Sustainable aviation fuel(SAF)production from biomass and biowaste streams is an attractive option for decarbonizing the aviation sector,one of the most-difficult-to-electrify transportation sectors.Despite ongoing co...Sustainable aviation fuel(SAF)production from biomass and biowaste streams is an attractive option for decarbonizing the aviation sector,one of the most-difficult-to-electrify transportation sectors.Despite ongoing commercialization efforts using ASTM-certified pathways(e.g.,lipid conversion,Fischer-Tropsch synthesis),production capacities are still inadequate due to limited feedstock supply and high production costs.New conversion technologies that utilize lignocellulosic feedstocks are needed to meet these challenges and satisfy the rapidly growing market.Combining bio-and chemo-catalytic approaches can leverage advantages from both methods,i.e.,high product selectivity via biological conversion,and the capability to build C-C chains more efficiently via chemical catalysis.Herein,conversion routes,catalysis,and processes for such pathways are discussed,while key challenges and meaningful R&D opportunities are identified to guide future research activities in the space.Bio-and chemo-catalytic conversion primarily utilize the carbohydrate fraction of lignocellulose,leaving lignin as a waste product.This makes lignin conversion to SAF critical in order to utilize whole biomass,thereby lowering overall production costs while maximizing carbon efficiencies.Thus,lignin valorization strategies are also reviewed herein with vital research areas identified,such as facile lignin depolymerization approaches,highly integrated conversion systems,novel process configurations,and catalysts for the selective cleavage of aryl C-O bonds.The potential efficiency improvements available via integrated conversion steps,such as combined biological and chemo-catalytic routes,along with the use of different parallel pathways,are identified as key to producing all components of a cost-effective,100%SAF.展开更多
Catalytic/initiated cracking of endothermic hydrocarbon fuels is an eff ective technology for cooling a hypersonic aircraft with a high Mach number(over 5).Catalysts and initiators can promote fuel cracking at low tem...Catalytic/initiated cracking of endothermic hydrocarbon fuels is an eff ective technology for cooling a hypersonic aircraft with a high Mach number(over 5).Catalysts and initiators can promote fuel cracking at low temperatures,increase fuel conversion and the heat sink capacity,and suppress coke deposition,thereby reducing waste heat.Catalysts mainly include metal oxide catalysts,noble metal catalysts and metal nanoparticles,zeolite catalysts,nanozeolite catalysts,and coating catalysts.Moreover,initiators roughly include nitrogenous compounds,oxygenated compounds,and hyperbranched polymer initiators.In this review,we aim to summarize the catalysts and initiators for cracking endothermic hydrocarbon fuels and their mechanisms for promoting cracking.This review will facilitate the development of the synthesis and exploration of catalysts and initiators.展开更多
Shipping plays a vital role in the world economy.Around 90%of the world's trade is transported by ship in a cost-effective and reliable manner.Global shipping is responsible for 2-3%of the total global CO2 emissio...Shipping plays a vital role in the world economy.Around 90%of the world's trade is transported by ship in a cost-effective and reliable manner.Global shipping is responsible for 2-3%of the total global CO2 emissions.In addition,shipping accounts for up to 4-9%of all sulphur,and 10-15%of all nitrous oxide emissions.Without taking any measures,these emissions would more than double as seaborne trade is expected to further grow from 30 billion tone miles in 2006 to more than 100 billion in 2050.To counter these emissions the international community has developed frameworks for energy efficiency measures,as well as emission reduction targets for SOx and NOx in appointed ECAs(Emission Control Areas).Biofuels satisfy fully or partially the new emission regulations and sulfur limits without compromising the economy.The goal of this work is to study and evaluate the physicochemical properties of conventional marine distillate fuel and its blends with renewable-alternative fuels(UCOME(Used Cooking Oils Methyl Esters)and HVO(Hydrogenated Vegetable Oils)).展开更多
Sulphur and emissions related limits which are imposed on marine fuels drive the maritime industry to look on alternative fuels. The maximum sulphur content of the fuel has already decreased in the ECAs SOx （Sulphur ...Sulphur and emissions related limits which are imposed on marine fuels drive the maritime industry to look on alternative fuels. The maximum sulphur content of the fuel has already decreased in the ECAs SOx （Sulphur Emission Control Areas） from 1.5% to 1% from 1 July, 2010, and to 0.1% from 1 January, 2015. Globally, the highest permitted sulphur content of fuel will be reduced, as from 1 January, 2020 to 0.5%. Increasing demand of low sulphur fuel is anticipated, leading to a substantial mitigation of marine fuels from residual to distillate ones. Biodiesel or else FAME （Fatty Acid Methyl Esters） and mixtures of it with conventional petroleum fuels, constitute alternative energy source for the maritime industry. The International Standard EN （European Norme） ISO （International Organization for Standardization） 8217 specifies the requirements of petroleum fuels for use in marine diesel engines. According to the previous version of EN ISO 8217：2012, distillate fuels should comply with the ＂de minimis level＂ of approximately 0.1% v/v FAME. Nevertheless, with the latest revision of EN ISO 8217 standard in 2017, the incorporation of FAME up to 7% v/v is allowed in specific marine distillate grades as DF （Distillate FAME） grades. Marine distillates can also include hydrocarbons from synthetic or renewable sources, similar to the composition of petroleum distillate fuels.展开更多
This proposal aims to assess the market introduction of advanced technologies for the production of 2nd generation solid biofuels, specifically technologies for the production of briquettes and pellets from agro-indus...This proposal aims to assess the market introduction of advanced technologies for the production of 2nd generation solid biofuels, specifically technologies for the production of briquettes and pellets from agro-industrial wastes. The development of this project will evaluate the socio-environmental and techno-economical feasibility and use of 2nd generation solid biofuels in the CMR （Campinas Metropolitan Region）. The successful introduction of second generation briquettes and pellets to market depends, mainly, on two aspects： logistics in supply chains which generate waste, and the efficiency of production technologies. The study of logistics （supply chain） is based on survey data of the main productive supply chains, analysis, and modeling to optimize the facility location in the network for each case. The evaluation of the efficiency of production technology is provided by testing specially designed waste compacting devices, and comparing these results with the resulting power consumption during the production, in demonstration-scale, of a round of briquettes. The costs and consumption during the demonstration-scale production of briquettes are used for validation and correction of an optimization model. This project was approved in late 2012 with a period of two years for its implementation. Later in 2013, it was decided also to extend its implementation to the Metropolitan Region of Manaus, Amazon. Due to its recent beginning, the results shown here are only preliminary.展开更多
