Towards a new avenue for rapid synthesis of electrocatalytic electrodes via laser-induced hydrothermal reaction for water splitting

Electrochemical production of hydrogen from water requires the development ofelectrocatalysts that are active,stable,and low-cost for water splitting.To address these challenges,researchers are increasingly exploring binder-free electrocatalytic integratedelectrodes (IEs) as an alternative to conventional powder-based electrode preparation methods,for the former is highly desirable to improve the catalytic activity and long-term stability for large-scale applications of electrocatalysts.Herein,we demonstrate a laser-inducedhydrothermal reaction (LIHR) technique to grow NiMoO4nanosheets on nickel foam,which is then calcined under H2/Ar mixed gases to prepare the IE IE-NiMo-LR.This electrode exhibits superior hydrogen evolution reaction performance,requiring overpotentials of 59,116 and143 mV to achieve current densities of 100,500 and 1000 mA·cm-2.During the 350 h chronopotentiometry test at current densities of 100 and 500 m A·cm-2,the overpotentialremains essentially unchanged.In addition,NiFe-layered double hydroxide grown on Ni foam is also fabricated with the same LIHR method and coupled with IE-NiMo-IR to achieve water splitting.This combination exhibits excellent durability under industrial current density.The energy consumption and production efficiency of the LIHR method are systematicallycompared with the conventional hydrothermal method.The LIHR method significantly improves the production rate by over 19 times,while consuming only 27.78%of the total energy required by conventional hydrothermal methods to achieve the same production.

Mapping out the reaction network of humin formation at the initial stage of fructose dehydration in water

The formation of humins hampers the large-scale production of 5-hydroxymethylfurfural(HMF)in biorefinery.Here,a detailed reaction network of humin formation at the initial stage of fructose-to-HMF dehydration in water is delineated by combined experimental,spectroscopic,and theoretical studies.Three bimolecular reaction pathways to build up soluble humins are demonstrated.That is,the intermolecular etherification of β-furanose at room temperature initiates the C12 path,whereas the C-C cleavage of a-furanose at 130-150℃ leads to C11 path,and that of open-chain fructose at 180℃ to C11' path.The successive intramolecular dehydrations and condensations of the as-formed bimolecular intermediates lead to three types of soluble humins.We show that the C12 path could be restrained by using HCl or AlCl_(3) catalyst,and both the C12 and C110 paths could be effectively inhibited by adding THF as a co-solvent or accelerating heating rate via microwave heating.

Theoretical analysis of the double-differential cross-sections of neutron,proton,deuteron,^(3)He,andαfor the p+^(6) Li reaction

Based on the unified Hauser–Feshbach and exciton model,which can describe the particle emission processes between discrete energy levels with energy,angular momentum,and parity conservations,a statistical theory of light nucleus reaction(STLN)is developed to calculate the double-differential cross-sections of the outgoing neutron and light charged particles for the proton-induced^(6) Li reaction.A significant difference is observed between the p+^(6) Li and p+^(7) Li reactions owing to the discrepancies in the energy-level structures of the targets.The reaction channels,including sequential and simultaneous emission processes,are analyzed in detail.Taking the double-differential cross-sections of the outgoing proton as an example,the influence of contaminations(such as^(1) H,^(7)Li,^(12)C,and^(16)O)on the target is identified in terms of the kinetic energy of the first emitted particles.The optical potential parameters of the proton are obtained by fitting the elastic scattering differential cross-sections.The calculated total double-differential cross-sections of the outgoing proton and deuteron at E_(p)=14 MeV agree well with the experimental data for different outgoing angles.Simultaneously,the mixed double differential cross-sections of^(3) He andαare in good agreement with the measurements.The agreement between the measured data and calculated results indicates that the two-body and three-body breakup reactions need to be considered,and the pre-equilibrium reaction mechanism dominates the reaction processes.Based on the STLN model,a PLUNF code for the p+^(6) Li reaction is developed to obtain an ENDF-6-formatted file of the double-differential cross-sections of the nucleon and light composite charged particles.

