The electrocatalytic nitrogen reduction reaction(NRR)is challenging but crucial for the sustainable development of both industry and agriculture.To enhance NRR performance,it is critically important to construct advan...The electrocatalytic nitrogen reduction reaction(NRR)is challenging but crucial for the sustainable development of both industry and agriculture.To enhance NRR performance,it is critically important to construct advanced electrocatalysts that offer satisfactory performance containing high activity and selectivity.However,the strong affinity of nitrogen-containing species on the Ru surface resulted in suboptimal NRR activity.Herein,we propose a dual-site catalyst,RuNi,to optimize the binding strength,which leads to superior electrocatalytic performance,achieving a high NH_(3)yield rate of 5.07μg h^(-1)cm^(-2)at-0.2 V vs.RHE and a Faradaic efficiency(FE)of 26.2%at-0.1 V vs.RHE in 0.1 mol/L Na_(2)SO_(4).Owing to the synergistic interaction between Ru and Ni,a remarkable performance is realized over the RuNi catalyst.In-situ characterization evidenced that hydrogen radicals(H^(*))on the Ni site of the RuNi catalyst participate in the dissociation of N_(2)adsorbed on the Ru site,and theoretical investigations indicated that RuNi reduces the adsorption strength of intermediates.This offers an effective approach to the synthesis of dual-site catalysts for electrocatalytic ammonia synthesis.展开更多
Rotor blade is one of the most significant components of helicopters. But due to its highspeed rotation characteristics, it is difficult to collect the vibration signals during the flight stage.Moreover, sensors are h...Rotor blade is one of the most significant components of helicopters. But due to its highspeed rotation characteristics, it is difficult to collect the vibration signals during the flight stage.Moreover, sensors are highly susceptible to damage resulting in the failure of the measurement.In order to make signal predictions for the damaged sensors, an operational modal analysis(OMA) together with the virtual sensing(VS) technology is proposed in this paper. This paper discusses two situations, i.e., mode shapes measured by all sensors(both normal and damaged) can be obtained using OMA, and mode shapes measured by some sensors(only including normal) can be obtained using OMA. For the second situation, it is necessary to use finite element(FE) analysis to supplement the missing mode shapes of damaged sensor. In order to improve the correlation between the FE model and the real structure, the FE mode shapes are corrected using the local correspondence(LC) principle and mode shapes measured by some sensors(only including normal).Then, based on the VS technology, the vibration signals of the damaged sensors during the flight stage can be accurately predicted using the identified mode shapes(obtained based on OMA and FE analysis) and the normal sensors signals. Given the high degrees of freedom(DOFs) in the FE mode shapes, this approach can also be used to predict vibration data at locations without sensors. The effectiveness and robustness of the proposed method is verified through finite element simulation, experiment as well as the actual flight test. The present work can be further used in the fault diagnosis and damage identification for rotor blade of helicopters.展开更多
The electrochemical nitrogen reduction reaction(NRR)under ambient conditions presents a promising approach for the eco-friendly and sustainable synthesis of ammonia,with a continuous emergence of potential electrocata...The electrochemical nitrogen reduction reaction(NRR)under ambient conditions presents a promising approach for the eco-friendly and sustainable synthesis of ammonia,with a continuous emergence of potential electrocatalysts.However,the low solubility and limited diffusion of N_(2)significantly hinder the achievement of satisfactory performance.In this context,we report an effective strategy to enhance NRR activity by introducing a metal-organic framework(MOF)membrane,specifically MIL-53(Al),onto a perovskite oxide(LiNbO_(3)),denoted as LN@MIL-X(X=0.2,0.4 and 0.6).The MIL-53(Al)membrane selectively recognizes and concentrates N_(2)at the catalyst interface while simultaneously repelling water molecules,thereby inhibiting the hydrogen evolution reaction(HER).This ultrathin nanostructure significantly improves the NRR performance of LN@MIL-X compared to pristine LiNbO_(3).Notably,LN@MIL-0.4 exhibits a maximum NH_(3)yield of 45.25 mg h^(-1)mg_(cat.)^(-1)with an impressive Faradaic efficiency(FE)of 86.41%at-0.45 V versus RHE in 0.1 mol L^(-1)Na_(2)SO_(4).This work provides a universal strategy for the design and synthesis of perovskite oxide electrocatalysts,facilitating high-efficiency ammonia synthesis.展开更多
Fe-based catalysts are widely used for CO_(2)hydrogenation to light olefins(C_(2–4)=);however,precise regulation of active phases and the balance between intermediate reactions remain significant challenges.Herein,we...Fe-based catalysts are widely used for CO_(2)hydrogenation to light olefins(C_(2–4)=);however,precise regulation of active phases and the balance between intermediate reactions remain significant challenges.Herein,we find that the addition of moderate amounts of Ti forms a strong interaction with Fe compositions,modulating the Fe_(3)O_(4)and Fe_(5)C_(2)contents.Enhanced interaction leads to an increased Fe_(5)C_(2)/Fe_(3)O_(4)ratio,which in turn enhances the adsorption of reactants and intermediates,promoting CO hydrogenation to unsaturated alkyl groups and facilitating C–C coupling.Furthermore,the strong Fe-Ti interaction induces the preferential growth of Fe_(5)C_(2)into prismatic structures that expose the(020),(–112),and(311)facets,forming compact active interfacial sites with Fe_(3)O_(4)nanoparticles.These facet and interfacial effects significantly promote the synergistic coupling of the reverse water gas shift and Fischer-Tropsch reactions.The optimized 3K/FeTi catalyst with the highest Fe_(5)C_(2)/Fe_(3)O_(4)ratio of 3.6 achieves a 52.2%CO_(2)conversion rate,with 44.5%selectivity for C2–4=and 9.5%for CO,and the highest space-time yield of 412.0 mg gcat^(–1)h^(–1)for C_(2–4)=.展开更多
