Steam reforming of long-chain hydrocarbon fuels for hydrogen production has received great attention for thermal management of the hypersonic vehicle and fuel-cell application.In this work,Pt catalysts supported on Ce...Steam reforming of long-chain hydrocarbon fuels for hydrogen production has received great attention for thermal management of the hypersonic vehicle and fuel-cell application.In this work,Pt catalysts supported on CeO_(2)and Tb-doped CeO_(2)were prepared by a precipitation method.The physical structure and chemical properties of the as-prepared catalysts were characterized by powder X-ray diffraction,scanning electron microscopy,transmission electron microscopy,Raman spectroscopy,H_(2)temperature programmed reduction,and X-ray photoelectron spectroscopy.The results show that Tb-doped CeO_(2)supported Pt possesses abundant surface oxygen vacancies,good inhibition of ceria sintering,and strong metal-support interaction compared with CeO_(2)supported Pt.The catalytic performance of hydrogen production via steam reforming of long-chain hydrocarbon fuels(n-dodecane)was tested.Compared with 2Pt/CeO_(2),2Pt/Ce_(0.9)Tb_(0.1)O_(2),and 2Pt/Ce_(0.5)Tb_(0.5)O_(2),the 2Pt/Ce_(0.7)Tb_(0.3)O_(2)has higher activity and stability for hydrogen production,on which the conversion of n-dodecane was maintained at about 53.2%after 600 min reaction under 700℃at liquid space velocity of 9 ml·g^(-1)·h^(-1).2Pt/CeO_(2)rapidly deactivated,the conversion of n-dodecane was reduced to only 41.6%after 600 min.展开更多
Understanding the relationship between the chemical composition and pyrolysis performance of endothermic hydrocarbon fuel(EHF) is of great significance for the design and optimization of advanced EHFs. In this work, t...Understanding the relationship between the chemical composition and pyrolysis performance of endothermic hydrocarbon fuel(EHF) is of great significance for the design and optimization of advanced EHFs. In this work, the effect of deep hydrogenation on the pyrolysis of commercial RP-3 is investigated.Fuels with different hydrogenation degrees were obtained by the partially and completely catalytic hydrogenation and their pyrolysis performances were investigated using an apparatus equipped with an electrically heated tubular reactor. The results show that with the increase of hydrogenation degree, fuel conversion almost remains constant during the pyrolysis process(500-650°C, 4 MPa);however, the heat sink increases slightly, and the anti-coking performance significantly improves, which are highly related to their H/C ratios. Detailed characterisations reveal that the difference of the pyrolysis performance can be ascribed to the content of aromatics and cycloalkanes: the former are prone to initiate secondary reactions to form coking precursors, while the latter could act as the hydrogen donor and release hydrogen, which will terminate the radical propagation reactions and suppress the coke deposition. This work should provide the guidance for upgrading EHFs by modulating the composition of EHFs.展开更多
High-energy-density fuels are important for volume-limited aerospace vehicles,but the increase in fuel energy density always leads to poor cryogenic performance.Herein,we investigated the transposed Paternò-B...High-energy-density fuels are important for volume-limited aerospace vehicles,but the increase in fuel energy density always leads to poor cryogenic performance.Herein,we investigated the transposed Paternò-Büchi reaction of biomass cyclic ketone and cyclic alkene to synthesize a new kind of alkyl-substituted polycyclic hydrocarbon fuel with high energy density and good cryogenic performance.The triplet-energy-quenching results and phosphorescent emission spectra reveal the sensitization mechanism of the reaction,including photosensitizer excitation,triplettriplet energy transfer,cyclization,and relaxation,and the possible reaction path was revealed by the density functional theory(DFT)calculations.The reaction conditions of photosensitizer type and addition,molar ratio of substrates,reaction temperature,and incident light intensity were optimized,with the target product yield achieving 65.5%.Moreover,the reaction dynamics of the reaction rate versus the light intensity are established.After the hydrogenation-deoxygenation reaction,three fuels with a high density of 0.864-0.938 g·ml^(-1) and a low freezing point of<-55℃ are obtained.This work provides a benign and effective approach to synthesize high-performance fuels.展开更多
Energetic nanofluid fuel has caught the attention of the field of aerospace liquid propellant for its high energy density(HED), but it suffers from the inevitable solid-liquid phase separation problem. To resolve this...Energetic nanofluid fuel has caught the attention of the field of aerospace liquid propellant for its high energy density(HED), but it suffers from the inevitable solid-liquid phase separation problem. To resolve this problem, herein we synthesized the high-Al-/B-containing(up to 30%(mass)) HED gelled fuels, with low-molecular-mass organic gellant Z, which show high net heat of combustion(NHOC), density, storage stability, and thixotropic properties. The characterizations indicate that the application of energetic particles to the gelled fuels obviously destroys their fibrous network structures but can provide the new particle-gellant gelation microstructures, resulting in the comparable stability between 1.0%(mass) Z/JP-10 + 30%(mass) Al or B and pure JP-10 gelled fuel. Moreover, the gelled fuels with high-content Al or B exhibit high shear-thinning property, recovery capability, and mechanical strength, which are favorable for their storage and utilization. Importantly, the prepared 1.0%(mass) Z/JP-10 + 30%(mass) B(or 1.0%(mass) Z/JP-10 + 30%(mass) Al) shows the density and NHOC 1.27 times(1.30) and 1.43 times(1.21)higher than pure JP-10, respectively. This work provides a facile and valid approach to the manufacturing of HED gelled fuels with high content of energetic particles for gel propellants.展开更多
