Boosting CO_(2) hydrogenation to high-value olefins with highly stable performance over Ba and Na co-modified Fe catalyst

CO_(2)hydrogenation has been considered to be a highly promising route for the production of high-value olefins(HVOs)while also mitigating CO_(2)emissions.However,it is challenging to achieve high selectivity and maintain stable performance for HVOs(ethylene,propylene,and linear a-olefins)over a prolonged reaction time due to the difficulty in precise control of carbon coupling and rapid catalyst deactivation.Herein,we present a selective Ba and Na co-modified Fe catalyst enriched with Fe_(5)C_(2)and Fe_(3)C active sites that can boost HVO synthesis with up to 66.1%selectivity at an average CO_(2)conversion of 38%for over 500 h.Compared to traditional NaFe catalyst,the combined effect of Ba and Na additives in the NaBaFe-0.5 catalyst suppressed excess oxidation of FeCxsites by H_(2)O.The absence of Fe3O4phase in the spent NaBaFe-0.5 catalyst reflects the stabilization effect of the co-modifiers on the FeCxsites.This study provides a strategy to design Fe-based catalysts that can be scaled up for the stable synthesis of HVOs from CO_(2)hydrogenation.

Nutrition impacts of non-solid cooking fuel adoption on under-five children in developing countries

This paper examines the nutrition impacts of using non-solid cooking fuel on under-five children in developing countries.We draw on data from more than 1.12 million children in 62 developing countries from the Demographic and Health Surveys(DHS).Results from both fixed effects(FE)and instrumental variable(IV)estimates show that using non-solid cooking fuel significantly improves the nutrition outcomes of under-five children.Compared with their peers from households mainly using solid fuel,children from households mainly using non-solid fuel exhibit a lower probability of experiencing stunting(by 5.9 percentage points)and being underweight(by 1.2 percentage points).Our further investigation provides evidence for several underlying mechanisms,such as improved indoor air quality,induced reduction in children’s respiratory symptoms,benefits on maternal health,and reduction in maternal time spent on fuel collection or cooking.Heterogenous analyses suggest that the nutrition benefits of using non-solid cooking fuel are more prominent among boys,children above three years old,and those from households of lower socioeconomic status,rural areas,and Southeast Asia.

Model reduction of fractional impedance spectra for time–frequency analysis of batteries, fuel cells, and supercapacitors

Joint time–frequency analysis is an emerging method for interpreting the underlying physics in fuel cells,batteries,and supercapacitors.To increase the reliability of time–frequency analysis,a theoretical correlation between frequency-domain stationary analysis and time-domain transient analysis is urgently required.The present work formularizes a thorough model reduction of fractional impedance spectra for electrochemical energy devices involving not only the model reduction from fractional-order models to integer-order models and from high-to low-order RC circuits but also insight into the evolution of the characteristic time constants during the whole reduction process.The following work has been carried out:(i)the model-reduction theory is addressed for typical Warburg elements and RC circuits based on the continued fraction expansion theory and the response error minimization technique,respectively;(ii)the order effect on the model reduction of typical Warburg elements is quantitatively evaluated by time–frequency analysis;(iii)the results of time–frequency analysis are confirmed to be useful to determine the reduction order in terms of the kinetic information needed to be captured;and(iv)the results of time–frequency analysis are validated for the model reduction of fractional impedance spectra for lithium-ion batteries,supercapacitors,and solid oxide fuel cells.In turn,the numerical validation has demonstrated the powerful function of the joint time–frequency analysis.The thorough model reduction of fractional impedance spectra addressed in the present work not only clarifies the relationship between time-domain transient analysis and frequency-domain stationary analysis but also enhances the reliability of the joint time–frequency analysis for electrochemical energy devices.