The liver is a key endoderm-derived multifunctional organ within the digestive system.Prospero homeobox 1(Prox1)is an essential transcription factor for liver development,but its specific function is not well understo...The liver is a key endoderm-derived multifunctional organ within the digestive system.Prospero homeobox 1(Prox1)is an essential transcription factor for liver development,but its specific function is not well understood.Here,we show that hepatic development,including the formation of intrahepatic biliary and vascular networks,is severely disrupted in prox1a mutant zebrafish.We find that Prox1a is essential for liver growth and proper differentiation but not required for early hepatic cell fate specification.Intriguingly,prox1a depletion leads to ectopic initiation of a Cdx1b-mediated intestinal program and the formation of intestinal lumen-like structures within the liver.Morpholino knockdown of cdx1b alleviates liver defects in the prox1a mutant zebrafish.Finally,chromatin immunoprecipitation analysis reveals that Prox1a binds directly to the promoter region of cdx1b,thereby repressing its expression.Overall,our findings indicate that Prox1a is required to promote and protect hepatic development by repression of Cdx1b-mediated intestinal cell fate in zebrafish.展开更多
Hierarchical SAPO‐34 crystals were synthesized by a facile acid etching post‐treatment. Butterfly‐shaped porous patterns on four side faces and hierarchical pores composed of micropores,mesopores and macropores wer...Hierarchical SAPO‐34 crystals were synthesized by a facile acid etching post‐treatment. Butterfly‐shaped porous patterns on four side faces and hierarchical pores composed of micropores,mesopores and macropores were formed after a nitric acid or oxalic acid treatment. The catalyticperformance of the hierarchical SAPO‐34 for the methanol to olefins (MTO) process showed that thesynergistic effect of the hierarchical pores and acid sites resulted in a longer catalyst lifetime (from210 to 390 min for the acid treated SAPO‐34) and higher selectivity to light olefins of 92%–94%.The ethylene selectivity can be adjusted between 37.4% and 51.5% by the pore size. No hierarchical SAPO‐34 was obtained after a treatment with butanedioic acid, and with this sample, fast deactivation was detected after 100 min.展开更多
Cu-Fe composite oxides were prepared by co-precipitation method and tested for higher alcohol synthesis from syngas. The selectivity to C2＋OH and C6＋OH in alcohol distribution was very high while the methane product...Cu-Fe composite oxides were prepared by co-precipitation method and tested for higher alcohol synthesis from syngas. The selectivity to C2＋OH and C6＋OH in alcohol distribution was very high while the methane product fraction in hydrocarbon distribution was rather low, demonstrating a promising potential in higher alcohols synthesis from syngas. The distribution of alcohols and hydrocarbons approximately obeyed Anderson-Schulz-Flory distribution with similar chain growth probability, indicating alcohols and hydrocarbons derived from the same intermediates. The effects of Cu/Fe molar ratio, reaction temperature and gas hourly space velocity （GHSV） on catalytic performance were studied in detail. The sample with a Cu/Fe molar ratio of 10/1 exhibited the best catalytic performance. Higher reaction temperature accelerated water-gas-shift reaction and led to lower total alcohols selectivity. GHSV showed great effect on catalytic performance and higher GHSV increased the total alcohol selectivity, indicating there existed visible dehydration reaction of alcohol into hydrocarbon.展开更多
A reaction-coupling strategy is often employed for CO_(2)hydrogenation to produce fuels and chemicals using oxide/zeolite bifunctional catalysts.Because the oxide components are responsible for CO_(2)activation,unders...A reaction-coupling strategy is often employed for CO_(2)hydrogenation to produce fuels and chemicals using oxide/zeolite bifunctional catalysts.Because the oxide components are responsible for CO_(2)activation,understanding the structural effects of these oxides is crucial,however,these effects still remain unclear.In this study,we combined In_(2)O_(3),with varying particle sizes,and SAPO‐34 as bifunctional catalysts for CO_(2)hydrogenation.The CO_(2)conversion and selectivity of the lower olefins increased as the average In_(2)O_(3)crystallite size decreased from 29 to 19 nm;this trend mainly due to the increasing number of oxygen vacancies responsible for CO_(2) and H_(2) activation.However,In_(2)O_(3)particles smaller than 19 nm are more prone to sintering than those with other sizes.The results suggest that 19 nm is the optimal size of In_(2)O_(3)for CO_(2)hydrogenation to lower olefins and that the oxide particle size is crucial for designing catalysts with high activity,high selectivity,and high stability.展开更多
A novel melting-assisted solvent-free route using solid oxalic acid was proposed for the post-treatment of SAPO-11 zeolite,followed by loading with 0.5 wt%Pt by the incipient wetness impregnation method.Subsequently,t...A novel melting-assisted solvent-free route using solid oxalic acid was proposed for the post-treatment of SAPO-11 zeolite,followed by loading with 0.5 wt%Pt by the incipient wetness impregnation method.Subsequently,the performance of the obtained bifunctional catalysts toward the hydroisomerization of n-dodecane was examined.The prepared samples were characterized by XRD,SEM,BET,XRF,Py-IR,and solid-state NMR.From the results,it was found that the high crystallinity and uniform morphology were retained after the post-treatment and that more(002)crystal faces were exposed,which was beneficial since more acid sites were provided.More importantly,the total Bronsted acid sites and the ratio(Ra)of the micropore area to the total surface area were optimized by this method.Thus,the catalytic performance was enhanced significantly,and the prepared Pt-SAPO-11-10%catalyst had the highest i-dodecane yield of 80.1%compared to 55.3%of Pt-SAPO-11.Expectedly,this facile and cost-effective method is promising for the hydroisomerization of normal paraffin in the production of lubricant base oils.展开更多