Selective photosynthesis of Z-olefins through crystalline metal-organic cage-initiated expeditious cascade reactions

The semi-hydrogenation of alkyne to form Z-olefins with high conversion and high selectivity is still a huge challenge in the chemical industry.Moreover,flammable and explosive hydrogen as the common hydrogen source of this reaction increases the cost and danger of industrial production.Herein,we connect the photocatalytic hydrogen evolution reaction and the semihydrogenation reaction of alkynes in series and successfully realize the high selective production of Z-alkenes using low-cost,safe,and green water as the proton source.Before the cascade reaction,a series of isomorphic metal–organic cage catalysts(Co_(x)Zn_(8−x)L_(6),x=0,3,4,5,and 8)are designed and synthesized to improve the yield of the photocatalytic hydrogen production.Among them,Co_(5)Zn_(3)L_(6) shows the highest photocatalytic activity,with a H_(2) generation rate of 8.81 mmol g^(−1) h^(−1).Then,Co_(5)Zn_(3)L_(6) is further applied in the above tandem reaction to efficiently reduce alkynes to Z-alkenes under ambient conditions,which can reach high conversion of>98%and high selectivity of>99%,and maintain original catalytic activity after multiple cycles.This“one-pot”tandem reaction can achieve a highly selective and safe stepwise conversion from water into hydrogen into Z-olefins under mild reaction conditions.

Photoinduced transposed Paternò-Büchi reaction for effective synthesis of high-performance jet fuel

High-energy-density fuels are important for volume-limited aerospace vehicles,but the increase in fuel energy density always leads to poor cryogenic performance.Herein,we investigated the transposed Paternò-Büchi reaction of biomass cyclic ketone and cyclic alkene to synthesize a new kind of alkyl-substituted polycyclic hydrocarbon fuel with high energy density and good cryogenic performance.The triplet-energy-quenching results and phosphorescent emission spectra reveal the sensitization mechanism of the reaction,including photosensitizer excitation,triplettriplet energy transfer,cyclization,and relaxation,and the possible reaction path was revealed by the density functional theory(DFT)calculations.The reaction conditions of photosensitizer type and addition,molar ratio of substrates,reaction temperature,and incident light intensity were optimized,with the target product yield achieving 65.5%.Moreover,the reaction dynamics of the reaction rate versus the light intensity are established.After the hydrogenation-deoxygenation reaction,three fuels with a high density of 0.864-0.938 g·ml^(-1) and a low freezing point of<-55℃ are obtained.This work provides a benign and effective approach to synthesize high-performance fuels.

Revealing Al-O/Al-F reaction dynamic effects on the combustion of aluminum nanoparticles in oxygen/fluorine containing environments:A reactive molecular dynamics study meshing together experimental validation

Improving the energy conversion efficiency in metallic fuel(e.g.,Al)combustion is always desirable but challenging,which often involves redox reactions of aluminum(Al)with various mixed oxidizing environments.For instance,Al-O reaction is the most common pathway to release limited energy while Al-F reaction has received much attentions to enhance Al combustion efficiency.However,microscopic understanding of the Al-O/Al-F reaction dynamics remains unsolved,which is fundamentally necessary to further improve Al combustion efficiency.In this work,for the first time,Al-O/Al-F reaction dynamic effects on the combustion of aluminum nanoparticles(n-Al)in oxygen/fluorine containing environments have been revealed via reactive molecular dynamics(RMD)simulations meshing together combustion experiments.Three RMD simulation systems of Al core/O_(2)/HF,n-Al/O_(2)/HF,and n-Al/O_(2)/CF4 with oxygen percentage ranging from 0%to 100%have been performed.The n-Al combustion in mixed O_(2)/CF_4 environments have been conducted by constant volume combustion experiments.RMD results show that Al-O reaction exhibits kinetic benefits while Al-F reaction owns thermodynamic benefits for n-Al combustion.In n-Al/O_(2)/HF,Al-O reaction gives faster energy release rate than Al-F reaction(1.1 times).The optimal energy release efficiency can be achieved with suitable oxygen percentage of 10%and 50%for n-Al/O_(2)/HF and n-Al/O_(2)/CF_4,respectively.In combustion experiments,90%of oxygen percentage can optimally enhance the peak pressure,pressurization rate and combustion heat.Importantly,Al-O reaction prefers to occur on the surface regions while Al-F reaction prefers to proceed in the interior regions of n-Al,confirming the kinetic/thermodynamic benefits of Al-O/Al-F reactions.The synergistic effect of Al-O/Al-F reaction for greatly enhancing n-Al combustion efficiency is demonstrated at atomicscale,which is beneficial for optimizing the combustion performance of metallic fuel.