This study presents a comprehensive analysis of the current energy landscape and the imperative transition toward renewable energy.It begins with an overview of current energy sources and trends,highlighting the dispa...This study presents a comprehensive analysis of the current energy landscape and the imperative transition toward renewable energy.It begins with an overview of current energy sources and trends,highlighting the disparity between supply and increasing demand.Adverse impacts of reliance on fossil fuels such as environmental degradation,economic volatility,and health hazards underscore the urgent need for a transition.The study then explores the vast potential of renewable energy sources(RES)such as solar,wind,hydrogen,and hydro,emphasizing their feasibility in the Southern African context.The positive impacts of integrating renewables are examined,including reduced greenhouse gas emissions,enhanced energy security,and economic diversification.Through case studies of regional examples,the success and failures of transitioning efforts are analyzed,providing valuable insights into best practices and pitfalls.The study identifies significant challenges in transitioning,particularly in grid-tied and off-grid scenarios,and discusses infrastructural,financial,and regulatory obstacles.The recommendations section outlines strategic steps for achieving a feasible transition,proposing either a full transition or specific percentages of renewable energy integration to meet energy demands.In conclusion,the study emphasizes the critical importance of adopting these strategies for sustainable development and global climate goals,advocating for continuous innovation and localized solutions to maximize the benefits of renewable energy.Key findings are that the environmental and economic effects of fossil fuel usage strain economies by increasing fossil fuel subsidies.RES are abundant in the Southern African region,and some projects have already been successfully implemented,especially in South Africa.Economic growth and technological advancement are some of the benefits of fully transitioning to renewables,but lack of skilled labor,infrastructure,necessary technology,and most importantly,high capital requirements,etc.,are some challenges being faced.Hence,the need for regional cooperation,policy frameworks,and infrastructure enhancement,and investment mobilization for an accelerated transition.展开更多
With the increasing demand for high-performance and safe fuels in aerospace propulsion systems,gelled fliels have attracted increasing attention.Because of their unique structure,gelled fuels exhibit the advantages of...With the increasing demand for high-performance and safe fuels in aerospace propulsion systems,gelled fliels have attracted increasing attention.Because of their unique structure,gelled fuels exhibit the advantages of both solid and liquid fliels,such as high energy density,controllable thrust and storage safety.This review provides an overview on design,preparation and performance characterization of gelled fuels.The composition,preparation process and gelation mechanism of gelled high-energy-density fuels are described.Considering these aspects,the rheology and flow behavior of gelled fuels is summarized in terms of the shear thinning property,dynamic viscoelasticity and thixotropy.Moreover,the progress of atomization of gelled fuels is reviewed with a focus on the effect of atomizing nozzles.In addition,the experiments and theoretical models of single droplet combustion and combustor combustion are described.Finally,research directions for the development and application of gelled fuels are suggested.展开更多
Multicomponent Gd_(1−x)Sm_(x)Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)double perovskites are optimized for application in terms of chemical composi-tion and morphology for the use as oxygen electrodes in solid oxide cells.Structur...Multicomponent Gd_(1−x)Sm_(x)Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)double perovskites are optimized for application in terms of chemical composi-tion and morphology for the use as oxygen electrodes in solid oxide cells.Structural studies of other physicochemical properties are con-ducted on a series of materials obtained by the sol-gel method with different ratios of Gd and Sm cations.It is documented that changing the x value,and the resulting adjustment of the average ionic radius,have a significant impact on the crystal structure,stability,as well as on the total conductivity and thermomechanical properties of the materials,with the best results obtained for the Gd_(0.75)Sm_(0.2)5Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)composition.Oxygen electrodes are prepared using the selected compound,allowing to obtain low polarization resistance values,such as 0.086Ω·cm^(2)at 800℃.Systematic studies of electrocatalytic activity are conducted using La_(0.8)Sr_(0.2)Ga_(0.8)Mg_(_(0.2))O_(3−δ)as the electrolyte for all electrodes,and Ce_(0.8)Gd_(0.2)O_(2−δ)electrolyte for the best performing Gd_(0.75)Sm_(0.2)5Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)electrodes.The electrochemical data are analyzed using the distribution of relaxation times method.Also,the influence of the preparation method of the electrode material is in-ve`stigated using the electrospinning technique.Finally,the performance of the Gd_(0.75)Sm_(0.2)5Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)electrodes is tested in a Ni-YSZ(yttria-stabilized zirconia)anode-supported cell with a Ce_(0.8)Gd_(0.2)O_(2−δ)buffer layer,in the fuel cell and electrolyzer operating modes.With the electrospun electrode,a power density of 462 mW·cm^(−2)is obtained at 700℃,with a current density of ca.0.2 A·cm^(−2)at 1.3 V for the electrolysis at the same temperature,indicating better performance compared to the sol-gel-based electrode.展开更多
Minimizing the thermal expansion coefficient(TEC)mismatch between the cathode and electrolyte in solid oxide fuel cells is crucial for achieving stable,durable operation and high performance.Recently,materials with ne...Minimizing the thermal expansion coefficient(TEC)mismatch between the cathode and electrolyte in solid oxide fuel cells is crucial for achieving stable,durable operation and high performance.Recently,materials with negative thermal expansion(NTE)have at-tracted significant attention as effective additives for tailoring the thermomechanical properties of electrodes and enhancing cell durability.In this work,for the first time,single-phase NTE perovskite Sm_(0.85)Zn_(0.15)MnO_(3−δ)(SZM15)was successfully synthesized via the sol-gel method,eliminating the unwanted ZnO phase typically observed in materials obtained through the conventional solid-state reaction route.The sol-gel approach proved highly advantageous,offering low cost,robustness,excellent chemical homogeneity,precise compositional control,and high phase purity.After optimization of synthesis parameters,a negative TEC of approximately−6.5×10^(−6)K^(−1)was achieved in the 400-850℃range.SZM15 was then incorporated as an additive(10wt%-50wt%)into a SmBa0.5Sr0.5CoCuO_(5+δ)(SBSCCO)cathode to tune the thermomechanical properties with a La_(0.8)Sr_(0.2)Ga_(0.8)Mg_(0.2)O_(3−δ)(LSGM)electrolyte,achieving a minimal TEC mismatch of only 1%.Notably,the SBSCCO+10wt%SZM15 composite cathode exhibited the lowest polarization resistance of 0.019Ω·cm^(2)at 900℃,showing approximately 70%lower than that of the pristine cathode.Excellent long-term stability after 100 h of operation was achieved.In addition,a high peak power density of 680 mW·cm^(−2)was achieved in a Ni-YSZ(yttria-stabilized zirconia)|YSZ|Ce_(0.9)Gd_(0.1)O_(2−δ)(GDC10)|SBSCCO+10wt%SZM15 anode-supported fuel cell at 850℃,highlighting the effectiveness of incorporating NTE materials as a promising strategy for regulating the thermomechanical properties and improving the long-term stability of intermediate temperature solid oxide fuel cells(IT-SOFCs).展开更多