Density‐functional theory calculations were carried out to study the strontium(Sr)‐doping effect on methane activation over a lanthanum‐oxide(La2O3)catalyst for the oxidative coupling of methane(OCM)using the clust...Density‐functional theory calculations were carried out to study the strontium(Sr)‐doping effect on methane activation over a lanthanum‐oxide(La2O3)catalyst for the oxidative coupling of methane(OCM)using the cluster model.Eight Sr‐doped La2O3cluster models were built from pure La2O3clusters that were used previously to model the La2O3catalyst.These form two distinct categories,namely,those without a radical character(LaSrO2(OH),La2SrO4,La3SrO5(OH),and La5SrO8(OH))and those with a radical character(LaSrO3,La2SrO4(OH),La3SrO6,and La5SrO9).The potential‐energy surface for CH4activation to form a CH3radical at different Sr-O and La-O pair sites on these Sr‐doped La2O3clusters was calculated to study the Sr‐doping effect on the OCM catalytic activity.CH4physisorption and chemisorption energies,and activation barriers,and CH3desorption energies were predicted.Compared with the pure La2O3clusters,in general,the Sr‐doped La2O3clusters are thermodynamically and kinetically more reactive with CH4.For the Sr‐doped La2O3clusters without the radical character,the Sr-O pair site is more reactive with CH4than the La-O pair site,although a direct release of the CH3radical is also highly endothermic as in the case of the pure La2O3clusters.In contrast,for the Sr‐doped La2O3clusters with a radical character,the activation of CH4at the oxygen radical site and the release of the CH3radical are much easier.Thus,our calculations suggest that the Sr dopant prompts the OCM catalytic activity of the La2O3catalyst by providing a highly active oxygen‐radical site and by strengthening the basicity of the M-O pair site,which leads to lower CH4activation energies and lower CH3desorption energies.展开更多
Large quantities of metal sulfides are widely distributed in uranium ores from the Middle Jurassic Zhiluo Formation of the Shuanglong uranium deposit,southern Ordos Basin,providing a convenient condition to study the ...Large quantities of metal sulfides are widely distributed in uranium ores from the Middle Jurassic Zhiluo Formation of the Shuanglong uranium deposit,southern Ordos Basin,providing a convenient condition to study the relationship between metal sulfides and uranium minerals.The morphology and composition of uranium minerals and metal sulfides are illustrated to study uranium mineralization and mechanisms of metallogenesis.Uranium minerals can be broadly categorized as pitchblende,coffinite and brannerite.Metal sulfides associated with uranium minerals are pyrite,sphalerite,chalcopyrite and galena.Some assemblages of various metal sulfides and uranium minerals indicate that they are coeval,but the order of formation is different.Based on mineralogical observations,paragenetic sequences for mineral assemblages are discussed.Alteration of Fe-Ti oxides forms Ti oxides,brannerite and pyrite.The formation of chalcopyrite was later than that of pyrite.Clausthalite(Pb Se)replaces sphalerite or shows isomorphism with galena.There are three genetic types of galena,of which typeⅠis related to tectonic thermal events and can interact with uranyl ions to form uranium oxides and Pb;.When sulfur activity is relatively high,Pb;can form new anhedral galena,that is,typeⅡ.TypeⅢof galena is related to the decay of uranium minerals.The genetic order of the main minerals was determined as follows:Fe-Ti oxides>Ti oxides/sphalerite/pyrite>clausthalite/galenaⅠ/chalcopyrite>galenaⅡ/uranium minerals>galenaⅢduring the diagenetic stage.Hydrogen sulfide(H;S)is a decisive factor in the interaction between metal sulfides and uranium.Metal ions can react with H;S,accompanied by precipitation and enrichment of uranium minerals.展开更多
Co2C‐based catalysts with SiO2,γ‐Al2O3,and carbon nanotubes(CNTs)as support materials were prepared and evaluated for the Fischer‐Tropsch to olefin(FTO)reaction.The combination of catalytic performance and structu...Co2C‐based catalysts with SiO2,γ‐Al2O3,and carbon nanotubes(CNTs)as support materials were prepared and evaluated for the Fischer‐Tropsch to olefin(FTO)reaction.The combination of catalytic performance and structure characterization indicates that the cobalt‐support interaction has a great influence on the Co2C morphology and catalytic performance.The CNT support facilitates the formation of a CoMn composite oxide during calcination,and Co2C nanoprisms were observed in the spent catalysts,resulting in a product distribution that greatly deviates from the classical Anderson‐Schulz‐Flory(ASF)distribution,where only 2.4 C%methane was generated.The Co3O4 phase for SiO2‐andγ‐Al2O3‐supported catalysts was observed in the calcined sample.After reduction,CoO,MnO,and low‐valence CoMn composite oxide were generated in theγ‐Al2O3‐supported sample,and both Co2C nanospheres and nanoprisms were identified in the corresponding spent catalyst.However,only separated phases of CoO and MnO were found in the reduced sample supported by SiO2,and Co2C nanospheres were detected in the spent catalyst without the evidence of any Co2C nanoprisms.The Co2C nanospheres led to a relatively high methane selectivity of 5.8 C%and 12.0 C%of theγ‐Al2O3‐and SiO2‐supported catalysts,respectively.These results suggest that a relatively weak cobalt‐support interaction is necessary for the formation of the CoMn composite oxide during calcination,which benefits the formation of Co2C nanoprisms with promising catalytic performance for the sustainable production of olefins via syngas.展开更多
The directly selective hydrogenolysis of xylitol to ethylene glycol(EG) and 1,2-propylene glycol(1,2-PDO)was performed on Cu–Ni–ZrO_2 catalysts prepared by a co-precipitation method. Upon optimizing the reaction con...The directly selective hydrogenolysis of xylitol to ethylene glycol(EG) and 1,2-propylene glycol(1,2-PDO)was performed on Cu–Ni–ZrO_2 catalysts prepared by a co-precipitation method. Upon optimizing the reaction conditions(518 K, 4.0 MPaH_2 and 3 h), 97.0% conversion of xylitol and 63.1% yield of glycols were obtained in water without extra inorganic base. The catalyst still remained stable activity after six cycles and above 80% total selectivity of glycols was obtained when using 20.0% xylitol concentration. XRD, TEM and ICP results indicated that Cu–Ni–ZrO_2 catalysts possess favorable stability. Cu and Ni are beneficial to the cleavage of C–O and C–H bond, respectively. To reduce the hydrogen consumption, isopropanol was added as in-situ hydrogen source and 96.4% conversion of xylitol with 43.6% yield of glycols were realized.展开更多
