Ethylene glycol(EG)plays a pivotal role as a primary raw material in the polyester industry,and the syngas-to-EG route has become a significant technical route in production.The carbon monoxide(CO)gas-phase catalytic ...Ethylene glycol(EG)plays a pivotal role as a primary raw material in the polyester industry,and the syngas-to-EG route has become a significant technical route in production.The carbon monoxide(CO)gas-phase catalytic coupling to synthesize dimethyl oxalate(DMO)is a crucial process in the syngas-to-EG route,whereby the composition of the reactor outlet exerts influence on the ultimate quality of the EG product and the energy consumption during the subsequent separation process.However,measuring product quality in real time or establishing accurate dynamic mechanism models is challenging.To effectively model the DMO synthesis process,this study proposes a hybrid modeling strategy that integrates process mechanisms and data-driven approaches.The CO gas-phase catalytic coupling mechanism model is developed based on intrinsic kinetics and material balance,while a long short-term memory(LSTM)neural network is employed to predict the macroscopic reaction rate by leveraging temporal relationships derived from archived measurements.The proposed model is trained semi-supervised to accommodate limited-label data scenarios,leveraging historical data.By integrating these predictions with the mechanism model,the hybrid modeling approach provides reliable and interpretable forecasts of mass fractions.Empirical investigations unequivocally validate the superiority of the proposed hybrid modeling approach over conventional data-driven models(DDMs)and other hybrid modeling techniques.展开更多
The microscopic heterogeneity of pore-throat structures in tight sandstone is a crucial parameter for understanding the transport mechanism of fluid flow.In this work,we firstly developed the new procedure to characte...The microscopic heterogeneity of pore-throat structures in tight sandstone is a crucial parameter for understanding the transport mechanism of fluid flow.In this work,we firstly developed the new procedure to characterize the pore size distribution(PSD)and throat size distribution(TSD)by combining the nuclear magnetic resonance(NMR),cast thin section(CTS),and constant-rate mercury injection(CRMI)tests,and used the permeability estimated model to verify the full-scale PSD and TSD.Then,we respectively analyzed the fractal feature of the pore and throat,and characterized the heterogeneity of pores and throats.Finally,we elaborated the effect of the pore and throat heterogeneity on the gas-phase seepage capacity base on the analysis of the simple capillary tube model and gas-flooding experiment.The results showed that(1)The PSD and TSD of the tight sandstone sample ranged from 0.01 to 10 mm and from 0.1 to 57 mm,respectively,mainly contributed by the micropores and mesopores.Meanwhile,the permeability estimated by the PSD and TSD was consistent with the experimental permeability,and relative error was lower than 8%.(2)The PSD and TSD exhibited multifractal characteristics,and singularity strength range,Δα,could be used as the indicator for characterizing the heterogeneity of pore and throat.Furthermore,the throat of the sample showed stronger heterogeneity than that the pore.(3)The throats played an important role for the fluid transport in the tight sandstone,and the effect of the throat heterogeneity on the gas-phase seepage capacity was different under the lower and higher injection pressure.The macropores and micropores maybe respectively become the preferential migration pathways at the lower and higher injection pressure.In the end,the identification plate was established in our paper,and could be described the relationship among the throat heterogeneity,injection pressure,permeability and flow path of the gas phase in the tight sandstone.展开更多
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 ...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.展开更多
High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion te...High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion technologies.Herein,we report a robust method for the synthesis of a bimetallic alkoxide for efficient oxygen evolution reaction(OER)for alkaline electrolysis,which yields current density of 10 mA cm^(-2)at an overpotential of 215 mV in 0.1 M KOH electrolyte.The catalyst demonstrates an excellent durability for more than 540 h operation with negligible degradation in activity.Raman spectra revealed that the catalyst underwent structure reconstruction during OER,evolving into oxyhydroxide,which was the active site proceeding OER in alkaline electrolyte.In-situ synchrotron X-ray absorption experiment combined with density functional theory calculation suggests a lattice oxygen involved electrocatalytic reaction mechanism for the in-situ generated nickel–iron bimetal-oxyhydroxide catalyst.This mechanism together with the synergy between nickel and iron are responsible for the enhanced catalytic activity and durability.These findings provide promising strategies for the rational design of nonnoble metal OER catalysts.展开更多
Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent year...Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.展开更多
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
Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performan...Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performance for hydrogen evolution reaction(HER). With the VS concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS_(2)-VS 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential(68 m V) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy(ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S-H* peak of the Ni S_(2)-VS 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the Ni S_(2)-VS 5.9% has the optimal |ΔG^(H*)| of 0.17 e V. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.展开更多
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 or...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.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
Transition-metal oxyhydroxides are attractive catalysts for oxygen evolution reactions(OERs).Further studies for developing transition-metal oxyhydroxide catalysts and understanding their catalytic mechanisms will ben...Transition-metal oxyhydroxides are attractive catalysts for oxygen evolution reactions(OERs).Further studies for developing transition-metal oxyhydroxide catalysts and understanding their catalytic mechanisms will benefit their quick transition to the next catalysts.Herein,Mo-doped CoOOH was designed as a high-performance model electrocatalyst with durability for 20 h at 10 mAcm−2.Additionally,it had an overpotential of 260 mV(glassy carbon)or 215 mV(nickel foam),which was 78 mV lower than that of IrO_(2)(338 mV).In situ,Raman spectroscopy revealed the transformation process of CoOOH.Calculations using the density functional theory showed that during OER,doped Mo increased the spin-up density of states and shrank the spin-down bandgap of the 3d orbits in the reconstructed CoOOH under the electrochemical activation process,which simultaneously optimized the adsorption and electron conduction of oxygen-related intermediates on Co sites and lowered the OER overpotentials.Our research provides new insights into the methodical planning of the creation of transition-metal oxyhydroxide OER catalysts.展开更多
The metallurgical quality control of magnesium(Mg)and Mg alloys in melting process is required to ensure a satisfied mechanical and corrosion performance,while the typical used steel crucible introduces impurities and...The metallurgical quality control of magnesium(Mg)and Mg alloys in melting process is required to ensure a satisfied mechanical and corrosion performance,while the typical used steel crucible introduces impurities and interfacial interaction during melting process.Therefore,a systematic study about impurities diffusion and interfacial interaction between molten Mg and steel is necessary.In the present study,the interfacial reaction between molten AZ91D Mg alloy and mild steel during melting process was investigated with the melting temperatures of 700℃,750℃ and 800℃.The results show that Al(Fe,Mn)intermetallic layer is the intermetallic primarily formed at the interfaces of AZ91D melt and mild steel.Meanwhile,Al_(8)(Mn,Fe)5is indexed between Al(Fe,Mn)and AZ91D.AlFe_(3)C appears between the mild steel and Al(Fe,Mn)at 700℃ and 750℃,but absent at 800℃ due to the increased solubility of carbon in Mg matrix.It is found that the growth of the intermetallic layer is controlled by diffusion mechanism,and Al and Mn are the dominant diffusing species in the whole interfacial reaction process.By measuring the thickness of different layers,the growth constant was calculated.It increases from 1.89(±0.03)×10^(-12)m^(2)·s^(-1)at 700℃ to 3.05(±0.05)×10^(-12)m^(2)·s^(-1)at 750℃,and 5.18(±0.05)×10^(-12)m^(2)·s^(-1)at 800℃.Meanwhile,the content of Fe is linearly increased in AZ91D with the increase of holding time at 700℃ and 750℃,while it shows a significantly increment after holding for 8 h at 800℃,indicating holding temperature is more crucial to determine the Fe content of AZ91D than holding time.展开更多
Based on the dinuclear system model,the calculated evaporation residue cross sections matched well with the current experimental results.The synthesis of superheavy elements Z=121 was systematically studied through co...Based on the dinuclear system model,the calculated evaporation residue cross sections matched well with the current experimental results.The synthesis of superheavy elements Z=121 was systematically studied through combinations of stable projectiles with Z=21-30 and targets with half-lives exceeding 50 d.The influence of mass asymmetry and isotopic dependence on the projectile and target nuclei was investigated in detail.The reactions^(254)Es(^(46)Ti,3n)^(297)121 and^(252)Es(^(46)Ti,3n)^(295)121 were found to be experimentally feasible for synthesizing superheavy element Z=121,with maximal evaporation residue cross sections of 6.619 and 4.123 fb at 219.9 and 223.9 MeV,respectively.展开更多