Fuel design is a complex multi-objective optimization problem in which facile and robust methods are urgently demanded.Herein,a complete workflow for designing a fuel blending scheme is presented,which is theoreticall...Fuel design is a complex multi-objective optimization problem in which facile and robust methods are urgently demanded.Herein,a complete workflow for designing a fuel blending scheme is presented,which is theoretically supported,efficient,and reliable.Based on the data distribution of the composition and properties of the blending fuels,a model of polynomial regression with appropriate hypothesis space was established.The parameters of the model were further optimized by different intelligence algorithms to achieve high-precision regression.Then,the design of a blending fuel was described as a multi-objective optimization problem,which was solved using a Nelder–Mead algorithm based on the concept of Pareto domination.Finally,the design of a target fuel was fully validated by experiments.This study provides new avenues for designing various blending fuels to meet the needs of next-generation engines.展开更多
Synthesizing high-density fuel from lignocellulose can not only achieve green and low-carbon development,but also expand the feedstock source of hydrocarbon fuel.Here,we reported a route of producing high-density fuel...Synthesizing high-density fuel from lignocellulose can not only achieve green and low-carbon development,but also expand the feedstock source of hydrocarbon fuel.Here,we reported a route of producing high-density fuel from lignin oil and hemicellulose derivative cyclopentanol through alkylation and hydrodeoxygenation,HY with SiO_(2)/Al_(2)O_(3) molar ratio of 5.3 was screened as the alkylation catalyst in the reaction of model phenolic compounds and mixtures,and the reaction conditions were optimized to achieve conversion of phenolic compounds higher than 87%and selectivity of bicyclic and tricyclic products higher than 99%.Then two phenolic pools simulating the composition of two typic lignin oils were studied to validate the alkylation and analyze the competition mechanism of phenolic compounds in mixture system.Finally,real lignin oil from depolymerized of beech powder was tested,and notably80%of phenolic monomers in the oil were converted into fuel precursor.After hydrodeoxygenation,the alkylated product was converted to fuel blend with a density of 0.91 g/mL at 20℃and a freezing point lower than-60℃,very promising as high density fuel.This work provides a facile and energyefficient way of synthesizing high-performance jet fuel directly from lignocellulosic derivatives,which decreases processing energy consumption and improve the utilization rate of feedstock.展开更多
Sluggish reaction kinetics of oxygen evolution reaction(OER), resulting from multistep proton-coupled electron transfer and spin constriction, limits overall efficiency for most reported catalysts. Herein, using model...Sluggish reaction kinetics of oxygen evolution reaction(OER), resulting from multistep proton-coupled electron transfer and spin constriction, limits overall efficiency for most reported catalysts. Herein, using modeled ZnFe_(2-x)Ni_xO_(4)(0 ≤ x ≤ 0.4) spinel oxides, we aim to develop better OER electrocatalyst through combining the construction of ferromagnetic(FM) ordering channels and generation of highly active reconstructed species. The number of symmetry-breaking Fe–O–Ni structure links to the formation of FM ordering electron transfer channels. Meanwhile, as the number of Ni^(3+)increases, more ligand holes are formed, beneficial for redirecting surface reconstruction. The electro-activated ZnFe_(1.6)Ni_(0.4)O_(4) shows the highest specific activity, which is 13 and 2.5 times higher than that of ZnFe_(2)O_(4) and unactivated ZnFe_(1.6)Ni_(0.4)O_(4), and even superior to the benchmark IrO_(2) under the overpotential of 350 mV. Applying external magnetic field can make electron spin more aligned, and the activity can be further improved to 39 times of ZnFe_(2)O_(4). We propose that intriguing FM exchange-field interaction at FM/paramagnetic interfaces can penetrate FM ordering channels into reconstructed oxyhydroxide layers, thereby activating oxyhydroxide layers as spin-filter to accelerate spin-selective electron transfer. This work provides a new guideline to develop highly efficient spintronic catalysts for water oxidation and other spin-forbidden reactions.展开更多