Palladium oxide(PdOx)and cobalt oxide(Co3O4)are efficient catalysts for methane(CH4)combustion,and Pd‐doped Co3O4catalysts have been found to exhibit better catalytic activities,which suggest synergism between the tw...Palladium oxide(PdOx)and cobalt oxide(Co3O4)are efficient catalysts for methane(CH4)combustion,and Pd‐doped Co3O4catalysts have been found to exhibit better catalytic activities,which suggest synergism between the two components.We carried out first‐principles calculations at the PBE+U level to investigate the Pd‐doping effect on CH4reactivity over the Co3O4catalyst.Because of the structural complexity of the Pd‐doped Co3O4catalyst,we built Pd‐doped catalyst models using Co3O4(001)slabs with two different terminations and examined CH4reactivity over the possible Pd?O active sites.A low energy barrier of0.68eV was predicted for CH4dissociation over the more reactive Pd‐doped Co3O4(001)surface,which was much lower than the0.98and0.89eV that was predicted previously over the more reactive pure Co3O4(001)and(011)surfaces,respectively.Using a simple model,we predicted CH4reaction rates over the pure Co3O4(001)and(011)surfaces,and Co3O4(001)surfaces with different amounts of Pd dopant.Our theoretical results agree well with the available experimental data,which suggests a strong synergy between the Pd dopant and the Co3O4catalyst,and leads to a significant increase in CH4reaction rate.展开更多
MnOx-promoted Ni-based catalyst supported by ZnO was developed to selectively hydrogenate glucose into polyols in water at 523 K with a yield of 64.9%. Using glucose, sorbitol, glycerol and LA as the rawmaterials, the...MnOx-promoted Ni-based catalyst supported by ZnO was developed to selectively hydrogenate glucose into polyols in water at 523 K with a yield of 64.9%. Using glucose, sorbitol, glycerol and LA as the rawmaterials, the roles of nickel, ZnO and MnOx were investigated. The results show that nickel provided a new pathway of glucose to sorbitol and played an important role in the hydrogenation of C3 intermediates to 1,2-propanediol(1,2-PDO). The high yield of 1, 2-PDO was attributed to effective C–C bond cleavage performance of ZnO support promoted by MnOx. ZnO and MnOx contribute to the conversion of glycerol to lactic acid(LA) and LA to 1, 2-PDO, respectively. A concise pathway for hydrogenation of glucose over Ni-based catalyst was proposed.展开更多
Nickel and potassium co-modified β-Mo2C catalysts were prepared and used for CO hydrogenation reaction. The major products over β-Mo2C were C1-C4 hydrocarbons, only few alcohols were obtained. Addition of potassium ...Nickel and potassium co-modified β-Mo2C catalysts were prepared and used for CO hydrogenation reaction. The major products over β-Mo2C were C1-C4 hydrocarbons, only few alcohols were obtained. Addition of potassium resulted in remarkable selectivity shift from hydrocarbons to alcohols at the expense of CO conversion over β-Mo2C. Moreover, it was found that potassium enhanced the ability of chain propagation with a higher C2＋OH production. Modified by nickel,β-Mo2C showed a relatively high CO conversion, however, the products were similar to those of pure β-Mo2C. When co-modified by nickel and potassium,β-Mo2C exhibited high activity and selectivity towards mixed alcohols synthesis, and also the whole chain propagation to produce alcohols especially for the stage of C1 OH to C2OH was remarkably enhanced. It was concluded that the Ni and K had, to some extent, synergistic effect on CO conversion.展开更多
Chinese fir(Cunninghamia lanceolata(Lamb.)Hook),a fast-growing and economically important timber tree species in China,is widely used in construction,furniture,and paper manufacture but has a long breeding cycle.Chemi...Chinese fir(Cunninghamia lanceolata(Lamb.)Hook),a fast-growing and economically important timber tree species in China,is widely used in construction,furniture,and paper manufacture but has a long breeding cycle.Chemical mutagens,such as ethyl methane sulfonate(EMS)and sodium azide(SA),are widely used in crops such as rice,wheat,cotton,soybean and sugarcane but their utility for tree breeding is unknown.In this study we examined the effects of EMS and S A on Chinese fir seed germination and growth.Chinese fir seeds were treated with the two chemical mutagens;were planted in Jiangle County,Fujian Province,China;and their heights were measured from 2011 to2017.The concentrations and durations of treatment with the two chemical mutagens were significantly associated with the Chinese fir seedling and mortality rates,as well as with the heights of trees from the seedling stage to 3 years old.We also generated 127 mutants with abnormal branches and reproductive growth.We report here the effects of two chemical mutagens on Chinese fir breeding;our data will contribute to knowledge of the utility of EMS and SA in forestry.展开更多
基金supported by the National Natural Science Foundation of China(Nos.U22A20418,22075196)the Research Project Supported by Shanxi Scholarship Council of China(No.2022–050)。
文摘The electrocatalytic nitrogen reduction reaction(NRR)is challenging but crucial for the sustainable development of both industry and agriculture.To enhance NRR performance,it is critically important to construct advanced electrocatalysts that offer satisfactory performance containing high activity and selectivity.However,the strong affinity of nitrogen-containing species on the Ru surface resulted in suboptimal NRR activity.Herein,we propose a dual-site catalyst,RuNi,to optimize the binding strength,which leads to superior electrocatalytic performance,achieving a high NH_(3)yield rate of 5.07μg h^(-1)cm^(-2)at-0.2 V vs.RHE and a Faradaic efficiency(FE)of 26.2%at-0.1 V vs.RHE in 0.1 mol/L Na_(2)SO_(4).Owing to the synergistic interaction between Ru and Ni,a remarkable performance is realized over the RuNi catalyst.In-situ characterization evidenced that hydrogen radicals(H^(*))on the Ni site of the RuNi catalyst participate in the dissociation of N_(2)adsorbed on the Ru site,and theoretical investigations indicated that RuNi reduces the adsorption strength of intermediates.This offers an effective approach to the synthesis of dual-site catalysts for electrocatalytic ammonia synthesis.
