Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticle...Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticles(NPs)on nitrogen-doped carbon;synthesized by using F127 as a stabilizer,as well as chitosan as a carbon and nitrogen source.The Pd/NCF catalyst was efficient and recyclable for oxidative carbonylation of phenol to diphenyl carbonate,exhibiting higher stability than Pd/NC prepared without F127 addition.The hydrogen bond between chitosan(CTS)and F127 was enhanced by F127,which anchored the N in the free amino group,increasing the N content of the carbon material and ensuring that the support could provide sufficient N sites for the deposition of Pd NPs.This process helped to improve metal dispersion.The increased metal-support interaction,which limits the leaching and coarsening of Pd NPs,improves the stability of the Pd/NCF catalyst.Furthermore,density functional theory calculations indicated that pyridine N stabilized the Pd^(2+)species,significantly inhibiting the loss of Pd^(2+)in Pd/NCF during the reaction process.This work provides a promising avenue towards enhancing the stability of nitrogen-doped carbon-supported metal catalysts.展开更多
A novel approach for analyzing coupled vibrations between vehicles and bridges is presented,taking into account spatiotemporal effects and mechanical phenomena resulting fromvehicle braking.Efficient modeling and solu...A novel approach for analyzing coupled vibrations between vehicles and bridges is presented,taking into account spatiotemporal effects and mechanical phenomena resulting fromvehicle braking.Efficient modeling and solution of bridge vibrations induced by vehicle deceleration are realized using this method.The method’s validity and reliability are substantiated through numerical examples.A simply supported beam bridge with a corrugated steel web is taken as an example and the effects of parameters such as the initial vehicle speed,braking acceleration,braking location,and road surface roughness on the mid-span displacement and impact factor of the bridge are analyzed.The results show that vehicle braking significantly amplifies mid-span displacement and impact factor responses in comparison to uniform vehicular motion across the bridge.Notably,the influence of wheelto-bridge friction forces is of particular significance and cannot be overlooked.When the vehicle initiates braking near the middle of the span,both the mid-span displacement and impact factor of the bridge exhibit substantial increases,further escalating with higher braking acceleration.Under favorable road surface conditions,the midspan displacement and the impact factor during vehicle braking may exceed the design values stipulated by codes.It is important to note that road surface roughness exerts a more pronounced effect on the impact factor of the bridge in comparison to the effects of vehicle braking.展开更多
The article takes a simply supported prestressed concrete small box girder bridge project as an example for inspection and evaluation after a fire incident.This includes appearance detection,concrete color hardness de...The article takes a simply supported prestressed concrete small box girder bridge project as an example for inspection and evaluation after a fire incident.This includes appearance detection,concrete color hardness detection,concrete strength detection,concrete surface damage layer detection,reinforcement protective layer detection,and concrete carbonation detection.It is hoped that this analysis can be used as a reference for the detection and evaluation of future bridge projects with fire incidents to smoothen its subsequent repair and maintenance.展开更多
Aqueous-phase reforming(APR)is an attractive process to produce bio-based hydrogen from waste biomass streams,during which the catalyst stability is often challenged due to the harsh reaction conditions.In this work,t...Aqueous-phase reforming(APR)is an attractive process to produce bio-based hydrogen from waste biomass streams,during which the catalyst stability is often challenged due to the harsh reaction conditions.In this work,three Pt-based catalysts supported on C,AlO(OH),and ZrO_(2)were investigated for the APR of hydroxyacetone solution in afixed bed reactor at 225℃and 35 bar.Among them,the Pt/C catalyst showed the highest turnover frequency for H_(2)production(TOF of 8.9 molH_(2)molPt^(-1)min^(-1))and the longest catalyst stability.Over the AlO(OH)and ZrO_(2)supported Pt catalysts,the side reactions consuming H_(2),formation of coke,and Pt sintering result in a low H_(2)production and the fast catalyst deactivation.The proposed reaction pathways suggest that a promising APR catalyst should reform all oxygenates in the aqueous phase,minimize the hydrogenation of the oxygenates,maximize the WGS reaction,and inhibit the condensation and coking reactions for maximizing the hydrogen yield and a stable catalytic performance.展开更多
Supported metal catalysts,particularly for precious metals,have gained increasing attention in green synthetic chemistry.They can make metal-catalyzed organic synthesis more sustainable and economical due to easy sepa...Supported metal catalysts,particularly for precious metals,have gained increasing attention in green synthetic chemistry.They can make metal-catalyzed organic synthesis more sustainable and economical due to easy separation of product with less metal residue,as well as reusability of the high-cost catalysts.Although great effort has been spent,the precise catalytic mechanism of supported metal-catalyzed reactions has not been clearly elucidated and the development of efficient and stable recyclable catalysts remains challenging.This highlight reveals a“molecular fence”metal stabilization strategy and discloses the metal evolution in Pd-catalyzed C-C bond formation reactions using Nheterocyclic carbene(NHC)-functionalized hypercrosslinked polymer support,wherein the polymeric skeleton isolates or confines the metal species involved in the catalytic reactions,and NHC captures free low-valent metal species in solution and stabilizes them on the support via strong metal-support coordination interaction.This strategy creates a novel route for the development of supported metal catalysts with high stability and provides insights into the reaction mechanism of heterogeneous catalysis.展开更多
