Sustainable production of high-energy-density jet fuel via cycloaddition reactions

Developing an energy supply-chain based on renewable biomass holds great potential to build a low carbon society.High-energy-density(HED)jet fuel,featuring unique fused/strained cycloalkanes,is of great significance for volume-limited military aircrafts,as their high density and combustion heat can extend flight duration and increase the payload.Therefore,the exploration of biomass-based routes towards HED fuel has drawn much attention over the past decade.Cycloaddition reaction features rapid construction of various carbocycles in an atom-and step-economical fashion.This elegant strategy has been widely applied in the manufacture of sustainable HED fuel.Here we carefully summarize the progress achieved in this fascinating area and the review is categorized by the cycloaddition patterns including[4+2],[2+2],[4+4],and[2+1]cycloadditions.Besides,the energy densities of the as-prepared biofuels and petroleumbased fuels(conventional Jet-A and advanced JP-10)are also compared.This review will provide important insights into rational design of new HED fuel with different ring-types/sizes and inspire the chemists to turn those literature studies into practical applications in military field.

Transforming liquid flow fuel cells to controllable reactors for highlyefficient oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid at low temperature

Highly-efficient oxidation of 5-hydroxymethylfurtural(HMF) to 2,5-furandicarboxylic acid(FDCA) at low temperature with air as the oxidant is still challenging.Herein,inspired by the respirato ry electron transport chain(ETC) of living cells mediated by electron carriers,we constructed artificial ETCs and transformed liquid flow fuel cells(LFFCs) to flexible reactors for efficient oxidation of HMF to produce FDCA under mild conditions.This LFFC reactor employed an electrodeposition modified nickel foam as an anode to promote HMF oxidation and(VO_(2))_(2)SO_(4) as a cathode electron carrier to facilitate the electron transfer to air.The reaction rate could be easily controlled by selecting the anode catalyst,adjusting the external loading and changing the cathodic electron carrier or oxidants.A maximal power density of 44.9 mW cm^(-2) at room temperature was achieved,while for FDCA production,short-circuit condition was preferred to achieve quick transfer of electrons.For a single batch operation with 0.1 M initial HMF,FDCA yield reached 97.1%.By fed-batch operation,FDCA concentration reached 144.5 g L^(-1) with a total yield of 96%.Ni^(2+)/Ni^(3+) redox couple was the active species mediating the electron transfer,while both experimental and DFT calculation results indicated that HMFCA pathway was the preferred reaction mechanism.

Development of High-Energy-Density Liquid Aerospace Fuel:A Perspective

Aerospace aircraft has significantly improved the life quality of human beings and extended the capability of space explosion since its appearance in 1903,in which liquid propellants or fuels provide the key power source.For jet fuels,its property of energy density plays an important role in determining the flight range,load,and performance of the aircraft.Therefore,the design and fabrication of high-energy-density(HED)fuels attract more and more attention from researchers all over the world.Herein,we briefly introduce the development of liquid jet fuels and HED fuels and demonstrate the future development of HED fuels.To further improve the energy density of fuel,the approaches of design and construction of multi-cyclic and stained molecule structures are proposed.To break through the density limit of hydrocarbon fuels,the addition of energetic nanoparticles in HED fuels to produce nanofluid or gelled fuels may provide a facile and effective method to significantly increase the energy density.This work provides the perspective for the development of HED fuels for advanced aircrafts.

Photocatalytic Synthesis of High-Energy-Density Fuel:Catalysts,Mechanisms,and Challenges

High-energy-density liquid hydrocarbon fuels are generally synthesized using various chemical reactions to improve the performance(e.g.,range,load,speed)of aerospace vehicles.Compared with conventional fuels,such as aviation kerosene and rocket kerosene,these liquid hydrocarbon fuels possess the advantages of high-energy-density and high volumetric calorifi c value;therefore,the fuels have important application value.The photocatalytic process has shown great potential for the synthesis of a diverse range of fuels on account of its unique properties,which include good effi ciency,clean atomic economy,and low energy consumption.These characteristics have led to the emergence of the photocatalytic process as a promising complement and alternative to traditional thermocatalytic reactions for fuel synthesis.Extensive eff ort has been made toward the construction of catalysts for the multiple photocatalytic syntheses of high-energy-density fuels.In this review,we aim to summarize the research progress on the photocatalytic synthesis of high-energy-density fuel by using homogeneous and heterogeneous catalytic reactions.Specifi cally,the synthesis routes,catalysts,mechanistic features,and future challenges for the photocatalytic synthesis of high-energy-density fuel are described in detail.The highlights of this review not only promote the development of the photocatalytic synthesis of high-energy-density fuel but also expand the applications of photocatalysis to other fi elds.

