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.

Effects of temperature on fracture behavior of Al-based in-situ composites reinforced with Mg_2Si and Si particles fabricated by centrifugal casting

An aluminum-based in-situ composites reinforced with Mg2Si and Si particles were produced by centrifugal casting A1-20Si-5Mg alloy. The microstructure of the composites was examined, and the effects of temperature on fracture behavior of the composite were investigated. The results show that the average fraction of primary Si and Mg2Si particles in the composites is as high as 38%, and ultimate tensile strengths （UTS） of the composites first increase then decrease with the increase of test temperature. Microstructures of broken specimens show that both the particle fracture and the interface debonding affect the fracture behavior of the composites, and the interface debonding becomes the dominant fracture mechanism with increasing test temperature. Comparative results indicate that rich particles in the composites and excellent interface strength play great roles in enhancing tensile property by preventing the movement of dislocations.

Interfacial reactions between Ti-1100 alloy and CaO crucible during casting process

Ti-1100 alloys were melted in a controlled atmospheric induction furnace equipped with a Ca O crucible. The microstructure, chemical composition, microhardness and metal-crucible interfacial reactions were systematically investigated. The results demonstrate that the primary solidification microstructure in the as-cast alloys was the typical Widmansttten structure. The interactions between crucible and molten alloys are attributed to slight chemical dissolution and weak physical erosion. According to the line scanning analysis, the interfacial layer（α-case） thicknesses of Ti-1100 samples in the bottom and side wall are about 18 and 17 μm, respectively, which are slightly lower than those presented from microhardness tests（25 and 20 μm）. The formation of α-case was caused by interstitial oxygen atoms. The standard Gibbs energy of reaction Ca O（s）=Ca＋O for Ti-1100 alloy was also determined. The equilibrium constant and the interaction parameter between calcium and oxygen were obtained as lg K=-3.14 and eCa O =-3.54.

Reaction between Ti and boron nitride based investment shell molds used for casting titanium alloys

The aim of this paper was to study the reaction between a Ti-6Al-4V alloy and boron nitride based investment shell molds used for investment casting titanium. In BN based investment shell molds, the face coatings are made of pretreated hexagonal boron nitride （hBN） with a few yttria （Y2O3） and colloidal yttria as binder. The Ti-6Al-4V alloy was melted in a controlled atmosphere induction furnace with a segment water-cooled copper crucible. The cross-section of reaction interface between Ti alloys and shell mold was investigated by electron probe micro-analyzer （EPMA） and microhardness tester. The results show that the reaction is not serious, the thickness of the reacting layer is about 30-50 μm, and the thickness of α-case is about 180-200 pro. Moreover the α-case formation mechanism was also discussed.

Reaction procedure of a graphite fiber reinforced Ti-Al composite produced by squeeze casting-in situ reaction

The in situ reaction procedure and microstructure evolution of a graphite fiber reinforced Ti-Al composite （Grf/Ti-Al） was investigated, and the stability of TiAl3 at high temperature was discussed. As-cast material was prepared by pressing molten pure aluminum into a preform, which was composed of titanium particles and graphite fibers. The in situ reaction procedure of the as-cast material was investigated by differential scanning calorimetry （DSC）, and phases in the products were detected by X-ray diffraction （XRD）. Experimental results showed that TiAl3 was formed first. With an increase in temperature, TiC and Al4C3 were observed, but TiAl3 decreased. In the final product, Al2O3 and TiO2 were observed. It was considered that the previous forming TiAl3 decomposed, then TiC precipitated, and subsequently, oxidation resulted in the formation of Al2O3 and TiO2.

In-situ observation of porosity formation during directional solidification of Al-Si casting alloys

In-situ observation of porosity formation during directional solidification of two Al-Si alloys (7%Si and 13%Si) was made by using of micro-focus X-ray imaging.In both alloys,small spherical pores initially form in the melt far away from the eutectic solid-liquid (S/L) interface and then grow and coagulate during solidification.Some pores can float and escape from the solidifying melt front at a relatively high velocity.At the end of solidification,the remaining pores maintain spherical morphology in the near eutectic alloy but become irregular in the hypoeutectic alloy.This is attributed to different solidification modes and aluminum dendrite interactions between the two alloys.The mechanism of the porosity formation is briefly discussed in this paper.

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.

