The reaction mechanism and interfacial crystallization of Al nanoparticle-embedded Ni under shock loading

The shock-induced reaction mechanism and characteristics of Ni/Al system,considering an Al nanoparticle-embedded Ni single crystal,are investigated through molecular dynamics simulation.For the shock melting of Al nanoparticle,interfacial crystallization and dissolution are the main characteristics.The reaction degree of Al particle first increases linearly and then logarithmically with time driven by rapid mechanical mixing and following dissolution.The reaction rate increases with the decrease of particle diameter,however,the reaction is seriously hindered by interfacial crystallization when the diameter is lower than 9 nm in our simulations.Meanwhile,we found a negative exponential growth in the fraction of crystallized Al atoms,and the crystallinity of B2-NiAl(up to 20%)is positively correlated with the specific surface area of Al particle.This can be attributed to the formation mechanism of B2-NiAl by structural evolution of finite mixing layer near the collapsed interface.For shock melting of both Al particle and Ni matrix,the liquid-liquid phase inter-diffusion is the main reaction mechanism that can be enhanced by the formation of internal jet.In addition,the enhanced diffusion is manifested in the logarithmic growth law of mean square displacement,which results in an almost constant reaction rate similar to the mechanical mixing process.

Study on trifluoromethanesulfonic acid-promoted synthesis of daidzein: Process optimization and reaction mechanism

Daidzein has been widely used in pharmaceuticals,nutraceuticals,cosmetics,feed additives,etc.Its preparation process and related reaction mechanism need to be further investigated.A cost-effective process for synthesizing daidzein was developed in this work.In this article,a two-step synthesis of daidzein(Friedel–Crafts acylation and[5+1]cyclization)was developed via the employment of trifluoromethanesulfonic acid(TfOH)as an effective promoting reagent.The effect of reaction conditions such as solvent,the amount of TfOH,reaction temperature,and reactant ratio on the conversion rate and the yield of the reaction,respectively,was systematically investigated,and daidzein was obtained in 74.0%isolated yield under optimal conditions.Due to the facilitating effect of TfOH,the Friedel–Crafts acylation was completed within 10 min at 90℃ and the[5+1]cyclization was completed within 180 min at 25℃.In addition,a possible reaction mechanism for this process was proposed.The results of the study may provide useful guidance for industrial production of daidzein on a large scale.

Cu-based materials for electrocatalytic CO_(2) to alcohols:Reaction mechanism,catalyst categories,and regulation strategies

Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)technology,which enables carbon capture storage and resource utilization by reducing CO_(2) to valuable chemicals or fuels,has become a global research hotspot in recent decades.Among the many products of CO_(2)RR(carbon monoxide,acids,aldehydes and alcohols,olefins,etc.),alcohols(methanol,ethanol,propanol,etc.)have a higher market value and energy density,but it is also more difficult to produce.Copper is known to be effective in catalyzing CO_(2) to high valueadded alcohols,but with poor selectivity.The progress of Cu-based catalysts for the selective generation of alcohols,including copper oxides,bimetals,single atoms and composites is reviewed.Meanwhile,to improve Cu-based catalyst activity and modulate product selectivity,the modulation strategies are straighten out,including morphological regulation,crystalline surface,oxidation state,as well as elemental doping and defect engineering.Based on the research progress of electrocatalytic CO_(2) reduction for alcohol production on Cu-based materials,the reaction pathways and the key intermediates of the electrocatalytic CO_(2)RR to methanol,ethanol and propanol are summarized.Finally,the problems of traditional electrocatalytic CO_(2)RR are introduced,and the future applications of machine learning and theoretical calculations are prospected.An in-depth discussion and a comprehensive review of the reaction mechanism,catalyst types and regulation strategies were carried out with a view to promoting the development of electrocatalytic CO_(2)RR to alcohols.

Study of the reaction mechanism for preparing powdered activated coke with SO_(2)adsorption capability via one-step rapid activation method under flue gas atmosphere

In this study,the impact of different reaction times on the preparation of powdered activated carbon(PAC)using a one-step rapid activation method under flue gas atmosphere is investigated,and the underlying reaction mechanism is summarized.Results indicate that the reaction process of this method can be divided into three stages:stage I is the rapid release of volatiles and the rapid consumption of O_(2),primarily occurring within a reaction time range of 0-0.5 s;stage II is mainly the continuous release and diffusion of volatiles,which is the carbonization and activation coupling reaction stage,and the carbonization process is the main in this stage.This stage mainly occurs at the reaction time range of 0.5 -2.0 s when SL-coal is used as material,and that is 0.5-3.0 s when JJ-coal is used as material;stage III is mainly the activation stage,during which activated components diffuse to both the surface and interior of particles.This stage mainly involves the reaction stage of CO_(2)and H2O(g)activation,and it mainly occurs at the reaction time range of 2.0-4.0 s when SL-coal is used as material,and that is 3.0-4.0 s when JJ-coal is used as material.Besides,the main function of the first two stages is to provide more diffusion channels and contact surfaces/activation sites for the diffusion and activation of the activated components in the third stage.Mastering the reaction mechanism would serve as a crucial reference and foundation for designing the structure,size of the reactor,and optimal positioning of the activator nozzle in PAC preparation.

