In-situ doping-induced lattice strain of NiCoP/S nanocrystals for robust wide pH hydrogen evolution electrocatalysis and supercapacitor

Developing high-efficiency multifunctional nanomaterials is promising for wide p H hydrogen evolution reaction(HER) and energy storage but still challenging. Herein, a novel in-situ doping-induced lattice strain strategy of NiCoP/S nanocrystals(NCs) was proposed through using seed crystal conversion approach with NiCo_(2)S_(4) spinel as precursor. The small amount of S atoms in NiCoP/S NCs perturbed the local electronic structure, leading to the atomic position shift of the nearest neighbor in the protocell and the nanoscale lattice strain, which optimized the H* adsorption free energy and activated H_(2)O molecules, resulting the dramatically elevated HER performance within a wide p H range. Especially, the NiCoP/S NCs displayed better HER electrocatalytic activity than comical 20% Pt/C at high current density in 1 M KOH and natural seawater: it only needed 266 m V vs. reversible hydrogen electrode(RHE) and660 m V vs. RHE to arrive the current density of 350 m A cm^(-2) in 1 M KOH and natural seawater, indicating the application prospect for industrial high current. Besides, NiCoP/S NCs also displayed excellent supercapacitor performance: it showed high specific capacity of 2229.9 F g^(-1) at 1 A g^(-1) and energy density of87.49 Wh kg^(-1), when assembled into an all-solid-state flexible device, exceeding performance of most transition metal phosphides. This work provides new insights into the regulation in electronic structure and lattice strain for electrocatalytic and energy storage applications.

A combined electrochemical and DFT study of the lattice strain effect on the surface reactivity of Pd

We report a combined study of electrochemical experiments and ab initio calculations on tuning the surface reactivity of Pd via a compressive lattice strain achieved by employing nanoparticles of Pd-Cu alloys with a Pd-rich surface. Surface oxygen-containing species were used as the probing molecule for revealing the surface reactivity. Both density functional theory （DFT） calculations and experiments showed linear relationships, with very close slopes, between the adsorption strength of OHads and the Pd lattice constant. Not only is this work a successful realization of controllable modulation in the surface reactivity, but it also provides valuable information for the rational design of Pd-based catalysts for fuel cell applications.

Surface chemical disorder and lattice strain of GaN implanted by 3-MeV Fe^(10+)ions

Chemical disorder on the surface and lattice strain in GaN implanted by Fe^(10+)ions are investigated.In this study,3-MeV Fe^(10+)ions fluence ranges from 1×10^(13)ions/cm^(2)to 5×10^(15)ions/cm^(2)at room temperature.X-ray photoelectron spectroscopy,high-resolution x-ray diffraction,and high-resolution transmission electron microscopy were used to characterize lattice disorder.The transition of Ga-N bonds to oxynitride bonding is caused by ion sputtering.The change of tensile strain out-of-plane with fluence was measured.Lattice disorder due to the formation of stacking faults prefers to occur on the basal plane.

Evolution of electrical and magnetotransport properties with lattice strain in La0.7Sr0.3MnO3 film

In this paper,we investigate the effects of lattice strain on the electrical and magnetotransport properties of La0.7Sr0.3MnO3(LSMO)films by changing film thickness and substrate.For electrical properties,a resistivity upturn emerges in LSMO films,i.e.,LSMO/STO and LSMO/LSAT with small lattice strain at a low temperature,which originates from the weak localization effect.Increasing film thickness weakens the weak localization effect,resulting in the disappearance of resistivity upturn.While in LSMO films with a large lattice strain(i.e.,LSMO/LAO),an unexpected semiconductor behavior is observed due to the linear defects.For magnetotransport properties,an anomalous in-plane magnetoresistance peak(pMR)occurs at low temperatures in LSMO films with small lattice strain,which is caused by two-dimensional electron gas(2DEG).Increasing film thickness suppresses the 2DEG,which weakens the pMR.Besides,it is found that the film orientation has no influence on the formation of 2DEG.While in LSMO/LAO films,the 2DEG cannot form due to the existence of linear defects.This work can provide an efficient way to regulate the film transport properties.

