In-Situ FT-IR Investigation Methane to Syngas over of Partial Oxidation of Rh/SiO2 Catalyst

Partial oxidation of methane to syngas （POM） over Rh/SiO2 catalyst was investigated using in-situ FT-IR. When methane interacted with 1.0wt%Rh/SiO2 catalyst, it was dissociated to adsorbed hydrogen and CHx species. The adsorbed hydrogen atoms were transferred to SiO2 surface by ＂spill-over＂ and reacted with lattice oxygen to form surface -OH species. POM mechanism was investigated over Rh/SiO2 catalyst using in-situ FT-IR. It was found that CO2 was formed before CO could be detected when CH4 and O2 were introduced over the preoxidized Rh/SiO2 catalyst, whereas CO was detected before CO2 was formed over the prereduced Rh/SiO2 catalyst.

In-situ interfacial passivation and self-adaptability synergistically stabilizing all-solid-state lithium metal batteries

The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.

Interplay of laser power and pore characteristics in selective laser melting of ZK60 magnesium alloys:A study based on in-situ monitoring and image analysis

This study offers significant insights into the multi-physics phenomena of the SLM process and the subsequent porosity characteristics of ZK60 Magnesium(Mg)alloys.High-speed in-situ monitoring was employed to visualise process signals in real-time,elucidating the dynamics of melt pools and vapour plumes under varying laser power conditions specifically between 40 W and 60 W.Detailed morphological analysis was performed using Scanning-Electron Microscopy(SEM),demonstrating a critical correlation between laser power and pore formation.Lower laser power led to increased pore coverage,whereas a denser structure was observed at higher laser power.This laser power influence on porosity was further confirmed via Optical Microscopy(OM)conducted on both top and cross-sectional surfaces of the samples.An increase in laser power resulted in a decrease in pore coverage and pore size,potentially leading to a denser printed part of Mg alloy.X-ray Computed Tomography(XCT)augmented these findings by providing a 3D volumetric representation of the sample internal structure,revealing an inverse relationship between laser power and overall pore volume.Lower laser power appeared to favour the formation of interconnected pores,while a reduction in interconnected pores and an increase in isolated pores were observed at higher power.The interplay between melt pool size,vapour plume effects,and laser power was found to significantly influence the resulting porosity,indicating a need for effective management of these factors to optimise the SLM process of Mg alloys.

In-situ X-ray computed tomography tensile tests and analysis of damage mechanism and mechanical properties in laser powder b e d fused Invar 36 alloy

Laser powder bed fusion(LPBF)is a potential additive manufacturing process to manufacture Invar 36 alloy components with complicated geometry.Whereas it inevitably introduces specific microstructures and pore defects,which will further influence the mechanical properties.Hence,aiming at exploring the LPBF process-related microstructures and pore defects,and especially their influences on the damage mechanism and mechanical properties,Invar 36 alloy was manufactured by LPBF under designed different laser scanning speeds.The microstructure observations reveal that higher scanning speeds lead to equiaxed and short columnar grains with higher dislocation density,while lower scanning speeds result in elongated columnar grains with lower dislocation density.The pore defects analyzed by X-ray computed tomography(XCT)suggest that the high laser scanning speed gives rise to numerous lamellar and large lack-of-fusion(LOF)pores,and the excessively low laser scanning speed produces relatively small keyhole pores with high sphericity.Moreover,the insitu XCT tensile tests were originally performed to evaluate the damage evolution and failure mechanism.Specifically,high laser scanning speed causes brittle fracture due to the rapid growth and coalescence of initial lamellar LOF pores along the scan-ning direction.Low laser scanning speed induces ductile fracture originating from unstable depressions in the surfaces,while metallurgical and keyhole pores have little impact on damage evolution.Eventually,the process-structure-property correlation is established.The presence of high volume fraction of lamel-lar LOF pores,resulting from high scanning speed,leads to inferior yield strength and ductility.Besides,specimens without LOF pores exhibit larger grain sizes and lower dislocation density at decreased scanning speeds,slightly reducing yield strength while slightly enhancing ductility.This understanding lays the foundation for widespread applications of LPBF-processed Invar 36 alloy.