Hydrogen fuel cells are expected to play a central role in the next-generation energy paradigm.However,owing to practical limitations,hydrogen is supplied in the form of refined hydrocarbons or alcohols in industrial ...Hydrogen fuel cells are expected to play a central role in the next-generation energy paradigm.However,owing to practical limitations,hydrogen is supplied in the form of refined hydrocarbons or alcohols in industrial applications.Among them,methanol is widely used as a hydrogen source,and CO is inevitably generated during its oxidation process.Even a small amount of CO(∼20 ppm)strongly binds to Pt used as a catalyst,and deactivates it.In addition to CO,surface adsorption of organic cations by binder or ionomer use in alkaline fuel cells is also one of the poisoning issues to be overcome.Herein,we propose FePt bimetallic catalysts that can resist unavoidable CO and organic cation poisoning.Our synthetic strategy,including annealing and acid treatment,allows the catalysts to possess different alloying degrees and surface structures,which in turn induce different levels of resistance to CO and organic-cation poisonings.The correlation between the surface and bulk structures of the catalysts and poisoning resistance was elucidated through X-ray photoemission spectroscopy and electrochemical analysis.The results revealed that an FePt catalyst having an ordered atomic arrangement displayed a better poisoning resistance than that having a disordered arrangement.展开更多
The commercialization of solid oxide fuel cells depends on the cathode,which possesses both high catalytic activity and a thermal-expansion coefficient(TEC)that aligns with the electrolyte.Although the cobalt-based ca...The commercialization of solid oxide fuel cells depends on the cathode,which possesses both high catalytic activity and a thermal-expansion coefficient(TEC)that aligns with the electrolyte.Although the cobalt-based cathode La_(0.6)Sr_(0.4)CoO_(3)(LSC)offers excellent catalytic performance,its TEC is significantly larger than that of the electrolyte.In this study,we mechanically mix Sm_(0.2)Ce_(0.8)O_(2−δ)(SDC)with LSC to create a composite cathode.By incorporating 50wt%SDC,the TEC decreases significantly from 18.29×10^(−6) to 13.90×10^(−6) K^(−1).Under thermal-shock conditions ranging from room temperature to 800℃,the growth rate of polarization resistance is only 0.658%per cycle,i.e.,merely 49%that of pure LSC.The button cell comprising the LSC-SDC composite cathode operates stably for over 900 h without Sr segregation,with a voltage growth rate of 1.11%/kh.A commercial flat-tube cell(active area:70 cm^(2))compris-ing the LSC-SDC composite cathode delivers 54.8 W at 750℃.The distribution of relaxation-time shows that the non-electrode portion is the main rate-limiting step.This study demonstrates that the LSC-SDC mixture strategy effectively improves the compatibility with the electrolyte while maintaining a high output,thus rendering it a promising commercial cathode material.展开更多
Ceramic matrix composites(CMCs)structural components encounter the dual challenges of severe mechanical conditions and complex electromagnetic environments due to the increasing demand for stealth technology in aerosp...Ceramic matrix composites(CMCs)structural components encounter the dual challenges of severe mechanical conditions and complex electromagnetic environments due to the increasing demand for stealth technology in aerospace field.To address various functional requirements,this study integrates a biomimetic strategy inspired by gradient bamboo vascular bundles with a novel dual-material 3D printing approach.Three distinct bamboo-inspired structural configurations Cf/SiC composites are designed and manufactured,and the effects of these different structural configurations on the CVI process are analyzed.Nanoindentation method is utilized to characterize the relationship between interface bonding strength and mechanical properties.The results reveal that the maximum flexural strength and fracture toughness reach 108.6±5.2 MPa and 16.45±1.52 MPa m1/2,respectively,attributed to the enhanced crack propagation resistance and path caused by the weak fiber-matrix interface.Furthermore,the bio-inspired configuration enhances the dielectric loss and conductivity loss,exhibiting a minimum reflection loss of−24.3 dB with the effective absorption band of 3.89 GHz.This work introduces an innovative biomimetic strategy and 3D printing method for continuous fiber-reinforced ceramic composites,expanding the application of 3D printing technology in the field of CMCs.展开更多
Developing highly active and stable air electrodes remains challenging for reversible solid oxide cells(R-SOCs).Herein,we re-port an A-site high-entropy engineered perovskite oxide,La_(0.2)Pr_(0.2)Nd_(0.2)Ba_(0.2)Sr_(...Developing highly active and stable air electrodes remains challenging for reversible solid oxide cells(R-SOCs).Herein,we re-port an A-site high-entropy engineered perovskite oxide,La_(0.2)Pr_(0.2)Nd_(0.2)Ba_(0.2)Sr_(0.2)Co_(0.8)Fe_(0.2)O_(3−δ)(HE-LSCF),and its electrocatalytic activity and stability property are systematically probed for tubular R-SOCs.The HE-LSCF air electrode exhibits excellent oxygen reduction reac-tion(ORR)activity with a low polarization resistance of 0.042Ω·cm^(2)at 700℃,which is much lower than that of La0.6Sr0.4Co_(0.8)Fe_(0.2)O_(3−δ)(LSCF),indicating the excellent catalytic activity of HE-LSCF.Meanwhile,the tubular R-SOCs with HE-LSCF shows a high peak power density of 1.18 W·cm^(−2)in the fuel cell mode and a promising electrolysis current density of−0.52 A·cm^(−2)at 1.5 V in the electrolysis mode with H_(2)(~10%H_(2)O)atmosphere at 700℃.More importantly,the tubular R-SOCs with HE-LSCF shows favorable stability under 180 h reversible cycling test.Our results show the high-entropy design can significantly enhance the activity and robustness of LSCF electrode for tubular R-SOCs.展开更多
S-scheme heterojunctions have gained widespread application in photocatalytic reactions due to their dis-tinctive carrier transport mechanism and remarkable redox capabilities.However,a significant challenge persists ...S-scheme heterojunctions have gained widespread application in photocatalytic reactions due to their dis-tinctive carrier transport mechanism and remarkable redox capabilities.However,a significant challenge persists in extending carrier lifetimes while simultaneously enhancing light absorption,both of which are essential for optimizing photocatalytic activity.Herein,we report the solvothermal synthesis of ul-trathin CdS nanosheets grown in situ on two-dimensional(2D)Ni-MOF to construct 2D/2D S-scheme heterojunctions.Comprehensive characterizations reveal that the incorporation of Ni-MOF(metal-organic framework)with ligand-to-metal charge transfer(LMCT)states not only broadens optical absorption but also significantly prolongs carrier lifetimes.This synergistic enhancement,coupled with the S-scheme charge transport mechanism,enables the composite to function as a bifunctional catalyst for photocat-alytic hydrogen production and simultaneous benzylamine coupling.The optimal system demonstrates an impressive hydrogen evolution rate of 8.5 mmol g^(-1) h^(-1) and an N-benzylidenebenzylamine yield of 4.6 mmol g^(-1) h^(-1) without requiring a cocatalyst.This work underscores the potential of integrating MOFs with LMCT states into S-scheme heterojunctions to enhance interfacial charge transfer,offering valuable insights for the design of S-scheme heterojunctions for artificial photosynthesis and related fields.展开更多
