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 hyperbo...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.展开更多
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 nan...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.展开更多
During the construction of cast-in-place piles in warm permafrost,the heat carried by concrete and the cement hydration reaction can cause strong thermal disturbance to the surrounding permafrost.Since the bearing cap...During the construction of cast-in-place piles in warm permafrost,the heat carried by concrete and the cement hydration reaction can cause strong thermal disturbance to the surrounding permafrost.Since the bearing capacity of the pile is quite small before the full freeze-back,the quick refreezing of the native soils surrounding the cast-in-place pile has become the focus of the infrastructure construction in permafrost.To solve this problem,this paper innovatively puts forward the application of the artificial ground freezing(AGF)method at the end of the curing period of cast-in-place piles in permafrost.A field test on the AGF was conducted at the Beiluhe Observation and Research Station of Frozen Soil Engineering and Environment(34°51.2'N,92°56.4'E)in the Qinghai Tibet Plateau(QTP),and then a 3-D numerical model was established to investigate the thermal performance of piles using AGF under different engineering conditions.Additionally,the long-term thermal performance of piles after the completion of AGF under different conditions was estimated.Field experiment results demonstrate that AGF is an effective method to reduce the refreezing time of the soil surrounding the piles constructed in permafrost terrain,with the ability to reduce the pile-soil interface temperatures to below the natural ground temperature within 3 days.Numerical results further prove that AGF still has a good cooling effect even under unfavorable engineering conditions such as high pouring temperature,large pile diameter,and large pile length.Consequently,the application of this method is meaningful to save the subsequent latency time and solve the problem of thermal disturbance in pile construction in permafrost.The research results are highly relevant for the spread of AGF technology and the rapid building of pile foundations in permafrost.展开更多
BACKGROUND As one of the fatal diseases with high incidence,lung cancer has seriously endangered public health and safety.Elderly patients usually have poor self-care and are more likely to show a series of psychologi...BACKGROUND As one of the fatal diseases with high incidence,lung cancer has seriously endangered public health and safety.Elderly patients usually have poor self-care and are more likely to show a series of psychological problems.AIM To investigate the effectiveness of the initial check,information exchange,final accuracy check,reaction(IIFAR)information care model on the mental health status of elderly patients with lung cancer.METHODS This study is a single-centre study.We randomly recruited 60 elderly patients with lung cancer who attended our hospital from January 2021 to January 2022.These elderly patients with lung cancer were randomly divided into two groups,with the control group taking the conventional propaganda and education and the observation group taking the IIFAR information care model based on the conventional care protocol.The differences in psychological distress,anxiety and depression,life quality,fatigue,and the locus of control in psychology were compared between these two groups,and the causes of psychological distress were analyzed.RESULTS After the intervention,Distress Thermometer,Hospital Anxiety and Depression Scale(HADS)for anxiety and the HADS for depression,Revised Piper’s Fatigue Scale,and Chance Health Locus of Control scores were lower in the observation group compared to the pre-intervention period in the same group and were significantly lower in the observation group compared to those of the control group(P<0.05).After the intervention,Quality of Life Questionnaire Core 30(QLQ-C30),Internal Health Locus of Control,and Powerful Others Health Locus of Control scores were significantly higher in the observation and the control groups compared to the pre-intervention period in their same group,and QLQ-C30 scores were significantly higher in the observation group compared to those of the control group(P<0.05).CONCLUSION The IIFAR information care model can help elderly patients with lung cancer by reducing their anxiety and depression,psychological distress,and fatigue,improving their tendencies on the locus of control in psychology,and enhancing their life qualities.展开更多
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,slu...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.展开更多
