Fe, V-co-doped C_(2)N for electrocatalytic N_(2)-to-NH_(3) conversion

Designing providential catalyst is the key to drive the electrochemical nitrogen reduction reactions(NRR),which is referring to multiple intermediates and products. By means of density functional theory(DFT)calculations, we studied heteronuclear bi-atom electrocatalyst(HBEC) for NRR. Our results revealed that compared to homonuclear bi-atom electrocatalyst(Fe_2@C_2N, V_2@C_2N), Fe, V-co-doped C_2N(Fe V@C_2N)had a smaller limiting potential of-0.17 V and could accelerate N_2-to-NH_3 conversion through the enzymatic pathway of NRR. Importantly, N–N bond length monotonically increases with increasing the Bader charges of adsorbed N_2 molecule but decreases with increasing the Bader charge difference of two adsorbed N atoms. Additionally, the Fe V@C_2N could suppress the production of H_2 by the preferential adsorption and reduction of N_2 molecule. Thus, the as-designed HBEC may have the outstanding electrochemical NRR performance. This work opens a new perspective for NRR by HBECs under mild conditions.

Fabrication of Y-junction Metal Nanowires by AAO Template-assisted AC Electrodeposition

In this communication,we report a synthetic approach to fabricate Y-junction Co nanowires and Y-junction Cu nanowires by AC electrodeposition using a hierarchically designed anodized aluminum oxide template.Morphology study showe that diameters of the stems and branches of the Y-junction nanowires were about 40 nm and 20 nm respectively.Structural analysis indicates that Co nanowires had a mixture of face-center-cubic and hexagonal-close-packed structures,whereas Cu nanowires had a face-center-cubic structure with a <110> texture.The Y-junction Co nanowires exhibited a longitudinal coercivity of 1300 Oe and remnant magnetization of 56%,which was affected by the growth direction and microstructure.The present method can be extended to other metallic systems and thus provides a simple and efficient way to fabricate Y-junction metal nanowires.

Tailoring nanoprecipitates for ultra-strong high-entropy alloys via machine learning and prestrain aging

The multi-principal-component concept of high-entropy alloys(HEAs) generates numerous new alloys.Among them,nanoscale precipitated HEAs have achieved superior mechanical properties and shown the potentials for structural applications.However,it is still a great challe nge to find the optimal alloy within the numerous candidates.Up to now,the reported nanoprecipitated HEAs are mainly designed by a trialand-error approach with the aid of phase diagram calculations,limiting the development of structural HEAs.In the current work,a novel method is proposed to accelerate the development of ultra-strong nanoprecipitated HEAs.With the guidance of physical metallurgy,the volume fraction of the required nanoprecipitates is designed from a machine learning of big data with thermodynamic foundation while the morphology of precipitates is kinetically tailored by prestrain aging.As a proof-of-principle study,an HEA with superior strength and ductility has been designed and systematically investigated.The newly developed γ’-strengthened HEA exhibits 1.31 GPa yield strength,1.65 GPa ultimate tensile strength,and 15% tensile elongation.Atom probe tomography and transmission electron microscope characterizations reveal the well-controlled high γ’ volume fraction(52%) and refined precipitate size(19 nm).The refinement of nanoprecipitates originates from the accelerated nucleation of the γ’ phase by prestrain aging.A deeper understanding of the excellent mechanical properties is illustrated from the aspect of strengthening mecha nisms.Finally,the versatility of the current design strategy to other precipitation-hardened alloys is discussed.

Carbon-supported layered double hydroxide nanodots for efficient oxygen evolution: Active site identification and activity enhancement

In this study,we developed a novel confinement-synthesis approach to layered double hydroxide nanodots(LDH-NDs)anchored on carbon nanoparticles,which formed a three-dimensional(3D)interconnected network within a porous carbon support derived from pyrolysis of metal-organic frameworks(C-MOF).The resultant LDH-NDs@C-MOF nonprecious metal catalysts were demonstrated to exhibit super-high catalytic performance for oxygen evolution reaction(OER)with excellent operation stability and low overpotential(-230 mV)at an exchange current density of 10 mA·cm^(-2).The observed overpotential for the LDH-NDs@C-MOF is much lower than that of large-sized LDH nanosheets(321 mV),pure carbonized MOF(411 mV),and even commercial RuO_(2)(281 mV).X-ray absorption measurements and density functional theory(DFT)calculations revealed partial charge transfer from Fe^(3+)through an O bridge to Ni^(2+)at the edge of LDH-NDs supported by C-MOF to produce the optimal binding energies for OER intermediates.This,coupled with a large number of exposed active sides and efficient charge and electrolyte/reactant/product transports associated with the porous 3D C-MOF support,significantly boosted the OER performance of the LDH-ND catalyst with respect to its nanosheet counterpart.Apart from the fact that this is the first active side identification for LDH-ND OER catalysts,this work provides a general strategy to enhance activities of nanosheet catalysts by converting them into edge-rich nanodots to be supported by 3D porous carbon architectures.

CrN-Encapsulated Hollow Cr-N-C Capsules Boosting Oxygen Reduction Catalysis in PEMFC

Understanding the origin of the catalytic activity for the development of efficient catalysts is critical yet challenging.Herein,we report a simple strategy for the synthesis of chromium nitride nanoparticles(CrNNPs)encapsulated into hollow chromium-nitrogen-carbon capsules(CrN@H-Cr-N_(x)-C).The CrN@H-Cr-N_(x)-C demonstrated excellent electrocatalytic activity for the oxygen reduction reaction(ORR)in acidic solutions.When applied as a cathode material in a proton-exchange membrane fuel cell(PEMFC),the CrN@H-Cr-N_(x)-C achieved outstanding initial performance,which is better than that of the PEMFC with H-Cr-N_(x)-C cathode material.The CrN@H-Cr-N_(x)-C cathode also showed good stability over 110 h of operation.These results demonstrated that the coexistence of atomically dispersed CrN_(x) sites and sufficient CrNNPs is essential for excellent PEMFC performances.Density functional theory(DFT)studies further corroborated that CrNNPs can boost the ORR activity of H-Cr-N_(x)-C.This finding opens a new avenue for the fabrication of low-cost,highly active,and durable ORR catalysts for PEMFC and other applications.

High-throughput investigations of configurational-transformation-dominated serrations in CuZr/Cu nanolaminates

Metallic amorphous/crystalline(A/C)nanolaminates exhibit excellent ductility while retaining their high strength.However,the underlying physical mechanisms and the resultant structural changes during plastic deformation still remain unclear.In the present work,the structure-property relationship of CuZr/Cu A/C nanolaminates is established through integrated high-throughput micro-compression tests and molecular dynamics simulations together with high-resolution transmission electron microcopy.The serrated flow of nanolaminates results from the formation of hexagonal-close-packed(HCP)-type stacking faults and twins inside the face-centered-cubic(FCC)Cu nano-grains,the body-centered-cubic(BCC)-type ordering at their grain boundaries,and the crystallization of the amorphous CuZr layers.The serration behavior of CuZr/Cu A/C nanolaminates is determined by several factors,including the formation of dense dislocation networks from the multiplication of initial dislocations that formed after yielding,weak-spots-related configurational-transitions and shear-transition-zone activities,and deformation-induced devitrification.The present work provides an insight into the heterogeneous deformation mechanism of A/C nanolaminates at the atomic scale,and mechanistic base for the microstructural design of self-toughening metallic-glass(MG)-based composites and A/C nanolaminates.