Carbon nanotube formation exemplifies atomically precise self-assembly,where atomic interactions dynamically engineer nanoscale architectures with emergent properties that transcend classical material boundaries.Howev...Carbon nanotube formation exemplifies atomically precise self-assembly,where atomic interactions dynamically engineer nanoscale architectures with emergent properties that transcend classical material boundaries.However,elucidating the transient molecular intermediates remains a critical mechanistic frontier.This study investigates the atomic-scale nucleation process of single-walled carbon nanotubes(SWCNTs)from acetylene on iron(Fe)clusters,utilizing GFN(-x)TB-based nanoreactor molecular dynamics simulations.The simulations reveal a consistent nucleation pathway,regardless of iron cluster size(Fe_(13),Fe_(38),Fe_(55)),where the chemisorption and dissociation of acetylene molecules on the Fe clusters lead to the formation of C_(2)H and C_(2)intermediates.These species then undergo oligomerization,initiating the growth of carbon chains.As the chains cross-link and cyclize,five-membered carbon rings are preferentially formed,which eventually evolve into six-membered rings and more complex sp2-hybridized carbon networks,resembling the cap structures of nascent SWCNTs.Although the nucleation mechanism remains similar across all cluster sizes,larger clusters show enhanced catalytic activity,leading to higher molecular weight hydrocarbons and more extensive carbocyclic networks due to their higher density of active sites per reacting molecule.Crucially,the study highlights the role of C_(2)H as the key active species in the carbon network formation process.These findings offer critical insights into the initial stages of SWCNT nucleation,contributing to a deeper understanding of the mechanisms driving SWCNT growth and guiding the development of optimized synthetic strategies.展开更多
A unitized regenerative fuel cell(URFC)is a device that may function reversibly as either a fuel cell(FC)or water elec-trolysis(WE).An important component of this device is the Membrane electrode assembly(MEA).Therefo...A unitized regenerative fuel cell(URFC)is a device that may function reversibly as either a fuel cell(FC)or water elec-trolysis(WE).An important component of this device is the Membrane electrode assembly(MEA).Therefore,this study aimed to compare the performance outcomes of MEA using electrodes with single and three catalyst layers.This study measured Electrochemical Surface Area(ECSA),Electrochemical Impedance Spectroscopy(EIS),X-ray Diffraction analysis(XRD),and X-ray Fluorescence(XRF).Furthermore,the round-trip efficiency(RTE)of the MEA,as w ell as the performance in FC and WE mode,was measured.In comparison,The ECSA values of Pt-Ru/C and Pt/C with three catalyst layers were higher than the single catalyst layer.This result was supported by electrode characterization data for XRD and XRF.The respective electrical conductivity values of Pt-Ru/C and Pt/C with three catalyst layers are also higher than the single cata-lyst layer,and the performance of URFC using MEA with three catalyst layers has the highest value of RTE among the MEA performances of URFC,which is 100%at a current density of 4 mA·cm-2.展开更多
Photocatalysis provides a promising solution to the worldwide shortages of energy and industrially important raw materials by utilizing sunlight for coupled hydrogen(H_(2))production with controllable organic transfor...Photocatalysis provides a promising solution to the worldwide shortages of energy and industrially important raw materials by utilizing sunlight for coupled hydrogen(H_(2))production with controllable organic transformation.Herein,we demonstrate that PtFeNiCoCu high-entropy alloy(HEA)nanocrystals can act as efficient cocatalysts for H_(2)evolution coupled with selective oxidation of cinnamyl alcohol to cinnamaldehyde by cubic cadmium sulfide(CdS)quantum dots(QDs)with uniform sizes of 4.0±0.5 nm.HEA nanocrystals were prepared via a simple solvothermal approach,and were successfully integrated with CdS QDs by an electrostatic self-assembly method to construct HEA/CdS composites.The optimized HEA/CdS sample presented an enhanced photocatalytic H_(2)production rate of 7.15 mmol g^(-1)h^(-1),which was 13 times that of pure CdS QDs.Moreover,a cinnamyl alcohol conversion of 96.2%with cinnamaldehyde selectivity of 99.5%was achieved after photoreaction for 3 h.The integration of HEA with CdS QDs extended the optical absorption edge from 475 to 484 nm.From d-band center analysis,Pt atoms in the HEA are the active sites for H_(2)evolution,exhibiting higher catalytic activity than pure Pt.Meanwhile,the band structure of the CdS QDs enables the oxidative transformation of cinnamyl alcohol to cinnamaldehyde with high selectivity.Moreover,femtosecond transient absorption spectroscopy shows that HEA can significantly promote the separation of photogenerated carriers in CdS,which is vital for achieving enhanced photocatalytic activity.This work inspires atomic-level design of photocatalytic materials for coordinated production of green energy carriers and value-added products.展开更多
This work investigates the transient performance and stability of CO_(2)/H_(2)O co-electrolysis in an air-free environment using a flat-tube solid oxide electrolysis cell(SOEC)stack.The results showed that the transie...This work investigates the transient performance and stability of CO_(2)/H_(2)O co-electrolysis in an air-free environment using a flat-tube solid oxide electrolysis cell(SOEC)stack.The results showed that the transient behavior of the stack with and without blowing gas into the air electrode is almost the same.With a current density of 0.67 A·cm^(-2)@750℃,the stack operated for over 200 h under co-electrolysis conditions without air blowing,and the voltage drop rate of the stack was approximately 0.203%/100 hours.Microstructure analysis revealed a significant loss of nickel particles and an apparent for-mation of an insulating phase strontium chromate(SrCrO4)on the surface of the current collection layer of the air electrode,which are identified as key factors contributing to the performance degradation of the stack.This study provides a reference for development of efficient fuel preparation technology based on SOEC stack in airless environments.展开更多