Facile lattice tensile strain compensation in mixed-cation halide perovskite solar cells

Despite the rapid development of power conversion efficiency(PCE)for halide perovskite solar cells(PSCs),the lattice strain engineering in perovskite thin films has been rarely probed in recent years.Herein,a strain compensation by homogeneous crystallization in perovskite films is achieved with the aid of precursor aging in the mixed-cation perovskite of Cs_(0.05)(FA_(0.83)MA_(0.17))Pb(I_(0.90)Br_(0.10))_(3)with near 20%PCE in inverted devices.The homogeneous crystallization releases the residual tensile stress and induces more compressive stress at the edges of perovskite films,thus elongating the carrier lifetime and reducing the trap-assisted carrier recombination.The high dependence on the perovskite components in strain engineering strategy was systematically revealed,wherein MAPbI_(3)and Cs_(0.05)(FA_(0.83)MA_(0.17))PbI_(3)film showed an increased compressive strain and FAPbI3 film showed adverse tensile strain after aging.The density functional theory(DFT)calculations are further performed to reveal the change of electronic features.The precursor aging-induced strain modulation was correlated with a systematic characterization of the charge carrier transport and recombination dynamics in the mixed-cation perovskite films.We believe that this facile approach provides a novel strain engineering strategy for PSCs technology.

Quantification of Compositional and Residual Stress Efects on Lattice Strain in Dual-phase Stainless Steels by Means of Diferential Aperture X-ray Micro-difraction

Residual stress is an important factor for evaluating the deformation and failure of engineering materials. Diffraction-based measurement assumes that the full measured lattice strain tensor contributes to residual stress according to Hookers Law. The present work focuses on the lattice strain determination of individual grains in a dual-phase stainless steel （DPSS） by means of differential-aperture X-ray micro-diffraction （DAXM）. The results show that the residual stress only takes part of the responsibility of the total measured lattice strain. In fact, the compositional variation inside the material was found to cause greater strain gradient in both ferrite （c~） and austenite （~） phases in DPSS. Therefore, quantification of compositional and residual stress effects on lattice strain was conducted in order to evaluate the true residual stress inside engineering materials.

Lattice strain suppresses point defect formation in halide perovskites

We computationally investigate the impact of crystal strain on the formation of native point defects likely to be formed in halide perovskites;A-site cation antisite(I_(A)),Pb antisite(I_(Pb)),A-site cation vacany(V_(A)),I vacancy(V_(I)),Pb vacancy(V_(Pb)),and I interstitial(I_(i)).We systematically identify compressive and tensile strain to CsPbI_(3),FAPbI_(3),and MAPbI_(3)perovskite structures.We observe that while each type of defect has a unique behaviour,overall,the defect formation in FAPbI3 is much more sensitive to the strain.The compressive strain can enhance the formation energy of neutral I_(Pb)and I_(i)up to 15%for FAPbI_(3),depending on the growth conditions.We show that the strain not only controls the formation of defects but also their transition levels in the band gap:A deep level can be transformed into a shallow level by the strain.We anticipate that tailoring the lattice strain can be used as a defect passivation mechanism for future studies.

Lattice strain driven dielectric insulation response of Sr_(1-x)Ca_(x)Bi_(2)Nb_(2)O_(9) ceramics

In this paper,effects of lttice strain on dielectric properties of Sr_(1-x)Ca_(x)Bi_(2)Nb_(2)O_(9)(x=0.0-0.5 in steps of 0.1)ceramics are reported.High frequency dipolar polarization is observed to increase for 10%calcium addition and suppresses thereafter on higher calcium concentrations.The dielectric loss values for all doped samples were lower compared to undoped one at frequencies beyond 1 kHz.The sample with x=0.1 shows room temperature dielectric constant in the range(130±12)over a wide frequency range from 50Hz to 1 MHz also minimum dielectric loss among all other sample for the same frequeny range.Remarkable increase in Curie temperature(T_(c))by 50℃ is recorded in the present work by increasing 10%calcium content in SBN compostion.All higher doped samples indicate increase in T_(c) by further higher amount.In addition,dc conductivity of all samples is measured for all samples and increase in calcium content is observed to generate more insulating compositions compared to undoped SBN with higher intrinsic activation energies.