In-situ coating and surface partial protonation co-promoting performance of single-crystal nickel-rich cathode in all-solid-state batteries

The poor electrochemical performance of all-solid-state batteries(ASSBs),which is assemblied by Ni-rich cathode and poly(ethylene oxide)(PEO)-based electrolytes,can be attributed to unstable cathodic interface and poor crystal structure stability of Ni-rich cathode.Several coating strategies are previously employed to enhance the stability of the cathodic interface and crystal structure for Ni-rich cathode.However,these methods can hardly achieve simplicity and high efficiency simultaneously.In this work,polyacrylic acid(PAA)replaced traditional PVDF as a binder for cathode,which can achieve a uniform PAA-Li(LixPAA(0<x≤1))coating layer on the surface of single-crystal LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)due to H^(+)/Li^(+)exchange reaction during the initial charging-discharging process.The formation of PAA-Li coating layer on cathode can promote interfacial Li^(+)transport and enhance the stability of the cathodic interface.Furthermore,the partially-protonated surface of SC-NCM83 casued by H^(+)/Li^(+)exchange reaction can restrict Ni ions transport to enhance the crystal structure stability.The proposed SC-NCM83-PAA exhibits superior cycling performance with a retention of 92%compared with that(57.3%)of SC-NCM83-polyvinylidene difluoride(PVDF)after 200 cycles.This work provides a practical strategy to construct high-performance cathodes for ASSBs.

Assessing the conservation impact of Chinese indigenous chicken populations between ex-situ and in-situ using genome-wide SNPs

Conservation programs require rigorous evaluation to ensure the preservation of genetic diversity and viability of conservation populations. In this study, we conducted a comparative analysis of two indigenous Chinese chicken breeds, Gushi and Xichuan black-bone, using whole-genome SNPs to understand their genetic diversity, track changes over time and population structure. The breeds were divided into five conservation populations(GS1, 2010, ex-situ;GS2, 2019, ex-situ;GS3, 2019, in-situ;XB1, 2010, in-situ;and XB2, 2019, in-situ) based on conservation methods and generations. The genetic diversity indices of three conservation populations of Gushi chicken showed consistent trends, with the GS3 population under in-situ strategy having the highest diversity and GS2 under ex-situ strategy having the lowest. The degree of inbreeding of GS2 was higher than that of GS1 and GS3. Conserved populations of Xichuan black-bone chicken showed no obvious changes in genetic diversity between XB1 and XB2. In terms of population structure, the GS3 population were stratified relative to GS1 and GS2. According to the conservation priority, GS3 had the highest contribution to the total gene and allelic diversity in GS breed, whereas the contribution of XB1 and XB2 were similar. We also observed that the genetic diversity of GS2 was lower than GS3, which were from the same generation but under different conservation programs(in-situ and ex-situ). While XB1 and XB2 had similar levels of genetic diversity. Overall, our findings suggested that the conservation programs performed in ex-situ could slow down the occurrence of inbreeding events, but could not entirely prevent the loss of genetic diversity when the conserved population size was small, while in-situ conservation populations with large population size could maintain a relative high level of genetic diversity.

In-situ AFM and quasi-in-situ studies for localized corrosion in Mg-9Al-1Fe-(Gd) alloys under 3.5 wt.% NaCl environment

Revealing the localized corrosion process of Mg alloy is considered as one of the most significant ways for improving its corrosion resistance.The reliable monitor should be high distinguishability and real-time in liquid environment.Herein,Mg-9Al-1Fe and Mg-9Al-1Fe-1Gd alloys were designed to highlight the impact of intermetallic on the corrosion behaviour.In-situ AFM with a special electrolyte circulation system and quasi-in-situ SEM observation were used to monitor the corrosion process of the designed alloys.SEM-EDS and TEM-SAED were applied to identify the intermetallic in the designed alloys,and their volta potentials were measured by SKPFM.According to the real-time and real-space in-situ AFM monitor,the corrosion process consisted of dissolution of anodicα-Mg phase,accumulation of corrosion products around cathodic phase and shedding of some fine cathodic phase.Then,the localized corrosion process of Mg alloy was revealed combined with the results of the monitor of corrosion process and Volta potential difference.

