In-situ imaging of strain-induced enhancement of hydrogen evolution activity on the extruded MoO_(2)sheets

Strain engineering is a useful strategy for modifying the catalytic activity of electrocatalysts.However,in-situ visual characterization of the strain effect on the catalytic activity at nanoscale remains a huge challenge.Herein,we performed in-situ electrochemical scanning tunneling microscopy(EC-STM)imaging measurements at the local strained regions of extruded singlecrystal molybdenum dioxide(MoO_(2))sheets with combination of current noise analysis(n-EC-STM).The intensity-enhanced noise was observed at the local strained region compared to the unstrained regions in the same frame,which reveals the positive effect of compressive strain on the hydrogen evolution reaction(HER)activity of MoO_(2)provided that the intensity of noise is positively correlated with catalytic HER Faradic current.Therefore,we clearly“see”the strain-induced enhancement of HER activity of MoO_(2)at nanoscale by means of noise visualization.This work extends the visual characterization of strain engineering in electrocatalysis and related fields.

Molecular Insights into the Structure-Activity Relationship in Cobalt Porphyrin Catalyzed Oxygen Reduction Reaction

We present a microscopic investigation on the structure-activity relationship of the Co-N4 site in the oxygen reduction reaction(ORR)by electrochemical scanning tunneling microscopy(ECSTM)at the molecular scale.The cobalt porphyrins with various substituents(CoTPPX_(4),X=Cl,H,OCH_(3))that delicately regulate the electronic structure of the active site were investigatedasmodel catalysts.Electrochemical measurements evidenced that the CoTPPCl_(4)exhibits better activity,higher product selectivity for H_(2)O,and lower stability.The CoTPPX_(4)-O_(2)complex with higher contrast can be observed in the STM images and the proportion of the CoTPPCl_(4)-O_(2)is appreciably larger than that of CoTPP-O_(2)and CoTPP(OCH_(3))4-O_(2).Theoretical simulations of the model catalysts and the reaction processes of the ORR reveal the relationship between the electronic structure and the catalytic behavior of the model catalysts.The transformation of the CoTPPX_(4)-O_(2)and CoTPPX_(4)in the electrocatalytic reaction was monitored by in situ ECSTM characterization.The structure-activity relationship clarified by experimental and theoretical investigations in this work should help to guide the rational design and optimization of high-performance catalysts.

Effect of Residual Stress on Corrosion Sensitivity of Carbon Steel Studied by SECM

The effect of compressive residual stress on the reactivity of carbon steel in a neutral chloride solution was investigated by means of potentiodynamic polarization and local electrochemical measurement with scanning electrochemical microscope（SECM）. Meanwhile, X-ray diffraction, as a nondestructive technique, was employed to determine the levels of residual stress in near-surface layers of carbon steel specimen. The results show that the resi- dual stress existed in the specimen fell into the category of compressive residual stress which was inversely propor- tional to the corrosion sensitivity of carbon steel specimen. By using I/I3 couple as a redox mediator in the current feedback mode of SECM measurements, the Faradaic current on Pt tip, which was relevant to the rate of the I3- ion reduction, fell with the increase of compressive residual stress. The correlation between compressive residual stress and heterogeneous electron transfer rate has been proposed based on the inference of the localized electrochemical reactions occurred on the specimen surface,