Water can be used as oxidant in conjunction with metal particles to form metal-water propellant to increase the energy of propellant.For this application,water needs to be stored in form of solid and capable of becomi...Water can be used as oxidant in conjunction with metal particles to form metal-water propellant to increase the energy of propellant.For this application,water needs to be stored in form of solid and capable of becoming liquid when use.Stable and thixotropic hydrogel has good potential as water-retaining material and oxidant of metal-based propellant.In this study,we prepared organic/inorganic composite hydrogels by combining inorganic gellants hectorite and fumed silica with organic gellant agarose,respectively.The total content of the gellants can be reduced to less than 2%by adding agarose.The influence of agarose on water content,phase transition temperature,centrifugal stability and other basic physical properties of composite hydrogels were discussed.The results show that the composite hydrogels have better thixotropy and stability than pure inorganic hydrogels,and the gel-sol transformation can be realized by applying shear force or heating to the phase transition temperature.The composite hydrogels have good shear thinning ability and improved mechanical stability.Fumed silica/agarose hydrogels have better physical stability,while the thixotropy and shear thinning ability of hectorite/agarose hydrogels are better.展开更多
Antioxidants addition is believed as a facile and effective way to improve jet fuel thermal oxidation stability.However,amine antioxidants,as one of the most important antioxidants,have not received sufficient attenti...Antioxidants addition is believed as a facile and effective way to improve jet fuel thermal oxidation stability.However,amine antioxidants,as one of the most important antioxidants,have not received sufficient attention in the field of jet fuel autoxidation yet.Herein,the inhibition efficiency and mechanism of decane and exo-tetrahydrodicyclopentadiene(THDCPD)oxidation by di-4-tert-butylphenylamine(diarylamine)was experimentally and theoretically investigated.The results show that diarylamine can significantly inhibit decane oxidation but is less efficient for THDCPD oxidation,which is attributed to the higher energy barrier of retro-carbonyl-ene reaction(rate-determining step)in THDCPD than that in decane during diarylamine regeneration.However,the addition of diarylamine will cause undesirable color change after accelerated oxidation and produce slightly more deposits during high-temperature thermal oxidative stress for both decane and THDCPD.The results provide significant implications for the future design of effective antioxidant additives for high-performance jet fuel.展开更多
Metal oxyhydroxides(MOOH)generated from irreversible reconstructions of transition metal compounds are intrinsic active species for oxygen evolution reaction,whose activities are still constrained by sluggish deproton...Metal oxyhydroxides(MOOH)generated from irreversible reconstructions of transition metal compounds are intrinsic active species for oxygen evolution reaction,whose activities are still constrained by sluggish deprotonation kinetics and inherent adsorption energy scaling relations.Herein,we construct a tunable proton acceptor(TPA)on oxyhydroxides by in-situ reconstruction of metal oxoacids such as NiC2O4to accelerate deprotonation and break adsorption energy scaling relations during OER.The modified C_(2)O_(4)^(2-)as a TPA can easily extract H of*OH(forming*HC2O4intermediate)and then promote deprotonation by the transmitted hydrogen bond with*OOH along conjugated(H...)O=C-O(-H)chain.As a result,Ni OOH-C2O4shows non-concerted proton-electron transfer and improved deprotonation rate,and delivers a good OER activity(270 mV@10 mA cm-2).The conjugate acidity coefficient(pKa)of the modified oxoacid group can be a descriptor for TPA selection.This TPA strategy can be universally applied to Co-,Fe-,and Ni-based oxyhydroxides to facilitate OER efficiency.展开更多
The Haber-Bosch process for industrial NH_(3) production is energy-intensive with heavy CO_(2) emissions.Electrochemical N_(2) reduction reaction(NRR)is an attractive carbon-neutral alternative for NH_(3) synthesis,wh...The Haber-Bosch process for industrial NH_(3) production is energy-intensive with heavy CO_(2) emissions.Electrochemical N_(2) reduction reaction(NRR)is an attractive carbon-neutral alternative for NH_(3) synthesis,while the challenge associated with N_(2) activation highlights the demand for efficient electrocatalysts.Herein,we demonstrate that PdCu nanoparticles with different Pd/Cu ratios anchored on boron nanosheet(PdCu/B)behave as efficient NRR electrocatalysts toward NH_(3) synthesis.Theoretical and experimental results confirm that the highly efficient NH_(3) synthesis can be achieved by regulating the charge transfer between interfaces and forming a symmetry-breaking site,which not only alleviates the hydrogen evolution but also changes the adsorption configuration of N_(2) and thus optimizes the reaction pathway of NRR over the separated Pd sites.Compared with monometallic Pd/B and Cu/B,the PdCu/B with the optimized Pd/Cu ratio of 1 exhibits superior activity and selectivity for NH_(3) synthesis.This study provides new insight into developing efficient catalysts for small energy molecule catalytic conversion via regulating the charge transfer between interfaces and constructing symmetry-breaking sites.展开更多
Water electrolysis,a process for producing green hydrogen from renewable energy,plays a crucial role in the transition toward a sustainable energy landscape and the realization of the hydrogen economy.Oxygen evolution...Water electrolysis,a process for producing green hydrogen from renewable energy,plays a crucial role in the transition toward a sustainable energy landscape and the realization of the hydrogen economy.Oxygen evolution reaction(OER)is a critical step in water electrolysis and is often limited by its slow kinetics.Two main mechanisms,namely the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM),are commonly considered in the context of OER.However,designing efficient catalysts based on either the AEM or the LOM remains a topic of debate,and there is no consensus on whether activity and stability are directly related to a certain mechanism.Considering the above,we discuss the characteristics,advantages,and disadvantages of AEM and LOM.Additionally,we provide insights on leveraging the LOM to develop highly active and stable OER catalysts in future.For instance,it is essential to accurately differentiate between reversible and irreversible lattice oxygen redox reactions to elucidate the LOM.Furthermore,we discuss strategies for effectively activating lattice oxygen to achieve controllable steady-state exchange between lattice oxygen and an electrolyte(OH^(-)or H_(2)O).Additionally,we discuss the use of in situ characterization techniques and theoretical calculations as promising avenues for further elucidating the LOM.展开更多