Reactions of C60 with Si(CH_3)_nCl_(4-n) (n=2,3)in the ion source of the mass spectrometer have been studied.The corresponding adduct ions[C60Si(CH_3)_mCl3_(-m)]^+(m=1,2,3),[C60SiCl]^+ and[C60CH_3]^+ were observed and...Reactions of C60 with Si(CH_3)_nCl_(4-n) (n=2,3)in the ion source of the mass spectrometer have been studied.The corresponding adduct ions[C60Si(CH_3)_mCl3_(-m)]^+(m=1,2,3),[C60SiCl]^+ and[C60CH_3]^+ were observed and their possible structures were discussed.The results indicated that C60 is very reactive to electrophiles in the gas phase.展开更多
Maillard reaction(MR)is a non-enzymatic browning reaction commonly seen in food processing,which occurs between reducing sugars and compounds with amino groups.Despite certain advantages based on Maillard reaction pro...Maillard reaction(MR)is a non-enzymatic browning reaction commonly seen in food processing,which occurs between reducing sugars and compounds with amino groups.Despite certain advantages based on Maillard reaction products(MRPs)found in some food for health and storage application have appeared,however,the MR occurring in human physiological environment can produce advanced glycation end products(AGEs)by non-enzymatic modification of macromolecules such as proteins,lipids and nucleic acid,which could change the structure and functional activity of the molecules themselves.In this review,we take AGEs as our main object,on the one hand,discuss physiologic aging,that is,age-dependent covalent cross-linking and modification of proteins such as collagen that occur in eyes and skin containing connective tissue.On the other hand,pathological aging associated with autoimmune and inflammatory diseases,neurodegenerative diseases,diabetes and diabetic nephropathy,cardiovascular diseases and bone degenerative diseases have been mainly proposed.Based on the series of adverse effects of accelerated aging and disease pathologies caused by MRPs,the possible harm caused by some MR can be slowed down or inhibited by artificial drug intervention,dietary pattern and lifestyle control.It also stimulates people's curiosity to continue to explore the potential link between the MR and human aging and health,which should be paid more attention to for the development of life sciences.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
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
Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability o...Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability of the organosulfur,as well as the mass-transfer resistance that exists in multiphase catalysis,have often limited the catalytic application of Cu-MOFs in C-S coupling reactions.In this paper,a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide(CTAB)was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB.Concurrently,elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.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
Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However...Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.展开更多
基金supported in part by the National Key Research and Development Program of China(2022YFB3305300)the National Natural Science Foundation of China(62173178).
文摘Ethylene glycol(EG)plays a pivotal role as a primary raw material in the polyester industry,and the syngas-to-EG route has become a significant technical route in production.The carbon monoxide(CO)gas-phase catalytic coupling to synthesize dimethyl oxalate(DMO)is a crucial process in the syngas-to-EG route,whereby the composition of the reactor outlet exerts influence on the ultimate quality of the EG product and the energy consumption during the subsequent separation process.However,measuring product quality in real time or establishing accurate dynamic mechanism models is challenging.To effectively model the DMO synthesis process,this study proposes a hybrid modeling strategy that integrates process mechanisms and data-driven approaches.The CO gas-phase catalytic coupling mechanism model is developed based on intrinsic kinetics and material balance,while a long short-term memory(LSTM)neural network is employed to predict the macroscopic reaction rate by leveraging temporal relationships derived from archived measurements.The proposed model is trained semi-supervised to accommodate limited-label data scenarios,leveraging historical data.By integrating these predictions with the mechanism model,the hybrid modeling approach provides reliable and interpretable forecasts of mass fractions.Empirical investigations unequivocally validate the superiority of the proposed hybrid modeling approach over conventional data-driven models(DDMs)and other hybrid modeling techniques.