Cyclic loads generated by environmental factors,such as winds,waves,and trains,will likely lead to performance degradation in pile foundations,resulting in issues like permanent displacement accumulation and bearing c...Cyclic loads generated by environmental factors,such as winds,waves,and trains,will likely lead to performance degradation in pile foundations,resulting in issues like permanent displacement accumulation and bearing capacity attenuation.This paper presents a semi-analytical solution for predicting the axial cyclic behavior of piles in sands.The solution relies on two enhanced nonlinear load-transfer models considering stress-strain hysteresis and cyclic degradation in the pile-soil interaction.Model parameters are calibrated through cyclic shear tests of the sand-steel interface and laboratory geotechnical testing of sands.A novel aspect involves the meticulous formulation of the shaft loadtransfer function using an interface constitutive model,which inherently inherits the interface model’s advantages,such as capturing hysteresis,hardening,degradation,and particle breakage.The semi-analytical solution is computed numerically using the matrix displacement method,and the calculated values are validated through model tests performed on non-displacement and displacement piles in sands.The results demonstrate that the predicted values show excellent agreement with the measured values for both the static and cyclic responses of piles in sands.The displacement pile response,including factors such as bearing capacity,mobilized shaft resistance,and convergence rate of permanent settlement,exhibit improvements compared to non-displacement piles attributed to the soil squeezing effect.This methodology presents an innovative analytical framework,allowing for integrating cyclic interface models into the theoretical investigation of pile responses.展开更多
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 use...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.展开更多
N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher ...N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.展开更多
Driven piles are used in many geological environments as a practical and convenient structural component.Hence,the determination of the drivability of piles is actually of great importance in complex geotechnical appl...Driven piles are used in many geological environments as a practical and convenient structural component.Hence,the determination of the drivability of piles is actually of great importance in complex geotechnical applications.Conventional methods of predicting pile drivability often rely on simplified physicalmodels or empirical formulas,whichmay lack accuracy or applicability in complex geological conditions.Therefore,this study presents a practical machine learning approach,namely a Random Forest(RF)optimized by Bayesian Optimization(BO)and Particle Swarm Optimization(PSO),which not only enhances prediction accuracy but also better adapts to varying geological environments to predict the drivability parameters of piles(i.e.,maximumcompressive stress,maximum tensile stress,and blow per foot).In addition,support vector regression,extreme gradient boosting,k nearest neighbor,and decision tree are also used and applied for comparison purposes.In order to train and test these models,among the 4072 datasets collected with 17model inputs,3258 datasets were randomly selected for training,and the remaining 814 datasets were used for model testing.Lastly,the results of these models were compared and evaluated using two performance indices,i.e.,the root mean square error(RMSE)and the coefficient of determination(R2).The results indicate that the optimized RF model achieved lower RMSE than other prediction models in predicting the three parameters,specifically 0.044,0.438,and 0.146;and higher R^(2) values than other implemented techniques,specifically 0.966,0.884,and 0.977.In addition,the sensitivity and uncertainty of the optimized RF model were analyzed using Sobol sensitivity analysis and Monte Carlo(MC)simulation.It can be concluded that the optimized RF model could be used to predict the performance of the pile,and it may provide a useful reference for solving some problems under similar engineering conditions.展开更多
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 ...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.展开更多
Calcium production and the stellar evolution of first-generation stars remain fascinating mysteries in astrophysics.As one possible nucleosynthesis scenario,break-out from the hot carbon–nitrogen–oxygen(HCNO)cycle w...Calcium production and the stellar evolution of first-generation stars remain fascinating mysteries in astrophysics.As one possible nucleosynthesis scenario,break-out from the hot carbon–nitrogen–oxygen(HCNO)cycle was thought to be the source of the calcium observed in these oldest stars.However,according to the stellar modeling,a nearly tenfold increase in the thermonuclear rate ratio of the break-out ^(19)F(p,γ)^(20) Ne reaction with respect to the competing ^(19)F(p,α)^(16) O back-processing reaction is required to reproduce the observed calcium abundance.We performed a direct measurement of this break-out reaction at the China Jinping underground laboratory.The measurement was performed down to the low-energy limit of E_(c.m.)