Influence of liquid bridge force on physical stability during fuel storage and transportation

The physical stability of solid-liquid fuel is a factor that needs to be considered for fuel product practicability for storage and transportation. To determine the Influence of liquid bridge force on physical stability, two detection devices were designed. The laws obtained from microscopic experiments are used to verify the physical stability of fuel under different component ratios. The liquid bridge force is found to increase with the droplet volume. Multiliquid bridges above one critical saturation can generate significant resultant forces compared to single-liquid bridges of the same volume. There exist four states of solid-liquid mixed fuel with increasing liquid saturation rate. The liquid bridge force between the solid and liquid plays a dominant role in the physical stability of the first three states. There may be two stages involved in the stratification process for state 4 fuel, and the liquid viscosity is another factor that cannot be ignored. In the process of selecting a fuel ratio, a larger liquid bridge force between the components can be obtained by properly improving the wetting effect so that the fuel shows better physical stability.

Perspective on synthesis of high-energy-density fuels:From petroleum to coal-based pathway

High-energy–density(HED)fuel is specifically pivotal to improve the performance of volume-limited aircrafts.The widely used HED fuels composed of polycyclic hydrocarbons are mainly synthesized from petroleum feedstocks.In order to ensure abundant supply,alternative resources such as coal should be considered.Herein,we summarize the synthesis methods and properties of typical HED fuels by using petroleum-derived cyclopentadiene(CPD)as key feedstock through dimerization,cycloaddition,hydrogenation and isomerization/photoisomerization reactions,and then propose a blueprint for synthesizing HED fuels from coal.The method to produce CPD from coal is analyzed and feasibility is demonstrated according to theoretical calculations and reported results.This review provides a novel route for synthesis of HED fuels from coal.

Photoinduced transposed Paternò-Büchi reaction for effective synthesis of high-performance jet fuel

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.

Modified electronic structure and enhanced hydroxyl adsorption make quaternary Pt-based nanosheets efficient anode electrocatalysts for formic acid-/alcohol-air fuel cells

Surface/interface engineering of a multimetallic nanostructure with diverse electrocatalytic properties for direct liquid fuel cells is desirable yet challenging.Herein,using visible light,a class of quaternary Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)ultrathin nanosheets is fabricated and used as high-performance anode electrocatalysts for formic acid-/alcohol-air fuel cells.The modified electronic structure of Pt,enhanced hydroxyl adsorption,and abundant exterior defects afford Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C high intrinsic anodic electrocatalytic activity to boost the power densities of direct formic acid-/methanol-/ethanol-/ethylene glycol-/glycerol-air fuel cells,and the corresponding peak power density of Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C is respectively 129.7,142.3,105.4,124.3,and 128.0 mW cm^(-2),considerably outperforming Pt/C.Operando in situ Fourier transform infrared reflection spectroscopy reveals that formic acid oxidation on Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C occurs via a CO_(2)-free direct pathway.Density functional theory calculations show that the presence of Ag,Bi,and Te in Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)suppresses CO^(*)formation while optimizing dehydrogenation steps and synergistic effect and modified Pt effectively enhance H_(2)O dissociation to improve electrocatalytic performance.This synthesis strategy can be extended to 43 other types of ultrathin multimetallic nanosheets(from ternary to octonary nanosheets),and efficiently capture precious metals(i.e.,Pd,Pt,Rh,Ru,Au,and Ag)from different water sources.

Pyrolysis of rice husk and sawdust for liquid fuel

The paper is focused on studying how to convert rice husk and sawdust into liquid fuel. Rice husk, sawdust and their mixture were pyrolyzed at the temperature between 420℃ and 540℃, and the main product of liquid fuel was obtained. The experimental result showed that the yield of liquid fuel heavily depended on the kind of feedstock and pyrolysis temperature. In the experiments, the maximum liquid yields for rice husk, sawdust and their mixture were 56% at 465 ℃, 61% at 490℃ and 60% at 475℃ respectively. Analysis with GC-MS and other apparatus indicated that the liquid fuel is a complicated organic compound with low caloric value and can be directly used as fuel oil without any up-grading. As a crude oil, the liquid fuel can be refined to be vehicle oil.

Desulfurization of Diesel Fuel by Extraction with [BF4]^--based Ionic Liquids

The extractive removal of sulfur compounds （S-compounds） from Dongying and Liaohe diesel fuels with [BF4]^--based ionic liquids were systematically investigated. The results show that the absorption capacity of an ionic liquid for the S-compounds in diesel fuels relies on its structure and its size. In the case of the two examined diesel fuels, both elongating the cation tail length and increasing the mass ratio of ionic liquid/diesel fuel promote the desulfurization ability of the examined ionic liquids. The results also show that imidazolium-based ionic liquids display higher extraction efficiencies than pyridinium-based ionic liquids, presumably owing to the fact that the rings of the S-compounds are similar to the imidazolium head ring. With the 1 ： 1 mass ratio of ionic liquid/diesel fuel, the rates of the first desulfurization of Dongying and Liaohe diesel fuels using [C8mim][BF4] amount to 29.96% and 39.76%, suggesting that [C8mim][BF4] is a promising extractant for desulfurization of these diesel fuels.