Liquid phosphoric acid(PA),as the proton carrier for high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs),presents challenges such as catalyst poisoning,high gas transport resistance and electrolyte los...Liquid phosphoric acid(PA),as the proton carrier for high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs),presents challenges such as catalyst poisoning,high gas transport resistance and electrolyte loss.These issues significantly impede the performance and durability of HT-PEMFCs,thereby limiting their potential for further application.In this study,poly(2,3,5,6-tetrafluorostylene-4-phosphonic acid)(PWN)with intrinsic proton conduction ability was employed as catalyst layer binder to reveal the impacts of the ionomer's molecular structure on mass transport within the catalyst layer.Our findings demonstrated that increasing the phosphorylation degree of PWN could enhance both pore formation at the catalyst layer and electrode acidophilic capability while improving proton conduction ability and reducing cells'internal resistance.However,adverse effects included increased local oxygen transport resistance and decreased catalyst utilization resulting from electrode acidophilic capability.This research offers valuable insights for the relationships between micro-scale molecule structure,mesoscale electrode architecture,and membrane electrode assembly design in HT-PEMFCs.展开更多
One of the most important of these emissions is fine particulate matter,which is a harmful emission of diesel engines,leading to the imposition of strict regulations.Biodiesel,with its high oxygen content,is an effect...One of the most important of these emissions is fine particulate matter,which is a harmful emission of diesel engines,leading to the imposition of strict regulations.Biodiesel,with its high oxygen content,is an effective alternative to significantly reduce these emissions.In this study,rapeseed methyl ester(RME)was used as a diesel engine fuel and the emitted particulate matter was comparedwith ultra-lowsulfur diesel(ULSD).Inmost experimental studies,the emission of soot wasmeasured.In this work,the effects of injection timing,injection pressure(IP),and engine load on fine particulate matter in both nucleation and accumulation modes were studied.The results show that IP increases the number of particles in the accumulation mode while the number of particles in the crystallization mode is higher for rapeseed methyl ester(RME)than for ultra-low sulfur diesel(ULSD).Conversely,the formation rates of particles in the accumulationmode are higher for ULSD.Cumulative concentration numbers(CCN)are generally higher for RME in crystallization mode but higher for ULSD in accumulation mode.Increasing the IP reduces the CCN values.The particle size in crystallizationmode reaches a maximum of 22 nm at IPs of 800 and 1000 bar but decreases to 15 nm at 1200 bar.Most fine particles fall in the 5–100 nm diameter range.High engine loads reduce the particle size distribution in nucleationmode for both fuels,with a slight increase in particle size in nucleationmode.Thestudy concluded that the use of rapeseed methyl ester as an engine fuel benefits the environment and improves air quality due to the significant reduction in the size,number,and concentration of nano-soot particles and total particles emitted from the engine.展开更多
基金supported by the Center for Bioenergy Innovation(CBI)supported by the Office of Biological and Environmental Research in the DOE Office of Science and led by Oak Ridge National Laboratory.Oak Ridge National Laboratory is managed by UT-Battelle,LLC for the US DOE under Contract Number DE-AC05-00OR22725+2 种基金authored in part by the Na-tional Renewable Energy Laboratory,operated by Alliance for Sustainable Energy,LLC,for the U.S.Department of Energy(DOE)under Contract No.DE-LC-000L054provided by the U.S.Department of Energy(DOE),Office of Energy Efficiency and Renewable Energy(EERE),and Bioenergy Technologies Office(BETO)at the Pacific Northwest National Laboratory(PNNL)under Contract No.DE-AC05-76RL01830supported by Laboratory Directed Research and Development(LDRD)funding from Argonne National Laboratory,provided by the Director,Office of Science,of the U.S.Department of Energy under Contract No.DE-AC02-06CH11357。
文摘Sustainable aviation fuel(SAF)production from biomass and biowaste streams is an attractive option for decarbonizing the aviation sector,one of the most-difficult-to-electrify transportation sectors.Despite ongoing commercialization efforts using ASTM-certified pathways(e.g.,lipid conversion,Fischer-Tropsch synthesis),production capacities are still inadequate due to limited feedstock supply and high production costs.New conversion technologies that utilize lignocellulosic feedstocks are needed to meet these challenges and satisfy the rapidly growing market.Combining bio-and chemo-catalytic approaches can leverage advantages from both methods,i.e.,high product selectivity via biological conversion,and the capability to build C-C chains more efficiently via chemical catalysis.Herein,conversion routes,catalysis,and processes for such pathways are discussed,while key challenges and meaningful R&D opportunities are identified to guide future research activities in the space.Bio-and chemo-catalytic conversion primarily utilize the carbohydrate fraction of lignocellulose,leaving lignin as a waste product.This makes lignin conversion to SAF critical in order to utilize whole biomass,thereby lowering overall production costs while maximizing carbon efficiencies.Thus,lignin valorization strategies are also reviewed herein with vital research areas identified,such as facile lignin depolymerization approaches,highly integrated conversion systems,novel process configurations,and catalysts for the selective cleavage of aryl C-O bonds.The potential efficiency improvements available via integrated conversion steps,such as combined biological and chemo-catalytic routes,along with the use of different parallel pathways,are identified as key to producing all components of a cost-effective,100%SAF.
基金supported by the National Natural Science Foundation of China(No.21978200).
文摘Catalytic/initiated cracking of endothermic hydrocarbon fuels is an eff ective technology for cooling a hypersonic aircraft with a high Mach number(over 5).Catalysts and initiators can promote fuel cracking at low temperatures,increase fuel conversion and the heat sink capacity,and suppress coke deposition,thereby reducing waste heat.Catalysts mainly include metal oxide catalysts,noble metal catalysts and metal nanoparticles,zeolite catalysts,nanozeolite catalysts,and coating catalysts.Moreover,initiators roughly include nitrogenous compounds,oxygenated compounds,and hyperbranched polymer initiators.In this review,we aim to summarize the catalysts and initiators for cracking endothermic hydrocarbon fuels and their mechanisms for promoting cracking.This review will facilitate the development of the synthesis and exploration of catalysts and initiators.
文摘Shipping plays a vital role in the world economy.Around 90%of the world's trade is transported by ship in a cost-effective and reliable manner.Global shipping is responsible for 2-3%of the total global CO2 emissions.In addition,shipping accounts for up to 4-9%of all sulphur,and 10-15%of all nitrous oxide emissions.Without taking any measures,these emissions would more than double as seaborne trade is expected to further grow from 30 billion tone miles in 2006 to more than 100 billion in 2050.To counter these emissions the international community has developed frameworks for energy efficiency measures,as well as emission reduction targets for SOx and NOx in appointed ECAs(Emission Control Areas).Biofuels satisfy fully or partially the new emission regulations and sulfur limits without compromising the economy.The goal of this work is to study and evaluate the physicochemical properties of conventional marine distillate fuel and its blends with renewable-alternative fuels(UCOME(Used Cooking Oils Methyl Esters)and HVO(Hydrogenated Vegetable Oils)).