Doping heteroatoms on carbon materials could bring some special advantages for using as catalyst support.In this work, a boron doped lamellar porous carbon(B-LPC) was prepared facilely and utilized as carbonbased supp...Doping heteroatoms on carbon materials could bring some special advantages for using as catalyst support.In this work, a boron doped lamellar porous carbon(B-LPC) was prepared facilely and utilized as carbonbased support to construct Cu/B-LPC catalyst for dimethyl oxalate(DMO) hydrogenation. Doping boron could make the B-LPC own more defects on surface and bigger pore size than B-free LPC, which were beneficial to disperse and anchor Cu nanoparticles. Moreover, the interaction between Cu species and B-LPC could be strengthened by the doped B, which not only stabilized the Cu nanoparticles, but also tuned the valence of Cu species to maintain more Cu^(+). Therefore, the B-doped Cu/B-LPC catalyst exhibited stronger hydrogenation ability and obtained higher alcohols selectivity than Cu/LPC, as well as high stability without decrease of DMO conversion and ethylene glycol selectivity even after 300 h of reaction at 240℃.展开更多
Lignin is the world's greatest renewable aromatic biofeedstock,and it has promising applications in high value-added chemical products.Herein,N-Co/ATP-CZO was used as a catalyst for the depolymerization of alkali ...Lignin is the world's greatest renewable aromatic biofeedstock,and it has promising applications in high value-added chemical products.Herein,N-Co/ATP-CZO was used as a catalyst for the depolymerization of alkali lignin in ethanol and isopropanol systems,and explored the effects of formic acid(FA)amount,reaction time,reaction temperature and other factors on the depolymerization of alkali lignin.Among them,formic acid serves as both catalytic and in situ-hydrogen donor.Ultimately,the highest yield of bio-oil(59.28%(mass)),including 30.05%(mass)of monomer,was obtained after a reaction of FA to alkali lignin mass ratio of 4 and 240°C for 8 h.Among the monomers,the yield of Guaiacol was the highest(5.94%(mass)),followed by 2-methoxy-4-methylphenol(5.74%(mass)).This study,the modification of attapulgite was carried out to reduce the acidity while enhancing the catalytic activity for depolymerization,and the selection of hydrogen donor was investigated.A feasible pathway for lignin depolymerization research was opened.展开更多
The origin and depositional characteristics of supported conglomerates in the Mahu Sag, Junggar Basin, Xinjiang, China, are examined. Based on the terminological comparison, modern sedimentary survey and core descript...The origin and depositional characteristics of supported conglomerates in the Mahu Sag, Junggar Basin, Xinjiang, China, are examined. Based on the terminological comparison, modern sedimentary survey and core description, the initial connotation and similarities and differences in definition between supported conglomerates and other similar concepts are discussed, the modern sedimentary environment in which supported conglomerates develop is analyzed, and the sedimentological characteristics of supported conglomerates formed in different depositional environments revealed by the cores of Mahu conglomerate oil field in the Junggar Basin are described. The supported conglomerate is similar in texture to grain supported conglomerate and openwork conglomerate but has differences from them, so it is suggested to keep the term "supported conglomerate", but the formation mechanism of supported conglomerate needs to be re-examined. Through field survey of modern sediments in Baiyanghe alluvial fan, Huangyangquan alluvial fan, and Wulungu Lake in Xinjiang, it is found that supported gravels not only formed by flooding events but also by sieving, avalanching, fluvial sorting as well as wind and wave reworking in the depositional environments such as inter-mountain creek, colluvium fan, gravel channel on gobi and the fan surface, lake beach, delta front, subaerial debris flow and subwater grain-flow etc. Supported gravels could form supported conglomerate after being buried. Supported conglomerates of seven different origins have been recognized in the cores of the Triassic and Permian stratum of Mahu Depression, Junggar Basin, namely, supported conglomerates in gravel channel deposits, in wind reworked channel deposits, in gravel beach bar deposits, in wave reworked delta front deposits, in mouth bar deposits and in debris flow deposits respectively. The study shows the supported conglomerates may be formed by a single depositional event or by multi-events during the post-depositional sedimentary reworking and even in diagenesis stage. Through flume experiment, numerical simulation, empirical model and modern sediment survey, infiltration process of gravelly channel can be reconstructed and the primary pore structure of supported gravel can be estimated. Statistics on physical properties of various types of reservoirs in Triassic Baikouquan Formation of Mahu oilfield show that granule conglomerate and pebbly conglomerate have higher porosity and permeability, while the cobble and coarse pebble conglomerate have lower permeability, which indicates that the supported gravels are easy to be reworked by post depositional filtration and diagenesis, and thus decrease in porosity and permeability.展开更多
The catalytic conversion of CO2 to CO via a reverse water gas shift(RWGS)reaction followed by well-established synthesis gas conversion technologies may provide a potential approach to convert CO2 to valuable chemical...The catalytic conversion of CO2 to CO via a reverse water gas shift(RWGS)reaction followed by well-established synthesis gas conversion technologies may provide a potential approach to convert CO2 to valuable chemicals and fuels.However,this reaction is mildly endothermic and competed by a strongly exothermic CO2 methanation reaction at low temperatures.Therefore,the improvement in the low-temperature activities and selectivity of the RWGS reaction is a key challenge for catalyst designs.We reviewed recent advances in the design strategies of supported metal catalysts for enhancing the activity of CO2 conversion and its selectivity to CO.These strategies include varying support,tuning metal–support interactions,adding reducible transition metal oxide promoters,forming bimetallic alloys,adding alkali metals,and enveloping metal particles.These advances suggest that enhancing CO2 adsorption and facilitating CO desorption are key factors to enhance CO2 conversion and CO selectivity.This short review may provide insights into future RWGS catalyst designs and optimization.展开更多