An in-situ study of static recrystallization in Mg using high temperature EBSD

It has been a common method to improve the mechanical properties of metals by manipulating their microstructures via static recrystallization,i.e.,through heat treatment.Therefore,the knowledge of recrystallization and grain growth is critical to the success of the technique.In the present work,by using in-situ high temperature EBSD,the mechanisms that control recrystallization and grain growth of an extruded pure Mg were studied.The experimental results revealed that the grains of priority for dynamic recrystallization exhibit fading competitiveness under static recrystallization.It is also found that grain boundary movement or grain growth is likely to show an inverse energy gradient effect,i.e.,low energy grains tend to swallow or grow into high energy grains,and grain boundaries of close to 30°exhibit superior growth advantage to others.Another finding is that{10-12}tensile twin boundaries are sites of hardly observed for recrystallization,and are finally swallowed by adjacent recrystallized grains.The above findings may give comprehensive insights of static recrystallization and grain growth of Mg,and may guide the design of advanced materials processing in microstructural engineering.

A continuous and long-term in-situ stress measuring method based on fiber optic. Part I: Theory of inverse differential strain analysis

A method for in-situ stress measurement via fiber optics was proposed. The method utilizes the relationship between rock mass elastic parameters and in-situ stress. The approach offers the advantage of long-term stress measurements with high spatial resolution and frequency, significantly enhancing the ability to measure in-situ stress. The sensing casing, spirally wrapped with fiber optic, is cemented into the formation to establish a formation sensing nerve. Injecting fluid into the casing generates strain disturbance, establishing the relationship between rock mass properties and treatment pressure.Moreover, an optimization algorithm is established to invert the elastic parameters of formation via fiber optic strains. In the first part of this paper series, we established the theoretical basis for the inverse differential strain analysis method for in-situ stress measurement, which was subsequently verified using an analytical model. This paper is the fundamental basis for the inverse differential strain analysis method.

An in-situ self-etching enabled high-power electrode for aqueous zinc-ion batteries

Sluggish storage kinetics is considered as the main bottleneck of cathode materials for fast-charging aqueous zinc-ion batteries(AZIBs).In this report,we propose a novel in-situ self-etching strategy to unlock the Palm tree-like vanadium oxide/carbon nanofiber membrane(P-VO/C)as a robust freestanding electrode.Comprehensive investigations including the finite element simulation,in-situ X-ray diffraction,and in-situ electrochemical impedance spectroscopy disclosed it an electrochemically induced phase transformation mechanism from VO to layered Zn_(x)V_(2)O_5·nH_(2)O,as well as superior storage kinetics with ultrahigh pseudocapacitive contribution.As demonstrated,such electrode can remain a specific capacity of 285 mA h g^(-1)after 100 cycles at 1 A g^(-1),144.4 mA h g^(-1)after 1500 cycles at 30 A g^(-1),and even 97 mA h g^(-1)after 3000 cycles at 60 A g^(-1),respectively.Unexpectedly,an impressive power density of 78.9 kW kg^(-1)at the super-high current density of 100 A g^(-1)also can be achieved.Such design concept of in-situ self-etching free-standing electrode can provide a brand-new insight into extending the pseudocapacitive storage limit,so as to promote the development of high-power energy storage devices including but not limited to AZIBs.