=186 keV in the center-of-mass frame.The key resonance was observed at 225.2 keV for the first time.At a temperature of approximately 0.1 GK,this new resonance enhanced the thermonuclear ^(19)F(p,γ)^(20) Ne rate by up to a factor of≈7.4,compared with the previously recommended NACRE rate.This is of particular interest to the study of the evolution of the first stars and implies a stronger breakdown in their“warm”CNO cycle through the ^(19)F(p,γ)^(20) Ne reaction than previously envisioned.This break-out resulted in the production of the calcium observed in the oldest stars,enhancing our understanding of the evolution of the first stars.展开更多
The alkaline volcanism of the Cameroon Volcanic Line in its northern domain has raised many fresh enclaves of peridotites. The samples selected come from five (05) different localities (Liri, in the plateau of Kapsiki...The alkaline volcanism of the Cameroon Volcanic Line in its northern domain has raised many fresh enclaves of peridotites. The samples selected come from five (05) different localities (Liri, in the plateau of Kapsiki, Mazélé in the NE of Ngaoundéré, Tello and Ganguiré in the SE of Ngaoundéré and Likok, locality located in the west of Ngaoundé). The peridotite enclaves of the above localities show restricted mineralogical variation. Most are four-phase spinel-lherzolites, indicating that this is the main lithology that forms the lithospheric mantle below the shallow zone. No traces of garnet or primary plagioclase were detected, which strongly limits the depth range from which the rock fragments were sampled. The textures and the wide equilibrium temperatures (884˚C - 1115˚C) indicate also entrainment of lherzolite xenoliths from shallow depths within the lithosphere and the presence of mantle diapirism. The exchange reactions and equilibrium state established in this work make it possible to characterize the chemical composition of the upper mantle of each region and test the equilibrium state of the phases between them. Variations of major oxides and incompatible elemental concentrations in clinopyroxene indicate a primary control by partial melting. The absence of typical “metasomatic” minerals, low equilibration temperatures and enriched LREE patterns indicate that the upper mantle below septentrional crust of Cameroun underwent an event of cryptic metasomatic enrichment prior to partial melting. The distinctive chemical features, LREE enrichment, strong U, Ce and Pr, depletion relative to Ba, Nb, La, Pb, and T, fractionation of Zr and Hf and therefore ligh high Zr/Hf ratio, low La/Yb, Nb/La and Ti/Eu are all results of interaction of refractory peridotite residues with carbonatite melts.展开更多
This research is concentrated on the longitudinal vibration of a tapered pipe pile considering the vertical support of the surrounding soil and construction disturbance.First,the pile-soil system is partitioned into f...This research is concentrated on the longitudinal vibration of a tapered pipe pile considering the vertical support of the surrounding soil and construction disturbance.First,the pile-soil system is partitioned into finite segments in the vertical direction and the Voigt model is applied to simulate the vertical support of the surrounding soil acting on the pile segment.The surrounding soil is divided into finite ring-shaped zones in the radial direction to consider the construction disturbance.Then,the shear complex stiffness at the pile-soil interface is derived by solving the dynamic equilibrium equation for the soil from the outermost to innermost zone.The displacement impedance at the top of an arbitrary pile segment is obtained by solving the dynamic equilibrium equation for the pile and is combined with the vertical support of the surrounding soil to derive the displacement impedance at the bottom of the upper adjacent segment.Further,the displacement impedance at the pile head is obtained based on the impedance function transfer technique.Finally,the reliability of the proposed solution is verified,followed by a sensitivity analysis concerning the coupling effect of the pile parameters,construction disturbance and the vertical support of the surrounding soil on the displacement impedance of the pile.展开更多