Structure and Performance of Fe-N_x-C Catalyst for Oxygen Reduction Reaction Prepared by Vacuum Casting Method and the Second Pyrolysis

Affordable non-precious metal（NPM） catalysts played a vital role in the wide application of polymer electrolyte membrane fuel cells（PEMFC）. In current work, a facile vacuum casting reacting method based on vacuum casting was introduced to prepare Fe-N_x-C oxygen reduction reaction（ORR） catalysts with high efficient in acid medium. The catalysts were prepared with ammonium ferrous sulfate hexahydrate（AFS） and 1,10-phenanthroline monohydrate utilizing homemade mesoporous silica template. The heat treatment and its influence on structure and performance were systematically evaluated to achieve superior ORR performance and some clues were found. And 850 ℃ was found to be the best temperature for the first and second pyrolysis. The linear sweep voltammetry（LSV） results showed that there were only 18 mV slightly negative shifts of half-wave potential（E_（1/2）） of the optimal catalyst（749 mV） compared with the commercial Pt/C（20 μg·Pt·cm^-2）. Besides, I850 R also showed better electrochemical stability and methanol-tolerance than that of Pt/C. All evidences proved that our vacuum casting reacting strategy and heat treatment process were prospective for the future R＆D of high performance Fe-N_x-C ORR catalysts.

Microstructure and interface reaction of investment casting TiAl alloys

In order to research the microstructure of TiAl alloy and TiAl-mould reaction between TiAl and ceramic mould shells prepared with the low cost binder in investment casting, the ceramic mould shells were prepared with low cost binder and refractory materials. Using two kinds of casting methods (gravity casting and centrifugal casting), the titanium aluminum alloys with rare earth element (Ti-47.5Al-2Cr-2Nb-0.3Y and Ti-45Al-5Nb-0.3Y) were cast into the mould shells. The microstructures of investment casting titanium aluminum alloys were observed by optical microscope (OM). The distributions of elements of topping investment on the surfaces of titanium aluminum alloys castings were analyzed by the means of electron probe micro-analysis (EPMA), and the mechanical properties were studied. The results show that the microstructures of two kinds of titanium aluminum alloys are both lamella shape, and lamella is thin. The thickness of reaction and diffusing layer of Ti-47.5Al-2Cr-2Nb-0.3Y alloy is about 80μm, and that of Ti-45Al-5Nb-0.3Y is less than 30μm.

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.

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.

Effects of Pouring Temperature on Interfacial Reaction between Ti-47-5Al-2-5V-1Cr Alloy and Mold during Centrifugal Casting

Pouring temperature and time are the most important influencing factors on interfacial reaction during the centrifugal casting. When cast at high temperatures, the crucible becomes brittle and prone to cracking, and shows a low stability. In this paper, we studied the centrifugal casting of Ti-47.5-Al-2.5V-1Cr alloy, and explored the effects of pouring temperature on the interfacial reaction. Castings at 1 600, 1 650, and 1 700 ℃ were obtained by controlling the other parameters constant in the experiments. The microstructure, elemental distribution, thickness of the reaction layer and phase composition of the castings at the interface were studied. The results show that the thickness at the interfacial reaction layer is increased by raising the pouring temperature. The elements in the mold and the matrix were double-diffused and reacted at the interface during the casting process, and formed solid solutions with the precipitation of many new phases such as AlOand TiO. The roughness of interface structure and layer thickness of reaction increase with the rise of temperature, and the interfacial reaction is more intense. There is a minimum layer thickness of the reaction layer that is 80 μm when the temperature is 1 600 ℃.

CAST池活性污泥除磷微生物群落特征研究

为掌握霞山水质净化厂CAST池各反应段活性污泥除磷微生物群落结构特征,特对CAST池内不同区活性污泥进行采样并DNA提取后高通量测序分析,结果表明CAST池各阶段活性污泥富集了丰富的具有良好除磷功能的菌。门水平上的优势除磷菌有变形杆菌门(Proteobacteria)、绿弯菌门(Chloroflexi)、放线菌门(Actinobacteriota)、酸杆菌门(Acidobacteriota)、厚壁菌门(Firmicutes)。属水平上的优势除磷菌为Norank_f_Caldilineaceae、Candidatus_Competibacter、Norank_f_norank_o_Saccharimonadales、Tetrasphaera、Norank_f_Blastocatellaceae等。该CAST池活性污泥中存在聚磷菌与聚糖菌共存的现象且两者相对丰度较高,两者的竞争及环境条件变化会导致除磷效果的波动。主反应区曝气使得好氧聚磷菌Tetrasphaera相对丰度远高于生物选择区和兼氧区。反硝化聚磷菌Streptococcus和Acinetobacter在生物选择区中相对丰度远高于兼氧区和主反应区。反硝化聚磷菌在生物选择区厌氧段更加适宜其生长导致其相对丰度较高,能增强该阶段除磷效果。在实际生产中应着力改善合适环境条件提升聚磷菌生物量以保障除磷效果。

Heat transfer behavior of AZ80-1%Y alloy during low-frequency electromagnetic casting

Heat transfer behaviors of AZ80?1%Y alloy during low frequency electromagnetic casting (LFEC) and direct chilling casting were studied by in-situ temperature measurement. The results demonstrated that the low frequency electromagnetic field (EM) caused forced convection in the melt during LFEC. The forced convection led to uniform solidification velocity and temperature field. EM frequency, excitation current intensity and casting temperature could control the heat transfer behavior. The forced convection could improve the microstructure and degrade the difference in microstructure between the edge and center of billet. Appropriate parameters of low frequency EM for casting Mg alloy are 20 Hz of frequency and 60 A of electric current intensity.