The development of advanced air transportation has raised new demands for high-performance liquid hydrocarbon fuels.However,the measurement of fuel properties is time-consuming,cost-intensive,and limited to the operat...The development of advanced air transportation has raised new demands for high-performance liquid hydrocarbon fuels.However,the measurement of fuel properties is time-consuming,cost-intensive,and limited to the operating conditions.The physicochemical properties of aerospace fuels are directly infl uenced by chemical composition.Thus,a thorough investigation should be conducted on the inherent relationship between fuel properties and composition for the design and synthesis of high-grade fuels and the prediction of fuel properties in the future.This work summarized the eff ects of fuel composition and hydrocarbon molecular structure on the fuel physicochemical properties,including density,net heat of combustion(NHOC),low-temperature fl uidity(viscosity and freezing point),fl ash point,and thermal-oxidative stability.Several correlations and predictions of fuel properties from chemical composition were reviewed.Additionally,we correlated the fuel properties with hydrogen/carbon molar ratios(n H/C)and molecular weight(M).The results from the least-square method implicate that the coupling of H/C molar ratio and M is suitable for the estimation of density,NHOC,viscosity and eff ectiveness for the design,manufacture,and evaluation of aviation hydrocarbon fuels.展开更多
Noble-metal-free hydrogen/oxygen evolution reaction(HER/OER) electrocatalysts, especially bifunctional electrocatalysts, are essential for overall water splitting, but their performance is impeded by many factors like...Noble-metal-free hydrogen/oxygen evolution reaction(HER/OER) electrocatalysts, especially bifunctional electrocatalysts, are essential for overall water splitting, but their performance is impeded by many factors like poor electrical conductivity. Herein, we fabricated cobalt phosphide(Co P) nanoparticles embedded in P and N co-doped carbon(PNC) matrix(Co P@PNC) to fully realize the high activity of Co P by maximizing its conductivity. Simply a carbonization coupled phosphidation approach was utilized where Co ions and organic ligands of Co-MOF were transferred into Co P and P and N co-doped carbon. The synthesized material shows an ideal electrical conductivity, excellent HER(overpotential of-84 m V and-120 m V @10 m A cmin acidic and alkaline medias, respectively) and OER(overpotential of 330 m V@10 m A cmin alkaline media) performances. Further, Co P@PNC acts as a superior catalyst for both anode and cathode to catalyze overall water splitting and only requires an voltage of 1.52 V to deliver a current density of 10 m A cm, superior to the noble-metal catalysts system(Pt/C//IrO) and the reported noble-metal-free bifunctional electrocatalysts.展开更多
Gelled fuels are the very promising propellants for new-generation rocket and ramjet propulsion.Here we report a new type of low-molecular mass organic gellant(Z),and prepared four kinds of stable gelled fuels based o...Gelled fuels are the very promising propellants for new-generation rocket and ramjet propulsion.Here we report a new type of low-molecular mass organic gellant(Z),and prepared four kinds of stable gelled fuels based on HD-01,HD-03,RP-3 and QC liquid fuels,with the critical gellant concentration less than 1%(mass).The characterizations show that the gellant can form 3D network structure,via hydrogen bonding,π-πstacking and van der Waals forces,to fix fuel molecules during the formation of gelled fuels.So,the gelled fuels show high stability,with the remaining gel mass of 0.25%(mass)Z/HD-01 more than 90%even at high centrifugal speed of 7500 r·min^(-1),but the rheological property test shows that all gelled fuels have obvious shear thinning property,which benefits its storage in gelled state while supply in liquid state.The gelation of liquid fuels by gellant Z can increase the volumetric net heat of combustion(for HD-01,it increases from 39.58 MJ·L^(-1) to 40.76 MJ·L^(-1) with 1%(mass)Z),and liquefied gelled fuels show the comparable ignition delay time with the pristine liquid fuels.So,the gelled fuels made by gellant Z have better stability,shear thinning and combustion performances,which have great potential for the practical application.展开更多
基金supported by the Key Research and Design Program of Qinhuangdao(202101A005)the Science and Technology Project of Hebei Education Department(QN2023094)+2 种基金the Cultivation Project for Basic Research and Innovation of Yanshan University(2021LGQN028)the Project for Research and Development of Metal Catalysts for Photo-thermal Decomposition of Waste Plastics to Prepare Value-added Chemicals(x2023322)the Subsidy for Hebei Key Laboratory of Applied Chemistry after Operation Performance(22567616H).