A Modified Lattice Model of the Reversible Effect of Axial Strain on the Critical Current of Polycrystalline REBa2Cu3O7-δ Films

The strain effect on the critical current is one of the most important properties for polycrystalline YBa2 Cu3O7-δ （REBCO, RE： rare earth） films, in which the reversible effect is intrinsic in the range of strain 0 and the irreversible strain εirr. By introducing the applied strain, a modified grain boundaries （GBs） in the REBCO film is developed. lattice model combining the strain and misorientation of A good agreement of the calculation on the lattice model with the experimental data shows that the lattice model is able to well describe the reversible effect of axial strain on the critical current of the REBCO film, and provides a good understanding of the mechanism of the reversible effect of the strain. Moreover, the effects of the crystallographic texture of the REBCO film and the residual strain εr on the variation of the critical current with the applied strain are extensively investigated. Furthermore by using the developed lattice model, the irreversible strain εirr of the REBCO film can be theoretically determined by comparing the calculation of the critical current-strain curve with the experimental data.

Anchimetamorphism of the Neoproterozoic and the Lower Paleozoic along the Profile of Yuanguping in Western Hunan Province, China

The Neoproterozoic and Lower Paleozoic along the profile of Yuanguping in western Hunan Province, China underwent anchimetamorphism. The illite crystallinity (IC) of the <2 μm fractions ranges from 0.23-0.34°△2θfor the Neoproterozoic to 0.23-0.35°△A2θ for the Lower Paleozoic (calibrated with the Kisch IC set, Kisch, 1991). This indicates that the metamorphic grade of the Neoproterozoic and Lower Paleozoic is the anchizone. The peak metamorphic temperature is estimated to be 290-210℃. This result does not agree with the greenschist or subgreenschist facies of the Banxi Group, nor with the lower-greenschist facies or sedimentary cover of the Sinian to Lower Paleozoic, as most previous researchers thought. The illite (K-mica) b0 values range from 0.9074 to 0.8963 (nm) for the Neoproterozoic and the Lower Paleozoic. Based on cumulative frequency curves of the illite (K-mica) b0, the peak metamorphic pressure of the Banxi Group was derived to be of a type that is slightly higher than that of the N. New Hampshire low-intermediate pressure type. Most illites occur as the 2M1 polytype and some in the Neoproterozoic as a mixture of the 2M1+1M types. The distributions of coherent scanning domains (CSDs) of illites along the profile, measured with the XRD method, display a lognormal model and spread out with decreasing Kubler Index of IC. It indicates that illites underwent an Ostwald ripening. The post-anchimetamorphic structural movement not only results in a series of faults but also induces the lattice strain in minerals along the faults and hence impacts the illite crystallinity and causes diagenetic samples to occur within the anchizone. Compared with the cases in eastern and central Hunan Province, the Neoproterozoic and Lower Paleozoic rocks in the west underwent a lower-temperature anchimetamorphism with a pressure lower than that in the east and higher than that in the center of Hunan Province.

A New Method for Clay Mineral Analysis and Its Application in Geology

X-ray diffraction (XRD) peaks in a low-angle diffraction section of clayminerals, especially those of authigenic origin, have broadening and tailing features in shape.Using the five basic parameters, peak position, peak height, width, shape coefficient and asymmetry,to describe an XRD peak is more accurate, comprehensive and integrated than using only 3 of them,position, height and width. Following the concept of the five basic parameters of an XRD peak, theprogram Decoform proposed in this study provides more information in mineralogical analyses byfitting actual XRD profiles. In combination with the HW-IR plot, Decoform can he systematically andaccurately used in the comprehensive analyses of crystallinity, domain size, lattice strain andquantitative phase. It is also of value for the geological investigations of diagenesis,metamorphism, basin maturity, structural stress field and so on.

Microstructures and mechanical properties of nanocrystalline NiTi intermetallics formed by mechanosynthesis

The formulation of nanocrystallinc NiTi shape memory alloys has potential effects in mechanical stimulation and medical im- plantology. The present work elucidates the effect of milling time on the product＇s structural characteristics, chemical composition, and mi- crohardness for NiTi synthesized by mechanical alloying for different milling durations. Increasing the milling duration led to the formation of a nanocrystalline NiTi intermetallic at a higher level. The formation of nanocrystalline materials was directed through cold fusion, fractur- ing, and the development of a steady state, which were influenced by the accumulation of strain energy. In the morphological study, uninter- rupted cold diffusion and fracturing were visualized using transmission electron microscopy. Particle size analysis revealed that the mean particle size was reduced to -93 μm after 20 h of milling. The mechanical strength was enhanced by the formation of a nanocrystalline in- termetallic phase at longer milling time, which was confirmed by the results of Vickers hardness analyses.