Review on the Relationship Between Liquid Aerospace Fuel Composition and Their Physicochemical Properties

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.

Radiation dose distribution of liquid fueled thorium molten salt reactor

A liquid fueled thorium molten salt reactor(TMSR-LF),one of the Generation IV reactors,was designed by the Shanghai Institute of Applied Physics,Chinese Academy of Sciences.This study uses the‘rt code to calculate the neutron and gamma dose rate distributions around the reactor.Multiple types of tallies and variance reduction techniques were employed to reduce calculation time and obtain convergent calculation results.Based on the calculation and analysis results,the TMSR-LF1 radiation shield with a 60-cm serpentine concrete layer and a 120-cm ordinary concrete layer is able to meet radiation requirements.The gamma dose rate outside the reactor biological shield was 16.1 mSv h-1;this is higher than the neutron dose rate of 3.71×10^(–2)mSv h^(-1).The maximum thermal neutron flux density outside the reactor biological shield was 1.899103 cm^(-2)s^(-1),which was below the 19105 cm^(-2)s^(-1)limit.

Efficient and sustainable V-catalyzed oxidative desulfurization of fuels assisted by ionic liquids

Fuel desulfurization is an appealing topic for the chemical industry since severe environmental regulations regarding SO_2 emissions have been legislated in many countries. In order to reduce the amount of sulfur-containing compounds in fuels,responsible for high SO_x emission levels,a green chemistry approach is compulsory. In this paper,vanadium salen and salophen complexes were used in the oxidation of a model aromatic sulfide,such as dibenzothiophene( DBT),in the presence of H_2O_2 as green oxidant. The oxidative process was successfully coupled with the extraction of the oxidized compounds by ionic liquids. The system resulted highly selective for sulfide oxidation,showing poor reactivity toward the oxidation of alkenes and allowing a significant reduction of S content in a model benzine. To note,the use of microwave in place of standard heating allowed to obtain 98% of DBT oxidation and almost complete sulfur extraction in the model fuel in 1000 s. For these reasons,this system was considered an easy,rapid and clean process to achieve fuel desulfurization.

Dealuminated ZSM-5 Zeolite Catalyst for Ethylene Oligomerization to Liquid Fuels

Ethylene oligomerization using ZSM-5 zeolite was investigated to study the role of Bronsted acid sites in the formation of higher hydrocarbons. The oligomerization of olefins, dependent on the acidity of ZSM-5 zeolite, is an important step in the conversion of natural gas to liquid fuels. The framework Si/Al ratio reflects the number of potential acid sites and the acid strength of the ZSM-5 catalyst. ZSM-5 with the mole ratio SiO2/Al2O3 equal to 30 was dealuminated for different periods of time according to the acidic ion-exchange method to produce ZSM-5 with various Si/Al ratios. The FT-IR analysis revealed that the integrated framework aluminum band, non-framework aluminum band, and silanol groups areas of the ZSM-5 zeolites decreased after being dealuminated. The performance of the dealuminated zeolite was tested for ethylene oligomerization. The results demonstrated that the dealumination of ZSM-5 led to higher ethylene conversion, but the gasoline selectivity was reduced compared to the performance of a ZSM-5 zeolite. The characterization results revealed the amount of aluminum in the zeolitic framework, the crystallinity of the ZSM-5 zeolite, and the Si/Al ratio affected the formation of Bronsted acid sites. The number of the Bronsted acid sites on the catalyst active sites is important in the olefin conversion to liquid hydrocarbons.

Atomically dispersed catalysts for small molecule electrooxidation in direct liquid fuel cells

Direct liquid fuel cells(DLFCs) have received increasing attention because of their high energy densities,instant recharging abilities, simple cell structure, and facile storage and transport. The main challenge for the commercialization of DLFCs is the high loading requirement of platinum group metals(PGMs) as catalysts. Atomically dispersed catalysts(ADCs) have been brought into recent focus for DLFCs due to their well-defined active sites, high selectivity, maximal atom-utilization, and anti-poisoning property. In this review, we summarized the structure–property relationship for unveiling the underlying mechanisms of ADCs for DLFCs. More specifically, different types of fuels used in DLFCs such as methanol, formic acid,and ethanol were discussed. At last, we highlighted current challenges, research directions, and future outlooks towards the practical application of DLFCs.