The composite pile consisting of core-pile and surrounding cement-enhanced soil is a promising pile foundation in recent years.However,how and to what extent the cement-enhanced soil influences the ultimate lateral re...The composite pile consisting of core-pile and surrounding cement-enhanced soil is a promising pile foundation in recent years.However,how and to what extent the cement-enhanced soil influences the ultimate lateral resistance has not been fully investigated.In this paper,the ultimate lateral resistance of the composite pile was studied by finite element limit analysis(FELA)and theoretical upper-bound analysis.The results of FELA and theoretical analysis revealed three failure modes of laterally loaded composite piles.The effects of the enhanced soil thickness,strength,and pile-enhanced soil interface characteristics on the ultimate lateral resistance were studied.The results show that increasing the enhanced soil thickness leads to a significant improvement on ultimate lateral resistance factor(N P),and there is a critical thickness beyond which the thickness no longer affects the N P.Increasing the enhanced soil strength induced 6.2%-232.6%increase of N P.However,no noticeable impact was detected when the enhanced soil strength was eight times higher than that of the natural soil.The maximum increment of N P is only 30.5%caused by the increase of interface adhesion factor(a).An empirical model was developed to calculate the N P of the composite pile,and the results show excellent agreement with the analytical results.展开更多
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 synthesi...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.展开更多
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...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.展开更多
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 o...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.展开更多
This work investigated the pyrolysis reaction of waste resin in a fluidized bed reactor.It was found that the pyrolysis-generated ash would adhere to the surface of ceramic particles,causing particle agglomeration and...This work investigated the pyrolysis reaction of waste resin in a fluidized bed reactor.It was found that the pyrolysis-generated ash would adhere to the surface of ceramic particles,causing particle agglomeration and defluidization.Adding kaolin could effectively inhibit the particle agglomeration during the fluidized pyrolysis reaction through physical isolation and chemical reaction.On the one hand,kaolin could form a coating layer on the surface of ceramic particles to prevent the adhesion of organic ash generated by the pyrolysis of resin.On the other hand,when a sufficient amount of kaolin(-0.2%(mass))was added,the activated kaolin could fully contact with the Na+ ions generated by the pyrolysis of resin and react to form a high-melting aluminosilicate mineral(nepheline),which could reduce the formation of low-melting-point sodium sulfate and thereby avoid the agglomeration of ceramic particles.展开更多
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-B...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.展开更多
Despite substantial efforts in developing high-performance catalysts for the oxygen reduction reaction(ORR),the persistent challenge lies in the high onset overpotential of the ORR,and the effect of the elec-trolyte s...Despite substantial efforts in developing high-performance catalysts for the oxygen reduction reaction(ORR),the persistent challenge lies in the high onset overpotential of the ORR,and the effect of the elec-trolyte solution cannot be ignored.Consequently,we have systematically investigated the impact of adsorbate species and concentration,as well as solution pH,on the ORR activity on Pt(111)and Pt(poly)electrodes.The results all tend to establish a linear quantitative relationship between the onset potential for ORR and the adsorption equilibrium potential of the adsorbate.This finding indicates the decisive role of adsorbates in the onset potential for ORR,suggesting that the adsorption potential of adsorbates can serve as an intuitive criterion for ORR activity.Additional support for this conclusion is derived from experimental results obtained from the oxygen evolution reaction on Pt(poly)with different adsorbate species and from the hydrogen evolution reaction on Pt(111)with iodine adsorption.We further propose both an empirical equation for the onset potential for ORR and the concept of a potential-regulated adsor-bate shielding effect to elucidate the influence of adsorbates on ORR activity.This study provides new insights into the high onset overpotential of the ORR and offers potential strategies for predicting and enhancingORRactivity inthefuture.展开更多
基金supported by the National Natural Science Foundation of China(21972131)。
文摘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.
基金supported by the State Key Program of National Natural Science Foundation of China(Grant No.12132003)State Key Laboratory of Explosion Science and Technology(Grant No.QNKT20-07)。
文摘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.
基金supported by the National Natural Science Foundation of China(Grant No.42071095)the Program of the State Key Laboratory of Frozen Soil Engineering(Grant No.SKLFSE-ZQ-59)+1 种基金the Science and Technology Project of Gansu Province(Grant No.22JR5RA086)the Science and Technology Research and Development Program of the Qinghai-Tibet Group Corporation(Grant No.QZ2022-G02).