Insights into the hydrogen evolution reaction in vanadium redox flow batteries:A synchrotron radiation based X-ray imaging study

The parasitic hydrogen evolution reaction(HER)in the negative half-cell of vanadium redox flow batteries(VRFBs)causes severe efficiency losses.Thus,a deeper understanding of this process and the accompanying bubble formation is crucial.This benchmarking study locally analyzes the bubble distribution in thick,porous electrodes for the first time using deep learning-based image segmentation of synchrotron X-ray micro-tomograms.Each large three-dimensional data set was processed precisely in less than one minute while minimizing human errors and pointing out areas of increased HER activity in VRFBs.The study systematically varies the electrode potential and material,concluding that more negative electrode potentials of-200 m V vs.reversible hydrogen electrode(RHE)and lower cause more substantial bubble formation,resulting in bubble fractions of around 15%–20%in carbon felt electrodes.Contrarily,the bubble fractions stay only around 2%in an electrode combining carbon felt and carbon paper.The detected areas with high HER activity,such as the border subregion with more than 30%bubble fraction in carbon felt electrodes,the cutting edges,and preferential spots in the electrode bulk,are potential-independent and suggest that larger electrodes with a higher bulk-to-border ratio might reduce HER-related performance losses.The described combination of electrochemical measurements,local X-ray microtomography,AI-based segmentation,and 3D morphometric analysis is a powerful and novel approach for local bubble analysis in three-dimensional porous electrodes,providing an essential toolkit for a broad community working on bubble-generating electrochemical systems.

Experimental study on reactions between alkaline basaltic melt and orthopyroxenes: constraints on the evolution of lithospheric mantle in the North China Craton

The experimental results of the reactions between an alkaline basaltic melt and mantle orthopyroxenes under high-temperature and high-pressure conditions of 1300–1400℃ and 2.0–3.0 GPa using a six-anvil apparatus are reported in this paper.The reactions are proposed to simulate the interactions between melts from the asthenospheric mantle and the lithospheric mantle.The starting melt in the experiments was made from the alkaline basalt occurring in Fuxin,Liaoning Province,and the orthopyroxenes were separated from the mantle xenoliths in Damaping,Hebei Province.The results show that clinopyroxenes were formed in all the reactions between the alkaline basaltic melt and orthopyroxenes under the studied P–T conditions.The formation of clinopyroxene in the reaction zone is mainly controlled by dissolution–crystallization,and the chemical compositions of the reacted melt are primarily infl uenced by the diff usion eff ect.Temperature is the most important parameter controlling the reactions between the melt and orthopyroxenes,which has a direct impact on the melting of orthopyroxenes and the diff usion of chemical components in the melt.Temperature also directly controls the chemical compositions of the newly formed clinopyroxenes in the reaction zone and the reacted melt.The formation of clinopyroxenes from the reactions between the alkaline basaltic melt and orthopyroxenes can result in an increase of CaO and Al_(2)O_(3) contents in the rocks containing this mineral.Therefore,the reactions between the alkaline basaltic melt from the asthenospheric mantle and orthopyroxenes from the lithospheric mantle can lead to the evolution of lithospheric mantle in the North China Craton from refractory to fertile with relatively high CaO and Al 2 O 3 contents.In addition,the reacted melts in some runs were transformed from the starting alkaline basaltic into tholeiitic after reactions,indicating that tholeiitic magma could be generated from alkaline basaltic one via reactions between the latter and orthopyroxene.