Supported ionic liquid(IL) catalysts [C_nmim]_3PMo_(12)O_(40)/Am TiO_2(amorphous TiO_2) were synthesized through a one-step method for extraction coupled catalytic oxidative desulfurization(ECODS) system. Characteriza...Supported ionic liquid(IL) catalysts [C_nmim]_3PMo_(12)O_(40)/Am TiO_2(amorphous TiO_2) were synthesized through a one-step method for extraction coupled catalytic oxidative desulfurization(ECODS) system. Characterizations such as FTIR, DRS,wide-angle XRD, N_2 adsorption–desorption and XPS were applied to analyze the morphology and Keggin structure of the catalysts. In ECODS with hydrogen peroxide as the oxidant, it was found that ILs with longer alkyl chains in the cationic moiety had a better effect on the removal of dibenzothiophene. The desulfurization could reach 100% under optimal conditions, and GC–MS analysis was employed to detect the oxidized product after the reaction. Factors affecting the desulfurization efficiencies were discussed, and a possible mechanism was proposed. In addition, cyclic experiments were also conducted to investigate the recyclability of the supported catalyst. The catalytic activity of [C_(16)mim]_3 PMo_(12)O_(40)/Am TiO_2 only dropped from 100% to 92.9% after ten cycles, demonstrating the good recycling performance of the catalyst and its potential industrial application.展开更多
In several previous studies,it was reported that a supported pipe with small geometric imperfections would lose stability when the internal flow velocity became sufficiently high.Recently,however,it has become clear t...In several previous studies,it was reported that a supported pipe with small geometric imperfections would lose stability when the internal flow velocity became sufficiently high.Recently,however,it has become clear that this conclusion may be at best incomplete.A reevaluation of the problem is undertaken here by essentially considering the flow-induced static deformation of a pipe.With the aid of the absolute nodal coordinate formulation(ANCF)and the extended Lagrange equations for dynamical systems containing non-material volumes,the nonlinear governing equations of a pipe with three different geometric imperfections are introduced and formulated.Based on extensive numerical calculations,the static equilibrium configuration,the stability,and the nonlinear dynamics of the considered pipe system are determined and analyzed.The results show that for a supported pipe with the geometric imperfection of a half sinusoidal wave,the dynamical system could not lose stability even if the flow velocity reaches an extremely high value of 40.However,for a supported pipe with the geometric imperfection of one or one and a half sinusoidal waves,the first-mode buckling instability would take place at high flow velocity.Moreover,based on a further parametric analysis,the effects of the amplitude of the geometric imperfection and the aspect ratio of the pipe on the static deformation,the critical flow velocity for buckling instability,and the nonlinear responses of the supported pipes with geometric imperfections are analyzed.展开更多
A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The cataly...A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The catalyst was characterized by FTIR and XRD analyses. Three solvents dioctyl sebacate(DOS), dibutyl sebacate(DBS) and 1-butyl-3-methylimidazolium tetrafluoroborate(BMIMBF_4) were investigated and compared; DOS gave better performance. The catalytic performances for thermal decomposition of HDC to HDI using DOS as solvent were then investigated, and the results showed that, under the optimized reaction conditions, i.e.,10 wt%concentration of HDC in DOS, 250 °C temperature, 60 min reaction time, 83.8% yield of HDI had been achieved over Zn–Co/ZSM-5. Decomposition of the intermediate hexamethylene-1-carbamate-6-isocyanate(HMI) over Zn–Co/ZSM-5 in DOS solvent was further studied and the results indicated that yield of HDI from HMI reached to 69.6%(98.6% HDI selectively) at 270 °C, which further increased the yield of the total HDI(HDI_(tol)) to as high as 95.0%. Recycling of catalyst showed that HDI and HMI yield slightly decreased, and by-product yield increased after the catalyst was reused for 4 times. At last possible reaction mechanism was proposed.展开更多
In this paper,AgBF_4/[emim][BF_4] supported ionic liquid membranes(SILMs) were prepared successfully for CO/N_2 separation using nitrogen pressure immobilization procedures.The incorporation of AgBF_4 could decrease m...In this paper,AgBF_4/[emim][BF_4] supported ionic liquid membranes(SILMs) were prepared successfully for CO/N_2 separation using nitrogen pressure immobilization procedures.The incorporation of AgBF_4 could decrease membrane weight loss,improve the pressure-resistant ability,and keep the critical pressure(0.45 MPa) of the SILMs.The high viscosity and undissolved Ag BF_4 solids in membrane liquid would disturb gas molecular transport through membrane and give rise to the gas transport resistance.Therefore,the gas permeability decreased remarkably with increasing AgBF_4 carrier content in the membrane.When the molar ratio of AgBF_4 to [emim][BF_4] increased from 0:1 to 0.3:1,the CO/N_2 selectivity of the SILMs showed a great increase from ～1 to ～9 at 20 °C and 0.4 MPa,suggesting that AgBF_4 was an effective carrier for CO facilitated transport.The permeabilities of N_2 and CO increased at higher transmembrane pressure,indicating that molecular transport would dominate the transport process at high pressure.The temperature-dependent gas permeability followed the Arrhenius equation.Moreover,the differences between the activation energies of CO and N_2 became larger after introducing AgBF_4,resulting in more obvious decrease in the CO/N_2 selectivity at higher operating temperature.展开更多
Direct cost-effective conversion of abundant methane to high value-added oxygenates(methanol,formic acid,acetic acid,etc.)under mild conditions is prospective for optimizing the structure of energy resources.However,t...Direct cost-effective conversion of abundant methane to high value-added oxygenates(methanol,formic acid,acetic acid,etc.)under mild conditions is prospective for optimizing the structure of energy resources.However,the CAH bond of products is more reactive than that of high thermodynamic stable methane.Exploring an appropriate approach to eliminate the‘‘seesaw effect"between methane conversion and oxygenate selectivity is significant.In this review,we briefly summarize the research progress in the past decade on low-temperature direct conversion of methane to oxygenates in gas-solid-liquid phase over various transition metal(Fe,Cu,Rh,Pd,Au Pd,etc.)based nanoparticle or single-atom catalyst.Furthermore,the prospects of catalyst design and catalysis process are also discussed.展开更多