文摘During the construction of cast-in-place piles in warm permafrost,the heat carried by concrete and the cement hydration reaction can cause strong thermal disturbance to the surrounding permafrost.Since the bearing capacity of the pile is quite small before the full freeze-back,the quick refreezing of the native soils surrounding the cast-in-place pile has become the focus of the infrastructure construction in permafrost.To solve this problem,this paper innovatively puts forward the application of the artificial ground freezing(AGF)method at the end of the curing period of cast-in-place piles in permafrost.A field test on the AGF was conducted at the Beiluhe Observation and Research Station of Frozen Soil Engineering and Environment(34°51.2'N,92°56.4'E)in the Qinghai Tibet Plateau(QTP),and then a 3-D numerical model was established to investigate the thermal performance of piles using AGF under different engineering conditions.Additionally,the long-term thermal performance of piles after the completion of AGF under different conditions was estimated.Field experiment results demonstrate that AGF is an effective method to reduce the refreezing time of the soil surrounding the piles constructed in permafrost terrain,with the ability to reduce the pile-soil interface temperatures to below the natural ground temperature within 3 days.Numerical results further prove that AGF still has a good cooling effect even under unfavorable engineering conditions such as high pouring temperature,large pile diameter,and large pile length.Consequently,the application of this method is meaningful to save the subsequent latency time and solve the problem of thermal disturbance in pile construction in permafrost.The research results are highly relevant for the spread of AGF technology and the rapid building of pile foundations in permafrost.
文摘BACKGROUND As one of the fatal diseases with high incidence,lung cancer has seriously endangered public health and safety.Elderly patients usually have poor self-care and are more likely to show a series of psychological problems.AIM To investigate the effectiveness of the initial check,information exchange,final accuracy check,reaction(IIFAR)information care model on the mental health status of elderly patients with lung cancer.METHODS This study is a single-centre study.We randomly recruited 60 elderly patients with lung cancer who attended our hospital from January 2021 to January 2022.These elderly patients with lung cancer were randomly divided into two groups,with the control group taking the conventional propaganda and education and the observation group taking the IIFAR information care model based on the conventional care protocol.The differences in psychological distress,anxiety and depression,life quality,fatigue,and the locus of control in psychology were compared between these two groups,and the causes of psychological distress were analyzed.RESULTS After the intervention,Distress Thermometer,Hospital Anxiety and Depression Scale(HADS)for anxiety and the HADS for depression,Revised Piper’s Fatigue Scale,and Chance Health Locus of Control scores were lower in the observation group compared to the pre-intervention period in the same group and were significantly lower in the observation group compared to those of the control group(P<0.05).After the intervention,Quality of Life Questionnaire Core 30(QLQ-C30),Internal Health Locus of Control,and Powerful Others Health Locus of Control scores were significantly higher in the observation and the control groups compared to the pre-intervention period in their same group,and QLQ-C30 scores were significantly higher in the observation group compared to those of the control group(P<0.05).CONCLUSION The IIFAR information care model can help elderly patients with lung cancer by reducing their anxiety and depression,psychological distress,and fatigue,improving their tendencies on the locus of control in psychology,and enhancing their life qualities.
基金the financial support from the National Natural Science Foundation of China(Grant Nos.92372107 and 52171219).
文摘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.
基金the financial support provided by the National Natural Science Foundation of China(Grant No.42272310).
