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.

Exponential Time Differencing Method for a Reaction-Diffusion System with Free Boundary

For reaction-diffusion equations in irregular domains with moving boundaries,the numerical stability constraints from the reaction and diffusion terms often require very restricted time step sizes,while complex geometries may lead to difficulties in the accuracy when discretizing the high-order derivatives on grid points near the boundary.It is very challenging to design numerical methods that can efficiently and accurately handle both difficulties.Applying an implicit scheme may be able to remove the stability constraints on the time step,however,it usually requires solving a large global system of nonlinear equations for each time step,and the computational cost could be significant.Integration factor(IF)or exponential time differencing(ETD)methods are one of the popular methods for temporal partial differential equations(PDEs)among many other methods.In our paper,we couple ETD methods with an embedded boundary method to solve a system of reaction-diffusion equations with complex geometries.In particular,we rewrite all ETD schemes into a linear combination of specificФ-functions and apply one state-of-the-art algorithm to compute the matrix-vector multiplications,which offers significant computational advantages with adaptive Krylov subspaces.In addition,we extend this method by incorporating the level set method to solve the free boundary problem.The accuracy,stability,and efficiency of the developed method are demonstrated by numerical examples.

Support design method for deep soft-rock tunnels in non-hydrostatic high in-situ stress field

Due to the long-term plate tectonic movements in southwestern China,the in-situ stress field in deep formations is complex.When passing through deep soft-rock mass under non-hydrostatic high in-situ stress field,tunnels will suffer serious asymmetric deformation.There is no available support design method for tunnels under such a situation in existing studies to clarify the support time and support stiffness.This study first analyzed the mechanical behavior of tunnels in non-hydrostatic in-situ stress field and derived the theoretical equations of the ground squeezing curve(GSC)and ground loosening curve(GLC).Then,based on the convergence confinement theory,the support design method of deep soft-rock tunnels under non-hydrostatic high in-situ stress field was established considering both squeezing and loosening pressures.In addition,this method can provide the clear support time and support stiffness of the second layer of initial support.The proposed design method was applied to the Wanhe tunnel of the China-Laos railway in China.Monitoring data indicated that the optimal support scheme had a good effect on controlling the tunnel deformation in non-hydrostatic high in-situ stress field.Field applications showed that the secondary lining could be constructed properly.

In-situ elemental reaction-regulated Ag_(2)S films enable the best thermoelectric performances

Silver sulfide thinfilm,with excellent thermoelectric properties,is few reported due to the complex and time-consuming high-temperature or high-pressure synthesis process.Here,a fast ionic conductor n-type Ag2Sfilm with good crystallinity and uniform density is prepared by sputtering metal Agfilms of different thicknesses on glass and then reacting in S precursor solution at low temperature.At 450 K,β-Ag2Sfilms can be obtained and underwent a phase transition fromα-Ag2S monoclinic,which had a significant effect on their electrical and thermal properties.The grain size of Ag2Sfilms increases with the increase offilm thickness.Before and after the phase transition,the carrier concentration and mobility cause obvious changes in the electrical properties of Ag2S.The carrier concentration of body-centered cubic phaseβ-Ag2S is about three orders of magnitude higher than that of monoclinic phaseα-Ag2S,and the mobility is also 2–3 times that of the latter.Especially,after the phase transition,the conductivity ofβ-Ag2S rises exponentially from the zero conductivity ofα-Ag2S and increases with the increase of temperature.The Ag2Sfilm shows the highestfigure of merit of 0.830.30 at 600 K from the sample with±∼1600 nm thickness,which is the highest record among Ag2S-based thermoelectric materials reported so far.

Comparison of the interface reaction behaviors of CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) solid-state systems based on the diffusion couple method