基金supported by grants from the High-Level Oversea Talent Introduction Plan,Chinathe Special Fund for Basic Scientific Research in Central Universities of China-Doctoral Research and Innovation Fund Project,China(No.3072023CFJ0206).
文摘Rotor blade is one of the most significant components of helicopters. But due to its highspeed rotation characteristics, it is difficult to collect the vibration signals during the flight stage.Moreover, sensors are highly susceptible to damage resulting in the failure of the measurement.In order to make signal predictions for the damaged sensors, an operational modal analysis(OMA) together with the virtual sensing(VS) technology is proposed in this paper. This paper discusses two situations, i.e., mode shapes measured by all sensors(both normal and damaged) can be obtained using OMA, and mode shapes measured by some sensors(only including normal) can be obtained using OMA. For the second situation, it is necessary to use finite element(FE) analysis to supplement the missing mode shapes of damaged sensor. In order to improve the correlation between the FE model and the real structure, the FE mode shapes are corrected using the local correspondence(LC) principle and mode shapes measured by some sensors(only including normal).Then, based on the VS technology, the vibration signals of the damaged sensors during the flight stage can be accurately predicted using the identified mode shapes(obtained based on OMA and FE analysis) and the normal sensors signals. Given the high degrees of freedom(DOFs) in the FE mode shapes, this approach can also be used to predict vibration data at locations without sensors. The effectiveness and robustness of the proposed method is verified through finite element simulation, experiment as well as the actual flight test. The present work can be further used in the fault diagnosis and damage identification for rotor blade of helicopters.
基金supported by the National Natural Science Foundation of China(No.U22A20418,22075196)the Research Project Supported by Shanxi Scholarship Council of China(2022–050).
文摘The electrochemical nitrogen reduction reaction(NRR)under ambient conditions presents a promising approach for the eco-friendly and sustainable synthesis of ammonia,with a continuous emergence of potential electrocatalysts.However,the low solubility and limited diffusion of N_(2)significantly hinder the achievement of satisfactory performance.In this context,we report an effective strategy to enhance NRR activity by introducing a metal-organic framework(MOF)membrane,specifically MIL-53(Al),onto a perovskite oxide(LiNbO_(3)),denoted as LN@MIL-X(X=0.2,0.4 and 0.6).The MIL-53(Al)membrane selectively recognizes and concentrates N_(2)at the catalyst interface while simultaneously repelling water molecules,thereby inhibiting the hydrogen evolution reaction(HER).This ultrathin nanostructure significantly improves the NRR performance of LN@MIL-X compared to pristine LiNbO_(3).Notably,LN@MIL-0.4 exhibits a maximum NH_(3)yield of 45.25 mg h^(-1)mg_(cat.)^(-1)with an impressive Faradaic efficiency(FE)of 86.41%at-0.45 V versus RHE in 0.1 mol L^(-1)Na_(2)SO_(4).This work provides a universal strategy for the design and synthesis of perovskite oxide electrocatalysts,facilitating high-efficiency ammonia synthesis.
文摘Fe-based catalysts are widely used for CO_(2)hydrogenation to light olefins(C_(2–4)=);however,precise regulation of active phases and the balance between intermediate reactions remain significant challenges.Herein,we find that the addition of moderate amounts of Ti forms a strong interaction with Fe compositions,modulating the Fe_(3)O_(4)and Fe_(5)C_(2)contents.Enhanced interaction leads to an increased Fe_(5)C_(2)/Fe_(3)O_(4)ratio,which in turn enhances the adsorption of reactants and intermediates,promoting CO hydrogenation to unsaturated alkyl groups and facilitating C–C coupling.Furthermore,the strong Fe-Ti interaction induces the preferential growth of Fe_(5)C_(2)into prismatic structures that expose the(020),(–112),and(311)facets,forming compact active interfacial sites with Fe_(3)O_(4)nanoparticles.These facet and interfacial effects significantly promote the synergistic coupling of the reverse water gas shift and Fischer-Tropsch reactions.The optimized 3K/FeTi catalyst with the highest Fe_(5)C_(2)/Fe_(3)O_(4)ratio of 3.6 achieves a 52.2%CO_(2)conversion rate,with 44.5%selectivity for C2–4=and 9.5%for CO,and the highest space-time yield of 412.0 mg gcat^(–1)h^(–1)for C_(2–4)=.