Operationally Simple Enantioselective Silane Reduction of Ketones by the [Ir(OMe)(cod)]2/Azolium Catalytic System

An operationally simple protocol was designed for the enantioselective silane reduction (ESR) of ketones using air- and moisture-stable [Ir(OMe)(cod)]2 (cod = 1,5-cyclooctadiene) (3) as a metal catalyst precursor. This reaction was driven by chiral hydroxyamide-functionalized azolium salt 2. The catalytic ESR reaction could be performed under benchtop conditions at room temperature. Treatment of 2 with 3 in THF yielded the monodentate IrCl(NHC)(cod) (NHC = N-heterocyclic carbene) complex 4 in 93% yield, herein the anionic methoxy ligand of 3 serves as an internal base that deprotonates the azolium ring of 2. The well-defined Ir complex 4 catalyzed the ESR reaction of propiophenone (6) with (EtO)2MeSiH using the pre-mixing reaction procedure. Based on this success, the catalytic ESR reaction was designed and implemented using an in situ-generated NHC/Ir catalyst derived from 2 and 3. Thus, a wide variety of aryl ketones could be reduced to the corresponding optically active alcohols in moderate to excellent stereoselectivities at room temperature without temperature control. Since the high catalytic activity of 3 was observed, we next evaluated several other transition metal catalyst precursors for the catalytic ESR reaction under the influence of 2. This evaluation revealed that Ir(acac)(cod) (acac = acetylacetonate) (28) and [IrCl(cod)]2 (5) can be successfully used as metal catalyst precursors in the ESR reaction.

Tuning electronic structure of RuO_(2)by single atom Zn and oxygen vacancies to boost oxygen evolution reaction in acidic medium

The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.

“Buckets effect”in the kinetics of electrocatalytic reactions

In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.

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.

Approaching Ultimate Synthesis Reaction Rate of Ni-Rich Layered Cathodes for Lithium-Ion Batteries

Nickel-rich layered oxide LiNi_(x)Co_(y)MnzO_(2)(NCM,x+y+z=1)is the most promising cathode material for high-energy lithium-ion batteries.However,conventional synthesis methods are limited by the slow heating rate,sluggish reaction dynamics,high energy consumption,and long reaction time.To overcome these chal-lenges,we first employed a high-temperature shock(HTS)strategy for fast synthesis of the NCM,and the approaching ultimate reaction rate of solid phase transition is deeply investigated for the first time.In the HTS process,ultrafast average reaction rate of phase transition from Ni_(0.6)Co_(0.2)Mn_(0.2)(OH)_(2) to Li-containing oxides is 66.7(%s^(-1)),that is,taking only 1.5 s.An ultrahigh heating rate leads to fast reaction kinetics,which induces the rapid phase transition of NCM cathodes.The HTS-synthesized nickel-rich layered oxides perform good cycling performances(94%for NCM523,94%for NCM622,and 80%for NCM811 after 200 cycles at 4.3 V).These findings might also assist to pave the way for preparing effectively Ni-rich layered oxides for lithium-ion batteries.

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.

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.

Synthesis of spherical nano-ZSM-5 zeolite with intergranular mesoporous for alkylation of ethylbenzene with ethanol to produce m-diethylbenzene

Catalytic synthesis of m-diethylbenzene(m-DEB)through alkylation of ethylbenzene(EB)may be a promising alternative route in comparison with traditional rectification of mixed DEB,for which the top priority is to develop efficient and stable heterogeneous catalysts.Here,the spherical nano-ZSM-5 zeolite with abundant intergranular mesoporous is synthesized by the seed-mediated growth method for alkylation of EB with ethanol to produce m-DEB.The results show that the spherical nano-ZSM-5 zeolite exhibits better stability and higher alkylation activity at a lower temperature than those of commercial micropore ZSM-5.And then,the spherical nano-ZSM-5 is further modified by La_(2)O_(3) through acid treatment followed by immersion method.The acid treatment causes nano-ZSM-5 to exhibit the increased pore size but decreased the acid sites,and subsequent La_(2)O_(3) loading reintroduces the weak acid sites.As a result,the HNO_(3)-La_(2)O_(3)-modified catalyst exhibits a slight increase in EB conversion and DEB yield in comparison with unmodified one,and meanwhile,it still maintains high m-DEB selectivity.The catalyst after acid treatment achieves higher catalytic stability besides maintaining the high alkylation activity of EB with ethanol.The present study on the spherical nano-HZSM-5 zeolite and its modification catalyst with excellent alkylation ability provides new insights into the production of mDEB.