The formation mechanism of calcium vanadate and manganese vanadate and the difference between calcium and manganese in the reaction with vanadium are basic issues in the calcification roasting and manganese roasting process with vanadium slag.In this work,CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples were prepared and roasted for different time periods to illustrate and compare the diffusion reaction mechanisms.Then,the changes in the diffusion product and diffusion coefficient were investigated and calculated based on scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) analysis.Results show that with the extension of the roasting time,the diffusion reaction gradually proceeds among the CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples.The regional boundaries of calcium and vanadium are easily identifiable for the CaO–V_(2)O_(5) diffusion couple.Meanwhile,for the MnO_(2)–V_(2)O_(5) diffusion couple,MnO_(2) gradually decomposes to form Mn_(2)O_(3),and vanadium diffuses into the interior of Mn_(2)O_(3).Only a part of vanadium combines with manganese to form the diffusion production layer.CaV_(2)O_(6) and MnV_(2)O_(6) are the interfacial reaction products of the CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples,respectively,whose thicknesses are 39.85 and 32.13μm when roasted for 16 h.After 16 h,both diffusion couples reach the reaction equilibrium due to the limitation of diffusion.The diffusion coefficient of the CaO–V_(2)O_(5) diffusion couple is higher than that of the MnO_(2)–V_(2)O_(5) diffusion couple for the same roasting time,and the diffusion reaction between vanadium and calcium is easier than that between vanadium and manganese.

Microstructure and mechanical properties of Fe/NbC composite layer prepared by in-situ reaction

NbC ceramic surface-reinforced steel matrix composites were prepared by an in-situ reaction method at different temperatures(1,050℃,1,100℃and 1,150℃)for different times(1 h,2 h and 3 h).The phase constitution,microstructure and fracture morphology of NbC ceramic surface-reinforced steel matrix composites were analyzed by XRD,SEM and EDS,and the effects of the in-situ reaction temperature and time on the mechanical properties were systematically studied.The results indicate that the NbC reinforcement layer is formed through the reaction between Nb atoms and carbon atoms diffused from the steel matrix to the Nb plate.The thickness of this reinforcement layer increases as the reaction time prolongs.Additionally,an increase in reaction temperature results in a thicker reinforcement layer,although the rate of increase gradually decreases.The relationship among the thickness of the Nb C reinforcement layer,the reaction time and temperature was established by data fitting.The optimal tensile performance is achieved at 1,100℃for 1 h,with a tensile strength of 228 MPa.It is also found that the defects between the reinforcement layer and the steel matrix are related to reaction temperature.At 1,100℃,these defects are minimal.Fracture mostly occurs in the NbC reinforced layer of the composites,and the fracture mode is characterized by typical intergranular brittle fracture.

Eutectic Solution Enables Powerful Click Reaction for In-Situ Construction of Advanced Gel Electrolytes

Thiol-ene click reaction is an intriguing strategy for preparing polymer electrolytes due to its high activity,atom economy and less side reaction.However,the explosive reaction rate and the use of non-electrolytic amine catalyst hamper its application in in-situ batteries.Herein,a nitrogen-containing eutectic solution is designed as both the catalyst of the thiol-ene reaction and the plasticizer to in-situ synthesize the gel polymer electrolytes,realizing a mild in-situ gelation process and the preparation of high-performance gel electrolytes.The obtained gel polymer electrolytes exhibit a high ionic conductivity of 4×10^(−4)S cm^(−1)and lithium-ion transference number(t_(Li)^(+))of 0.51 at 60°C.The as-assembled Li/LiFePO_(4)(LFP)cell delivers a high initial discharge capacity of 155.9 mAh g^(-1),and a favorable cycling stability with the capacity retention of 82%after 800 cycles at 1 C is also obtained.In addition,this eutectic solution significantly improves the rate performance of the LFP cell with high specific capacity of 141.5 and 126.8 mAh g^(-1)at 5 C and 10 C,respectively,and the cell can steadily work at various charge–discharge rate for 200 cycles.This powerful and efficient strategy may provide a novel way for in-situ preparing gel polymer electrolytes with desirable comprehensive performances.

Synthesis strategies of covalent organic frameworks: An overview from nonconventional heating methods and reaction media

Covalent organic frameworks(COFs), as an emerging class of porous crystalline materials constructed by covalent links between the building monomers, have gained tremendous attention. Over the past 15 years, COFs have made rapid progress and substantial development in the chemistry and materials fields. However, the synthesis of COFs has been dominated by solvothermal methods for a long time and it usually involves high temperature, high pressure and toxic organic solvents, which created many challenges for environmental considerations. Recently,the exploration of new approaches for facile fabrication of COFs has aroused extensive interest. Hence, in this review, we comprehensively describe the synthetic strategies of COFs from the aspects of nonconventional heating methods and reaction media. In addition, the advantages,limitations and properties of the preparation methods are compared. Finally, we outline the main challenges and development prospects of the synthesis of COFs in the future and propose some possible solutions.

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.