文摘Steam reforming of long-chain hydrocarbon fuels for hydrogen production has received great attention for thermal management of the hypersonic vehicle and fuel-cell application.In this work,Pt catalysts supported on CeO_(2)and Tb-doped CeO_(2)were prepared by a precipitation method.The physical structure and chemical properties of the as-prepared catalysts were characterized by powder X-ray diffraction,scanning electron microscopy,transmission electron microscopy,Raman spectroscopy,H_(2)temperature programmed reduction,and X-ray photoelectron spectroscopy.The results show that Tb-doped CeO_(2)supported Pt possesses abundant surface oxygen vacancies,good inhibition of ceria sintering,and strong metal-support interaction compared with CeO_(2)supported Pt.The catalytic performance of hydrogen production via steam reforming of long-chain hydrocarbon fuels(n-dodecane)was tested.Compared with 2Pt/CeO_(2),2Pt/Ce_(0.9)Tb_(0.1)O_(2),and 2Pt/Ce_(0.5)Tb_(0.5)O_(2),the 2Pt/Ce_(0.7)Tb_(0.3)O_(2)has higher activity and stability for hydrogen production,on which the conversion of n-dodecane was maintained at about 53.2%after 600 min reaction under 700℃at liquid space velocity of 9 ml·g^(-1)·h^(-1).2Pt/CeO_(2)rapidly deactivated,the conversion of n-dodecane was reduced to only 41.6%after 600 min.
基金support from National Key Research and Development Program of China(2021YFC2103701)the National Postdoctoral Program of China(GZB20230630)the National Natural Science Foundation of China(22208295).
文摘Understanding the relationship between the chemical composition and pyrolysis performance of endothermic hydrocarbon fuel(EHF) is of great significance for the design and optimization of advanced EHFs. In this work, the effect of deep hydrogenation on the pyrolysis of commercial RP-3 is investigated.Fuels with different hydrogenation degrees were obtained by the partially and completely catalytic hydrogenation and their pyrolysis performances were investigated using an apparatus equipped with an electrically heated tubular reactor. The results show that with the increase of hydrogenation degree, fuel conversion almost remains constant during the pyrolysis process(500-650°C, 4 MPa);however, the heat sink increases slightly, and the anti-coking performance significantly improves, which are highly related to their H/C ratios. Detailed characterisations reveal that the difference of the pyrolysis performance can be ascribed to the content of aromatics and cycloalkanes: the former are prone to initiate secondary reactions to form coking precursors, while the latter could act as the hydrogen donor and release hydrogen, which will terminate the radical propagation reactions and suppress the coke deposition. This work should provide the guidance for upgrading EHFs by modulating the composition of EHFs.
基金support from National Key Research and Development Program of China(2021YFC2103704)the National Natural Science Foundation of China(22222808,21978200)the Haihe Laboratory of Sustainable Chemical Transformations.
文摘High-energy-density fuels are important for volume-limited aerospace vehicles,but the increase in fuel energy density always leads to poor cryogenic performance.Herein,we investigated the transposed Paternò-Büchi reaction of biomass cyclic ketone and cyclic alkene to synthesize a new kind of alkyl-substituted polycyclic hydrocarbon fuel with high energy density and good cryogenic performance.The triplet-energy-quenching results and phosphorescent emission spectra reveal the sensitization mechanism of the reaction,including photosensitizer excitation,triplettriplet energy transfer,cyclization,and relaxation,and the possible reaction path was revealed by the density functional theory(DFT)calculations.The reaction conditions of photosensitizer type and addition,molar ratio of substrates,reaction temperature,and incident light intensity were optimized,with the target product yield achieving 65.5%.Moreover,the reaction dynamics of the reaction rate versus the light intensity are established.After the hydrogenation-deoxygenation reaction,three fuels with a high density of 0.864-0.938 g·ml^(-1) and a low freezing point of<-55℃ are obtained.This work provides a benign and effective approach to synthesize high-performance fuels.
基金support from the National Natural Science Foundation of China (22222808, 21978200)the Haihe Laboratory of Sustainable Chemical Transformations for financial support
文摘Energetic nanofluid fuel has caught the attention of the field of aerospace liquid propellant for its high energy density(HED), but it suffers from the inevitable solid-liquid phase separation problem. To resolve this problem, herein we synthesized the high-Al-/B-containing(up to 30%(mass)) HED gelled fuels, with low-molecular-mass organic gellant Z, which show high net heat of combustion(NHOC), density, storage stability, and thixotropic properties. The characterizations indicate that the application of energetic particles to the gelled fuels obviously destroys their fibrous network structures but can provide the new particle-gellant gelation microstructures, resulting in the comparable stability between 1.0%(mass) Z/JP-10 + 30%(mass) Al or B and pure JP-10 gelled fuel. Moreover, the gelled fuels with high-content Al or B exhibit high shear-thinning property, recovery capability, and mechanical strength, which are favorable for their storage and utilization. Importantly, the prepared 1.0%(mass) Z/JP-10 + 30%(mass) B(or 1.0%(mass) Z/JP-10 + 30%(mass) Al) shows the density and NHOC 1.27 times(1.30) and 1.43 times(1.21)higher than pure JP-10, respectively. This work provides a facile and valid approach to the manufacturing of HED gelled fuels with high content of energetic particles for gel propellants.