Deformable Catalytic Material Derived from Mechanical Flexibility for Hydrogen Evolution Reaction

Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.

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.

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 infrared, Raman and X-ray spectroscopy for the mechanistic understanding of hydrogen evolution reaction

Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the calculation results need to be supported by experimental results and direct evidence to confirm the mechanistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spectroscopy(XAS) and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination environment during HER.

Antagonism effect of residual S triggers the dual-path mechanism for water oxidation

Transition metal chalcogenides(TMCs)are recognized as pre-catalysts,and their(oxy)hydroxides derived from electrochemical reconstruction are the active species in the water oxidation.However,understanding the role of the residual chalcogen in the reconstructed layer is lacking in detail,and the corresponding catalytic mechanism remains controversial.Here,taking Cu_(1-x)Co_(x)S as a platform,we explore the regulating effect and existence form of the residual S doped into the reconstructive layer for oxygen evolution reaction(OER),where a dual-path OER mechanism is proposed.First-principles calculations and operando~(18)O isotopic labeling experiments jointly reveal that the residual S in the reconstructive layer of Cu_(1-x)Co_(x)S can wisely balance the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM)by activating lattice oxygen and optimizing the adsorption/desorption behaviors at metal active sites,rather than change the reaction mechanism from AEM to LOM.Following such a dual-path OER mechanism,Cu_(0.4)Co_(0.6)S-derived Cu_(0.4)Co_(0.6)OSH not only overcomes the restriction of linear scaling relationship in AEM,but also avoids the structural collapse caused by lattice oxygen migration in LOM,so as to greatly reduce the OER potential and improved stability.

The role of titanium at the interface of hematite photoanode in multisite mechanism:Reactive site or cocatalyst site?

Hematite(α-Fe_(2)O_(3))constitutes one of the most promising photoanode materials for oxygen evolution reaction(OER).Recent research on Fe_(2)O_(3) have found a fast OER rate dependence on surface hole density,suggesting a multisite reaction pathway.However,the effect of heteroatom in Fe_(2)O_(3) on the multisite mechanism is still poorly understood.Herein we synthesized Fe_(2)O_(3) on Ti substrates(Fe_(2)O_(3)/Ti)to study the oxygen intermediates of OER by light-dark electrochemical scans.We identified the Fe-OH species disappeared and Ti-OH intermediates appeared on Fe_(2)O_(3)/Ti when pH=11‒14,which significantly improved the OER performance of Fe_(2)O_(3)/Ti.Combined with the density functional theory calculations,we propose that Ti atom acts as cocatalyst site and captures proton from neighboring Fe-OH species under highly alkaline condition,thereby promoting the coupling of Fe=O and reducing the energy barrier of the non-electrochemical step.Our work provides a new insight into the role of heteroatom in OER multisite mechanism based on clarifying the reaction intermediates.

Microstructure,interfacial reaction behavior,and mechanical properties of Ti_3AlC_(2)reinforced Al6061 composites

The interfacial reaction behavior of Al and Ti_3AlC_(2)at different pouring temperatures and its effect on the microstructure and mechanical properties of the composites were investigated.The results show that the addition of3.0 wt.%Ti_3AlC_(2)refines the average grain size ofα(Al)in the composite by 50.1%compared to Al6061 alloy.Morphological analyses indicate that an in-situ Al_(3Ti)transition layer of-180 nm in thickness is generated around the edge of Ti_3AlC_(2)at 720℃,forming a well-bonded Al-Al_(3Ti)interface.At this processing temperature,the ultimate tensile strength of A16061-3.0 wt.%Ti_3AlC_(2)composite is 199.2 MPa,an improvement of 41.5%over the Al6061 matrix.Mechanism analyses further elucidate that 720℃is favourable for forming the nano-sized transition layer at the Ti_3AlC_(2)edges.And,the thermal mismatch strengthening plays a dominant role in this state,with a strengthening contribution of about 74.8%.