Microstructural characterization and mechanical properties of(TiC+TiB)/TA15 composites prepared by an in-situ synthesis method

Titanium matrix composites reinforced with ceramic particles are considered a promising engineering material due to their combination of high specific strength,low density,and high modulus.In this study,the TA15-based composites reinforced with a volume fraction of 10% to 25%(TiB+TiC)were prepared using powder metallurgy and casting technique.Microstructural characterization and phase constitution were examined using optical microscopy(OM),scanning electron microscopy(SEM),and X-ray diffraction(XRD).In addition,the microhardness,room temperature(RT)and high temperature(HT)tensile properties of the composites were evaluated.Results revealed that the reinforcements are distributed uniformly even in the composites with a high volume of TiB and TiC.However,as the volume fraction exceeds 15%,TiB and TiC particles become coarsening and exhibit rod-like and dendritic-like morphology.Microhardness increases gradually from 321.2 HV for the base alloy to a maximum of 473.3 HV as the reinforcement increases to 25vol.%.Tensile test results indicate that a reinforcement volume fraction above 20% is beneficial for enhancing tensile strength and yield strength at high temperatures,but it has an adverse effect on room temperature elongation.Conversely,if the reinforcement volume fraction is below 20%,it can improve high-temperature elongation when the temperature exceeds 600℃.

A review of in-situ high-temperature characterizations for understanding the processes in metallurgical engineering

For the rational manipulation of the production quality of high-temperature metallurgical engineering,there are many challenges in understanding the processes involved because of the black box chemical/electrochemical reactors.To overcome this issue,various in-situ characterization methods have been recently developed to analyze the interactions between the composition,microstructure,and solid-liquid interface of high-temperature electrochemical electrodes and molten salts.In this review,recent progress of in-situ hightemperature characterization techniques is discussed to summarize the advances in understanding the processes in metallurgical engineering.In-situ high-temperature technologies and analytical methods mainly include synchrotron X-ray diffraction(s-XRD),laser scanning confocal microscopy,and X-ray computed microtomography(X-rayμ-CT),which are important platforms for analyzing the structure and morphology of the electrodes to reveal the complexity and variability of their interfaces.In addition,laser-induced breakdown spectroscopy,high-temperature Raman spectroscopy,and ultraviolet-visible absorption spectroscopy provide microscale characterizations of the composition and structure of molten salts.More importantly,the combination of X-rayμ-CT and s-XRD techniques enables the investigation of the chemical reaction mechanisms at the two-phase interface.Therefore,these in-situ methods are essential for analyzing the chemical/electrochemical kinetics of high-temperature reaction processes and establishing the theoretical principles for the efficient and stable operation of chemical/electrochemical metallurgical processes.

Recent advances and key perspectives of in-situ studies for oxygen evolution reaction in water electrolysis

Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key half-reaction of performance-limiting in water splitting.Given the complicated reaction process and surface reconstruction of the involved catalysts under actual working conditions,unraveling the real active sites,probing multiple reaction intermediates and clarifying catalytic pathways through in-situ characterization techniques and theoretical calculations are essential.In this review,we summarize the recent advancements in understanding the catalytic process,unlocking the water oxidation active phase and elucidating catalytic mechanism of water oxidation by various in-situ characterization techniques.Firstly,we introduce conventionally proposed traditional catalytic mechanisms and novel evolutionary mechanisms of OER,and highlight the significance of optimal catalytic pathways and intrinsic stability.Next,we provide a comprehensive overview of the fundamental working principles,different detection modes,applicable scenarios,and limitations associated with the in-situ characterization techniques.Further,we exemplified the in-situ studies and discussed phase transition detection,visualization of speciation evolution,electronic structure tracking,observation of reaction active intermediates,and monitoring of catalytic products,as well as establishing catalytic structure-activity relationships and catalytic mechanism.Finally,the key challenges and future perspectives for demystifying the water oxidation process are briefly proposed.