The aerodynamic performance of high-speed trains passing each other was investigated on a simply supported box girder bridge,with a span of 32 m,under crosswinds.The bridge and train models,modeled at a geometric scal...The aerodynamic performance of high-speed trains passing each other was investigated on a simply supported box girder bridge,with a span of 32 m,under crosswinds.The bridge and train models,modeled at a geometric scale ratio of 1:30,were used to test the aerodynamic forces of the train,with the help of a designed moving test rig in the XNJD-3 wind tunnel.The effects of wind speed,train speed,and yaw angle on the aerodynamic coefficients of the train were analyzed.The static and moving model tests were compared to demonstrate how the movement of the train influences its aerodynamic characteristics.The results show that the sheltering effect introduced by trains passing each other can cause a sudden change in force on the leeward train,which is further influenced by the wind and running speeds.Detailed analyses related to the effect of wind and train speeds on the aerodynamic coefficients were conducted.The relationship between the change in aerodynamic coefficients and yaw angle was finally described by a series of proposed fitting formulas.展开更多
Developing of non-metallic catalyst to replace metal catalyst is a meaningful and challenging direction.In this work,the non-metallic catalyst was synthetized successfully by loading ionic liquid onto the silica surfa...Developing of non-metallic catalyst to replace metal catalyst is a meaningful and challenging direction.In this work,the non-metallic catalyst was synthetized successfully by loading ionic liquid onto the silica surface,which was applied for the gas-phase dehydrochlorination of 1,1,2,2-tetrachloroethane.The 12%TPPC/SiO2(wt%)showed the best results with the conversion of 1,1,2,2-tetrachloroethane reaching 100%.The selectivity of 1,1,2-trichloroethylene was 100%,and no deactivation was found during the evaluation period.The catalytic mechanism was investigated and possible reaction route was given,which was a reference for fabricating and design of solid base catalyst.展开更多
Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS a...Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS analyses and they were tested in partial oxidation of methane(CPO). The catalytic reaction was carried out at atmospheric pressure in a temperature range of 400–800℃ with a feed gas mixture containing methane and oxygen in a molecular ratio CH4/O2=2. The Ni catalyst exhibited 60% methane conversion with 60% selectivity to CO already at 500℃. On the contrary, the Ni–Ce catalyst was inert to CPO up to 700℃. Moreover, the former catalyst reproduced its activity at the descending temperatures maintaining a good stability at 600℃, over a reaction time of 80 h, whereas the latter one completely deactivated. Test of CH4 temperature programmed surface reaction(CH4-TPSR) revealed a higher methane activation temperature(> 100℃) for the Ni–Ce catalyst as compared to the Ni one. Noticeable improvement of the ceria containing catalyst occurred when the reaction test started at a temperature higher than the methane decomposition temperature. In this case, the sample achieved the same catalytic behavior of the Ni catalyst. As confirmed by XPS analyses, the distinct electronic state of the supported nickel was responsible for the differences in catalytic behavior.展开更多
In order to validate the accuracy of nonlinear fire simulation programs,comparison analysis is carried out between simulation and experiment induced from small-scale specimens,and then fire resistance of large-scale p...In order to validate the accuracy of nonlinear fire simulation programs,comparison analysis is carried out between simulation and experiment induced from small-scale specimens,and then fire resistance of large-scale prestressed concrete slabs is further investigated through parameter expansion.The influences on fire resistance ratings controlled by deflection are explored and discussed,including effective span,concrete cover thickness,load level,prestress degree,effective prestress,composite reinforcement index and other factors.The calculated results indicate that fire resistance ratings of large-scale bonded prestressed concrete simply supported slabs are bigger than those of small-scale ones.Finally,the calculation formulas of fire resistance ratings controlled by deflection are established,which rationally consider the influence of effective span,concrete cover thickness,load level,composite reinforcement index and so on key factors.展开更多
The composition distribution （CD） and microisotacticity distribution （ID） of propene/1-hexene copolymer synthesized by MgCl<sub>2</sub>/DIBP/TiCl<sub>4</sub> （DIBP: diisobutyl phthalate） ...The composition distribution （CD） and microisotacticity distribution （ID） of propene/1-hexene copolymer synthesized by MgCl<sub>2</sub>/DIBP/TiCl<sub>4</sub> （DIBP: diisobutyl phthalate） weredetermined by fractionating the copolymers according to crystallinity and characterizingthe fractions by <sup>13</sup>CNMR. The effects of two alkoxysilane donors, triethoxyphenylsilane（PTES） and dimethoxydi-tert-butylsilane （TBMS）, on CD and ID of the copolymrs werecompared. Three main parts in the CD diagram of each copolymer were distinguished,which were correlated to active center distribution （ACD） based on three groupe of dif-ferent active centers. By studying the changes in 1-hexene content, microisotacticity andreactivity ratio product of three typical fractions, the effects of external donor on ACDwere better elucidated. It was found that TBMS shows much stronger effects on ACD thanPTES. In the former system, most fractions were produced on active centers with relativelylower r<sub>1</sub>r<sub>2</sub>, higher reactivity to 1-hexene, and higher stereospecificity as compared to thesystem without external donor. It is concluded that the observed very extensive changesin ACD are mainly resulted by the formation of new types of active centers, possibly bycoordination of external donor to certain positions on the catalyst.展开更多
基金support by the National Natural Science Foundation of China(U21A20306,U20A20152)Natural Science Foundation of Hebei Province(B2022202077).