“Capture-activation-recapture” mechanism-guided design of double-atom catalysts for electrocatalytic nitrogen reduction

Compared with the traditional industrial nitrogen fixation, electrocatalytic methods, especially those utilizing double-atom catalysts containing nonmetals, can give good consideration to the economy and environmental protection. However, the existing “acceptance-donation” mechanism is only applicable to bimetallic catalysts and nonmetallic double-atom catalysts containing boron atoms. Herein, a novel “capture-activation-recapture” mechanism for metal-nonmetal double-atom catalyst is proposed to solve the problem by adjusting the coordination environments of nonmetallic atoms and utilizing the activation effect of metal atoms on nitrogen. Based on this mechanism, the nitrogen reduction reaction (NRR) activity of 48 structures is calculated by density functional theory calculation, and four candidates are selected as outstanding electrocatalytic nitrogen reduction catalysts: Si-Fe@NG (U_(L) = –0.14 V), Si-Co@NG (U_(L)= –0.15 V), Si-Mo@BP1 (U_(L) = 0 V), and Si-Re@BP1 (U_(L) = –0.02 V). The analyses of electronic properties further confirm “capture-activation-recapture” mechanism and suggest that the difference in valence electron distribution between metal and Si atoms triggers the activation of N≡N bonds. In addition, a machine learning approach is utilized to generate an expression and an intrinsic descriptor that considers the coordination environment to predict the limiting potential. This study offers profound insight into the synergistic mechanism of TM and Si for NRR and guidance in the design of novel double-atom nitrogen fixation catalysts.

Progress on the mechanisms of Ru-based electrocatalysts for the oxygen evolution reaction in acidic media

Water electrolysis using proton-exchange membranes is one of the most promising technologies for carbon-neutral and sustainable energy production.Generally,the overall efficiency of water splitting is limited by the oxygen evolution reaction(OER).Nevertheless,a trade-off between activity and stability exists for most electrocatalytic materials in strong acids and oxidizing media,and the development of efficient and stable catalytic materials has been an important focus of research.In this view,gaining in-depth insights into the OER system,particularly the interactions between reaction intermediates and active sites,is significantly important.To this end,this review introduces the fundamentals of the OER over Ru-based materials,including the conventional adsorbate evolution mechanism,lattice oxygen oxidation mechanism,and oxide path mechanism.Moreover,the up-to-date progress of representative modifications for improving OER performance is further discussed with reference to specific mechanisms,such as tuning of geometric,electronic structures,incorporation of proton acceptors,and optimization of metal-oxygen covalency.Finally,some valuable insights into the challenges and opportunities for OER electrocatalysts are provided with the aim to promote the development of next-generation catalysts with high activity and excellent stability.

Recent Advances in the Comprehension and Regulation of Lattice Oxygen Oxidation Mechanism in Oxygen Evolution Reaction

Water electrolysis,a process for producing green hydrogen from renewable energy,plays a crucial role in the transition toward a sustainable energy landscape and the realization of the hydrogen economy.Oxygen evolution reaction(OER)is a critical step in water electrolysis and is often limited by its slow kinetics.Two main mechanisms,namely the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM),are commonly considered in the context of OER.However,designing efficient catalysts based on either the AEM or the LOM remains a topic of debate,and there is no consensus on whether activity and stability are directly related to a certain mechanism.Considering the above,we discuss the characteristics,advantages,and disadvantages of AEM and LOM.Additionally,we provide insights on leveraging the LOM to develop highly active and stable OER catalysts in future.For instance,it is essential to accurately differentiate between reversible and irreversible lattice oxygen redox reactions to elucidate the LOM.Furthermore,we discuss strategies for effectively activating lattice oxygen to achieve controllable steady-state exchange between lattice oxygen and an electrolyte(OH^(-)or H_(2)O).Additionally,we discuss the use of in situ characterization techniques and theoretical calculations as promising avenues for further elucidating the LOM.

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.

Mechanism Study of BF_(3)/n-Butanol-catalyzed 1-Decene Oligomerization Reaction

The active catalysts of the BF_(3)/n-C_(4)H_(9)OH-catalyzed 1-decene oligomerization reaction,as well as the distribution of the reaction products,was investigated by molecular simulation.The calculation results show that(BF_(3))_(2)·n-C_(4)H_(9)OH catalyzes the 1-decene oligomerization reaction with higher activity compared to BF_(3)·n-C_(4)H_(9)OH,which is the most catalytically active substance in the BF_(3)/n-C_(4)H_(9)OH catalyst system.The reaction energy barriers and heats of reaction of chain initiation,chain growth,and chain termination in BF_(3)/n-C_(4)H_(9)OH-catalyzed 1-decene oligomerization are calculated to reveal the product distribution.The calculation results show that the contents of the oligomerization reaction products in descending order are trimer,tetramer,pentamer,and dimer.The calculated results were consistent with the experimentally obtained product distribution.