文摘Sulphur and emissions related limits which are imposed on marine fuels drive the maritime industry to look on alternative fuels. The maximum sulphur content of the fuel has already decreased in the ECAs SOx （Sulphur Emission Control Areas） from 1.5% to 1% from 1 July, 2010, and to 0.1% from 1 January, 2015. Globally, the highest permitted sulphur content of fuel will be reduced, as from 1 January, 2020 to 0.5%. Increasing demand of low sulphur fuel is anticipated, leading to a substantial mitigation of marine fuels from residual to distillate ones. Biodiesel or else FAME （Fatty Acid Methyl Esters） and mixtures of it with conventional petroleum fuels, constitute alternative energy source for the maritime industry. The International Standard EN （European Norme） ISO （International Organization for Standardization） 8217 specifies the requirements of petroleum fuels for use in marine diesel engines. According to the previous version of EN ISO 8217：2012, distillate fuels should comply with the ＂de minimis level＂ of approximately 0.1% v/v FAME. Nevertheless, with the latest revision of EN ISO 8217 standard in 2017, the incorporation of FAME up to 7% v/v is allowed in specific marine distillate grades as DF （Distillate FAME） grades. Marine distillates can also include hydrocarbons from synthetic or renewable sources, similar to the composition of petroleum distillate fuels.
文摘This proposal aims to assess the market introduction of advanced technologies for the production of 2nd generation solid biofuels, specifically technologies for the production of briquettes and pellets from agro-industrial wastes. The development of this project will evaluate the socio-environmental and techno-economical feasibility and use of 2nd generation solid biofuels in the CMR （Campinas Metropolitan Region）. The successful introduction of second generation briquettes and pellets to market depends, mainly, on two aspects： logistics in supply chains which generate waste, and the efficiency of production technologies. The study of logistics （supply chain） is based on survey data of the main productive supply chains, analysis, and modeling to optimize the facility location in the network for each case. The evaluation of the efficiency of production technology is provided by testing specially designed waste compacting devices, and comparing these results with the resulting power consumption during the production, in demonstration-scale, of a round of briquettes. The costs and consumption during the demonstration-scale production of briquettes are used for validation and correction of an optimization model. This project was approved in late 2012 with a period of two years for its implementation. Later in 2013, it was decided also to extend its implementation to the Metropolitan Region of Manaus, Amazon. Due to its recent beginning, the results shown here are only preliminary.
文摘This study presents a comprehensive analysis of the current energy landscape and the imperative transition toward renewable energy.It begins with an overview of current energy sources and trends,highlighting the disparity between supply and increasing demand.Adverse impacts of reliance on fossil fuels such as environmental degradation,economic volatility,and health hazards underscore the urgent need for a transition.The study then explores the vast potential of renewable energy sources(RES)such as solar,wind,hydrogen,and hydro,emphasizing their feasibility in the Southern African context.The positive impacts of integrating renewables are examined,including reduced greenhouse gas emissions,enhanced energy security,and economic diversification.Through case studies of regional examples,the success and failures of transitioning efforts are analyzed,providing valuable insights into best practices and pitfalls.The study identifies significant challenges in transitioning,particularly in grid-tied and off-grid scenarios,and discusses infrastructural,financial,and regulatory obstacles.The recommendations section outlines strategic steps for achieving a feasible transition,proposing either a full transition or specific percentages of renewable energy integration to meet energy demands.In conclusion,the study emphasizes the critical importance of adopting these strategies for sustainable development and global climate goals,advocating for continuous innovation and localized solutions to maximize the benefits of renewable energy.Key findings are that the environmental and economic effects of fossil fuel usage strain economies by increasing fossil fuel subsidies.RES are abundant in the Southern African region,and some projects have already been successfully implemented,especially in South Africa.Economic growth and technological advancement are some of the benefits of fully transitioning to renewables,but lack of skilled labor,infrastructure,necessary technology,and most importantly,high capital requirements,etc.,are some challenges being faced.Hence,the need for regional cooperation,policy frameworks,and infrastructure enhancement,and investment mobilization for an accelerated transition.
文摘With the increasing demand for high-performance and safe fuels in aerospace propulsion systems,gelled fliels have attracted increasing attention.Because of their unique structure,gelled fuels exhibit the advantages of both solid and liquid fliels,such as high energy density,controllable thrust and storage safety.This review provides an overview on design,preparation and performance characterization of gelled fuels.The composition,preparation process and gelation mechanism of gelled high-energy-density fuels are described.Considering these aspects,the rheology and flow behavior of gelled fuels is summarized in terms of the shear thinning property,dynamic viscoelasticity and thixotropy.Moreover,the progress of atomization of gelled fuels is reviewed with a focus on the effect of atomizing nozzles.In addition,the experiments and theoretical models of single droplet combustion and combustor combustion are described.Finally,research directions for the development and application of gelled fuels are suggested.
基金funded by the National Science Centre,Poland,on the basis of the decision number UMO-2020/37/B/ST8/02097supported by the program“Excellence Initiative-Research University”for the AGH University of Krakow(IDUB AGH,No.501.696.7996,Action 4,ID 9880).
文摘Multicomponent Gd_(1−x)Sm_(x)Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)double perovskites are optimized for application in terms of chemical composi-tion and morphology for the use as oxygen electrodes in solid oxide cells.Structural studies of other physicochemical properties are con-ducted on a series of materials obtained by the sol-gel method with different ratios of Gd and Sm cations.It is documented that changing the x value,and the resulting adjustment of the average ionic radius,have a significant impact on the crystal structure,stability,as well as on the total conductivity and thermomechanical properties of the materials,with the best results obtained for the Gd_(0.75)Sm_(0.2)5Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)composition.Oxygen electrodes are prepared using the selected compound,allowing to obtain low polarization resistance values,such as 0.086Ω·cm^(2)at 800℃.Systematic studies of electrocatalytic activity are conducted using La_(0.8)Sr_(0.2)Ga_(0.8)Mg_(_(0.2))O_(3−δ)as the electrolyte for all electrodes,and Ce_(0.8)Gd_(0.2)O_(2−δ)electrolyte for the best performing Gd_(0.75)Sm_(0.2)5Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)electrodes.The electrochemical data are analyzed using the distribution of relaxation times method.Also,the influence of the preparation method of the electrode material is in-ve`stigated using the electrospinning technique.Finally,the performance of the Gd_(0.75)Sm_(0.2)5Ba_(0.5)Sr_(0.5)CoCuO_(5+δ)electrodes is tested in a Ni-YSZ(yttria-stabilized zirconia)anode-supported cell with a Ce_(0.8)Gd_(0.2)O_(2−δ)buffer layer,in the fuel cell and electrolyzer operating modes.With the electrospun electrode,a power density of 462 mW·cm^(−2)is obtained at 700℃,with a current density of ca.0.2 A·cm^(−2)at 1.3 V for the electrolysis at the same temperature,indicating better performance compared to the sol-gel-based electrode.
基金supported by the research project within the program“Excellence Initiative-Research University”for the AGH University of Krakow(IDUB AGH,Action 21)Kun Zheng acknowledges financial support from AGH University of Krakow(No.16.16.210.476).