文摘Cyclic loads generated by environmental factors,such as winds,waves,and trains,will likely lead to performance degradation in pile foundations,resulting in issues like permanent displacement accumulation and bearing capacity attenuation.This paper presents a semi-analytical solution for predicting the axial cyclic behavior of piles in sands.The solution relies on two enhanced nonlinear load-transfer models considering stress-strain hysteresis and cyclic degradation in the pile-soil interaction.Model parameters are calibrated through cyclic shear tests of the sand-steel interface and laboratory geotechnical testing of sands.A novel aspect involves the meticulous formulation of the shaft loadtransfer function using an interface constitutive model,which inherently inherits the interface model’s advantages,such as capturing hysteresis,hardening,degradation,and particle breakage.The semi-analytical solution is computed numerically using the matrix displacement method,and the calculated values are validated through model tests performed on non-displacement and displacement piles in sands.The results demonstrate that the predicted values show excellent agreement with the measured values for both the static and cyclic responses of piles in sands.The displacement pile response,including factors such as bearing capacity,mobilized shaft resistance,and convergence rate of permanent settlement,exhibit improvements compared to non-displacement piles attributed to the soil squeezing effect.This methodology presents an innovative analytical framework,allowing for integrating cyclic interface models into the theoretical investigation of pile responses.
基金the immense support provided by the National Research Foundation of Korea(NRF)Grant funded by the Korean Government(MSIT)(RS-2023–00210114)the National R&D Program through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(2021M3D1A2051636)。
文摘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.
基金We acknowledge the National Natural Science Foundation of China(No.22275134)for fi nancial support.
文摘N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.
基金supported by the National Science Foundation of China(42107183).
文摘Driven piles are used in many geological environments as a practical and convenient structural component.Hence,the determination of the drivability of piles is actually of great importance in complex geotechnical applications.Conventional methods of predicting pile drivability often rely on simplified physicalmodels or empirical formulas,whichmay lack accuracy or applicability in complex geological conditions.Therefore,this study presents a practical machine learning approach,namely a Random Forest(RF)optimized by Bayesian Optimization(BO)and Particle Swarm Optimization(PSO),which not only enhances prediction accuracy but also better adapts to varying geological environments to predict the drivability parameters of piles(i.e.,maximumcompressive stress,maximum tensile stress,and blow per foot).In addition,support vector regression,extreme gradient boosting,k nearest neighbor,and decision tree are also used and applied for comparison purposes.In order to train and test these models,among the 4072 datasets collected with 17model inputs,3258 datasets were randomly selected for training,and the remaining 814 datasets were used for model testing.Lastly,the results of these models were compared and evaluated using two performance indices,i.e.,the root mean square error(RMSE)and the coefficient of determination(R2).The results indicate that the optimized RF model achieved lower RMSE than other prediction models in predicting the three parameters,specifically 0.044,0.438,and 0.146;and higher R^(2) values than other implemented techniques,specifically 0.966,0.884,and 0.977.In addition,the sensitivity and uncertainty of the optimized RF model were analyzed using Sobol sensitivity analysis and Monte Carlo(MC)simulation.It can be concluded that the optimized RF model could be used to predict the performance of the pile,and it may provide a useful reference for solving some problems under similar engineering conditions.
基金financial support from The University of Manchester to cover his PhD tuition fees for him to carry out this workChina National High-end Foreign Experts Recruitment Plan Project (G2023018001L) for partially supporting the work。
文摘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.
基金supported by the National Natural Science Foundation of China(Nos.12075027,1232509,11961141004,and 12175152)the National Science Foundation(Nos.Phys-2011890 and Phy-1430152)。
文摘Calcium production and the stellar evolution of first-generation stars remain fascinating mysteries in astrophysics.As one possible nucleosynthesis scenario,break-out from the hot carbon–nitrogen–oxygen(HCNO)cycle was thought to be the source of the calcium observed in these oldest stars.However,according to the stellar modeling,a nearly tenfold increase in the thermonuclear rate ratio of the break-out ^(19)F(p,γ)^(20) Ne reaction with respect to the competing ^(19)F(p,α)^(16) O back-processing reaction is required to reproduce the observed calcium abundance.We performed a direct measurement of this break-out reaction at the China Jinping underground laboratory.The measurement was performed down to the low-energy limit of E_(c.m.)=186 keV in the center-of-mass frame.The key resonance was observed at 225.2 keV for the first time.At a temperature of approximately 0.1 GK,this new resonance enhanced the thermonuclear ^(19)F(p,γ)^(20) Ne rate by up to a factor of≈7.4,compared with the previously recommended NACRE rate.This is of particular interest to the study of the evolution of the first stars and implies a stronger breakdown in their“warm”CNO cycle through the ^(19)F(p,γ)^(20) Ne reaction than previously envisioned.This break-out resulted in the production of the calcium observed in the oldest stars,enhancing our understanding of the evolution of the first stars.