Theoretical and experimental study on the inhibition of jet fuel oxidation by diarylamine

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.

A Direct Liquid Fuel Cell with High Power Density Using Reduced Phosphotungstic Acid as Redox Fuel

Direct liquid fuel cells(DLFCs)are proposed to address the problems of high cost and complex storage and transportation of hydrogen in traditional hydrogen-oxygen proton exchange membrane fuel cells.However,present fuels of organic small molecules used in DLFCs are restricted to problems of sluggish electrochemical kinetics and easily poisoning of precious metal catalysts.Herein,we demonstrate reduced phosphotungstic acid as a liquid fuel for DLFCs based on its advantages of high chemical and electrochemical stability,high electrochemical activity on common carbon material electrodes,and low permeability through proton exchange membranes.The application of phosphotungstic acid fuel effectively solves the problems of high cost of anode catalysts and serious fuel permeation loss in traditional DLFCs.A phosphotungstic acid fuel cell achieves a peak power density of466 mW cm^(-2)at a cell voltage of 0.42 V and good stability at current densities in the range from 20 to 200 mA cm^(-2).

Fabrication and performance of atmospheric plasma sprayed solid oxide fuel cells with liquid antimony anodes

A solid oxide fuel cell(SOFC)with a liquid antimony anode(LAA)is a potential energy conversion technology for the use of impurity-containing fuels.Atmospheric plasma spraying(APS)technology has become a promising LAASOFC preparation method because of its economy and convenience.In this paper,button SOFCs with different cathode materials and ratios of pore former were prepared by the APS method and were operated at 750C.The effect of the cathode structure on the electrochemical performance of the LAA-SOFCs was analyzed,and an optimized spraying method for LAA-SOFCs was developed.A tubular LAA-SOFC was prepared using the APS method based on the optimized spraying method,and a peak power of 2.5 W was reached.The tubular cell was also measured at a constant current of 2 A for 20 h and was fed with a sulfur-containing fuel to demonstrate its impurity resistance and electrode stability.

Development and validation of a new oxide fuel rod performance analysis code for the liquid metal fast reactor

The integrity and reliability of fuel rods under both normal and accidental operating conditions are of great importance for nuclear reactors.In this study,considering various irradiation behaviors,a fuel rod performance analysis code,named KMC-Fueltra,was developed to evaluate the thermal–mechanical performance of oxide fuel rods under both normal and transient conditions in the LMFR.The accuracy and reliability of the KMC-Fueltra were validated by analytical solutions,as well as the results obtained from codes and experiments.The results indicated that KMC-Fueltra can predict the performance of oxide fuel rods under both normal and transient conditions in the LMFR.

Stepwise Pyrolysis by LBCR Downstream to Enhance of Gasoline Fraction of Liquid Fuel from MMSW

Pyrolysis is one of the thermal cracking methods to convert hydrocarbon to liquid fuel.The quantity and quality of the process are dependent on several condition including temperature,reaction time,catalyst,and the type of reactor.Meanwhile,a gasoline fraction was maximum product to be considered in the pyrolisis process.Therefore,this study aims to increase the gasoline fraction in liquid fuel using stepwise pyrolysis with a long bed catalytic reactor downstream(LBCR).The LBCR downstream was equipped with the top and bottom outlet and the fed source was mixed municipal solid waste(MMSW).The activated natural dolomite at 500℃ was used to allow the repetition of the secondary cracking.Also,the reactor temperature was setup at around 200℃-300℃ and the pyrolizer was 400℃.To analyze the gasoline fraction and physical properties of liquid fuel,Gas Chromatography-Mass Spectroscopy(GC-MS)and ASTM standard were employed.The experimental results showed there was a significant increase in the gasoline fraction of liquid fuels compared to using direct catalytic cracking and absence of catalysts.By using a LBCR at 250℃,the liquid fuel obtained at top outlet(TO)and bottom outlet(BO)have 84.08 and 56.94 percent peak area of gasoline fraction(C5-C12),respectively.The average value(TO and BO)of the fraction at 250℃ by LBCR was 70.51 percent peak area and it was increased by about 93.6%and 51.14%compared to without catalyst and direct catalytic,respectively.Furthermore,pyrolytic liquid oils were found to have kinematic viscosity of 2.979 and 0.789 cSt,density of 0.781 and 0.782 g/cm^(3),and flash point<−5℃ for BO-250 and TO-250 liquid fuel,respectively.These results showed BO liquid fuel was comparable to diesel conventional fuel while TO liquid fuel was comparable to gasoline.Evidently,the presence of LBCR made a major contribution to generate multi secondary cracking and to produce more gasoline fraction from mixed MMSW feedstock,as well as to increase the physical properties of liquid fuel.