文摘Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticles(NPs)on nitrogen-doped carbon;synthesized by using F127 as a stabilizer,as well as chitosan as a carbon and nitrogen source.The Pd/NCF catalyst was efficient and recyclable for oxidative carbonylation of phenol to diphenyl carbonate,exhibiting higher stability than Pd/NC prepared without F127 addition.The hydrogen bond between chitosan(CTS)and F127 was enhanced by F127,which anchored the N in the free amino group,increasing the N content of the carbon material and ensuring that the support could provide sufficient N sites for the deposition of Pd NPs.This process helped to improve metal dispersion.The increased metal-support interaction,which limits the leaching and coarsening of Pd NPs,improves the stability of the Pd/NCF catalyst.Furthermore,density functional theory calculations indicated that pyridine N stabilized the Pd^(2+)species,significantly inhibiting the loss of Pd^(2+)in Pd/NCF during the reaction process.This work provides a promising avenue towards enhancing the stability of nitrogen-doped carbon-supported metal catalysts.
基金supported by the Henan Provincial Science and Technology Research Project under Grant(152102310295).
文摘A novel approach for analyzing coupled vibrations between vehicles and bridges is presented,taking into account spatiotemporal effects and mechanical phenomena resulting fromvehicle braking.Efficient modeling and solution of bridge vibrations induced by vehicle deceleration are realized using this method.The method’s validity and reliability are substantiated through numerical examples.A simply supported beam bridge with a corrugated steel web is taken as an example and the effects of parameters such as the initial vehicle speed,braking acceleration,braking location,and road surface roughness on the mid-span displacement and impact factor of the bridge are analyzed.The results show that vehicle braking significantly amplifies mid-span displacement and impact factor responses in comparison to uniform vehicular motion across the bridge.Notably,the influence of wheelto-bridge friction forces is of particular significance and cannot be overlooked.When the vehicle initiates braking near the middle of the span,both the mid-span displacement and impact factor of the bridge exhibit substantial increases,further escalating with higher braking acceleration.Under favorable road surface conditions,the midspan displacement and the impact factor during vehicle braking may exceed the design values stipulated by codes.It is important to note that road surface roughness exerts a more pronounced effect on the impact factor of the bridge in comparison to the effects of vehicle braking.
文摘The article takes a simply supported prestressed concrete small box girder bridge project as an example for inspection and evaluation after a fire incident.This includes appearance detection,concrete color hardness detection,concrete strength detection,concrete surface damage layer detection,reinforcement protective layer detection,and concrete carbonation detection.It is hoped that this analysis can be used as a reference for the detection and evaluation of future bridge projects with fire incidents to smoothen its subsequent repair and maintenance.
基金support from European Union Seventh Frame-work Programme(FP7/2007-2013 project SusFuelCat,grant No.310490)is acknowledged.
文摘Aqueous-phase reforming(APR)is an attractive process to produce bio-based hydrogen from waste biomass streams,during which the catalyst stability is often challenged due to the harsh reaction conditions.In this work,three Pt-based catalysts supported on C,AlO(OH),and ZrO_(2)were investigated for the APR of hydroxyacetone solution in afixed bed reactor at 225℃and 35 bar.Among them,the Pt/C catalyst showed the highest turnover frequency for H_(2)production(TOF of 8.9 molH_(2)molPt^(-1)min^(-1))and the longest catalyst stability.Over the AlO(OH)and ZrO_(2)supported Pt catalysts,the side reactions consuming H_(2),formation of coke,and Pt sintering result in a low H_(2)production and the fast catalyst deactivation.The proposed reaction pathways suggest that a promising APR catalyst should reform all oxygenates in the aqueous phase,minimize the hydrogenation of the oxygenates,maximize the WGS reaction,and inhibit the condensation and coking reactions for maximizing the hydrogen yield and a stable catalytic performance.
基金support of the Start-up Research Fund of Dongguan University of Technology(KCYKYQD2017015).
文摘Supported metal catalysts,particularly for precious metals,have gained increasing attention in green synthetic chemistry.They can make metal-catalyzed organic synthesis more sustainable and economical due to easy separation of product with less metal residue,as well as reusability of the high-cost catalysts.Although great effort has been spent,the precise catalytic mechanism of supported metal-catalyzed reactions has not been clearly elucidated and the development of efficient and stable recyclable catalysts remains challenging.This highlight reveals a“molecular fence”metal stabilization strategy and discloses the metal evolution in Pd-catalyzed C-C bond formation reactions using Nheterocyclic carbene(NHC)-functionalized hypercrosslinked polymer support,wherein the polymeric skeleton isolates or confines the metal species involved in the catalytic reactions,and NHC captures free low-valent metal species in solution and stabilizes them on the support via strong metal-support coordination interaction.This strategy creates a novel route for the development of supported metal catalysts with high stability and provides insights into the reaction mechanism of heterogeneous catalysis.