基金financial support from the Youth Science and Technology Innovation Team of Southwest Petroleum University(No.2018CXTD10)the National Natural Science Foundation Project of China(No.51874248 and No.U19B2010).
文摘The microscopic heterogeneity of pore-throat structures in tight sandstone is a crucial parameter for understanding the transport mechanism of fluid flow.In this work,we firstly developed the new procedure to characterize the pore size distribution(PSD)and throat size distribution(TSD)by combining the nuclear magnetic resonance(NMR),cast thin section(CTS),and constant-rate mercury injection(CRMI)tests,and used the permeability estimated model to verify the full-scale PSD and TSD.Then,we respectively analyzed the fractal feature of the pore and throat,and characterized the heterogeneity of pores and throats.Finally,we elaborated the effect of the pore and throat heterogeneity on the gas-phase seepage capacity base on the analysis of the simple capillary tube model and gas-flooding experiment.The results showed that(1)The PSD and TSD of the tight sandstone sample ranged from 0.01 to 10 mm and from 0.1 to 57 mm,respectively,mainly contributed by the micropores and mesopores.Meanwhile,the permeability estimated by the PSD and TSD was consistent with the experimental permeability,and relative error was lower than 8%.(2)The PSD and TSD exhibited multifractal characteristics,and singularity strength range,Δα,could be used as the indicator for characterizing the heterogeneity of pore and throat.Furthermore,the throat of the sample showed stronger heterogeneity than that the pore.(3)The throats played an important role for the fluid transport in the tight sandstone,and the effect of the throat heterogeneity on the gas-phase seepage capacity was different under the lower and higher injection pressure.The macropores and micropores maybe respectively become the preferential migration pathways at the lower and higher injection pressure.In the end,the identification plate was established in our paper,and could be described the relationship among the throat heterogeneity,injection pressure,permeability and flow path of the gas phase in the tight sandstone.
基金supported by the Taishan Scholar Program of Shandong Province,China (tsqn202211162)the National Natural Science Foundation of China (22102079)the Natural Science Foundation of Shandong Province of China (ZR2021YQ10,ZR2022QB163)。
文摘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.
基金the staff at Beamline (BL08U1-A and BL11B)of the Shanghai Synchrotron Radiation Facility (SSRF)the support from the National Key Research&Development Program of China (2022YFB3803700)+2 种基金the National Natural Science Foundation of China (52171186)the support through the Overseas Outstanding Youth Fund and Shanghai Pujiang Talent Project (21PJ1408500)the financial support from the Center of Hydrogen Science,Shanghai Jiao Tong University。
文摘High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion technologies.Herein,we report a robust method for the synthesis of a bimetallic alkoxide for efficient oxygen evolution reaction(OER)for alkaline electrolysis,which yields current density of 10 mA cm^(-2)at an overpotential of 215 mV in 0.1 M KOH electrolyte.The catalyst demonstrates an excellent durability for more than 540 h operation with negligible degradation in activity.Raman spectra revealed that the catalyst underwent structure reconstruction during OER,evolving into oxyhydroxide,which was the active site proceeding OER in alkaline electrolyte.In-situ synchrotron X-ray absorption experiment combined with density functional theory calculation suggests a lattice oxygen involved electrocatalytic reaction mechanism for the in-situ generated nickel–iron bimetal-oxyhydroxide catalyst.This mechanism together with the synergy between nickel and iron are responsible for the enhanced catalytic activity and durability.These findings provide promising strategies for the rational design of nonnoble metal OER catalysts.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.51902101 and 21875203)the Natural Science Foundation of Hunan Province(Nos.2021JJ40044 and 2023JJ50287)Natural Science Foundation of Jiangsu Province(No.BK20201381).
文摘Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.