基金partially supported by grants from the National Key Research and Development Program of China and the National Natural Science Foundation of China(2018YFA0801000,32270889,2019YFA0802800,32070824,2015CB942800,2016YFA0100500,31871458,31671500,and 81371264)supported by Beijing Natural Science Foundation(5242009)a grant from the Fisheries Innovation Team of Beijing Agriculture Innovation Consortium(BAIC07-2023-02).
文摘The liver is a key endoderm-derived multifunctional organ within the digestive system.Prospero homeobox 1(Prox1)is an essential transcription factor for liver development,but its specific function is not well understood.Here,we show that hepatic development,including the formation of intrahepatic biliary and vascular networks,is severely disrupted in prox1a mutant zebrafish.We find that Prox1a is essential for liver growth and proper differentiation but not required for early hepatic cell fate specification.Intriguingly,prox1a depletion leads to ectopic initiation of a Cdx1b-mediated intestinal program and the formation of intestinal lumen-like structures within the liver.Morpholino knockdown of cdx1b alleviates liver defects in the prox1a mutant zebrafish.Finally,chromatin immunoprecipitation analysis reveals that Prox1a binds directly to the promoter region of cdx1b,thereby repressing its expression.Overall,our findings indicate that Prox1a is required to promote and protect hepatic development by repression of Cdx1b-mediated intestinal cell fate in zebrafish.
基金supported by the National Natural Science Foundation of China (21403279, 21507141, 21506243)the Science and Technology Commission of Shanghai Municipality (14DZ1207602, 14DZ1203700)~~
文摘Hierarchical SAPO‐34 crystals were synthesized by a facile acid etching post‐treatment. Butterfly‐shaped porous patterns on four side faces and hierarchical pores composed of micropores,mesopores and macropores were formed after a nitric acid or oxalic acid treatment. The catalyticperformance of the hierarchical SAPO‐34 for the methanol to olefins (MTO) process showed that thesynergistic effect of the hierarchical pores and acid sites resulted in a longer catalyst lifetime (from210 to 390 min for the acid treated SAPO‐34) and higher selectivity to light olefins of 92%–94%.The ethylene selectivity can be adjusted between 37.4% and 51.5% by the pore size. No hierarchical SAPO‐34 was obtained after a treatment with butanedioic acid, and with this sample, fast deactivation was detected after 100 min.
基金the State Key Fundamental Research Program(Ministry of Science and Technology of China,No.2011CBA00501)Shanghai Municipal Science and Technology Commission,China(Grant No:11DZ1200300)the Foundation of State Key Laboratory of Coal Conversion(Grant No:1112610)
文摘Cu-Fe composite oxides were prepared by co-precipitation method and tested for higher alcohol synthesis from syngas. The selectivity to C2＋OH and C6＋OH in alcohol distribution was very high while the methane product fraction in hydrocarbon distribution was rather low, demonstrating a promising potential in higher alcohols synthesis from syngas. The distribution of alcohols and hydrocarbons approximately obeyed Anderson-Schulz-Flory distribution with similar chain growth probability, indicating alcohols and hydrocarbons derived from the same intermediates. The effects of Cu/Fe molar ratio, reaction temperature and gas hourly space velocity （GHSV） on catalytic performance were studied in detail. The sample with a Cu/Fe molar ratio of 10/1 exhibited the best catalytic performance. Higher reaction temperature accelerated water-gas-shift reaction and led to lower total alcohols selectivity. GHSV showed great effect on catalytic performance and higher GHSV increased the total alcohol selectivity, indicating there existed visible dehydration reaction of alcohol into hydrocarbon.
文摘A reaction-coupling strategy is often employed for CO_(2)hydrogenation to produce fuels and chemicals using oxide/zeolite bifunctional catalysts.Because the oxide components are responsible for CO_(2)activation,understanding the structural effects of these oxides is crucial,however,these effects still remain unclear.In this study,we combined In_(2)O_(3),with varying particle sizes,and SAPO‐34 as bifunctional catalysts for CO_(2)hydrogenation.The CO_(2)conversion and selectivity of the lower olefins increased as the average In_(2)O_(3)crystallite size decreased from 29 to 19 nm;this trend mainly due to the increasing number of oxygen vacancies responsible for CO_(2) and H_(2) activation.However,In_(2)O_(3)particles smaller than 19 nm are more prone to sintering than those with other sizes.The results suggest that 19 nm is the optimal size of In_(2)O_(3)for CO_(2)hydrogenation to lower olefins and that the oxide particle size is crucial for designing catalysts with high activity,high selectivity,and high stability.
基金supported by the National Natural Science Foundation of China(21776295)the Youth Innovation Promotion Association,CAS(2017355)~~
文摘A novel melting-assisted solvent-free route using solid oxalic acid was proposed for the post-treatment of SAPO-11 zeolite,followed by loading with 0.5 wt%Pt by the incipient wetness impregnation method.Subsequently,the performance of the obtained bifunctional catalysts toward the hydroisomerization of n-dodecane was examined.The prepared samples were characterized by XRD,SEM,BET,XRF,Py-IR,and solid-state NMR.From the results,it was found that the high crystallinity and uniform morphology were retained after the post-treatment and that more(002)crystal faces were exposed,which was beneficial since more acid sites were provided.More importantly,the total Bronsted acid sites and the ratio(Ra)of the micropore area to the total surface area were optimized by this method.Thus,the catalytic performance was enhanced significantly,and the prepared Pt-SAPO-11-10%catalyst had the highest i-dodecane yield of 80.1%compared to 55.3%of Pt-SAPO-11.Expectedly,this facile and cost-effective method is promising for the hydroisomerization of normal paraffin in the production of lubricant base oils.