文摘The alkaline volcanism of the Cameroon Volcanic Line in its northern domain has raised many fresh enclaves of peridotites. The samples selected come from five (05) different localities (Liri, in the plateau of Kapsiki, Mazélé in the NE of Ngaoundéré, Tello and Ganguiré in the SE of Ngaoundéré and Likok, locality located in the west of Ngaoundé). The peridotite enclaves of the above localities show restricted mineralogical variation. Most are four-phase spinel-lherzolites, indicating that this is the main lithology that forms the lithospheric mantle below the shallow zone. No traces of garnet or primary plagioclase were detected, which strongly limits the depth range from which the rock fragments were sampled. The textures and the wide equilibrium temperatures (884˚C - 1115˚C) indicate also entrainment of lherzolite xenoliths from shallow depths within the lithosphere and the presence of mantle diapirism. The exchange reactions and equilibrium state established in this work make it possible to characterize the chemical composition of the upper mantle of each region and test the equilibrium state of the phases between them. Variations of major oxides and incompatible elemental concentrations in clinopyroxene indicate a primary control by partial melting. The absence of typical “metasomatic” minerals, low equilibration temperatures and enriched LREE patterns indicate that the upper mantle below septentrional crust of Cameroun underwent an event of cryptic metasomatic enrichment prior to partial melting. The distinctive chemical features, LREE enrichment, strong U, Ce and Pr, depletion relative to Ba, Nb, La, Pb, and T, fractionation of Zr and Hf and therefore ligh high Zr/Hf ratio, low La/Yb, Nb/La and Ti/Eu are all results of interaction of refractory peridotite residues with carbonatite melts.
基金National Natural Science Foundation of China under Grand No.51808190the Central Government Guides Local Science and Technology Development Fund Projects under Grand No.XZ202301YD0019C+2 种基金the Foundation of Key Laboratory of Soft Soils and Geoenvironmental Engineering(Zhejiang University)Ministry of Education under Grand No.2022P04the Central University Basic Research Fund of China under Grand No.B220202017。
文摘This research is concentrated on the longitudinal vibration of a tapered pipe pile considering the vertical support of the surrounding soil and construction disturbance.First,the pile-soil system is partitioned into finite segments in the vertical direction and the Voigt model is applied to simulate the vertical support of the surrounding soil acting on the pile segment.The surrounding soil is divided into finite ring-shaped zones in the radial direction to consider the construction disturbance.Then,the shear complex stiffness at the pile-soil interface is derived by solving the dynamic equilibrium equation for the soil from the outermost to innermost zone.The displacement impedance at the top of an arbitrary pile segment is obtained by solving the dynamic equilibrium equation for the pile and is combined with the vertical support of the surrounding soil to derive the displacement impedance at the bottom of the upper adjacent segment.Further,the displacement impedance at the pile head is obtained based on the impedance function transfer technique.Finally,the reliability of the proposed solution is verified,followed by a sensitivity analysis concerning the coupling effect of the pile parameters,construction disturbance and the vertical support of the surrounding soil on the displacement impedance of the pile.
基金The work was supported by the National Natural Science Foundation of China(Grant No.51978540).