Highly mass activity electrocatalysts with ultralow Pt loading on carbon black for hydrogen evolution reaction

Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.

Synthesis methods and powder quality of titanium monocarbide

Titanium monocarbide(TiC),which is the most stable titanium-based carbide,has attracted considerable interest in the fields of energy,catalysis,and structural materials due to its excellent properties.Synthesis of high-quality TiC powders with low cost and high efficiency is crucial for industrial applications;however major challenges face its realization.Herein,the methods for synthesizing TiC powders based on a reaction system are reviewed.This analysis is focused on the underlying mechanisms by which synthesis methods affect the quality of powders.Notably,strategies for improving the synthesis of highquality powders are analyzed from the perspective of enhancing heat and mass transfer processes.Furthermore,the critical issues,challenges,and development trends of the synthesis technology and application of high-quality TiC powder are discussed.

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.

Highly Defective Dark TiO_(2) Modified with Pt: Effects of Precursor Nature and Preparation Method on Photocatalytic Properties

The study focused on the modification with platinum of dark defective titania obtained via pulsed laser ablation. Both the method of Pt introduction and the nature of the Pt precursor were varied. All samples exhibited similar phase compositions, specific surface areas, and Pt contents. High-resolution transmission electron microscopy coupled with pulsed CO adsorption revealed increased dispersity when photoreduction and the hydroxonitrate complex (Me _(4) N) _(2) [Pt _(2) (OH) _(2) (NO _(3) ) _(8) ] were used. The sample featured a high content of single-atom species and subnano-sized Pt clusters. The X-ray photoelectron spectroscopy results showed that the photoreduction method facilitated the appearance of a larger number of Pt ^(2+) states, which appeared owing to the strong metal-support interaction (SMSI) eff ect of the transfer of electron density from the electron-saturated defects on the TiO _(2) surface to Pt ^(4+) . In the hydrogen evolution reaction, samples with a significant fraction of the Pt ^(2+) ionic component, capable of generating short-lived Pt^(0) single-atom sites under irradiation due to the SMSI eff ect, exhibited the highest photocatalytic activity. The 0.5Pt(C)/TiO_(2) -Ph sample exhibited the highest hydrogen yield with a quantum efficiency of 0.53, retaining its activity even after 8 h of operation.

Prediction of the Photofading of Selected Derivatives of 5-(4-X-Phenylazo)-3-Cyano-1-(H or Ethyl)-6-Hydroxy-4-Methyl-2-Pyridone: Theoretical Studies, Comparison of AM1 and PM3 Methods

We analysed the photooxidation reaction in the electro-(1O2) and nucleophilic (O2•−) reaction of 2-pyridone azo derivatives. First, we calculated the energy (enthalpies) of tautomers formation, which is a measure of durability and the probability of their formation. We performed the light fastness calculations of the monoazopyridone dyes. Using the semi-empirical methods of quantum chemistry AM1 and PM3, the reactivity indicators of superdelocalisability (SrE(N)) and the electron density distribution in ground state on the highest occupied HOMO orbital and the lowest unoccupied excited state LUMO in 2-pyridone phenylazo derivatives were calculated. Superdelocalisability coefficients enable the stability to oxidising agents of various chemical molecules depending on the tautomeric forms in which they may occur. The results of the electron density calculations at the HOMO and LUMO boundary orbitals allow to determine the tendency to electrophilic attack with singlet oxygen 1O2 or nucleophilic attack of the superoxide anion O2•−on a specific atom in the molecule. The structure of the dyes was optimised with MM+, MD and AM1 or PM3 until a constant energy value was achieved with a convergence criterion of 0.01 kcal/mol.

Preparation and wear properties of TiB_2/Al-30Si composites via in-situ melt reactions under high-energy ultrasonic field

TiB2/Al-30Si composites were fabricated via in-situ melt reaction under high-energy ultrasonic field. The microstructure and wear properties of the composite were investigated by XRD, SEM and dry sliding testing. The results indicate that TiB2 reinforcement particles are uniformly distributed in the aluminum matrix under high-energy ultrasonic field. The morphology of the TiB2 particles is in circle-shape or quadrangle-shape, and the size of the particles is 0.1-1.5μm. The primary silicon particles are in quadrangle-shape and the average size of them is about 10μm. Hardness values of the Al-30Si matrix alloy and the TiB2/Al-30Si composites considerably increase as the high energy ultrasonic power increases. In particular, the maximum hardness value of the in-situ composites is about 1.3 times as high as that of the matrix alloy when the ultrasonic power is 1.2 kW, reaching 412 MPa. Meanwhile, the wear resistance of the in-situ TiB2/Al-30Si composites prepared under high-energy ultrasonic field is obviously improved and is insensitive to the applied loads of the dry sliding testing.