基金financially supported by the National Natural Science Foundation of China (22008166)Natural Science Foundation of Shanxi (201901D211047)Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi (2019L0185)。
文摘Doping heteroatoms on carbon materials could bring some special advantages for using as catalyst support.In this work, a boron doped lamellar porous carbon(B-LPC) was prepared facilely and utilized as carbonbased support to construct Cu/B-LPC catalyst for dimethyl oxalate(DMO) hydrogenation. Doping boron could make the B-LPC own more defects on surface and bigger pore size than B-free LPC, which were beneficial to disperse and anchor Cu nanoparticles. Moreover, the interaction between Cu species and B-LPC could be strengthened by the doped B, which not only stabilized the Cu nanoparticles, but also tuned the valence of Cu species to maintain more Cu^(+). Therefore, the B-doped Cu/B-LPC catalyst exhibited stronger hydrogenation ability and obtained higher alcohols selectivity than Cu/LPC, as well as high stability without decrease of DMO conversion and ethylene glycol selectivity even after 300 h of reaction at 240℃.
基金financially supported by National Natural Science Foundation of China (21774059)。
文摘Lignin is the world's greatest renewable aromatic biofeedstock,and it has promising applications in high value-added chemical products.Herein,N-Co/ATP-CZO was used as a catalyst for the depolymerization of alkali lignin in ethanol and isopropanol systems,and explored the effects of formic acid(FA)amount,reaction time,reaction temperature and other factors on the depolymerization of alkali lignin.Among them,formic acid serves as both catalytic and in situ-hydrogen donor.Ultimately,the highest yield of bio-oil(59.28%(mass)),including 30.05%(mass)of monomer,was obtained after a reaction of FA to alkali lignin mass ratio of 4 and 240°C for 8 h.Among the monomers,the yield of Guaiacol was the highest(5.94%(mass)),followed by 2-methoxy-4-methylphenol(5.74%(mass)).This study,the modification of attapulgite was carried out to reduce the acidity while enhancing the catalytic activity for depolymerization,and the selection of hydrogen donor was investigated.A feasible pathway for lignin depolymerization research was opened.
基金Supported by the the National Natural Science Foundation of China(41772094)China National Science and Technology Major Project(2016ZX05027-002-007)
文摘The origin and depositional characteristics of supported conglomerates in the Mahu Sag, Junggar Basin, Xinjiang, China, are examined. Based on the terminological comparison, modern sedimentary survey and core description, the initial connotation and similarities and differences in definition between supported conglomerates and other similar concepts are discussed, the modern sedimentary environment in which supported conglomerates develop is analyzed, and the sedimentological characteristics of supported conglomerates formed in different depositional environments revealed by the cores of Mahu conglomerate oil field in the Junggar Basin are described. The supported conglomerate is similar in texture to grain supported conglomerate and openwork conglomerate but has differences from them, so it is suggested to keep the term "supported conglomerate", but the formation mechanism of supported conglomerate needs to be re-examined. Through field survey of modern sediments in Baiyanghe alluvial fan, Huangyangquan alluvial fan, and Wulungu Lake in Xinjiang, it is found that supported gravels not only formed by flooding events but also by sieving, avalanching, fluvial sorting as well as wind and wave reworking in the depositional environments such as inter-mountain creek, colluvium fan, gravel channel on gobi and the fan surface, lake beach, delta front, subaerial debris flow and subwater grain-flow etc. Supported gravels could form supported conglomerate after being buried. Supported conglomerates of seven different origins have been recognized in the cores of the Triassic and Permian stratum of Mahu Depression, Junggar Basin, namely, supported conglomerates in gravel channel deposits, in wind reworked channel deposits, in gravel beach bar deposits, in wave reworked delta front deposits, in mouth bar deposits and in debris flow deposits respectively. The study shows the supported conglomerates may be formed by a single depositional event or by multi-events during the post-depositional sedimentary reworking and even in diagenesis stage. Through flume experiment, numerical simulation, empirical model and modern sediment survey, infiltration process of gravelly channel can be reconstructed and the primary pore structure of supported gravel can be estimated. Statistics on physical properties of various types of reservoirs in Triassic Baikouquan Formation of Mahu oilfield show that granule conglomerate and pebbly conglomerate have higher porosity and permeability, while the cobble and coarse pebble conglomerate have lower permeability, which indicates that the supported gravels are easy to be reworked by post depositional filtration and diagenesis, and thus decrease in porosity and permeability.
基金the National Key Research and Development Program of China(No.2016YFB0600900)the National Natural Science Foundation of China(Nos.21676194 and 21873067)for their support。
文摘The catalytic conversion of CO2 to CO via a reverse water gas shift(RWGS)reaction followed by well-established synthesis gas conversion technologies may provide a potential approach to convert CO2 to valuable chemicals and fuels.However,this reaction is mildly endothermic and competed by a strongly exothermic CO2 methanation reaction at low temperatures.Therefore,the improvement in the low-temperature activities and selectivity of the RWGS reaction is a key challenge for catalyst designs.We reviewed recent advances in the design strategies of supported metal catalysts for enhancing the activity of CO2 conversion and its selectivity to CO.These strategies include varying support,tuning metal–support interactions,adding reducible transition metal oxide promoters,forming bimetallic alloys,adding alkali metals,and enveloping metal particles.These advances suggest that enhancing CO2 adsorption and facilitating CO desorption are key factors to enhance CO2 conversion and CO selectivity.This short review may provide insights into future RWGS catalyst designs and optimization.
