MOF-related electrocatalysts for sulfur reduction/evolution reactions:Composition modulation,structure design,and mechanism research

The electrocatalytic sulfur reduction reaction(SRR)and sulfur evolution reaction(SER),two fundamental multistep conversion processes in lithium–sulfur batteries(LSBs),are root-cause solutions to overcome sluggish redox kinetics and the polysulfide shuttling effect.Metal–organic framework(MOF)electrocatalysts have emerged as good platforms for catalyzing SRR and SER,but their catalytic performance is challenged by poor electrical conductivity and limited chemical stability.Functionalized MOFs and their hybrids may be beneficial for stabilizing and improving the desired catalytic properties to achieve high-performance LSBs.This review provides a detailed overview of engineering principles for improving the activity,selectivity,and stability of MOFrelated electrocatalysts via composition modulation and nanostructure design as well as hybrid assembly.It presents and discusses the various advances achieved by using in situ characterization techniques,simulations,and theoretical calculations to reveal the dynamic evolution of MOF-related electrocatalysts,enabling an in-depth understanding of the catalysis mechanism at the molecular/atomic level.Lastly,prospects and possible research directions for MOF-related sulfur electrocatalysts are proposed.

Inter-facet composition modulation of III-nitride nanowires over pyramid textured Si substrates by stationary molecular beam epitaxy

InGaN nanowires (NWs) are grown on pyramid textured Si substrates by stationary plasma-assisted molecular beam epitaxy (PA-MBE). The incidence angles of the highly directional source beams vary for different pyramid facets, inducing a distinct inter-facet modulation of the In content of the InGaN NWs, which is verified by spatial element distribution analysis. The resulting multi-wavelength emission is confirmed by photoluminescence (PL) and cathodoluminescence (CL). Pure GaN phase formation dominates on certain facets, which is attributed to extreme local growth conditions, such as low active N flux. On the same facets, InGaN NWs exhibit a morphology change close to the pyramid ridge, indicating inter-facet atom migration. This cross-talk effect due to inter-facet atom migration is verified by a decrease of the inter-facet In content modulation amplitude with shrinking pyramid size. A detailed analysis of the In content variation across individual pyramid facets and element distribution line profiles reveals that the cross-talk effect originates mainly from the inter-facet atom migration over the convex pyramid ridge facet boundaries rather than the concave base line facet boundaries. This is understood by first-principles calculations showing that the pyramid baseline facet boundary acts as an energy barrier for atom migration, which is much higher than that of the ridge facet boundary. The influence of the growth temperature on the inter-facet In content modulation is also presented. This work gives deep insight into the composition modulation for the realization of multi-color light-emitting devices based on the monolithic growth of InGaN NWs on pyramid textured Si substrates.

Surface Modification With Zinc and Zn-Ni Alloy Compositionally Modulated Multilayer Coatings

Zinc and Zn-Ni alloy compositionally modulated multilayer （CMM） coatings were electrodeposited on to a steel substrate by the successive deposition of zinc and Zn-Ni alloy sublayers from dual baths. The coated samples were evaluated in terms of the surface appearance, surface and cross-sectional morphologies, as well as corrosion resistance. The microstructural characteristics that were examined using the field emission gun scanning electron microscopy （FEGSEM） confirmed the layered structure, grain refinement of the zinc and Zn-Ni alloy CMM coatings, and revealed the existence of microcracks caused by the internal stress in the thick Zn-Ni alloy sublayers. The corrosion resistance that was evaluated by means of the salt spray test shows that the zinc and Zn-Ni alloy CMM coatings were more corrosion-resistant than the monolithic coatings of zinc or Zn-Ni alloy of the same thickness. The possible reasons for the better protective performance of Zn-Ni/Zn CMM coatings were given on the basis of the analysis on the micrographic features of zinc and Zn-Ni alloy CMM eoatings after the corrosion test. A probable corrosion mechanism of zinc and Zn-Ni alloy CMM coatings was also proposed.

Performance improvement of charge trap flash memory by using a composition-modulated high-k trapping layer

A composition-modulated （HfO2）x（Al2O3）1-x charge trapping layer is proposed for charge trap flash memory by controlling the A1 atom content to form a peak and valley shaped band gap. It is found that the memory device using the composition-modulated （HfO2）x（Al2O3）l-x as the charge trapping layer exhibits a larger memory window of 11.5 V, improves data retention even at high temperature, and enhances the program/erase speed. Improvements of the memory characteristics are attributed to the special band-gap structure resulting from the composition-modulated trapping layer. Therefore, the composition-modulated charge trapping layer may be useful in future nonvolatile flash memory device application.

STRUCTURE AND MAGNETIC PROPERTIES OF Fe/Pd COMPOSITIONALLY MODULATED FILMS

Metal Fe/Pd compositionally modulated films(CMFs) were prepared by vapour depo- sition from two sources onto glass substrate under vacuum.The modulation and crystal structures of the films were examined by X-ray diffraction.The magnetic properties were determined by vibrating sample magnetometer.The Pd layers in the Fe/Pd CMFs are of fcc structure,and the Fe layer structure transits from bcc into amorphous,state with decreasing thickness of Fe layer.The dependence of specific saturation magnetization on thickness of Fe layers has also been discussed.

