Novel ternary metals-based telluride electrocatalyst with synergistic effects of high valence non-3d metal and oxophilic Te for pH-universal hydrogen evolution reaction

Electrocatalyst designs based on oxophilic foreign atoms are considered a promising approach for developing efficient pH-universal hydrogen evolution reaction(HER)electrocatalysts by overcoming the sluggish alkaline HER kinetics.Here,we design ternary transition metals-based nickel telluride(Mo WNi Te)catalysts consisting of high valence non-3d Mo and W metals and oxophilic Te as a first demonstration of non-precious heterogeneous electrocatalysts following the bifunctional mechanism.The Mo WNi Te showed excellent HER catalytic performance with overpotentials of 72,125,and 182 mV to reach the current densities of 10,100,and 1000 mA cm^(-2),respectively,and the corresponding Tafel slope of 47,52,and 58 mV dec-1in alkaline media,which is much superior to commercial Pt/C.Additionally,the HER performance of Mo WNi Te is well maintained up to 3000 h at the current density of 100 mA cm^(-2).It is further demonstrated that the Mo WNi Te exhibits remarkable HER activities with an overpotential of 45 mV(31 mV)and Tafel slope of 60 mV dec-1(34 mV dec-1)at 10 mA cm^(-2)in neutral(acid)media.The superior HER performance of Mo WNi Te is attributed to the electronic structure modulation,inducing highly active low valence states by the incorporation of high valence non-3d transition metals.It is also attributed to the oxophilic effect of Te,accelerating water dissociation kinetics through a bifunctional catalytic mechanism in alkaline media.Density functional theory calculations further reveal that such synergistic effects lead to reduced free energy for an efficient water dissociation process,resulting in remarkable HER catalytic performances within universal pH environments.

Antimony oxides-protected ultrathin Ir-Sb nanowires as bifunctional hydrogen electrocatalysts

Developing electrocatalysts with fast kinetics and long-term stability for alkaline hydrogen oxidation reaction(HOR)and hydrogen evolution reaction(HER)is of considerable importance for the industrial production of green and sustainable energy.Here,an ultrathin Ir-Sb nanowires(Ir-Sb NWs)protected by antimony oxides(SbO_(x))was synthesized as an efficient bifunctional catalyst for both HOR and HER under alkaline media.Except from the much higher mass activities of Ir-Sb nanowires than those of Ir nanowires(Ir NWs)and commercial Pt/C,the SbO_(x) protective layer also contributes to the maintenance of morphology and anti-CO poisoning ability,leading to the long-term cycling performance in the presence of CO.Specifically,the Ir-Sb NW/SbO_(x) exhibits the highest catalytic activities,which are about 3.5 and 4.8 times to those of Ir NW/C and commercial Pt/C toward HOR,respectively.This work provides that the ultrathin morphology and H_(2)O-occupied Sb sites can exert the intrinsic high activity of Ir and effectively optimize the absorption of OH*both in alkaline HER/HOR electrolysis.

Deciphering dynamic surface of PtRu alloy nanocatalysts to revisit their synergistic effects during the electrooxidation

Correlating dynamic structural transformation of catalysts with the surface intermediate species under operating conditions is critical for updating the understanding of structure–performance relationships.Here,we probe the electrochemical potentialdependent surface structures and adsorbed intermediates on PtRu binary alloy nanocatalysts to revisit its synergistic mechanisms for CO electrooxidation enhanced activity.In-situ spectral characteristics by using modified shell-isolated nanoparticle-enhanced Raman spectroscopy,show that in acidic solution,when the potential is positively scanned from 0.1 V to 1.5 V relative to reversible hydrogen electrode(RHE),the surface of the alloy catalyst evolves from metallic PtRu to adsorbed oxygen gradually covering and accumulating on Ru sites(denoted as PtRuO_(x),x≤2),forming segregated RuO_(2),and finally forming a threedimensional oxide layer(denoted as 3D PtRuO_(4)).Moreover,molecular evidence associated with periodic density functional theory calculations reveals that electronic effects promote ruthenium to become more oxidizable and oxophilic.In particular,we found here that ^(*)O and ^(*)OH at surface RuO_(x) sites are highly efficient CO oxidation active species in comparison to the same entities adsorbed on metallic Ru sites.This work sheds light on the complex surface dynamic process of practical Pt-based binary nanocatalysts and improves the understanding of synergistic mechanism for the development of fuel cell devices.