxygen reduction reaction(ORR)candidates due to their insignificant Fenton reactivity,high abundance,and intriguing electrocatalytic performance.However,current MnN_(x)/C single-atom electrocatalysts suffer from high overpotentials because of their low intrinsic activity and unsatisfactory chemical stability.Herein,through an in-situ polymerization-assisted pyrolysis,the Co as a second metal is introduced into the Mn-N_(x)/C system to construct Co,Mn-N_(x)dual-metallic sites,which atomically disperse in N-doped 1D carbon nanorods,denoted as Co,Mn-N/CNR and hereafter.Using electron microscopy and X-ray absorption spectroscopy(XAS)techniques,we verify the uniform dispersion of CoN4and MnN4atomic sites and confirm the effect of Co doping on the MnN_(4) electronic structure.Density functional theory(DFT)calculations further elucidate that the energy barrier of ratedetermining step(^(*)OH desorption)decreases over the 2 N-bridged MnCoN_(6) moieties related to the pure MnN_(4).This work provides an effective strategy to modulate the local coordination environment and electronic structure of MnN_(4) active sites for improving their ORR activity and stability.

Recent Advances in Stability Improvement Strategies of M-N_(x)/C Catalysts Towards Oxygen Reduction Reaction

Although fuel cells possess advantages of high energy conversion efficiency and zero-carbon emission,their large-scale commercialization is restricted by expensive and scarce platinum(Pt)catalysts.Metal-nitrogen-carbon(M-Nx/C)catalysts are hailed as the most promising candidates to replace Pt due to their considerable oxygen reduction reaction(ORR)activity and low cost.Despite tremendous progress in terms of active site identification and activity improvement being achieved in the past few decades,the M-Nx/C catalysts still suffer from insufficient durability,which drastically limits their practical application.In this regard,understanding degradation mechanisms and customizing stabilization strategies are of significant importance yet challengeable.In this review,we summarize the recent advances in the stability improvement of M-Nx/C catalysts.The stability test protocols of the M-Nx/C are firstly introduced.Subsequently,with the combination of advanced ex situ and in situ characterization techniques and density functional theory calculation,we present a comprehensive overview of the main degradation mechanisms during ORR process.Aiming at these deactivation issues,a variety of novel improvement strategies are developed to enhance the stability of M-Nx/C.Finally,the current challenges and prospects to design highly stable M-Nx/C catalysts are also proposed.