Corrosion behaviors of zinc and Zn-Ni alloy compositionally modulated multilayer coatings

Zinc and Zn-Ni alloy compositionally modulated multilayer （CMM） coatings were electrodeposited from dual baths. The coated samples were evaluated in terms of surface appearance, surface and cross-sectional morphologies, as well as corrosion resistance. The results obtained from the salt spray test show that the zinc and Zn-Ni alloy CMM coatings are more corrosion-resistant than the monolithic coatings of zinc or Zn-Ni alloy alone with a similar thickness. The corrosion potential measurement and anodic polarisation tests were undertaken to examine the probable corrosion mechanisms of zinc and Zn-Ni alloy CMM coatings. Analysis on the micrographic features of zinc and Zn-Ni alloy CMM coatings after the corrosion test explains the probable reasons why the Zn-Ni/Zn CMM coatings have a better protective performance. Surface morphologies and compositional analysis of the remaining coating material of Zn-Ni alloy deposit after the corrosion test confirms the dezincification mechanism of the Zn-Ni alloy deposit during the corrosion process.

Compositional modulation in ZnGa_(2)0_(4) via Zn^(2+)/Ge^(4+)co-doping to simultaneously lower sintering temperature and improve microwave dielectric properties

AB_(2)O_(4)-type spinels with low relative permittivity(ε_(τ))and high quality factor(Q×f)are crucial to high-speed signal propagation systems.In this work,Zn^(2+)/Ge^(4+) co-doping to substitute Ga in ZnGa_(2)O_(4) was designed to lower the sintering temperature and adjust the thermal stability of resonance frequency simultaneously.Zn_(1+2)Ga_(2-2x)Ge_(x)O_(4)(0.1≤x≤0.5)ceramics were synthesised by the conventional solid state method.Zn^(2+)/Ge^(4+) co-substitution induced minimal variation in the macroscopical spinel structure,which effectively lowered the sintering temperature from 1385 to 1250℃.All compositions crystallized in a normal spinel structure and exhibited dense microstructures and excellent microwave dielectric properties.The compositional dependent quality factor was related to the microstructural variation,being confirmed by Raman features.A composition with x=0.3 shows the best dielectric properties with ε_(τ) ≈10.09,Q×f≈112,700 THz,and ε_(τ) ≈-75.6 ppm/℃.The negative τf value was further adjusted to be near-zero through the formation of composite ceramics with TiO_(2).

A low-firing melilite ceramic Ba2CuGe207 and compositional modulation on microwave dielectric properties through Mg substitution

A melilite Ba2CuGe2O7 ceramic was characterized by low sintering temperature and moderate microwave dielectric properties.Sintered at 960℃,the Ba2CuGe2O7 ceramic had a high relative density 97%,a low relative permittivity(εr)9.43,a quality factor(Q×f)of 20,000 GHz,and a temperature coefficient of resonance frequency(τf)-76 ppm/℃.To get a deep understanding of the relationship between composition,structure,and dielectric performances,magnesium substitution for copper in Ba2CuGe2O7 was conducted.Influences of magnesium doping on the sintering behavior,crystal structure,and microwave dielectric properties were studied.Mg doping in Ba2CuGe2O7 caused negligible changes in the macroscopic crystal structure,grain morphology,and size distribution,while induced visible variation in the local structure as revealed by Raman analysis.Microwave dielectric properties exhibit a remarkable dependence on composition.On increasing the magnesium content,the relative permittivity featured a continuous decrease,while both the quality factor and the temperature coefficient of resonance frequency increased monotonously.Such variations in dielectric performances were clarified in terms of the polarizability,packing fraction,and band valence theory.

Enhanced thermoelectric performance in p-type ZrCoSb based half-Heusler alloys employing nanostructuring and compositional modulation

ZrCoSb based half-Heusler(HH)alloys have been widely studied as a p-type thermoelectric(TE)material for power generation applications in the mid-temperature regime.However,their intrinsically high thermal conductivity has been found to be detrimental for the improvement in their thermoelectric figure-of-merit(ZT),which presently is far below unity.In the current work,a state-of-the-art ZT~1.1 at 873 K was realized in an optimized composition of nanostructured Zr1-xHfxCoSb_(0.9)Sn_(0.1) HH alloys by employing compositional modulation i.e.grain-by-grain compositional variations,which leads to a substantial increase in its power factor coupled with a concurrent decrease in its thermal conductivity.Significant reduction in the phonon mean-free-path is observed on Hf substitution,which is comparable to the average crystallite size(~25 nm),thus leading to a very low thermal conductivity of~2.2Wm^(-1)K^(-1) at 873 K,which is amongst the lowest reported in HH alloys.The TE device characteristics,estimated using cumulative temperature dependence model for quantitative evaluation of TE performance,yielded an output power density of~10 Wcm
2 with a leg efficiency of~10%in the optimized composition of nanostructured Zr_(1-x)Hf_(x)CoSb_(0.9)Sn_(0.1) HH alloys,which is comparable to the reported efficiencies of other state-of-the-art TE materials.