基金the support from the National Key R&D Program of China(No.2021YFC2103701)the National Natural Science Foundation of China(No.22178248)the Haihe Laboratory of Sustainable Chemical Transformations。
文摘Fuel design is a complex multi-objective optimization problem in which facile and robust methods are urgently demanded.Herein,a complete workflow for designing a fuel blending scheme is presented,which is theoretically supported,efficient,and reliable.Based on the data distribution of the composition and properties of the blending fuels,a model of polynomial regression with appropriate hypothesis space was established.The parameters of the model were further optimized by different intelligence algorithms to achieve high-precision regression.Then,the design of a blending fuel was described as a multi-objective optimization problem,which was solved using a Nelder–Mead algorithm based on the concept of Pareto domination.Finally,the design of a target fuel was fully validated by experiments.This study provides new avenues for designing various blending fuels to meet the needs of next-generation engines.
基金supported by the National Key Research and Development Program(2021YFC2104400)the Tianjin Science and Technology Plan Project(21JCQNJC00340)the Haihe Laboratory of Sustainable Chemical Transformations。
文摘Synthesizing high-density fuel from lignocellulose can not only achieve green and low-carbon development,but also expand the feedstock source of hydrocarbon fuel.Here,we reported a route of producing high-density fuel from lignin oil and hemicellulose derivative cyclopentanol through alkylation and hydrodeoxygenation,HY with SiO_(2)/Al_(2)O_(3) molar ratio of 5.3 was screened as the alkylation catalyst in the reaction of model phenolic compounds and mixtures,and the reaction conditions were optimized to achieve conversion of phenolic compounds higher than 87%and selectivity of bicyclic and tricyclic products higher than 99%.Then two phenolic pools simulating the composition of two typic lignin oils were studied to validate the alkylation and analyze the competition mechanism of phenolic compounds in mixture system.Finally,real lignin oil from depolymerized of beech powder was tested,and notably80%of phenolic monomers in the oil were converted into fuel precursor.After hydrodeoxygenation,the alkylated product was converted to fuel blend with a density of 0.91 g/mL at 20℃and a freezing point lower than-60℃,very promising as high density fuel.This work provides a facile and energyefficient way of synthesizing high-performance jet fuel directly from lignocellulosic derivatives,which decreases processing energy consumption and improve the utilization rate of feedstock.
基金supported by the National Key R&D Program of China (2020YFA0710000)the National Natural Science Foundation of China (22278307, 22008170, 21978200, 22161142002, and 22121004)+2 种基金the Applied Basic Research Program of Qinghai Province (2023-ZJ-701)the Haihe Laboratory of Sustainable Chemical Transformationsthe Tianjin Research Innovation Project for Postgraduate Students (2022BKYZ035)。
文摘Sluggish reaction kinetics of oxygen evolution reaction(OER), resulting from multistep proton-coupled electron transfer and spin constriction, limits overall efficiency for most reported catalysts. Herein, using modeled ZnFe_(2-x)Ni_xO_(4)(0 ≤ x ≤ 0.4) spinel oxides, we aim to develop better OER electrocatalyst through combining the construction of ferromagnetic(FM) ordering channels and generation of highly active reconstructed species. The number of symmetry-breaking Fe–O–Ni structure links to the formation of FM ordering electron transfer channels. Meanwhile, as the number of Ni^(3+)increases, more ligand holes are formed, beneficial for redirecting surface reconstruction. The electro-activated ZnFe_(1.6)Ni_(0.4)O_(4) shows the highest specific activity, which is 13 and 2.5 times higher than that of ZnFe_(2)O_(4) and unactivated ZnFe_(1.6)Ni_(0.4)O_(4), and even superior to the benchmark IrO_(2) under the overpotential of 350 mV. Applying external magnetic field can make electron spin more aligned, and the activity can be further improved to 39 times of ZnFe_(2)O_(4). We propose that intriguing FM exchange-field interaction at FM/paramagnetic interfaces can penetrate FM ordering channels into reconstructed oxyhydroxide layers, thereby activating oxyhydroxide layers as spin-filter to accelerate spin-selective electron transfer. This work provides a new guideline to develop highly efficient spintronic catalysts for water oxidation and other spin-forbidden reactions.