基金financially supported by the National Natural Science Foundation of China (Nos. 21576122, 21646001, 21506080)Natural Science Foundation of Jiangsu Province (Nos. BK20150485, BK20170528)+2 种基金China Postdoctoral Science Foundation (2017M611727)Jiangsu Planned Projects for Postdoctoral Research Funds (1701104B)supported by the Student Innovation and Entrepreneurship Training Program (201810299332 W)
文摘Supported ionic liquid(IL) catalysts [C_nmim]_3PMo_(12)O_(40)/Am TiO_2(amorphous TiO_2) were synthesized through a one-step method for extraction coupled catalytic oxidative desulfurization(ECODS) system. Characterizations such as FTIR, DRS,wide-angle XRD, N_2 adsorption–desorption and XPS were applied to analyze the morphology and Keggin structure of the catalysts. In ECODS with hydrogen peroxide as the oxidant, it was found that ILs with longer alkyl chains in the cationic moiety had a better effect on the removal of dibenzothiophene. The desulfurization could reach 100% under optimal conditions, and GC–MS analysis was employed to detect the oxidized product after the reaction. Factors affecting the desulfurization efficiencies were discussed, and a possible mechanism was proposed. In addition, cyclic experiments were also conducted to investigate the recyclability of the supported catalyst. The catalytic activity of [C_(16)mim]_3 PMo_(12)O_(40)/Am TiO_2 only dropped from 100% to 92.9% after ten cycles, demonstrating the good recycling performance of the catalyst and its potential industrial application.
基金supported by the National Natural Science Foundation of China(Nos.11972167,12072119)the Alexander von Humboldt Foundation。
文摘In several previous studies,it was reported that a supported pipe with small geometric imperfections would lose stability when the internal flow velocity became sufficiently high.Recently,however,it has become clear that this conclusion may be at best incomplete.A reevaluation of the problem is undertaken here by essentially considering the flow-induced static deformation of a pipe.With the aid of the absolute nodal coordinate formulation(ANCF)and the extended Lagrange equations for dynamical systems containing non-material volumes,the nonlinear governing equations of a pipe with three different geometric imperfections are introduced and formulated.Based on extensive numerical calculations,the static equilibrium configuration,the stability,and the nonlinear dynamics of the considered pipe system are determined and analyzed.The results show that for a supported pipe with the geometric imperfection of a half sinusoidal wave,the dynamical system could not lose stability even if the flow velocity reaches an extremely high value of 40.However,for a supported pipe with the geometric imperfection of one or one and a half sinusoidal waves,the first-mode buckling instability would take place at high flow velocity.Moreover,based on a further parametric analysis,the effects of the amplitude of the geometric imperfection and the aspect ratio of the pipe on the static deformation,the critical flow velocity for buckling instability,and the nonlinear responses of the supported pipes with geometric imperfections are analyzed.
基金Supported by the National Natural Science Foundation of China(21476244,21406245)Transformational Technologies for Clean Energy and Demonstration,Strategic Priority Research Program of the Chinese Academy of Sciences,(XDA 21030600)the Youth Innovation Promotion Association CAS(2016046)
文摘A non-phosgene route for the synthesis of hexamethylene-1,6-diisocyanate(HDI) was developed via catalytic decomposition of hexamethylene-1,6-dicarbamate(HDC) over Zn–Co bi-metallic supported ZSM-5 catalyst.The catalyst was characterized by FTIR and XRD analyses. Three solvents dioctyl sebacate(DOS), dibutyl sebacate(DBS) and 1-butyl-3-methylimidazolium tetrafluoroborate(BMIMBF_4) were investigated and compared; DOS gave better performance. The catalytic performances for thermal decomposition of HDC to HDI using DOS as solvent were then investigated, and the results showed that, under the optimized reaction conditions, i.e.,10 wt%concentration of HDC in DOS, 250 °C temperature, 60 min reaction time, 83.8% yield of HDI had been achieved over Zn–Co/ZSM-5. Decomposition of the intermediate hexamethylene-1-carbamate-6-isocyanate(HMI) over Zn–Co/ZSM-5 in DOS solvent was further studied and the results indicated that yield of HDI from HMI reached to 69.6%(98.6% HDI selectively) at 270 °C, which further increased the yield of the total HDI(HDI_(tol)) to as high as 95.0%. Recycling of catalyst showed that HDI and HMI yield slightly decreased, and by-product yield increased after the catalyst was reused for 4 times. At last possible reaction mechanism was proposed.
基金Financial support from the National Natural Science Foundation of China (21406235)
文摘In this paper,AgBF_4/[emim][BF_4] supported ionic liquid membranes(SILMs) were prepared successfully for CO/N_2 separation using nitrogen pressure immobilization procedures.The incorporation of AgBF_4 could decrease membrane weight loss,improve the pressure-resistant ability,and keep the critical pressure(0.45 MPa) of the SILMs.The high viscosity and undissolved Ag BF_4 solids in membrane liquid would disturb gas molecular transport through membrane and give rise to the gas transport resistance.Therefore,the gas permeability decreased remarkably with increasing AgBF_4 carrier content in the membrane.When the molar ratio of AgBF_4 to [emim][BF_4] increased from 0:1 to 0.3:1,the CO/N_2 selectivity of the SILMs showed a great increase from ～1 to ～9 at 20 °C and 0.4 MPa,suggesting that AgBF_4 was an effective carrier for CO facilitated transport.The permeabilities of N_2 and CO increased at higher transmembrane pressure,indicating that molecular transport would dominate the transport process at high pressure.The temperature-dependent gas permeability followed the Arrhenius equation.Moreover,the differences between the activation energies of CO and N_2 became larger after introducing AgBF_4,resulting in more obvious decrease in the CO/N_2 selectivity at higher operating temperature.
