Catalytic activity of V_(2)CO_(2) MXene supported transition metal single atoms for oxygen reduction and hydrogen oxidation reactions:A density functional theory calculation study

Two-dimensional(2D)MXene and single-atom(SA)catalysts are two frontier research fields in catalysis.2D materials with unique geometric and electronic structures can modulate the catalytic performance of supported SAs,which,in turn,affect the intrinsic activity of 2D materials.Density functional theory calculations were used to systematically explore the potential of O-terminated V2C MXene(V_(2)CO_(2))-supported transition metal(TM)SAs,including a series of 3d,4d,and 5d metals,as oxygen reduction reaction(ORR)and hydrogen oxidation reaction(HOR)catalysts.The combination of TM SAs and V_(2)CO_(2)changes their electronic structure and enriches the active sites,and consequently regulates the intermediate adsorption energy and catalytic activity for ORR and HOR.Among the investigated TM-V_(2)CO_(2)models,Sc-,Mn-,Rh-,and PtMCCh showed high ORR activity,while Sc-,Ti-,V-,Cr-,and Mn-V_(2)CO_(2)exhibited high HOR activity.Specifically,Mn-and Sc-V_(2)CO_(2)are expected to serve as highly efficient and cost-effective bifunctional catalysts for fuel cells because of their high catalytic activity and stability.This work provides theoretical guidance for the rational design of efficient ORR and HOR bifunctional catalysts.

Insight into the boosted activity of TiO2–CoP composites for hydrogen evolution reaction:Accelerated mass transfer,optimized interfacial water,and promoted intrinsic activity

The use of abundant elements in the earth as electrocatalytic hydrogen production catalysts is of great significance for hydrogen energy cycling.Herein,we report amorphous TiO_(2)-decorated CoP/NF(TiO_(2)–CoP/NF)as an excellent electrocatalyst for alkaline hydrogen evolution reaction(HER).The welldispersed amorphous TiO_(2)on nanoneedle-like CoP arrays preserves the crystal structure of CoP and changes its electronic structure by interfacial charge transfer.Compared to CoP/NF catalyst,the Ti O_(2)–CoP/NF composite catalyst exhibits high HER activity with an overpotential of 61 mV at 10 mA cm^(-2)and high stability.Importantly,it almost maintains the Volmer step as a rate-determining step(RDS)and the Tafel slope at a wide cathodic potential range showing the fast kinetics under large polarization regions.Theoretical simulations reveal that the combination of TiO_(2)and CoP selectively accelerates the hydrated K+diffusion,regulates the interfacial water orientation to adapt to the subsequent smooth water dissociation,and optimizes*H adsorption/H_(2)desorption.The strengthened coupling of HER multi-scale-processes on transition metal compound composites catalysts is the underlying mechanism for improving HER activity.

Investigations of the superlubricity of sapphire against ruby under phosphoric acid lubrication

In this study,we address the superlubricity behavior of sapphire against ruby(or sapphire against itself)under phosphoric acid solution lubrication.An ultra-low friction coefficient of 0.004 was obtained under a very high contact pressure,with a virgin contact pressure up to 2.57 GPa.Related experiments have indicated that the load,sliding speed,and humidity of the test environment can affect superlubricity to some degree,so we tested variations in these conditions.When superlubricity appears in this study a thin film is present,consisting of a hydrogen bond network of phosphoric acid and water molecules adsorbed on the two friction surfaces,which accounts for the ultra-low friction.Most significantly,the wear rate of the sapphire and ruby in the friction process is very slow and the superlubricity state is very stable,providing favorable conditions for future technological applications.

Hydrodynamic effect on the superlubricity of phosphoric acid between ceramic and sapphire

In this work,a super-low friction coefficient of 0.003 was found between a silicon nitride ball and a sapphire plate lubricated by phosphoric acid solution.The wear mainly occurred in the running-in period and disappeared after superlubricity was achieved.The friction coefficient was effectively reduced from 0.3 to 0.003 at a constant speed of 0.076 m/s,accompanied by a 12-nm-thickness film.The lubrication regime was indicated to change from boundary lubrication in the running-in period to elastohydrodynamic lubrication in the superlubricity period,which is also supported by the results of the friction coefficient versus sliding speed.In addition,the experimental results showed good agreement with theoretical calculations based on the elastohydrodynamic lubrication theory,suggesting a significant hydrodynamic effect of phosphoric acid on superlubricity.

The contribution of water molecules to the hydrogen evolution reaction

Traditionally,water molecules act as solvents in most chemical reactions,whereas they act as solvents and reactants in the alkaline electrolyte for the hydrogen evolution reaction(HER).It is well known that there is a current plateau in the linear potential–current dependence for HER in neutral or near-neutral electrolytes,showing that the HER is governed by the mass transport of reactive hydronium species at a given overpotential.The sharp rise in the current signal after the plateau at a slightly higher overpotential indicates that HER is supported by a new reactant,namely the water molecules rather than the limited hydronium species.Herein,in combination with our own research experience in water electrolysis,we review the relevant literature in these years about the HER activity descriptor and mainly focus on the contribution of water molecules to the HER,including their dissociation,configuration,and composition in regulating the pH-dependent HER.Finally,we try to provide new insights into understanding the mechanism of the HER in terms of interfacial water enrichment,orientation,and configuration with the electric field strength of electrode/electrolyte interface and electrode compositions.