Dynamically-evolved surface heterojunction in iridium nanocrystals boosting acidic oxygen evolution and overall water splitting

Simultaneously realizing improved activity and stability of acidic oxygen evolution reaction(OER) electrocatalysts is highly promising for developing cost-effective sustainable energy in the splitting of water technique.Herein,we report iridium nanocrystals embedded into 3D conductive clothes(Ir-NCT/CC) as a low iridium electrocatalyst realizing ultrahigh acidic OER activity and robust stability.The well-designed Ir-NCT/CC requires a low overpotential of 202 mV to reach the current density of 10 mA cm^(-2)with a high mass activity of 1754 A g^(-1).Importantly,in acidic overall water splitting,Ir-NCT/CC merely delivers a cell voltage of 1.469 V at a typical current density of 10 mA cm^(-2)and also maintains robust durability under continuous operation.We identify that a low working voltage drives the formation of a highly stable amorphous IrOxactive phase over the surface of Ir nanocrystals(surface heterojunction IrOx/Ir-NCT) during operating conditions,which contributes to an effective and durable OER process.

Asymmetricalπback-donation of hetero-dicationic Mo^(4+)-Mo^(6+)pairs for enhanced electrochemical nitrogen reduction

The breaking of nonpolar N≡N bond of dinitrogen is the biggest dilemma for electrocatalytic nitrogen reduction reaction(NRR)application,driving electron migration between catalysts and N≡N bond(termed“πback-donation”process)is crucial for attenuating interfacial energy barrier but still remains challenging.Herein,using density functional theory calculations,we revealed that constructing a unique hetero-dicationic Mo^(4+)-Mo^(6+)pair could effectively activate N≡N bond with a lying-down chemisorption configuration by an asymmetrical“πback-donation”process.As a proof-of-concept demonstration,we synthesized MoO_(2)@MoO_(3)heterostructure with double Mo sites(Mo^(4+)-Mo^(6+)),which are embedded in graphite,for electrochemical nitrogen reduction.Impressively,this hetero-dicationic Mo^(4+)-Mo^(6+)pair catalysts display more excellent catalytic performance with a high NH_(3)yield(60.9μg·h^(-1)·mg^(-1))and Faradic efficiency(23.8%)as NRR catalysts under ambient conditions than pristine MoO_(2)and MoO_(3).Operando characterizations using synchrotron-based spectroscopic techniques identified the emergence of a key^(*)N_(2)Hy intermediate on Mo sites during NRR,which indicates that the Mo sites are active sites and the NRR process tends to follow an associative mechanism.This novel type of hetero-dicationic catalyst has tremendous potential as a new class of transition metal-based catalysts with promising applications in electrocatalysis and catalysts for energy conversion and storage.

Ultrahigh-temperature ferromagnetism in MoS_(2) Moirésuperlattice/graphene hybrid heterostructures

Realizing high-temperature ferromagnetism in two-dimensional(2D)semiconductor nanosheets is significant for their applications in next-generation magnetic and electronic nanodevices.Herein,this goal could be achieved on a MoS_(2) Moirésuperlattice grown on the reduced graphene oxide(RGO)substrate by a hydrothermal approach.The as-synthesized bilayer MoS_(2) superlattice structure with rotating angle(ϕ=13°±1°)of two hexagonal MoS_(2) lattices,possesses outstanding ferromagnetic property and an ultra-high Curie temperature of 990 K.The X-ray absorption near-edge structure and ultraviolet photoelectron spectroscopies combined with density functional theory calculation indicate that the covalent interactions between MoS_(2) Moirésuperlattice and RGO substrate lead to the formation of interfacial Mo-S-C bonds and complete spin polarization of Mo 4d electrons near the Fermi level.This design could be generalized and may open up a possibility for tailoring the magnetism of other 2D materials.