Study on concentration distribution and detonation characteristics for non-axisymmetric fuel dispersal

The study of non-axisymmetric fuel dispersal and detonation can provide reference for the prevention of industrial cloud explosion accidents and the design of fuel air explosive(FAE).The concentration and detonation fields of 85 kg cylindrical and fan-shaped fuel are investigated by experiments and numerical simulations.A dynamic model of the whole process for fuel dispersal and detonation is built.The concentration distribution of fuel is used as the initial condition to calculate the detonation stage,thus solving the initial value problem of detonation field.The phase and component changes of fuel cloud at different locations are compared.The fuel cloud is divided into directions of 0°,90°,135°and 180°.The results show that the maximum cloud radius is 20.94 m in 135°and the minimum is 12.04 m in 0°.The diameter of the detonation fireball is 53.6 m,and the peak temperature is 3455 K.The highest peak overpressure is 3.44 MPa in 0°and the lowest is 2.97 MPa in 135°.The proportion of liquid phase in 0°is22.90%,and the fuel loss is 11.8% and 9% higher than that in 135°and cylindrical charge,respectively.The stable propagation distance of blast wave in 135°is 42.50% longer than 0°and 28.37% longer than cylindrical charge.

Preparation and properties of high-energy-density aluminum/boroncontaining gelled fuels

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.

A thermodynamic perspective on electrode poisoning in solid oxide fuel cells

A critical challenge to the commercialization of clean and high-efficiency solid oxide fuel cell(SOFC)technology is the insuf-ficient stack lifespan caused by a variety of degradation mechanisms,which are associated with cell components and chemical feedstocks.Cell components related degradation refers to thermal/chemical/electrochemical deterioration of cell materials under operating conditions,whereas the latter regards impurities in feedstocks of oxidant(air)and reductant(fuel).This article provides a thermodynamic perspective on the understanding of the impurities-induced degradation mechanisms in SOFCs.The discussion focuses on using thermodynamic ana-lysis to elucidate poisoning mechanisms in cathodes by impurity species such as Cr,CO_(2),H_(2)O,and SO_(2) and in the anode by species such as S(or H_(2)S),SiO_(2),and P_(2)(or PH_(3)).The author hopes the presented fundamental insights can provide a theoretical foundation for search-ing for better technical solutions to address the critical degradation challenges.

Correction to:Assembly-level analysis on temperature coefficient of reactivity in a graphite-moderated fuel salt reactor fueled with low-enriched uranium

Following publication of the original article,the authors observed that both Fig.5 and Fig.4 depict the same image.Figure 5 was inaccurately referenced and displayed.The correct Fig.5 is copied below:The original article has been updated.

Catalyst design and structure control for photocatalytic refineries of cellulosic biomass to fuels and chemicals

Lignocellulosic biomass is the largest renewable hydrocarbon resource on earth.Converting cellulose,one of the major components of lignocellulose,powered by solar energy is a promising way of providing lowcarbon-footprint energy chemicals such as H_(2),HCOOH,CO,and transportation fuels.State-of-the-art biorefineries target the full use of biomass feedstocks as they have a maximum collection radius of 75-100 km,requesting efficient and selective photocatalysts that significantly influence the outcome of photocatalytic biorefineries.Well-performed photocatalysts can harvest a broad solar spectrum and are active in breaking the chemical bonds of cellulose,decreasing the capital investments of biorefineries.Besides,photocatalysts should control the selectivity of cellulose conversion,originating target products to level down separation costs.Charge separation in photocatalysts and interfacial charge transfer between photocatalysts and cellulose affect the activity and selectivity of cellulose refineries to H2 and carbonaceous chemicals.To account for the challenges above,this review summarizes photocatalysts for the refineries of cellulose and downstream platform molecules based on the types of products,with the structure features of different types of photocatalysts discussed in relation to the targets of either improving the activity or product selectivity.In addition,this review also sheds light on the methods for designing and regulating photocatalyst structures to facilitate photocatalytic refineries of cellulose and platform molecules,meanwhile summarizing proposed future research challenges and opportunities for designing efficient photocatalysts.

Relationship between hydrogenation degree and pyrolysis performance of jet fuel

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.

Tandem hydroalkylation and deoxygenation of lignin-derived phenolics to synthesize high-density fuels

Lignin is the most abundant naturally phenolic biomass,and the synthesis of high-performance renewable fuel from lignin has attracted significant attention.We propose the efficient synthesis of high-density fuels using simulated lignin cracked oil in tandem with hydroalkylation and deoxygenation reactions.First,we investigated the reaction pathway for the hydroalkylation of phenol,which competes with the hydrodeoxygenation form cyclohexane.And then,we investigated the effects of metal catalyst types,the loading amount of metallic,acid dosage,and reactant ratio on the reaction results.The phenol hydroalkylation and hydrodeoxygenation were balanced when 180℃ and 5 MPa H_(2)with the alkanes yield of 95%.By extending the substrate to other lignin-derived phenolics and simulated lignin cracked oil,we obtained the polycyclic alkane fuel with high density of 0.918 g·ml^(-1)and calorific value of41.2 MJ·L^(-1).Besides,the fuel has good low-temperature properties(viscosity of 9.3 mm^(2)·s^(-1)at 20℃ and freezing point below-55℃),which is expected to be used as jet fuel.This work provides a promising way for the easy and green production of high-density fuel directly from real lignin oil.