A novelty strategy induced pinning effect and defect structure in Ni-rich layered cathodes towards boosting its electrochemical performance

Layered Ni-rich transition metal oxide is treated as the most promising alternative cathode due to their high-capacity and flexible composition.However,the severe lattice strain and slow Li-ion migration kinetics severely restrict their practical application.Herein,a novelty strategy induced pinning effect and defect structure in layered Ni-rich transition metal oxide cathodes is proposed via a facile cation(iron ion)/anion(polyanion)co-doping method.Subsequently,the effects of pinning effect and defect structure on element valence state,crystal structure,morphology,lattice strain,and electrochemical performance during lithiation/delithiation are systematically explored.The detailed characterizations(soft X-ray absorption spectroscopy(sXAS),in-situ X-ray diffraction(XRD),etc.)and density functional theory(DFT)calculation demonstrate that the pinning effects built-in LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)materials by the dual-site occupation of iron ions on lithium and transition metal sites effectively alleviate the abrupt lattice strain caused by an unfavorable phase transition and the subsequent induction of defect structures in the Li layer can greatly reduce the lithium-ion diffusion barrier.Therefore,the modified LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)exhibits a high-capacity of 206.5 mAh g^(-1)and remarkably enhanced capacity retention of 93.9%after 100 cycles,far superior to~14.1%of the pristine cathodes.Besides,an excellent discharge capacity of 180.1 mAh g^(-1)at 10 C rate is maintained,illustrating its remarkable rate capability.This work reports a pinning effect and defect engineering method to suppress the lattice strain and alleviate lithium-ion kinetic barriers in the Ni-rich layered cathodes,providing a roadmap for understanding the fundamental mechanism of an intrinsic activity modulation and structural design of layered cathode materials.

Improved efficiency and photo-stability of methylamine-free perovskite solar cells via cadmium doping

Although perovskite solar cells containing methylamine cation can show high power conversion efficiency,stability is a concern.Here,methylamine-free perovskite material Csx FA1–x PbI3 was synthesized by a one-step method.In addition,we incorporated smaller cadmium ions into mixed perovskite lattice to partially replace Pb ions to address the excessive internal strain in perovskite structure.We have found that the introduction of Cd can improve the crystallinity and the charge carrier lifetime of perovskite films.Consequently,a power conversion efficiency as high as 20.59%was achieved.More importantly,the devices retained 94%of their initial efficiency under 1200 h of continuous illumination.

Lattice-strained nanotubes facilitate efficient natural sunlight-driven CO_(2) photoreduction

Photocatalytic reduction of CO_(2) holds tremendous promise for alleviating the energy crisis.Despite the progress that has been,made,there are still some challenges to overcome,such as the realization under real sunlight rather than the simulation condition.In this work,ultrathin Ni_(2)(OH)(PO_(4))nanotubes(NTs)prepared through hydrothermal route are applied as a novel catalyst for photocatalytic reduction of CO_(2) under real sunlight.The prepared Ni_(2)(OH)(PO_(4))NTs exhibit a 11.3 μmol·h^(-1) CO production rate with,96.1% CO selectivity.Interestingly,Ni_(2)(OH)(PO_(4))NTs have a positive impact on the facilitation of photoreduction in diluted CO_(2).Notably,when the system is performed under real sunlight,Ni_(2)(OH)(PO_(4))NTs afford an accumulated CO of ca.26.8 nmol with,96.9% CO selectivity,exceeding most previous inorganic catalysts under simulated irradiation in the laboratory.Our experimental results demonstrate that the multisynergetic effects induced by surface-OH and the lattice strain serve as highly active sites for CO_(2) molecular adsorption and activation as well as electron transfer,hence enhancing photoreduction activity.Therefore,this work provides experimental basis that CO_(2) photocatalysis can be put into practical use.

Static strength of gold compressed up to 127 GPa

Gold powder is compressed non-hydrostatically up to 127 GPa in a diamond anvil cell （DAC）, and its angle dispersive X-ray diffraction patterns are recorded. The compressive strength of gold is investigated in a framework of the lattice strain theory by the line shift analysis. The result shows that the compressive strength of gold increases continuously with the pressure up to 106 GPa and reaches 2.8 GPa at the highest experimental pressure （127 GPa） achieved in our study. This result is in good agreement with our previous experimental result in a relevant pressure range. The compressive strength of gold may be the major source of the error in the equation-of-state measurement in various pressure environments.