In-situ electrochemical study on the eff ects of Fe(Ⅲ)on kinetics of pyrite acidic pressure oxidation

Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electrochemical investigation was performed using a flow-through autoclave system in acidic pressure oxidation environment.The results illustrated that increasing Fe(Ⅲ)concentrations led to raising in redox potential of the solution,and decreased passivation of pyrite caused by deposition of elemental sulfur.Reduction of Fe(Ⅲ)at pyrite surface was a fast reaction with low activation energy,it was only slightly promoted by rising temperatures.While,the oxidation rate of pyrite at all investigated Fe(Ⅲ)concentrations increased obviously with rising temperatures,the anodic reaction was the rate-limiting step in the overall reaction.Activation energy of pyrite oxidation decreased from 47.74 to 28.79 kJ/mol when Fe(Ⅲ)concentration was increased from 0.05 to 0.50 g/L,showing that the reaction kinetics were limited by the rate of electrochemical reaction at low Fe(Ⅲ)concentrations,while,it gradually turned to be diffusion control with increasing Fe(Ⅲ)concentrations.

Probing the Nucleation and Growth Kinetics of Bismuth Nanoparticles via In-situ Transmission Electron Microscopy

The nucleation and growth mechanism of nanoparticles is an important theory,which can guide the preparation of nanomaterials.However,it is still lacking in direct observation on the details of the evolution of intermediate state structure during nucleation and growth.In this work,the evolution process of bismuth nanoparticles induced by electron beam was revealed by in-situ transmission electron microscopy(TEM)at atomic scale.The experimental results demonstrate that the size,stable surface and crystallographic defect have important influences on the growth of Bi nanoparticles.Two non-classical growth paths including single crystal growth and polycrystalline combined growth,as well as,corresponding layer-by-layer growth mechanism along{012}stable crystal plane of Bi nanoparticles with dodecahedron structure were revealed by in-situ TEM directly.These results provide important guidance and a new approach for in-depth understanding of the nucleation and growth kinetics of nanoparticles.

In-situ polymerized PEO-based solid electrolytes contribute better Li metal batteries:Challenges,strategies,and perspectives

Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteries(SSLMBs).However,PEO-based SPEs suffer from low ionic conductivity at room temperature and high interfacial resistance with the electrodes due to poor interfacial contact,seriously hindering their practical applications.As an emerging technology,in-situ polymerization process has been widely used in PEO-based SPEs because it can effectively increase Li-ion transport at the interface and improve the interfacial contact between the electrolyte and electrodes.Herein,we review recent advances in design and fabrication of in-situ polymerized PEO-based SPEs to realize enhanced performance in LMBs.The merits and current challenges of various SPEs,as well as their stabilizing strategies are presented.Furthermore,various in-situ polymerization methods(such as free radical polymerization,cationic polymerization,anionic polymerization)for the preparation of PEO-based SPEs are summarized.In addition,the application of in-situ polymerization technology in PEO-based SPEs for adjustment of the functional units and addition of different functional filler materials was systematically discussed to explore the design concepts,methods and working mechanisms.Finally,the challenges and future prospects of in-situ polymerized PEO-based SPEs for SSLMBs are also proposed.

Development review and the prospect of oil shale in-situ catalysis conversion technology

As an unconventional resource, oil shale possesses abundant reserves and significant potential for industrial applications. The rational and efficient development of oil shale resources holds immense importance in reducing national energy demand. In-situ catalytic technology, characterized by its high efficiency, low pollution, and minimal energy consumption, represents a key direction for future oil shale development. This paper provides a comprehensive review of research progress in in-situ oil shale mining technology, oil shale pyrolysis catalysts, the pyrolysis mechanism of kerogen, and the compatibility of different heating processes and catalysts. Furthermore, the paper proposes future research directions and prospects for oil shale in-situ catalytic technology, including reservoir modification, highefficiency catalyst synthesis, injection processes, and high-efficiency heating technology. These insights serve as valuable technical references for the advancement of oil shale in-situ catalytic technology.