基金supported by the National Natural Science Foundation of China(21473233,21403277)the Frontier Science Program of Shell Global Solutions International B.V.(PT32281)+1 种基金the Ministry of Science and Technology of China(2016YFA0202802)the Shanghai Municipal Science and Technology Commission(14ZR1444600)~~
文摘Density‐functional theory calculations were carried out to study the strontium(Sr)‐doping effect on methane activation over a lanthanum‐oxide(La2O3)catalyst for the oxidative coupling of methane(OCM)using the cluster model.Eight Sr‐doped La2O3cluster models were built from pure La2O3clusters that were used previously to model the La2O3catalyst.These form two distinct categories,namely,those without a radical character(LaSrO2(OH),La2SrO4,La3SrO5(OH),and La5SrO8(OH))and those with a radical character(LaSrO3,La2SrO4(OH),La3SrO6,and La5SrO9).The potential‐energy surface for CH4activation to form a CH3radical at different Sr-O and La-O pair sites on these Sr‐doped La2O3clusters was calculated to study the Sr‐doping effect on the OCM catalytic activity.CH4physisorption and chemisorption energies,and activation barriers,and CH3desorption energies were predicted.Compared with the pure La2O3clusters,in general,the Sr‐doped La2O3clusters are thermodynamically and kinetically more reactive with CH4.For the Sr‐doped La2O3clusters without the radical character,the Sr-O pair site is more reactive with CH4than the La-O pair site,although a direct release of the CH3radical is also highly endothermic as in the case of the pure La2O3clusters.In contrast,for the Sr‐doped La2O3clusters with a radical character,the activation of CH4at the oxygen radical site and the release of the CH3radical are much easier.Thus,our calculations suggest that the Sr dopant prompts the OCM catalytic activity of the La2O3catalyst by providing a highly active oxygen‐radical site and by strengthening the basicity of the M-O pair site,which leads to lower CH4activation energies and lower CH3desorption energies.
基金supported by the National Key Research and Development Program of China(No.2018YFC0604202)the National Science Fund Project(No.42172128)the International Geoscience Programme(No.IGCP-675)
文摘Large quantities of metal sulfides are widely distributed in uranium ores from the Middle Jurassic Zhiluo Formation of the Shuanglong uranium deposit,southern Ordos Basin,providing a convenient condition to study the relationship between metal sulfides and uranium minerals.The morphology and composition of uranium minerals and metal sulfides are illustrated to study uranium mineralization and mechanisms of metallogenesis.Uranium minerals can be broadly categorized as pitchblende,coffinite and brannerite.Metal sulfides associated with uranium minerals are pyrite,sphalerite,chalcopyrite and galena.Some assemblages of various metal sulfides and uranium minerals indicate that they are coeval,but the order of formation is different.Based on mineralogical observations,paragenetic sequences for mineral assemblages are discussed.Alteration of Fe-Ti oxides forms Ti oxides,brannerite and pyrite.The formation of chalcopyrite was later than that of pyrite.Clausthalite(Pb Se)replaces sphalerite or shows isomorphism with galena.There are three genetic types of galena,of which typeⅠis related to tectonic thermal events and can interact with uranyl ions to form uranium oxides and Pb;.When sulfur activity is relatively high,Pb;can form new anhedral galena,that is,typeⅡ.TypeⅢof galena is related to the decay of uranium minerals.The genetic order of the main minerals was determined as follows:Fe-Ti oxides>Ti oxides/sphalerite/pyrite>clausthalite/galenaⅠ/chalcopyrite>galenaⅡ/uranium minerals>galenaⅢduring the diagenetic stage.Hydrogen sulfide(H;S)is a decisive factor in the interaction between metal sulfides and uranium.Metal ions can react with H;S,accompanied by precipitation and enrichment of uranium minerals.
文摘Co2C‐based catalysts with SiO2,γ‐Al2O3,and carbon nanotubes(CNTs)as support materials were prepared and evaluated for the Fischer‐Tropsch to olefin(FTO)reaction.The combination of catalytic performance and structure characterization indicates that the cobalt‐support interaction has a great influence on the Co2C morphology and catalytic performance.The CNT support facilitates the formation of a CoMn composite oxide during calcination,and Co2C nanoprisms were observed in the spent catalysts,resulting in a product distribution that greatly deviates from the classical Anderson‐Schulz‐Flory(ASF)distribution,where only 2.4 C%methane was generated.The Co3O4 phase for SiO2‐andγ‐Al2O3‐supported catalysts was observed in the calcined sample.After reduction,CoO,MnO,and low‐valence CoMn composite oxide were generated in theγ‐Al2O3‐supported sample,and both Co2C nanospheres and nanoprisms were identified in the corresponding spent catalyst.However,only separated phases of CoO and MnO were found in the reduced sample supported by SiO2,and Co2C nanospheres were detected in the spent catalyst without the evidence of any Co2C nanoprisms.The Co2C nanospheres led to a relatively high methane selectivity of 5.8 C%and 12.0 C%of theγ‐Al2O3‐and SiO2‐supported catalysts,respectively.These results suggest that a relatively weak cobalt‐support interaction is necessary for the formation of the CoMn composite oxide during calcination,which benefits the formation of Co2C nanoprisms with promising catalytic performance for the sustainable production of olefins via syngas.