基金the Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘Water can be used as oxidant in conjunction with metal particles to form metal-water propellant to increase the energy of propellant.For this application,water needs to be stored in form of solid and capable of becoming liquid when use.Stable and thixotropic hydrogel has good potential as water-retaining material and oxidant of metal-based propellant.In this study,we prepared organic/inorganic composite hydrogels by combining inorganic gellants hectorite and fumed silica with organic gellant agarose,respectively.The total content of the gellants can be reduced to less than 2%by adding agarose.The influence of agarose on water content,phase transition temperature,centrifugal stability and other basic physical properties of composite hydrogels were discussed.The results show that the composite hydrogels have better thixotropy and stability than pure inorganic hydrogels,and the gel-sol transformation can be realized by applying shear force or heating to the phase transition temperature.The composite hydrogels have good shear thinning ability and improved mechanical stability.Fumed silica/agarose hydrogels have better physical stability,while the thixotropy and shear thinning ability of hectorite/agarose hydrogels are better.
基金the financial support from the Postdoctoral Science Foundation of China(2021M702810)the Haihe Laboratory of Sustainable Chemical Transformations(CYZC202103)the National Natural Science Foundation of China(21978200 and 22222808)。
文摘Antioxidants addition is believed as a facile and effective way to improve jet fuel thermal oxidation stability.However,amine antioxidants,as one of the most important antioxidants,have not received sufficient attention in the field of jet fuel autoxidation yet.Herein,the inhibition efficiency and mechanism of decane and exo-tetrahydrodicyclopentadiene(THDCPD)oxidation by di-4-tert-butylphenylamine(diarylamine)was experimentally and theoretically investigated.The results show that diarylamine can significantly inhibit decane oxidation but is less efficient for THDCPD oxidation,which is attributed to the higher energy barrier of retro-carbonyl-ene reaction(rate-determining step)in THDCPD than that in decane during diarylamine regeneration.However,the addition of diarylamine will cause undesirable color change after accelerated oxidation and produce slightly more deposits during high-temperature thermal oxidative stress for both decane and THDCPD.The results provide significant implications for the future design of effective antioxidant additives for high-performance jet fuel.
基金the support from the National Key R&D Program of China(2020YFA0710000)the National Natural Science Foundation of China(22278307,22222808,21978200)the Haihe Laboratory of Sustainable Chemical Transformations。
文摘Metal oxyhydroxides(MOOH)generated from irreversible reconstructions of transition metal compounds are intrinsic active species for oxygen evolution reaction,whose activities are still constrained by sluggish deprotonation kinetics and inherent adsorption energy scaling relations.Herein,we construct a tunable proton acceptor(TPA)on oxyhydroxides by in-situ reconstruction of metal oxoacids such as NiC2O4to accelerate deprotonation and break adsorption energy scaling relations during OER.The modified C_(2)O_(4)^(2-)as a TPA can easily extract H of*OH(forming*HC2O4intermediate)and then promote deprotonation by the transmitted hydrogen bond with*OOH along conjugated(H...)O=C-O(-H)chain.As a result,Ni OOH-C2O4shows non-concerted proton-electron transfer and improved deprotonation rate,and delivers a good OER activity(270 mV@10 mA cm-2).The conjugate acidity coefficient(pKa)of the modified oxoacid group can be a descriptor for TPA selection.This TPA strategy can be universally applied to Co-,Fe-,and Ni-based oxyhydroxides to facilitate OER efficiency.
基金National Key R&D Program of China,Grant/Award Number:2020YFA0710000National Natural Science Foundation of China,Grant/Award Numbers:22008170,21978200,22161142002,22121004。
文摘The Haber-Bosch process for industrial NH_(3) production is energy-intensive with heavy CO_(2) emissions.Electrochemical N_(2) reduction reaction(NRR)is an attractive carbon-neutral alternative for NH_(3) synthesis,while the challenge associated with N_(2) activation highlights the demand for efficient electrocatalysts.Herein,we demonstrate that PdCu nanoparticles with different Pd/Cu ratios anchored on boron nanosheet(PdCu/B)behave as efficient NRR electrocatalysts toward NH_(3) synthesis.Theoretical and experimental results confirm that the highly efficient NH_(3) synthesis can be achieved by regulating the charge transfer between interfaces and forming a symmetry-breaking site,which not only alleviates the hydrogen evolution but also changes the adsorption configuration of N_(2) and thus optimizes the reaction pathway of NRR over the separated Pd sites.Compared with monometallic Pd/B and Cu/B,the PdCu/B with the optimized Pd/Cu ratio of 1 exhibits superior activity and selectivity for NH_(3) synthesis.This study provides new insight into developing efficient catalysts for small energy molecule catalytic conversion via regulating the charge transfer between interfaces and constructing symmetry-breaking sites.