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.

Recent progress on mechanisms,principles,and strategies for high-activity and high-stability non-PGM fuel cell catalyst design

The commercialization of a polymer membrane H2-O2 fuel cell and its widespread use call for the development of cost-effective oxygen reduction reaction(ORR)nonplatinum group metal(NPGM)catalysts.Nevertheless,to meet the requests for the real-world fuel cell application and replacing platinum catalysts,it still needs to address some challenges for NPGM catalysts regarding the sluggish ORR kinetics in the cathode and their poor durability in acidic environment.In response to these issues,numerous efforts have been made to study NPGM catalysts both theoretically and experimentally,developed these into the atomically dispersed coordinated metal-nitrogen-carbon(M-N-C)form over the past decades.In this review,we present a comprehensive summary of recent advancements on NPGM catalysts with high activity and durability.Catalyst design strategies in terms of optimizing active-site density and enhancing catalyst stability against demetalization and carbon corrosion are highlighted.It is also emphasized the importance of understanding the mechanisms and principles behind those strategies through a combination of theoretical modeling and experimental work.Especially,further understanding the mechanisms related to the active-site structure and the formation process of the single-atom active site under pyrolysis conditions is critical for active-site engineering.Optimizing the active-site distance is the basic principle for improving catalyst activity through increasing the catalyst active-site density.Theoretical studies for the catalyst deactivation mechanism and modeling stable active-site structures provide both mechanisms and principles to improve the NPGM catalyst durability.Finally,currently remained challenges and perspectives in the future on designing high-performance atomically dispersed NPGM catalysts toward fuel cell application are discussed.

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.

Recent progresses in the development of tubular segmented-in-series solid oxide fuel cells:Experimental and numerical study

Solid oxide fuel cells(SOFCs)have attracted a great deal of interest because they have the highest efficiency without using any noble metal as catalysts among all the fuel cell technologies.However,traditional SOFCs suffer from having a higher volume,current leakage,complex connections,and difficulty in gas sealing.To solve these problems,Rolls-Royce has fabricated a simple design by stacking cells in series on an insulating porous support,resulting in the tubular segmented-in-series solid oxide fuel cells(SIS-SOFCs),which achieved higher output voltage.This work systematically reviews recent advances in the structures,preparation methods,perform-ances,and stability of tubular SIS-SOFCs in experimental and numerical studies.Finally,the challenges and future development of tubular SIS-SOFCs are also discussed.The findings of this work can help guide the direction and inspire innovation of future development in this field.

Effect of bipolar-plates design on corrosion,mass and heat transfer in proton-exchange membrane fuel cells and water electrolyzers:A review

Attaining a decarbonized and sustainable energy system,which is the core solution to global energy issues,is accessible through the development of hydrogen energy.Proton-exchange membrane water electrolyzers(PEMWEs)are promising devices for hydrogen production,given their high efficiency,rapid responsiveness,and compactness.Bipolar plates account for a relatively high percentage of the total cost and weight compared with other components of PEMWEs.Thus,optimization of their design may accelerate the promotion of PEMWEs.This paper reviews the advances in materials and flow-field design for bipolar plates.First,the working conditions of proton-exchange membrane fuel cells(PEMFCs)and PEMWEs are compared,including reaction direction,operating temperature,pressure,input/output,and potential.Then,the current research status of bipolar-plate substrates and surface coatings is summarized,and some typical channel-rib flow fields and porous flow fields are presented.Furthermore,the effects of materials on mass and heat transfer and the possibility of reducing corrosion by improving the flow field structure are explored.Finally,this review discusses the potential directions of the development of bipolar-plate design,including material fabrication,flow-field geometry optimization using threedimensional printing,and surface-coating composition optimization based on computational materials science.