Stable water droplets on composite structures formed by embedded water into fully hydroxylated β-cristobalite silica

Using molecular dynamics simulations, we have revealed a novel wetting phenomenon with a droplet on composite structures formed by embedded water into(111) surface of β-cristobalite hydroxylated silica. This can be attributed to the formation of a composite structure composed of embedded water molecules and the surface hydroxyl(–OH) groups,which reduces the number of hydrogen bonds between the composite structure and the water droplet above the composite structure. Interestingly, a small uniform strain(±3%) applied to the crystal lattice of the hydroxylated silica surface can result in a notable change of the contact angles(> 40°) on the surface. The finding provides new insights into the correlation between the molecular-scale interfacial water structures and the macroscopic wettability of the hydroxylated silica surface.

Atomic insights into heterogeneous nucleation and growth kinetics of Al on TiB_(2) particles in undercooled Al-5Ti-1B melt

Titanium diboride(TiB_(2))is an effective grain refiner of Al alloys in the industry that facilitates casting processes by forming uniformly refined microstructures.Although our understanding of the underlying refinement mechanisms has advanced,the atomic kinetics of heterogeneous nucleation of Al on TiB2 remains unknown.Here,we report atomic-scale observations of the heterogeneous nucleation and growth kinetics of Al on self-formed TiB_(2) particles by in situ heating of undercooled Al-5Ti-1B films.We demonstrate that an ordered Al monolayer forms on the Ti-terminated{0001}TiB_(2) surface;then,the surrounding Al atoms are initiated to form an island-shaped Al nucleus with face-centered cubic{111}stacking without the assistance of a Ti-rich buffer layer.The interfacial lattice mismatch between{111}Al and{0001}TiB_(2) causes remarkable out-of-plane strain that decreases gradually with Al nucleus layers increasing to 6 atomic layers.The elastic strain energy originating from this interfacial strain increases the free energy of the Al/TiB2 heterostructure,hence impeding the rapid growth of the Al nucleus.We found that TiB2 particles stabilize the Al nuclei rather than activating their free growth into grains when the experimental undercoolingΔT is lower than the onset undercoolingΔT fg in Greer's free growth model.Our findings provide an atomic-scale physical image of the heterogeneous nucleation and growth mechanisms of Al with inoculator participation and elucidate the strain-dependent growth kinetics of Al nuclei.

Core-shell gold-copper nanoparticles:Evolution of copper shells on gold cores at different gold/copper precursor ratios

Core-shell nanostructures usually exhibit tunable catalytic properties in comparison with their single core or shell counterpart due to electronic interaction and lattice strain between the core and shell regions.Herein,we report the intriguing evolution of copper(Cu)shells on the gold(Au)cores at different Au/Cu precursor ratios during the synthesis of core-shell Au-Cu nanoparticles at an organic medium via seed-mediated growth method.In brief,at relatively low Cu ratios,quasi-spherical Au-Cu nanoparticles with conventional core-shell structures are the majority products,in which the Cu shell thickness increases with the increase of Cu precursor ratios.The dif-ference is that at high Cu ratios,the Cu shells no longer increase their thickness,but evolve into a dendritic structure.Interestingly,the core-shell Au-Cu nanoparticles with dendritic Cu shells could be transformed into interesting Au-Cu cage-bell structures after a ripening process at elevated temperature.Further,through galvanic replacement reaction with Pt precursors,the thin Cu shells could be converted into CuPt alloy shells on the Au cores,which exhibit enhanced activity towards methanol oxidation reaction with satisfactory durability,in comparison with that of commercial Pt/C catalysts.

调控超细高熵合金晶格应变用于高活性和高稳定性甲醇氧化

高熵合金(HEAs)因其非常规的组成和独特的物理化学性质而得到广泛研究.本文,我们首次提出了一种表面应变策略来调控HEAs的电子结构用于高效的甲醇电氧化反应(MOR).高分辨像差校正扫描透射电子显微镜(STEM)和元素分布分析表明,在Pt Fe CoNi Cu HEAs中各原子分散均匀,并形成FCC晶体结构.700℃热处理所得HEA-700的压缩应变比400℃热处理所得HEA-400的压缩应变高0.94%.正如预期,HEA-700的比活性和质量活性远超HEA-400和目前大多数最先进的催化剂.MOR活性的增强归因于压缩应变导致HEA-700中Pt–Pt键距缩短.同时,核中的非贵金属原子通过转移电子到表面Pt层产生压缩应变和d带中心的下移.这项工作为高性能HEAs电催化剂的设计提供了一个新的视角.