基金the support from the National Key R&D Program of China(2020YFA0710000)the National Natural Science Foundation of China(Nos.22008170,22278307,22222808,21978200)+1 种基金the Haihe Laboratory of Sustainable Chemical Transformationsthe Tianjin Research Innovation Project for Postgraduate Students(2022B KYZ035)。
文摘Water electrolysis,a process for producing green hydrogen from renewable energy,plays a crucial role in the transition toward a sustainable energy landscape and the realization of the hydrogen economy.Oxygen evolution reaction(OER)is a critical step in water electrolysis and is often limited by its slow kinetics.Two main mechanisms,namely the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM),are commonly considered in the context of OER.However,designing efficient catalysts based on either the AEM or the LOM remains a topic of debate,and there is no consensus on whether activity and stability are directly related to a certain mechanism.Considering the above,we discuss the characteristics,advantages,and disadvantages of AEM and LOM.Additionally,we provide insights on leveraging the LOM to develop highly active and stable OER catalysts in future.For instance,it is essential to accurately differentiate between reversible and irreversible lattice oxygen redox reactions to elucidate the LOM.Furthermore,we discuss strategies for effectively activating lattice oxygen to achieve controllable steady-state exchange between lattice oxygen and an electrolyte(OH^(-)or H_(2)O).Additionally,we discuss the use of in situ characterization techniques and theoretical calculations as promising avenues for further elucidating the LOM.
基金This work was supported by the Scientific Research Projects of the Ministry of Education of China(6141A02033522)the National Natural Science Foundation of China(No.21978200).
文摘The development of advanced air transportation has raised new demands for high-performance liquid hydrocarbon fuels.However,the measurement of fuel properties is time-consuming,cost-intensive,and limited to the operating conditions.The physicochemical properties of aerospace fuels are directly infl uenced by chemical composition.Thus,a thorough investigation should be conducted on the inherent relationship between fuel properties and composition for the design and synthesis of high-grade fuels and the prediction of fuel properties in the future.This work summarized the eff ects of fuel composition and hydrocarbon molecular structure on the fuel physicochemical properties,including density,net heat of combustion(NHOC),low-temperature fl uidity(viscosity and freezing point),fl ash point,and thermal-oxidative stability.Several correlations and predictions of fuel properties from chemical composition were reviewed.Additionally,we correlated the fuel properties with hydrogen/carbon molar ratios(n H/C)and molecular weight(M).The results from the least-square method implicate that the coupling of H/C molar ratio and M is suitable for the estimation of density,NHOC,viscosity and eff ectiveness for the design,manufacture,and evaluation of aviation hydrocarbon fuels.
基金support from the National Natural Science Foundation of China(51661145026,21676193,21506156)the Tianjin Municipal Natural Science Foundation(15JCZDJC37300)
文摘Noble-metal-free hydrogen/oxygen evolution reaction(HER/OER) electrocatalysts, especially bifunctional electrocatalysts, are essential for overall water splitting, but their performance is impeded by many factors like poor electrical conductivity. Herein, we fabricated cobalt phosphide(Co P) nanoparticles embedded in P and N co-doped carbon(PNC) matrix(Co P@PNC) to fully realize the high activity of Co P by maximizing its conductivity. Simply a carbonization coupled phosphidation approach was utilized where Co ions and organic ligands of Co-MOF were transferred into Co P and P and N co-doped carbon. The synthesized material shows an ideal electrical conductivity, excellent HER(overpotential of-84 m V and-120 m V @10 m A cmin acidic and alkaline medias, respectively) and OER(overpotential of 330 m V@10 m A cmin alkaline media) performances. Further, Co P@PNC acts as a superior catalyst for both anode and cathode to catalyze overall water splitting and only requires an voltage of 1.52 V to deliver a current density of 10 m A cm, superior to the noble-metal catalysts system(Pt/C//IrO) and the reported noble-metal-free bifunctional electrocatalysts.
基金the support from the National Natural Science Foundation of China(21978200)the Scientific Research Projects of the Ministry of Education of China(6141A02033522)。
文摘Gelled fuels are the very promising propellants for new-generation rocket and ramjet propulsion.Here we report a new type of low-molecular mass organic gellant(Z),and prepared four kinds of stable gelled fuels based on HD-01,HD-03,RP-3 and QC liquid fuels,with the critical gellant concentration less than 1%(mass).The characterizations show that the gellant can form 3D network structure,via hydrogen bonding,π-πstacking and van der Waals forces,to fix fuel molecules during the formation of gelled fuels.So,the gelled fuels show high stability,with the remaining gel mass of 0.25%(mass)Z/HD-01 more than 90%even at high centrifugal speed of 7500 r·min^(-1),but the rheological property test shows that all gelled fuels have obvious shear thinning property,which benefits its storage in gelled state while supply in liquid state.The gelation of liquid fuels by gellant Z can increase the volumetric net heat of combustion(for HD-01,it increases from 39.58 MJ·L^(-1) to 40.76 MJ·L^(-1) with 1%(mass)Z),and liquefied gelled fuels show the comparable ignition delay time with the pristine liquid fuels.So,the gelled fuels made by gellant Z have better stability,shear thinning and combustion performances,which have great potential for the practical application.