Introducing hydroxyl groups to tailor the d-band center of Ir atom through side anchoring for boosted ORR and HER

Tuning the coordination atoms of central metal is an effective means to improve the electrocatalytic activity of atomic catalysts.Herein,iridium(Ir) is proposed to be asymmetrically anchored by sp-N and pyridinic N of hydrogen-substituted graphdiyne(HsGDY),and coordinated with OH as an Ir atomic catalyst(Ir_(1)-N-HsGDY).The electron structures,especially the d-band center of Ir atom,are optimized by these specific coordination atoms.Thus,the as-synthesized Ir_(1)-N-HsGDY exhibits excellent electrocatalytic performances for oxygen reduction and hydrogen evolution reactions in both acidic and alkaline media.Benefiting from the unique structure of HsGDY,IrN_(2)(OH)_(3) has been developed and demonstrated to act as the active site in these electrochemical reactions.All those indicate the fresh role of the sp-N in graphdiyne in producing a new anchor way and contributing to promote the electrocatalytic activity,showing a new strategy to design novel electrochemical catalysts.

Diffusion and reaction mechanism of limestone and quartz in fluxed iron ore pellet roasting process

The increase to the proportion of fluxed pellets in the blast furnace burden is a useful way to reduce the carbon emissions in the ironmaking process.In this study,the interaction between calcium carbonate and iron ore powder and the mineralization mechanism of fluxed iron ore pellet in the roasting process were investigated through diffusion couple experiments.Scanning electron microscopy with energy dispersive spectroscopy was used to study the elements’diffusion and phase transformation during the roasting process.The results indicated that limestone decomposed into calcium oxide,and magnetite was oxidized to hematite at the early stage of preheating.With the increase in roasting temperature,the diffusion rate of Fe and Ca was obviously accelerated,while the diffusion rate of Si was relatively slow.The order of magnitude of interdiffusion coefficient of Fe_(2)O_(3)-CaO diffusion couple was 10^(−10) m^(2)·s^(−1) at a roasting temperature of 1200℃for 9 h.Ca_(2)Fe_(2)O_(5) was the initial product in the Fe_(2)O_(3)-CaO-SiO_(2) diffusion interface,and then Ca_(2)Fe_(2)O_(5) continued to react with Fe_(2)O_(3) to form CaFe_(2)O_(4).With the expansion of the diffusion region,the sillico-ferrite of calcium liquid phase was produced due to the melting of SiO_(2) into CaFe_(2)O_(4),which can strengthen the consolidation of fluxed pellets.Furthermore,andradite would be formed around a small part of quartz particles,which is also conducive to the consolidation of fluxed pellets.In addition,the principle diagram of limestone and quartz diffusion reaction in the process of fluxed pellet roasting was discussed.

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.

Exploring nitrogen reduction reaction mechanisms in electrocatalytic ammonia synthesis:A comprehensive review

The electrochemical nitrogen reduction reaction(eNRR)holds significant promise as a sustainable alternative to the conventional large-scale Haber Bosch process,offering a carbon footprint-free approach for ammonia synthesis.While the process is thermodynamically feasible at ambient temperature and pressure,challenges such as the competing hydrogen evolution reaction,low nitrogen solubility in electrolytes,and the activation of inert dinitrogen(N_(2))gas adversely affect the performance of ammonia production.These hurdles result in low Faradaic efficiency and low ammonia production rate,which pose obstacles to the commercialisation of the process.Researchers have been actively designing and proposing various electrocatalysts to address these issues,but challenges still need to be resolved.A key strategy in electrocatalyst design lies in understanding the underlying mechanisms that govern the success or failure of the electrocatalyst in driving the electrochemical reaction.Through mechanistic studies,we gain valuable insights into the factors affecting the reaction,enabling us to propose optimised designs to overcome the barriers.This review aims to provide a comprehensive understanding of the various mechanisms involved in eNRR on the electrocatalyst surface.It delves into the various mechanisms such as dissociative,associative,Mars-van Krevelen,lithium-mediated nitrogen reduction and surface hydrogenation mechanisms of nitrogen reduction.By unravelling the intricacies of eNRR mechanisms and exploring promising avenues,we can pave the way for more efficient and commercially viable ammonia synthesis through this sustainable electrochemical process by designing an efficient electrocatalyst.