基金financial supports provided by the National Natural Science Foundation of China (21406255)the Shanghai Science and Technology Committee (16dz1207200)the Youth Innovation Promotion Association CAS (2015231)
文摘The directly selective hydrogenolysis of xylitol to ethylene glycol(EG) and 1,2-propylene glycol(1,2-PDO)was performed on Cu–Ni–ZrO_2 catalysts prepared by a co-precipitation method. Upon optimizing the reaction conditions(518 K, 4.0 MPaH_2 and 3 h), 97.0% conversion of xylitol and 63.1% yield of glycols were obtained in water without extra inorganic base. The catalyst still remained stable activity after six cycles and above 80% total selectivity of glycols was obtained when using 20.0% xylitol concentration. XRD, TEM and ICP results indicated that Cu–Ni–ZrO_2 catalysts possess favorable stability. Cu and Ni are beneficial to the cleavage of C–O and C–H bond, respectively. To reduce the hydrogen consumption, isopropanol was added as in-situ hydrogen source and 96.4% conversion of xylitol with 43.6% yield of glycols were realized.
基金supported by the National Natural Science Foundation of China(21473233,21403277)the Energy Technologies Institute LLP,UK~~
文摘Palladium oxide(PdOx)and cobalt oxide(Co3O4)are efficient catalysts for methane(CH4)combustion,and Pd‐doped Co3O4catalysts have been found to exhibit better catalytic activities,which suggest synergism between the two components.We carried out first‐principles calculations at the PBE+U level to investigate the Pd‐doping effect on CH4reactivity over the Co3O4catalyst.Because of the structural complexity of the Pd‐doped Co3O4catalyst,we built Pd‐doped catalyst models using Co3O4(001)slabs with two different terminations and examined CH4reactivity over the possible Pd?O active sites.A low energy barrier of0.68eV was predicted for CH4dissociation over the more reactive Pd‐doped Co3O4(001)surface,which was much lower than the0.98and0.89eV that was predicted previously over the more reactive pure Co3O4(001)and(011)surfaces,respectively.Using a simple model,we predicted CH4reaction rates over the pure Co3O4(001)and(011)surfaces,and Co3O4(001)surfaces with different amounts of Pd dopant.Our theoretical results agree well with the available experimental data,which suggests a strong synergy between the Pd dopant and the Co3O4catalyst,and leads to a significant increase in CH4reaction rate.
基金financially supported by the National Science Foundation of China (21671132)Shanghai Science and Technology Committee(16dz1207200)the Youth Innovation Promotion Association CAS(2015231)
文摘MnOx-promoted Ni-based catalyst supported by ZnO was developed to selectively hydrogenate glucose into polyols in water at 523 K with a yield of 64.9%. Using glucose, sorbitol, glycerol and LA as the rawmaterials, the roles of nickel, ZnO and MnOx were investigated. The results show that nickel provided a new pathway of glucose to sorbitol and played an important role in the hydrogenation of C3 intermediates to 1,2-propanediol(1,2-PDO). The high yield of 1, 2-PDO was attributed to effective C–C bond cleavage performance of ZnO support promoted by MnOx. ZnO and MnOx contribute to the conversion of glycerol to lactic acid(LA) and LA to 1, 2-PDO, respectively. A concise pathway for hydrogenation of glucose over Ni-based catalyst was proposed.
基金supported by the National Key Project for Basic Research of China (973 Project) (No. 2005CB221400)
文摘Nickel and potassium co-modified β-Mo2C catalysts were prepared and used for CO hydrogenation reaction. The major products over β-Mo2C were C1-C4 hydrocarbons, only few alcohols were obtained. Addition of potassium resulted in remarkable selectivity shift from hydrocarbons to alcohols at the expense of CO conversion over β-Mo2C. Moreover, it was found that potassium enhanced the ability of chain propagation with a higher C2＋OH production. Modified by nickel,β-Mo2C showed a relatively high CO conversion, however, the products were similar to those of pure β-Mo2C. When co-modified by nickel and potassium,β-Mo2C exhibited high activity and selectivity towards mixed alcohols synthesis, and also the whole chain propagation to produce alcohols especially for the stage of C1 OH to C2OH was remarkably enhanced. It was concluded that the Ni and K had, to some extent, synergistic effect on CO conversion.
基金supported by grants from the Guangdong Provincial Science and Technology Plan Project(2016B020201002)the Science and Technology Research Project of Beijing Forestry University(2018WS01)+2 种基金the Research and Development Project of Beijing Forestry University(2016BLPX13)the National Natural Science Foundation of China(31700581)the Key Project of the National Forestry Bureau(2012–06)。
文摘Chinese fir(Cunninghamia lanceolata(Lamb.)Hook),a fast-growing and economically important timber tree species in China,is widely used in construction,furniture,and paper manufacture but has a long breeding cycle.Chemical mutagens,such as ethyl methane sulfonate(EMS)and sodium azide(SA),are widely used in crops such as rice,wheat,cotton,soybean and sugarcane but their utility for tree breeding is unknown.In this study we examined the effects of EMS and S A on Chinese fir seed germination and growth.Chinese fir seeds were treated with the two chemical mutagens;were planted in Jiangle County,Fujian Province,China;and their heights were measured from 2011 to2017.The concentrations and durations of treatment with the two chemical mutagens were significantly associated with the Chinese fir seedling and mortality rates,as well as with the heights of trees from the seedling stage to 3 years old.We also generated 127 mutants with abnormal branches and reproductive growth.We report here the effects of two chemical mutagens on Chinese fir breeding;our data will contribute to knowledge of the utility of EMS and SA in forestry.