基金funded by National Natural Science Foundation of China(22022814,21878283)Youth Innovation Promotion Association CAS(2017223)+1 种基金"Strategic Priority Research Program"of the Chinese academy of Sciences(XDB17020100)the National Key projects for Fundamental Research and Development of China(2016YFA0202801)。
文摘Direct cost-effective conversion of abundant methane to high value-added oxygenates(methanol,formic acid,acetic acid,etc.)under mild conditions is prospective for optimizing the structure of energy resources.However,the CAH bond of products is more reactive than that of high thermodynamic stable methane.Exploring an appropriate approach to eliminate the‘‘seesaw effect"between methane conversion and oxygenate selectivity is significant.In this review,we briefly summarize the research progress in the past decade on low-temperature direct conversion of methane to oxygenates in gas-solid-liquid phase over various transition metal(Fe,Cu,Rh,Pd,Au Pd,etc.)based nanoparticle or single-atom catalyst.Furthermore,the prospects of catalyst design and catalysis process are also discussed.
基金This work was financially supported by the National Natural Science Foundation of China (U1434205, 51708645).
文摘The aerodynamic performance of high-speed trains passing each other was investigated on a simply supported box girder bridge,with a span of 32 m,under crosswinds.The bridge and train models,modeled at a geometric scale ratio of 1:30,were used to test the aerodynamic forces of the train,with the help of a designed moving test rig in the XNJD-3 wind tunnel.The effects of wind speed,train speed,and yaw angle on the aerodynamic coefficients of the train were analyzed.The static and moving model tests were compared to demonstrate how the movement of the train influences its aerodynamic characteristics.The results show that the sheltering effect introduced by trains passing each other can cause a sudden change in force on the leeward train,which is further influenced by the wind and running speeds.Detailed analyses related to the effect of wind and train speeds on the aerodynamic coefficients were conducted.The relationship between the change in aerodynamic coefficients and yaw angle was finally described by a series of proposed fitting formulas.
基金financed by the National Natural Science Foundation of China(NSFC-21476207,91534114,21776256)。
文摘Developing of non-metallic catalyst to replace metal catalyst is a meaningful and challenging direction.In this work,the non-metallic catalyst was synthetized successfully by loading ionic liquid onto the silica surface,which was applied for the gas-phase dehydrochlorination of 1,1,2,2-tetrachloroethane.The 12%TPPC/SiO2(wt%)showed the best results with the conversion of 1,1,2,2-tetrachloroethane reaching 100%.The selectivity of 1,1,2-trichloroethylene was 100%,and no deactivation was found during the evaluation period.The catalytic mechanism was investigated and possible reaction route was given,which was a reference for fabricating and design of solid base catalyst.
基金The Executive Programme for Cooperation between Italy and India (Prot.No.MAE01054762017)。
文摘Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS analyses and they were tested in partial oxidation of methane(CPO). The catalytic reaction was carried out at atmospheric pressure in a temperature range of 400–800℃ with a feed gas mixture containing methane and oxygen in a molecular ratio CH4/O2=2. The Ni catalyst exhibited 60% methane conversion with 60% selectivity to CO already at 500℃. On the contrary, the Ni–Ce catalyst was inert to CPO up to 700℃. Moreover, the former catalyst reproduced its activity at the descending temperatures maintaining a good stability at 600℃, over a reaction time of 80 h, whereas the latter one completely deactivated. Test of CH4 temperature programmed surface reaction(CH4-TPSR) revealed a higher methane activation temperature(> 100℃) for the Ni–Ce catalyst as compared to the Ni one. Noticeable improvement of the ceria containing catalyst occurred when the reaction test started at a temperature higher than the methane decomposition temperature. In this case, the sample achieved the same catalytic behavior of the Ni catalyst. As confirmed by XPS analyses, the distinct electronic state of the supported nickel was responsible for the differences in catalytic behavior.
基金Sponsored by the National Natural Science Foundation of China(Grant No.50678050)
文摘In order to validate the accuracy of nonlinear fire simulation programs,comparison analysis is carried out between simulation and experiment induced from small-scale specimens,and then fire resistance of large-scale prestressed concrete slabs is further investigated through parameter expansion.The influences on fire resistance ratings controlled by deflection are explored and discussed,including effective span,concrete cover thickness,load level,prestress degree,effective prestress,composite reinforcement index and other factors.The calculated results indicate that fire resistance ratings of large-scale bonded prestressed concrete simply supported slabs are bigger than those of small-scale ones.Finally,the calculation formulas of fire resistance ratings controlled by deflection are established,which rationally consider the influence of effective span,concrete cover thickness,load level,composite reinforcement index and so on key factors.
文摘The composition distribution （CD） and microisotacticity distribution （ID） of propene/1-hexene copolymer synthesized by MgCl<sub>2</sub>/DIBP/TiCl<sub>4</sub> （DIBP: diisobutyl phthalate） weredetermined by fractionating the copolymers according to crystallinity and characterizingthe fractions by <sup>13</sup>CNMR. The effects of two alkoxysilane donors, triethoxyphenylsilane（PTES） and dimethoxydi-tert-butylsilane （TBMS）, on CD and ID of the copolymrs werecompared. Three main parts in the CD diagram of each copolymer were distinguished,which were correlated to active center distribution （ACD） based on three groupe of dif-ferent active centers. By studying the changes in 1-hexene content, microisotacticity andreactivity ratio product of three typical fractions, the effects of external donor on ACDwere better elucidated. It was found that TBMS shows much stronger effects on ACD thanPTES. In the former system, most fractions were produced on active centers with relativelylower r<sub>1</sub>r<sub>2</sub>, higher reactivity to 1-hexene, and higher stereospecificity as compared to thesystem without external donor. It is concluded that the observed very extensive changesin ACD are mainly resulted by the formation of new types of active centers, possibly bycoordination of external donor to certain positions on the catalyst.