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.

In-situ self-templated preparation of porous core-shell Fe_(1-x)S@N,S co-doped carbon architecture for highly efficient oxygen reduction reaction

Transition metal compound(TMC)/carbon hybrids,as prospering electrocatalyst,have attracted great attention in the field of oxygen reduction reaction(ORR).Their morphology,structure and composition often play a crucial role in determining the ORR performance.In this work,we for the first time report the successful fabrication of porous core-shell Fe_(1-x)S@N,S co-doped carbon(Fe_(1-x)S@NSC-t,t represents etching time)by a novel in-situ self-template induced strategy using Fe3O4 nanospheres and pyrrole as sacrificial self-template.The post-polymerization of pyrrole can be accomplished by the Fe^(3+)released through the etching of Fe_(3)O_(4) by HCl acid.Thus,the etching time has a significant effect on the morphology,structure,composition a nd ORR performance of Fe_(1-x)S@NSC-t.Based on the cha racterizations,we find Fe_(1-x)S@NSC-24 can realize effective and balanced combination of Fe_(1-x)S and NSC,possessing porous core-shell architecture,optimized structure defect,specific surface area and doped heteroatoms configurations(especially for pyridinic N,graphitic N and Fe-N structure).These features thus lead to outstanding catalytic activity and cycling stability towards ORR.Our work provides a good guidance on the design of TMC/carbon-based electrodes with unique stable morphology and optimized structure and composition.

In-situ monitoring of dynamic behavior of catalyst materials and reaction intermediates in semiconductor catalytic processes

Semiconductor photocatalysis, as a key part of solar energy utilization, has far-reaching implications for industrial, agricultural, and commercial development. Lack of understanding of the catalyst evolution and the reaction mechanism is a critical obstacle for designing efficient and stable photocatalysts. This review summarizes the recent progress of in-situ exploring the dynamic behavior of catalyst materials and reaction intermediates. Semiconductor photocatalytic processes and two major classes of in-situ techniques that include microscopic imaging and spectroscopic characterization are presented. Finally, problems and challenges in in-situ characterization are proposed, geared toward developing more advanced in-situ techniques and monitoring more accurate and realistic reaction processes, to guide designing advanced photocatalysts.

Dense copper azide synthesized by in-situ reaction of assembled nanoporous copper microspheres and its initiation performance

Copper azide with high density was successfully synthesized by in-situ reaction of nanoporous copper(NPC)precursor with HN_(3) gaseous.NPC with pore size of about 529 nm has been prepared by electroless plating using polystyrene(PS)as templates.The copper shells thickness of NPC was controlled by adjusting the PS loading amount.The effects of copper shell on the morphology,structure and density of copper azide were investigated.The conversion increased from 87.12%to 95.31%when copper shell thickness decrease from 100 to 50 nm.Meanwhile,the density of copper azide prepared by 529 nm NPC for 24 h was up to 2.38 g/cm^(3).The hollow structure of this NPC was filled by swelling of copper azide which guaranteed enough filling volume for keeping the same shape as well as improving the charge density.Moreover,HNS-IV explosive was successfully initiated by copper azide with minimum charge thickness of 0.55 mm,showing that copper azide prepared has excellent initiation performance,which has more advantages in the application of miniaturized explosive systems.

A Review of In‑Situ Techniques for Probing Active Sites and Mechanisms of Electrocatalytic Oxygen Reduction Reactions

Electrocatalytic oxygen reduction reaction(ORR)is one of the most important reactions in electrochemical energy technologies such as fuel cells and metal–O2/air batteries,etc.However,the essential catalysts to overcome its slow reaction kinetic always undergo a complex dynamic evolution in the actual catalytic process,and the concomitant intermediates and catalytic products also occur continuous conversion and reconstruction.This makes them difficult to be accurately captured,making the identification of ORR active sites and the elucidation of ORR mechanisms difficult.Thus,it is necessary to use extensive in-situ characterization techniques to proceed the real-time monitoring of the catalyst structure and the evolution state of intermediates and products during ORR.This work reviews the major advances in the use of various in-situ techniques to characterize the catalytic processes of various catalysts.Specifically,the catalyst structure evolutions revealed directly by in-situ techniques are systematically summarized,such as phase,valence,electronic transfer,coordination,and spin states varies.In-situ revelation of intermediate adsorption/desorption behavior,and the real-time monitoring of the product nucleation,growth,and reconstruction evolution are equally emphasized in the discussion.Other interference factors,as well as in-situ signal assignment with the aid of theoretical calculations,are also covered.Finally,some major challenges and prospects of in-situ techniques for future catalysts research in the ORR process are proposed.