文摘The composite pile consisting of core-pile and surrounding cement-enhanced soil is a promising pile foundation in recent years.However,how and to what extent the cement-enhanced soil influences the ultimate lateral resistance has not been fully investigated.In this paper,the ultimate lateral resistance of the composite pile was studied by finite element limit analysis(FELA)and theoretical upper-bound analysis.The results of FELA and theoretical analysis revealed three failure modes of laterally loaded composite piles.The effects of the enhanced soil thickness,strength,and pile-enhanced soil interface characteristics on the ultimate lateral resistance were studied.The results show that increasing the enhanced soil thickness leads to a significant improvement on ultimate lateral resistance factor(N P),and there is a critical thickness beyond which the thickness no longer affects the N P.Increasing the enhanced soil strength induced 6.2%-232.6%increase of N P.However,no noticeable impact was detected when the enhanced soil strength was eight times higher than that of the natural soil.The maximum increment of N P is only 30.5%caused by the increase of interface adhesion factor(a).An empirical model was developed to calculate the N P of the composite pile,and the results show excellent agreement with the analytical results.
基金the Science and Technology Planning Project of Guangdong Province(2016B090934002)Guangdong Provincial Natural Science Foundation(2023A1515011640)for financial support.
文摘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.
基金the National Natural Science Foundation of China(No.21875149)111 project(B17030)the Basal Research Fund of the Central University.
文摘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.
基金supported by NSFC(Grant Nos.92061101,22271104,21871141,22225109,and 21901123)the Excellent Youth Foundation of Jiangsu Scientific Committee(BK20211593)+2 种基金the project funded by the China Postdoctoral Science Foundation(2018M630572)the Priority Academic Program Development of Jiangsu Higher Education Institutions,and the Foundation of Jiangsu Collaborative Innovation Center of Biomedical Functional Materials,the National Key Research and Development Project of China(Grant No.2021YFC2100100)the Natural Science Foundation of Jiangsu Province(Grant No.BK20190694)。
文摘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.
基金support and encouragement of the Joint Funds of the National Natural Science Foundation of China(No.U21B2095)the Major Research Project of National Natural Science Foundation of China(No.91834303).
文摘This work investigated the pyrolysis reaction of waste resin in a fluidized bed reactor.It was found that the pyrolysis-generated ash would adhere to the surface of ceramic particles,causing particle agglomeration and defluidization.Adding kaolin could effectively inhibit the particle agglomeration during the fluidized pyrolysis reaction through physical isolation and chemical reaction.On the one hand,kaolin could form a coating layer on the surface of ceramic particles to prevent the adhesion of organic ash generated by the pyrolysis of resin.On the other hand,when a sufficient amount of kaolin(-0.2%(mass))was added,the activated kaolin could fully contact with the Na+ ions generated by the pyrolysis of resin and react to form a high-melting aluminosilicate mineral(nepheline),which could reduce the formation of low-melting-point sodium sulfate and thereby avoid the agglomeration of ceramic particles.
基金support from National Key Research and Development Program of China(2021YFC2103704)the National Natural Science Foundation of China(22222808,21978200)the Haihe Laboratory of Sustainable Chemical Transformations.
文摘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.
基金supported by the National Natural Science Foundation of China(no.22372154,21972131).
文摘Despite substantial efforts in developing high-performance catalysts for the oxygen reduction reaction(ORR),the persistent challenge lies in the high onset overpotential of the ORR,and the effect of the elec-trolyte solution cannot be ignored.Consequently,we have systematically investigated the impact of adsorbate species and concentration,as well as solution pH,on the ORR activity on Pt(111)and Pt(poly)electrodes.The results all tend to establish a linear quantitative relationship between the onset potential for ORR and the adsorption equilibrium potential of the adsorbate.This finding indicates the decisive role of adsorbates in the onset potential for ORR,suggesting that the adsorption potential of adsorbates can serve as an intuitive criterion for ORR activity.Additional support for this conclusion is derived from experimental results obtained from the oxygen evolution reaction on Pt(poly)with different adsorbate species and from the hydrogen evolution reaction on Pt(111)with iodine adsorption.We further propose both an empirical equation for the onset potential for ORR and the concept of a potential-regulated adsor-bate shielding effect to elucidate the influence of adsorbates on ORR activity.This study provides new insights into the high onset overpotential of the ORR and offers potential strategies for predicting and enhancingORRactivity inthefuture.