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funded by the National Natural Science Foundation of China (NSFC) (Nos. 22221001, 22201115, 21931001, and 21922105)the Special Fund Project of Guiding Scientific and Technological Innovation Development of Gansu Province (2019ZX–04)+3 种基金the 111 Project (B20027)by the Fundamental Research Funds for the Central Universities (lzujbky-2023-eyt03)support Natural Science Foundation of Gansu Providence (22JR5RA540)Gansu Province Youth Science and Technology Talent Promotion Project (GXH202220530-02)。
文摘Ef fective and robust catalyst is the core of water splitting to produce hydrogen.Here, we report an anionic etching method to tailor the sulfur vacancy(VS) of NiS_(2) to further enhance the electrocatalytic performance for hydrogen evolution reaction(HER). With the VS concentration change from 2.4% to 8.5%, the H* adsorption strength on S sites changed and NiS_(2)-VS 5.9% shows the most optimized H* adsorption for HER with an ultralow onset potential(68 m V) and has long-term stability for 100 h in 1 M KOH media. In situ attenuated-total-reflection Fourier transform infrared spectroscopy(ATR-FTIRS) measurements are usually used to monitor the adsorption of intermediates. The S-H* peak of the Ni S_(2)-VS 5.9% appears at a very low voltage, which is favorable for the HER in alkaline media. Density functional theory calculations also demonstrate the Ni S_(2)-VS 5.9% has the optimal |ΔG^(H*)| of 0.17 e V. This work offers a simple and promising pathway to enhance catalytic activity via precise vacancies strategy.
基金support of Shanxi Province Major Science and Technology Projects,China (No.20191101002).
文摘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.
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The National Natural Science Foundation of China(Grant Nos.52072114 and 51922008)the 111 Project(Grant No.D17007),the Henan Center for Outstanding Overseas Scientists(Grant No.GZS2018003)+2 种基金Xinxiang Major Science and Technology Projects(Grant No.21ZD001)Guangdong Innovative and Entrepreneurial Research Team Program(2016ZT06N500)Guangdong Provincial Key Laboratory of Energy Materials for Electric Power(2018B030322001)all provided financial support for this work.
文摘Transition-metal oxyhydroxides are attractive catalysts for oxygen evolution reactions(OERs).Further studies for developing transition-metal oxyhydroxide catalysts and understanding their catalytic mechanisms will benefit their quick transition to the next catalysts.Herein,Mo-doped CoOOH was designed as a high-performance model electrocatalyst with durability for 20 h at 10 mAcm−2.Additionally,it had an overpotential of 260 mV(glassy carbon)or 215 mV(nickel foam),which was 78 mV lower than that of IrO_(2)(338 mV).In situ,Raman spectroscopy revealed the transformation process of CoOOH.Calculations using the density functional theory showed that during OER,doped Mo increased the spin-up density of states and shrank the spin-down bandgap of the 3d orbits in the reconstructed CoOOH under the electrochemical activation process,which simultaneously optimized the adsorption and electron conduction of oxygen-related intermediates on Co sites and lowered the OER overpotentials.Our research provides new insights into the methodical planning of the creation of transition-metal oxyhydroxide OER catalysts.
基金supported by the Natural Science Foundation of Chongqing,China(Grant Nos.cstc2020jcyj-msxm X0544,CSTB2022NSCQ-MSX0352,CSTB2022NSCQ-MSX0891,cstc2020jcyj-msxm X0184)Scientific and Technological Research Program of Chongqing Municipal Education Commission(Grant No.KJQN202001416)National Natural Science Foundation of China(Grant Nos.11847077,52001028)。
文摘The metallurgical quality control of magnesium(Mg)and Mg alloys in melting process is required to ensure a satisfied mechanical and corrosion performance,while the typical used steel crucible introduces impurities and interfacial interaction during melting process.Therefore,a systematic study about impurities diffusion and interfacial interaction between molten Mg and steel is necessary.In the present study,the interfacial reaction between molten AZ91D Mg alloy and mild steel during melting process was investigated with the melting temperatures of 700℃,750℃ and 800℃.The results show that Al(Fe,Mn)intermetallic layer is the intermetallic primarily formed at the interfaces of AZ91D melt and mild steel.Meanwhile,Al_(8)(Mn,Fe)5is indexed between Al(Fe,Mn)and AZ91D.AlFe_(3)C appears between the mild steel and Al(Fe,Mn)at 700℃ and 750℃,but absent at 800℃ due to the increased solubility of carbon in Mg matrix.It is found that the growth of the intermetallic layer is controlled by diffusion mechanism,and Al and Mn are the dominant diffusing species in the whole interfacial reaction process.By measuring the thickness of different layers,the growth constant was calculated.It increases from 1.89(±0.03)×10^(-12)m^(2)·s^(-1)at 700℃ to 3.05(±0.05)×10^(-12)m^(2)·s^(-1)at 750℃,and 5.18(±0.05)×10^(-12)m^(2)·s^(-1)at 800℃.Meanwhile,the content of Fe is linearly increased in AZ91D with the increase of holding time at 700℃ and 750℃,while it shows a significantly increment after holding for 8 h at 800℃,indicating holding temperature is more crucial to determine the Fe content of AZ91D than holding time.