Effects of reaction parameters on preparation of Cu nanoparticles via aqueous solution reduction method with NaBH_4

The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions for preparing well-dispersed nanoparticles were found as follows: 0.4 mol/L NaBH4 was added into solution containing 0.2 mol/L Cu2+, 1.0% gelatin dispersant in mass fraction, and 1.2 mol/L NH3?H2O at pH 12 and 313 K. In addition, a series of experiments were performed to discover the reaction process. NH3?H2O was found to be able to modulate the reaction process. At pH=10, Cu2+ was transformed to Cu(NH3)42+ as precursor after the addition of NH3?H2O, and then Cu(NH3)42+ was reduced by NaBH4 solution. At pH=12, Cu2+ was transformed to Cu(OH)2 as precursor after the addition of NH3?H2O, and Cu(OH)2 was then reduced by NaBH4 solution.

Extracting reaction mechanism analysis of Zn and Si from zinc oxide ore by NaOH roasting method

The orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore with NaOH aiming to comprehensively utilize zinc oxide ore.The optimized reaction conditions were molar ratio of NaOH to zinc oxide ore 6:1,roasting temperature 450°C,holding time 150 min.The molar ratio of NaOH to zinc oxide ore was the most predominant factor affecting the extraction ratios of zinc oxide and silica.The mineral phase transformations were investigated by testing the phases of specimens obtained at different temperatures.The process was that silica reacted with molten NaOH to form Na_2SiO_3 at first,then transformed into Na_4SiO_4 with temperature rising.ZnCO_3 and its decomposing product ZnO reacted with NaOH to form Na_2ZnO_2.Na_2ZnSiO_4was also obtained.The reaction rate was investigated using unreacted shrinking core model.Two models used were chemical reaction at the particle surface and diffusion through the product layer.The results indicated that the reaction rate was combine-controlled by two models.The activation energy and frequency factor were obtained as 24.12 k J/mol and 0.0682,respectively.

Preparation of Al-Al_3Ti in situ composites by direct reaction method

Al-Al3Ti composites were prepared by a direct reaction method, in which Al3Ti was formed by the reaction of Ti and Al in aluminum alloy melt. The morphology of Al3Ti changes apparently from the fine particle, needle-like to large block with the increase of Al3Ti content. The addition of magnesium can markedly change the morphology of Al3Ti and reduce their size. Short rod-like Al3Ti was formed and homogeneous distribution was obtained with the addition of 3 wt.% Mg. The effect of Al3Ti and Mg on the microstructure of Al-Al3Ti composites and the mechanism were also discussed.

ASYMPTOTIC METHOD OF TRAVELLING WAVE SOLUTIONS FOR A CLASS OF NONLINEAR REACTION DIFFUSION EQUATION

In this article the travelling wave solution for a class of nonlinear reaction diffusion problems are considered. Using the homotopic method and the theory of travelling wave transform, the approximate solution for the corresponding problem is obtained.

Stress initialization methods for dynamic numerical simulation of rock mass with high in-situ stress

In the context of deep rock engineering,the in-situ stress state is of major importance as it plays an important role in rock dynamic response behavior.Thus,stress initialization becomes crucial and is the first step for the dynamic response simulation of rock mass in a high in-situ stress field.In this paper,stress initialization methods,including their principles and operating procedures for reproducing steady in-situ stress state in LS-DYNA,are first introduced.Then the most popular four methods,i.e.,explicit dynamic relaxation(DR)method,implicit-explicit sequence method,Dynain file method and quasi-static method,are exemplified through a case analysis by using the RHT and plastic hardening rock material models to simulate rock blasting under in-situ stress condition.Based on the simulations,it is concluded that the stress initialization results obtained by implicit-explicit sequence method and dynain file method are closely related to the rock material model,and the explicit DR method has an obvious advantage in solution time when compared to other methods.Besides that,it is recommended to adopt two separate analyses for the whole numerical simulation of rock mass under the combined action of in-situ stress and dynamic disturbance.