文摘Minimizing the thermal expansion coefficient(TEC)mismatch between the cathode and electrolyte in solid oxide fuel cells is crucial for achieving stable,durable operation and high performance.Recently,materials with negative thermal expansion(NTE)have at-tracted significant attention as effective additives for tailoring the thermomechanical properties of electrodes and enhancing cell durability.In this work,for the first time,single-phase NTE perovskite Sm_(0.85)Zn_(0.15)MnO_(3−δ)(SZM15)was successfully synthesized via the sol-gel method,eliminating the unwanted ZnO phase typically observed in materials obtained through the conventional solid-state reaction route.The sol-gel approach proved highly advantageous,offering low cost,robustness,excellent chemical homogeneity,precise compositional control,and high phase purity.After optimization of synthesis parameters,a negative TEC of approximately−6.5×10^(−6)K^(−1)was achieved in the 400-850℃range.SZM15 was then incorporated as an additive(10wt%-50wt%)into a SmBa0.5Sr0.5CoCuO_(5+δ)(SBSCCO)cathode to tune the thermomechanical properties with a La_(0.8)Sr_(0.2)Ga_(0.8)Mg_(0.2)O_(3−δ)(LSGM)electrolyte,achieving a minimal TEC mismatch of only 1%.Notably,the SBSCCO+10wt%SZM15 composite cathode exhibited the lowest polarization resistance of 0.019Ω·cm^(2)at 900℃,showing approximately 70%lower than that of the pristine cathode.Excellent long-term stability after 100 h of operation was achieved.In addition,a high peak power density of 680 mW·cm^(−2)was achieved in a Ni-YSZ(yttria-stabilized zirconia)|YSZ|Ce_(0.9)Gd_(0.1)O_(2−δ)(GDC10)|SBSCCO+10wt%SZM15 anode-supported fuel cell at 850℃,highlighting the effectiveness of incorporating NTE materials as a promising strategy for regulating the thermomechanical properties and improving the long-term stability of intermediate temperature solid oxide fuel cells(IT-SOFCs).
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(Nos.2022M3J1A1063917 and 2021M3H4A3A02086681).
文摘Hydrogen fuel cells are expected to play a central role in the next-generation energy paradigm.However,owing to practical limitations,hydrogen is supplied in the form of refined hydrocarbons or alcohols in industrial applications.Among them,methanol is widely used as a hydrogen source,and CO is inevitably generated during its oxidation process.Even a small amount of CO(∼20 ppm)strongly binds to Pt used as a catalyst,and deactivates it.In addition to CO,surface adsorption of organic cations by binder or ionomer use in alkaline fuel cells is also one of the poisoning issues to be overcome.Herein,we propose FePt bimetallic catalysts that can resist unavoidable CO and organic cation poisoning.Our synthetic strategy,including annealing and acid treatment,allows the catalysts to possess different alloying degrees and surface structures,which in turn induce different levels of resistance to CO and organic-cation poisonings.The correlation between the surface and bulk structures of the catalysts and poisoning resistance was elucidated through X-ray photoemission spectroscopy and electrochemical analysis.The results revealed that an FePt catalyst having an ordered atomic arrangement displayed a better poisoning resistance than that having a disordered arrangement.
基金the financial support from the National Natural Science Foundation of China(No.22209191)Ningbo Key R&D Project(No.2023Z155).
文摘The commercialization of solid oxide fuel cells depends on the cathode,which possesses both high catalytic activity and a thermal-expansion coefficient(TEC)that aligns with the electrolyte.Although the cobalt-based cathode La_(0.6)Sr_(0.4)CoO_(3)(LSC)offers excellent catalytic performance,its TEC is significantly larger than that of the electrolyte.In this study,we mechanically mix Sm_(0.2)Ce_(0.8)O_(2−δ)(SDC)with LSC to create a composite cathode.By incorporating 50wt%SDC,the TEC decreases significantly from 18.29×10^(−6) to 13.90×10^(−6) K^(−1).Under thermal-shock conditions ranging from room temperature to 800℃,the growth rate of polarization resistance is only 0.658%per cycle,i.e.,merely 49%that of pure LSC.The button cell comprising the LSC-SDC composite cathode operates stably for over 900 h without Sr segregation,with a voltage growth rate of 1.11%/kh.A commercial flat-tube cell(active area:70 cm^(2))compris-ing the LSC-SDC composite cathode delivers 54.8 W at 750℃.The distribution of relaxation-time shows that the non-electrode portion is the main rate-limiting step.This study demonstrates that the LSC-SDC mixture strategy effectively improves the compatibility with the electrolyte while maintaining a high output,thus rendering it a promising commercial cathode material.
基金supported by The National Key Research and Development Program of China(No.2019YFB1901001).
文摘Ceramic matrix composites(CMCs)structural components encounter the dual challenges of severe mechanical conditions and complex electromagnetic environments due to the increasing demand for stealth technology in aerospace field.To address various functional requirements,this study integrates a biomimetic strategy inspired by gradient bamboo vascular bundles with a novel dual-material 3D printing approach.Three distinct bamboo-inspired structural configurations Cf/SiC composites are designed and manufactured,and the effects of these different structural configurations on the CVI process are analyzed.Nanoindentation method is utilized to characterize the relationship between interface bonding strength and mechanical properties.The results reveal that the maximum flexural strength and fracture toughness reach 108.6±5.2 MPa and 16.45±1.52 MPa m1/2,respectively,attributed to the enhanced crack propagation resistance and path caused by the weak fiber-matrix interface.Furthermore,the bio-inspired configuration enhances the dielectric loss and conductivity loss,exhibiting a minimum reflection loss of−24.3 dB with the effective absorption band of 3.89 GHz.This work introduces an innovative biomimetic strategy and 3D printing method for continuous fiber-reinforced ceramic composites,expanding the application of 3D printing technology in the field of CMCs.
基金support provided by the National Key R&D Program of China(No.2024YFE0101500)the National Natural Science Foundation of China(No.52272257)the Natural Science Foundation of Jiangsu Province(No.BK20240109).
文摘Developing highly active and stable air electrodes remains challenging for reversible solid oxide cells(R-SOCs).Herein,we re-port an A-site high-entropy engineered perovskite oxide,La_(0.2)Pr_(0.2)Nd_(0.2)Ba_(0.2)Sr_(0.2)Co_(0.8)Fe_(0.2)O_(3−δ)(HE-LSCF),and its electrocatalytic activity and stability property are systematically probed for tubular R-SOCs.The HE-LSCF air electrode exhibits excellent oxygen reduction reac-tion(ORR)activity with a low polarization resistance of 0.042Ω·cm^(2)at 700℃,which is much lower than that of La0.6Sr0.4Co_(0.8)Fe_(0.2)O_(3−δ)(LSCF),indicating the excellent catalytic activity of HE-LSCF.Meanwhile,the tubular R-SOCs with HE-LSCF shows a high peak power density of 1.18 W·cm^(−2)in the fuel cell mode and a promising electrolysis current density of−0.52 A·cm^(−2)at 1.5 V in the electrolysis mode with H_(2)(~10%H_(2)O)atmosphere at 700℃.More importantly,the tubular R-SOCs with HE-LSCF shows favorable stability under 180 h reversible cycling test.Our results show the high-entropy design can significantly enhance the activity and robustness of LSCF electrode for tubular R-SOCs.