Effect of carbon material and surfactant on ink property and resulting surface cracks of fuel-cell microporous layers

Ensuring the consistency of electrode structure in proton-exchange-membrane fuel cells is highly desired yet challenging because of wide-existing and unguided cracks in the microporous layer(MPL). The first thing is to evaluate the homogeneity of MPL with cracks quantitatively. This paper proposes the homogeneity index of a full-scale MPL with an area of 50 cm~2, which is yet to be reported in the literature to our knowledge. Besides, the effects of the carbon material and surfactant on the ink and resulting MPL structure have been studied. The ink with a high network development degree produces an MPL with low crack density, but the ink with high PDI produces an MPL with low crack homogeneity. The polarity of the surfactant and the non-polarity of polytetrafluoroethylene(PTFE) are not mutually soluble,resulting in the heterogeneous PTFE distribution. The findings of this study provide guidelines for MPL fabrication.

Analysis of the Influence of Geometrical Parameters on the Performance of a Proton Exchange Membrane Fuel Cell

A suitable channel structure can lead to efficient gas distribution and significantly improve the power density of fuel cells.In this study,the influence of two channel design parameters is investigated,namely,the ratio of the channel width to the bipolar plate ridge width(i.e.,the channel ridge ratio)and the channel depth.The impact of these parameters is evaluated with respect to the flow pattern,the gas composition distribution,the temperature field and the fuel cell output capability.The results show that a decrease in the channel ridge ratio and an increase in the channel depth can effectively make the distributions of velocity,temperature and concentration more uniform in each channel and improve the output capability of the fuel cell.An increase in the channel ridge ratio and depth obviously reduces the flow resistance and improves the flow characteristics.

Effect of Nozzle Inclination Angle on Fuel-Air Mixing and Combustion in a Heavy Fuel Engine

Heavy-fuel engines are widely used in UAVs(Unmanned Autonomous Vehicles)because of their reliability and high-power density.In this study,a combustion model for an in-cylinder direct injection engine has been imple-mented using the AVL FIRE software.The effects of the angle of nozzle inclination on fuel evaporation,mixture distribution,and combustion in the engine cylinder have been systematically studied at 5500 r/min and consider-ing full load cruise conditions.According to the results,as the angle of nozzle inclination increases,the maximum combustion explosion pressure in the cylinderfirst increases and then it decreases.When the angle of nozzle incli-nation is less than 45°,the quality of the mixture in the cylinder and the combustion performance can be improved by increasing the angle.When the angle of nozzle inclination is greater than 45°,however,the mixture unevenness increases slightly with the angle,leading to a deterioration of the combustion performances.When the angle of nozzle inclination is between 35°and 55°,the overall combustion performance of the engine is rela-tively good.When the angle of nozzle inclination is 45°,the combustion chamber’s geometry and the cylinder’s airflow are well matched with the fuel spray,and the mixture quality is the best.Compared with 25°,the peak heat release rate increases by 20%,and the maximum combustion burst pressure increases by 5.5%.

Effects of baffle position in serpentine flow channel on the performance of proton exchange membrane fuel cells

This study used a three-dimensional numerical model of a proton exchange membrane fuel cell with five types of channels:a smooth channel(Case 1);eight rectangular baffles were arranged in the upstream(Case 2),midstream(Case 3),downstream(Case 4),and the entire cathode flow channel(Case 5)to study the effects of baffle position on mass transport,power density,net power,etc.Moreover,the effects of back pressure and humidity on the voltage were investigated.Results showed that compared to smooth channels,the oxygen and water transport facilitation at the diffusion layer-channel interface were added 11.53%-20.60%and 7.81%-9.80%at 1.68 A·cm^(-2)by adding baffles.The closer the baffles were to upstream,the higher the total oxygen flux,but the lower the flux uniformity the worse the water removal.The oxygen flux of upstream baffles was 8.14%higher than that of downstream baffles,but oxygen flux uniformity decreased by 18.96%at 1.68 A·cm^(-2).The order of water removal and voltage improvement was Case 4>Case 5>Case 3>Case 2>Case 1.Net power of Case 4 was 9.87%higher than that of the smooth channel.To the Case 4,when the cell worked under low back pressure or high humidity,the voltage increments were higher.The potential increment for the back pressure of 0 atm was 0.9%higher than that of 2 atm(1 atm=101.325 kPa).The potential increment for the humidity of 100%was 7.89%higher than that of 50%.

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.