Performance of water-coupled charge blasting under different in-situ stresses

Water-coupled charge blasting is a promising technique to efficiently break rock masses.In this study,numerical models of double boreholes with water-coupled charge are established using LS-DYNA and are calibrated by the tests of rock masses subjected to explosion loads to examine its performance.The crack levels of rock mass induced by water-coupled charge blasting and air-coupled charge blasting are first compared.It is found that water-coupled charge blasting is more appropriate to fracture deep rock mass than air-coupled charge blasting.In addition,the effects of rock properties,water-coupled charge coefficients,and borehole connection angles on the performance of water-coupled charge blasting are investigated.The results show that rock properties and water-coupled charge coefficients can greatly influence the crack and fragmentation levels of rock mass induced by water-coupled charge blasting under uniform and non-uniform in-situ stresses.However,changing borehole-connection angles can only affect crack and fragmentation levels of rock mass under non-uniform in-situ stresses but barely affect those under uniform in-situ stresses.A formula is finally proposed by considering the above-mentioned factors to provide the design suggestion of water-coupled charge blasting to fracture rock mass with different in-situ stresses.

Progress in in-situ electrochemical nuclear magnetic resonance for battery research

A thorough understanding of the fundamental electrochemical and chemical processes in batteries is crucial to advancing energy density and power density.However,the characterizations of such processes are complex.In-situ electrochemical nuclear magnetic resonance(EC-NMR)offers the capability to collect real-time data during battery operation,furnishing insights into the local structures and ionic dynamics of materials by monitoring changes in the chemical environment around the nuclei.EC-NMR also has the advantages of being both quantitative and non-destructive.This paper systematically reviews the design of EC-NMR approach,and delves into the applications and progress of EC-NMR concerning battery reaction mechanisms,failure mechanisms,and overall battery systems.The review culminates in a comprehensive summary of the perspective and challenges associated with EC-NMR.

Effect of solution treatment on the microstructure,phase transformation behavior and functional properties of NiTiNb ternary shape memory alloys fabricated via laser powder bed fusion in-situ alloying

Post-heat treatment is commonly employed to improve the microstructural homogeneity and enhance the mechanical performances of the additively manufactured metallic materials.In this work,a ternary(NiTi)91Nb9(at.%)shape memory alloy was produced by laser powder bed fusion(L-PBF)using pre-alloyed NiTi and elemental Nb powders.The effect of solution treatment on the microstructure,phase transformation behavior and mechanical/functional performances was investigated.The in-situ alloyed(NiTi)91Nb9 alloy exhibits a submicron cellular-dendritic structure surrounding the supersaturated B2-NiTi matrix.Upon high-temperature(1273 K)solution treatment,Nb-rich precipitates were precipitated from the supersaturated matrix.The fragmentation and spheroidization of the NiTi/Nb eutectics occurred during solution treatment,leading to a morphological transition from mesh-like into rod-like and sphere-like.Coarsening of theβ-Nb phases occurred with increasing holding time.The martensite transformation temperature increases after solution treatment,mainly attributed to:(i)reduced lattice distortion due to the Nb expulsion from the supersaturated B2-NiTi,and(ii)the Ti expulsion from theβ-Nb phases that lowers the ratio Ni/Ti in the B2-NiTi matrix,which resulted from the microstructure changes from non-equilibrium to equilibrium state.The thermal hysteresis of the solutionized alloys is around 145 K after 20%pre-deformation,which is comparable to the conventional NiTiNb alloys.A short-term solution treatment(i.e.at 1273 K for 30 min)enhances the ductility and strength of the as-printed specimen,with the increase of fracture stress from(613±19)MPa to(781±20)MPa and the increase of fracture strain from(7.6±0.1)%to(9.5±0.4)%.Both the as-printed and solutionized samples exhibit good tensile shape memory effects with recovery rates>90%.This work suggests that post-process heat treatment is essential to optimize the microstructure and improve the mechanical performances of the L-PBF in-situ alloyed parts.