基金the National Key R&D Program of China(No.2023YFA1606401)the National Natural Science Foundation of China(Nos.12135004,11635003 and 11961141004).
文摘Based on the dinuclear system model,the calculated evaporation residue cross sections matched well with the current experimental results.The synthesis of superheavy elements Z=121 was systematically studied through combinations of stable projectiles with Z=21-30 and targets with half-lives exceeding 50 d.The influence of mass asymmetry and isotopic dependence on the projectile and target nuclei was investigated in detail.The reactions^(254)Es(^(46)Ti,3n)^(297)121 and^(252)Es(^(46)Ti,3n)^(295)121 were found to be experimentally feasible for synthesizing superheavy element Z=121,with maximal evaporation residue cross sections of 6.619 and 4.123 fb at 219.9 and 223.9 MeV,respectively.
文摘Reactions of C60 with Si(CH_3)_nCl_(4-n) (n=2,3)in the ion source of the mass spectrometer have been studied.The corresponding adduct ions[C60Si(CH_3)_mCl3_(-m)]^+(m=1,2,3),[C60SiCl]^+ and[C60CH_3]^+ were observed and their possible structures were discussed.The results indicated that C60 is very reactive to electrophiles in the gas phase.
基金financially supported by grants from the National Natural Science Foundation of China (82170873,81871095)the National Natural Science Foundation of China (81974503)the Tsinghua University Spring Breeze Fund (20211080005)。
文摘Maillard reaction(MR)is a non-enzymatic browning reaction commonly seen in food processing,which occurs between reducing sugars and compounds with amino groups.Despite certain advantages based on Maillard reaction products(MRPs)found in some food for health and storage application have appeared,however,the MR occurring in human physiological environment can produce advanced glycation end products(AGEs)by non-enzymatic modification of macromolecules such as proteins,lipids and nucleic acid,which could change the structure and functional activity of the molecules themselves.In this review,we take AGEs as our main object,on the one hand,discuss physiologic aging,that is,age-dependent covalent cross-linking and modification of proteins such as collagen that occur in eyes and skin containing connective tissue.On the other hand,pathological aging associated with autoimmune and inflammatory diseases,neurodegenerative diseases,diabetes and diabetic nephropathy,cardiovascular diseases and bone degenerative diseases have been mainly proposed.Based on the series of adverse effects of accelerated aging and disease pathologies caused by MRPs,the possible harm caused by some MR can be slowed down or inhibited by artificial drug intervention,dietary pattern and lifestyle control.It also stimulates people's curiosity to continue to explore the potential link between the MR and human aging and health,which should be paid more attention to for the development of life sciences.
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support from the National Natural Science Foundation of China(22078130)the Fundamental Research Funds for the Central Universities(1042050205225990/010)Starting Research Fund of Qingyuan Innovation Laboratory(00523001).
文摘Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability of the organosulfur,as well as the mass-transfer resistance that exists in multiphase catalysis,have often limited the catalytic application of Cu-MOFs in C-S coupling reactions.In this paper,a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide(CTAB)was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB.Concurrently,elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.
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supported by the National Natural Science Foundation of China(22168002,22108070,21878078)the Natural Science Foundation of Guangxi Province(2020GXNSFAA159119)+2 种基金the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2021Z012)the Open Fund of the State Key Laboratory of Molecular Reaction Dynamics in DICP(SKLMRD-K202106)the Young Elite Scientists Sponsorship Program by CAST(2022QNRC001)。
文摘Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.