Research Article Local structure and magnetic properties of a nanocrystalline Mnrich Cantor alloy thin film down to the atomic scale

The huge atomic heterogeneity of high-entropy materials along with a possibility to unravel the behavior of individual components at the atomic scale suggests a great promise in designing new compositionally complex systems with the desired multifunctionality.Herein,we apply multi-edge X-ray absorption spectroscopy(extended X-ray absorption fine structure(EXAFS),Xray absorption near edge structure(XANES),and X-ray magnetic circular dichroism(XMCD))to probe the structural,electronic,and magnetic properties of all individual constituents in the single-phase face-centered cubic(fcc)-structured nanocrystalline thin film of Cr_(20)Mn_(26)Fe_(18)Co_(19)Ni_(17)(at.%)high-entropy alloy on the local scale.The local crystallographic ordering and componentdependent lattice displacements were explored within the reverse Monte Carlo approach applied to EXAFS spectra collected at the K absorption edges of several constituents at room temperature.A homogeneous short-range fcc atomic environment around the absorbers of each type with very similar statistically averaged interatomic distances(2.54-2.55Å)to their nearest-neighbors and enlarged structural relaxations of Cr atoms were revealed.XANES and XMCD spectra collected at the L2,3 absorption edges of all principal components at low temperature from the oxidized and in situ cleaned surfaces were used to probe the oxidation states,the changes in the electronic structure,and magnetic behavior of all constituents at the surface and in the sub-surface volume of the film.The spin and orbital magnetic moments of Fe,Co,and Ni components were quantitatively evaluated.The presence of magnetic phase transitions and the co-existence of different magnetic phases were uncovered by conventional magnetometry in a broad temperature range.

Exposing Cu-rich {110} active facets in PtCu nanostars for boosting electrochemical performance toward multiple liquid fuels electrooxidation

In catalysis,tuning the structural composition of the metal alloy is known as an efficient way to optimize the catalytic activity.This work presents the synthesis of compositional segregated six-armed PtCu nanostars via a facile solvothermal method and their distinct composition-structure-dependent performances in electrooxidation processes.The alloy is shown to have a unique six arms with a Cu-rich dodecahedral core,mainly composed of {110} facets and exhibit superior catalytic activity toward alcohols electrooxidation compared to the hollow counterpart where Cu was selectively etched.Density functional theory (DFT) calculations suggest that the formation of hydroxyl intermediate (OH^*) is crucial to detoxify CO poisoning during the electrooxidation processes.The addition of Cu is found to effectively adjust the d band location of the alloy catalyst and thus enhance the formation of ^*OH intermediate from water splitting,which decreases the coverage of ^*CO intermediate.Our work demonstrates that the unique compositional anisotropy in alloy catalyst may boost their applications in electrocatalysis and provides a methodology for the design of this type catalyst.

Al-driven peculiarities of local coordination and magnetic properties in single-phase Al_(x)-CrFeCoNi high-entropy alloys

Modern design of superior multi-functional alloys composed of several principal components requires in-depth studies of their local structure for developing desired macroscopic properties.Herein,peculiarities of atomic arrangements on the local scale and electronic states of constituent elements in the single-phase face-centered cubic(fcc)-and body-centered cubic(bcc)-structured high-entropy Alx-CrFeCoNi alloys(x=0.3 and 3,respectively)are explored by element-specific X-ray absorption spectroscopy in hard and soft X-ray energy ranges.Simulations based on the reverse Monte Carlo approach allow to perform a simultaneous fit of extended X-ray absorption fine structure spectra recorded at K absorption edges of each 3d constituent and to reconstruct the local environment within the first coordination shells of absorbers with high precision.The revealed unimodal and bimodal distributions of all five elements are in agreement with structure-dependent magnetic properties of studied alloys probed by magnetometry.A degree of surface atoms oxidation uncovered by soft X-rays suggests different kinetics of oxide formation for each type of constituents and has to be taken into account.X-ray magnetic circular dichroism technique employed at L2,3 absorption edges of transition metals demonstrates reduced magnetic moments of 3d metal constituents in the sub-surface region of in situ cleaned fcc-structured Al0.3-CrFeCoNi compared to their bulk values.Extended to nanostructured versions of multicomponent alloys,such studies would bring new insights related to effects of high entropy mixing on low dimensions.