Light Inducing the Geometric Conversion of NiO_(6) to Trigger a Faster Oxygen Evolution Reaction Pathway:The Coupled Oxygen Evolution Mechanism

Developing highly active and robust oxygen evolution reaction(OER)electrocatalysts is still a critical challenge for water electrolyzers and metal-air batteries.Realizing the dynamic evolution of the intermediate and charge transfer during OER and developing a clear OER mechanism is crucial to design high-performance OER catalysts.Recently in Nature,Xue and colleagues revealed a new OER mechanism,coupled oxygen evolution mechanism(COM),which involves a switchable metal and oxygen redox under light irradiation in nickel oxyhydroxide-based materials.This newly developed mechanism requires a reversible geometric conversion between octahedron(NiO_(6))and square planar(NiO_(4))to achieve electronic states with both“metal redox”and“oxygen redox”during OER.The asymmetric structure endows NR-NiOOH with a nonoverlapping region between the dz^(2) orbitals and a_(1g)^(*)bands,which facilitate the geometric conversion and enact the COM pathway.As a result,NR-NiOOH exhibited better OER activity and stability than the traditional NiOOH.

Microstructure and mechanism of in-situ Al_2O_(3(p))/Al nano-composites synthesized by sonochemistry melt reaction

The Al2O3（p）/Al nano-composites were fabricated from Al-K2ZrF6-Na2B4O7 system by sonochemistry in situ reaction. The fabrication mechanisms, including high intensity ultrasonic influence on microstructures and reinforcement particles-aluminum matrix interface, were investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM） and transmission electron microscopy （TEM）. The XRD results show that the component of the as-prepared composites is Al2O3 reinforcement. The SEM analysis results indicate that Al2O3 particles are uniformly distributed in the aluminum matrix. The TEM results show that the morphologies of Al2O3 particles present in nearly sphere-shape, the sizes are in the range of 20-100 nm, and the interfaces are net and no interfacial outgrowth is observed. Analysis with secondary development Image-J software shows that Al2O3 recoveries are firstly improved and then decreased with increasing ultrasonic power. When the power is 0.4 kW, the distribution is the best, and a maximum number of particles are obtained. The reaction mechanisms were investigated.

Mechanism for thermite reactions of aluminum/iron-oxide nanocomposites based on residue analysis

Sol-gel method was employed to combine Al and iron-oxide to form nanocomposites （nano-Al/xero-Fe2O3 and micro-Al/xero-Fe2O3）. SEM, EDS and XRD analyses were used to characterize the nanocomposites and the results indicated that nano-Al and micro-Al were compactly wrapped by amorphous iron-oxide nanoparticles （about 20 nm）, respectively. The iron-oxide showed the mass ratio of Fe to O as similar as that in Fe2O3. Thermal analyses were performed on two nanocomposites, and four simple mixtures （nano-Al＋xero-Fe2O3, nano-Al＋micro-Fe2O3, micro-Al＋xero-Fe2O3, and micro-Al＋micro-Fe2O3） were also analyzed. There were not apparent distinctions in the reactions of thermites fueled by nano-Al. For thermites fueled by micro-Al, the DSC peak temperatures of micro-Al/Xero-Fe2O3 were advanced by 68.1 ℃ and 76.8 ℃ compared with micro-Al＋xero-Fe2O3 and micro-Al＋micro-Fe2O3, respectively. Four thermites, namely, nano-Al/xero-Fe2O3, nano-Al＋micro-Fe2O3, micro-Al/xero-Fe2O3, and micro-Al＋micro-Fe2O3, were heated from ambient temperature to 1020 ℃, during which the products at 660 ℃ and 1020 ℃ were collected and analyzed by XRD. Crystals of Fe, FeAl2O4, Fe3O4,α-Fe2O3, Al,γ-Fe2O3, Al2.667O4, FeO andα-Al2O3 were indexed in XRD patterns. For each thermite, according to the specific products, the possible equations were given. Based on the principle of the minimum free energy, the most reasonable equations were inferred from the possible reactions.

Reaction mechanisms of low-grade molybdenum concentrate during calcification roasting process

The effects of Ca-based additives on roasting properties of low-grade molybdenum concentrate were studied. The resultsshow that calcium-based additives can react with molybdenum concentrate to form CaSO4 and CaMoO4. The initial oxidationtemperature of MoS2 is 450℃, while the formation of CaMoO4 and CaSO4 occurs above 500℃. The whole calcification reactionsare nearly completed between 600 and 650℃. However, raising the temperature further helps for the formation of CaMoO4 but isdisadvantageous to sulfur fixing rate and molybdenum retention rate. Calcification efficiency of Ca-based additives follows theorder： Ca（OH）2〉CaO〉CaCO3. With increasing the dosage of Ca（OH）2, the molybdenum retention rate and sulfur-fixing rate rise, butexcessive dosages would consume more acid during leaching process. The appropriate mass ratio of Ca（OH）2 to molybdenumconcentrate is 1：1. When roasted at 650 ℃ for 90 min, the molybdenum retention rate and the sulfur-fixing rate of low-grademolybdenum concentrate reach 100% and 92.92%, respectively, and the dissolution rate of molybdenum achieves 99.12% withcalcines being leached by sulphuric acid.