Mechanically mixing copper and silver into self-supporting electrocatalyst for hydrogen evolution

Commercial hydrogen production involves the development of efficient hydrogen evolution reaction catalysts.Herein,we adopted a friction stir processing(FSP)technique to mix immiscible metals homogenously and obtain a self-supporting copper-silver(CuAg)catalyst.The gust of Ag atoms with larger atomic sizes caused a tensile strain in the Cu matrix.Meanwhile,the chemical-potential difference induced electron transfer from Cu to Ag,and the two factors jointly led to the upshift of Cu d-band and improved the catalytic activity.Consequently,the CuAg electrode exhibited a high turnover frequency(12 times that of pure Cu),a low overpotential at high current density(superior to platinum foil),and high durability(1.57%decay over 180 h).Our work demonstrates that FSP is a powerful method for preparing self-supporting catalysts of immiscible alloys with high catalytic performance.

Edge dislocation-induced strains break the limit of PtNi alloys in boosting Pt mass activity for efficient alkaline hydrogen evolution

Creating lattice defects and alloying to produce strain effect in Pt-based bimetallic alloys are both effective methods to optimize the crystal and electronic structure and improve the electrocatalytic performance.Unfortunately,the principles that govern the alkaline hydrogen evolution reaction(HER)performance remain unclear,which is detrimental to the rational design of efficient Pt-based electrocatalysts.Herein,PtNi alloys with different Pt/Ni ratios and edge dislocations were synthesized,and the effects of Pt/Ni composition and edge dislocations on the alkaline HER electrocatalytic activity of PtNi alloys were systematically studied.Combined experimental and theoretical investigations reveal that tuning Pt/Ni ratio results in only 1.1 times enhancements in Pt mass activity,whereas edge dislocations-induced extra tensile strain on Ni site and compressive strain on Pt site further boost the alkaline HER intrinsic activity at all Pt/Ni ratios.Impressively,the introduction of edge dislocations in PtNi alloys could break the limit of alloying in boosting Pt mass activity and result in up to 13.7-fold enhancement,in the case that Pt and Ni contents are nearly identical and thus edge dislocation density reaches the maximum.Fundamental mechanism studies demonstrate that the edge dislocation strategy could make a breakthrough in facilitating water dissociation kinetics of PtNi alloys.

Real time imaging of two-dimensional iron oxide spherulite nanostructure formation

The formation of complex hierarchical nanostructures has attracted a lot of attention from both the fundamental science and potential applications point of view.Spherulite structures with radial fibrillar branches have been found in various solids;however,their growth mechanisms remain poorly understood.Here,we report real time imaging of the formation of two-dimensional(2D)iron oxide spherulite nanostructures in a liquid cell using transmission electron microscopy(TEM).By tracking the growth trajectories,we show the characteristics of the reaction front and growth kinetics.Our observations reveal that the tip of a growing branch splits as the width exceeds certain sizes(5.5–8.5 nm).The radius of a spherulite nanostructure increases linearly with time at the early stage,transitioning to nonlinear growth at the later stage.Furthermore,a thin layer of solid is accumulated at the tip and nanoparticles from secondary nucleation also appear at the growing front which later develop into fibrillar branches.The spherulite nanostructure is polycrystalline with the co-existence of ferrihydrite and Fe3O4 through-out the growth.A growth model is further established,which provides rational explanations on the linear growth at the early stage and the nonlinearity at the later stage of growth.

A Rational Design of Heterojunction Photocatalyst Cd S Interfacing with One Cycle of ALD Oxide

Photo-corrosion is one of the major obstacles for CdS application in wet chemical fields, and atomic layer deposition （ALD） has been proposed as an effective way to suppress the corrosion. Here, prior to ALD coating, CdS, one facilely corrosive photocatalyst, was synthesized via hydrothermal synthesis to access the fundamental corrosion mechanism and the according corrosive sites. X-ray photoelectron spectros- copy （XPS） and X-ray diffraction （XRD） demonstrated that the failure of catalytic decomposition of methylene blue originated from the formation of soluble CdSO4 by oxidizing S2 of as-prepared CdS. High resolu- tion transmission electron microscopy （HRTEM） further identified the active sites in the V-shaped regions ofCdS nanoparticles, confirmed by the simulated electric field distribution. To rationally coat oxides on CdS, the right candidates and their thicknesses have been considered by our tunneling model with trans- fer matrix method based on quantum mechanism, upon which the thickness of protective layer should be less than 0.5 nm to maintain a high tunneling probability, and thus one cycle of ALD TiO2 or AbO3 was proposed to passivate the CdS powder to balance the carrier transportation and corrosion suppres- sion. Based on HRTEM results, we found that the active V-shaped region was covered by ALD oxides （TiO2 or AbO3）. For each case, no soluble CdSO4 has been found before and after photocatalytic reactions based XPS measurements. Importantly, we noticed that with the passivation of one cycle of ALD, the catalyst＇s lifetime was elongated up to 〉14 times higher than that of the as-prepared CdS.