基金financially supported by the National Key Re-search and Development Program of China(Nos.2022YFB3803600 and 2022YFE0115900)the National Natural Science Foundation of China(Nos.U24A2071,22278324,22238009,22361142704,22202187,and U23A20102)+1 种基金the National Science Foundation of Hubei Province of China(No.2022CFA001)Key R&D Program Projects in Hubei Province(No.2023BAB113).
文摘S-scheme heterojunctions have gained widespread application in photocatalytic reactions due to their dis-tinctive carrier transport mechanism and remarkable redox capabilities.However,a significant challenge persists in extending carrier lifetimes while simultaneously enhancing light absorption,both of which are essential for optimizing photocatalytic activity.Herein,we report the solvothermal synthesis of ul-trathin CdS nanosheets grown in situ on two-dimensional(2D)Ni-MOF to construct 2D/2D S-scheme heterojunctions.Comprehensive characterizations reveal that the incorporation of Ni-MOF(metal-organic framework)with ligand-to-metal charge transfer(LMCT)states not only broadens optical absorption but also significantly prolongs carrier lifetimes.This synergistic enhancement,coupled with the S-scheme charge transport mechanism,enables the composite to function as a bifunctional catalyst for photocat-alytic hydrogen production and simultaneous benzylamine coupling.The optimal system demonstrates an impressive hydrogen evolution rate of 8.5 mmol g^(-1) h^(-1) and an N-benzylidenebenzylamine yield of 4.6 mmol g^(-1) h^(-1) without requiring a cocatalyst.This work underscores the potential of integrating MOFs with LMCT states into S-scheme heterojunctions to enhance interfacial charge transfer,offering valuable insights for the design of S-scheme heterojunctions for artificial photosynthesis and related fields.
基金supported by the National Key R&D Program of China(2022YFA1604100)the National Natural Science Foundation of China(22302220,22372187,1972157,21972160,22402218)+2 种基金the National Science Fund for Distinguished Young Scholars of China(22225206)the Fundamental Research Program of Shanxi Province(202203021222403)the Youth Innovation Promotion Association CAS(2020179)。
文摘Carbon nanotube formation exemplifies atomically precise self-assembly,where atomic interactions dynamically engineer nanoscale architectures with emergent properties that transcend classical material boundaries.However,elucidating the transient molecular intermediates remains a critical mechanistic frontier.This study investigates the atomic-scale nucleation process of single-walled carbon nanotubes(SWCNTs)from acetylene on iron(Fe)clusters,utilizing GFN(-x)TB-based nanoreactor molecular dynamics simulations.The simulations reveal a consistent nucleation pathway,regardless of iron cluster size(Fe_(13),Fe_(38),Fe_(55)),where the chemisorption and dissociation of acetylene molecules on the Fe clusters lead to the formation of C_(2)H and C_(2)intermediates.These species then undergo oligomerization,initiating the growth of carbon chains.As the chains cross-link and cyclize,five-membered carbon rings are preferentially formed,which eventually evolve into six-membered rings and more complex sp2-hybridized carbon networks,resembling the cap structures of nascent SWCNTs.Although the nucleation mechanism remains similar across all cluster sizes,larger clusters show enhanced catalytic activity,leading to higher molecular weight hydrocarbons and more extensive carbocyclic networks due to their higher density of active sites per reacting molecule.Crucially,the study highlights the role of C_(2)H as the key active species in the carbon network formation process.These findings offer critical insights into the initial stages of SWCNT nucleation,contributing to a deeper understanding of the mechanisms driving SWCNT growth and guiding the development of optimized synthetic strategies.
基金support from the Ministry of Higher Education Malaysia under grant HICOE-2023-005.
文摘A unitized regenerative fuel cell(URFC)is a device that may function reversibly as either a fuel cell(FC)or water elec-trolysis(WE).An important component of this device is the Membrane electrode assembly(MEA).Therefore,this study aimed to compare the performance outcomes of MEA using electrodes with single and three catalyst layers.This study measured Electrochemical Surface Area(ECSA),Electrochemical Impedance Spectroscopy(EIS),X-ray Diffraction analysis(XRD),and X-ray Fluorescence(XRF).Furthermore,the round-trip efficiency(RTE)of the MEA,as w ell as the performance in FC and WE mode,was measured.In comparison,The ECSA values of Pt-Ru/C and Pt/C with three catalyst layers were higher than the single catalyst layer.This result was supported by electrode characterization data for XRD and XRF.The respective electrical conductivity values of Pt-Ru/C and Pt/C with three catalyst layers are also higher than the single cata-lyst layer,and the performance of URFC using MEA with three catalyst layers has the highest value of RTE among the MEA performances of URFC,which is 100%at a current density of 4 mA·cm-2.
文摘Photocatalysis provides a promising solution to the worldwide shortages of energy and industrially important raw materials by utilizing sunlight for coupled hydrogen(H_(2))production with controllable organic transformation.Herein,we demonstrate that PtFeNiCoCu high-entropy alloy(HEA)nanocrystals can act as efficient cocatalysts for H_(2)evolution coupled with selective oxidation of cinnamyl alcohol to cinnamaldehyde by cubic cadmium sulfide(CdS)quantum dots(QDs)with uniform sizes of 4.0±0.5 nm.HEA nanocrystals were prepared via a simple solvothermal approach,and were successfully integrated with CdS QDs by an electrostatic self-assembly method to construct HEA/CdS composites.The optimized HEA/CdS sample presented an enhanced photocatalytic H_(2)production rate of 7.15 mmol g^(-1)h^(-1),which was 13 times that of pure CdS QDs.Moreover,a cinnamyl alcohol conversion of 96.2%with cinnamaldehyde selectivity of 99.5%was achieved after photoreaction for 3 h.The integration of HEA with CdS QDs extended the optical absorption edge from 475 to 484 nm.From d-band center analysis,Pt atoms in the HEA are the active sites for H_(2)evolution,exhibiting higher catalytic activity than pure Pt.Meanwhile,the band structure of the CdS QDs enables the oxidative transformation of cinnamyl alcohol to cinnamaldehyde with high selectivity.Moreover,femtosecond transient absorption spectroscopy shows that HEA can significantly promote the separation of photogenerated carriers in CdS,which is vital for achieving enhanced photocatalytic activity.This work inspires atomic-level design of photocatalytic materials for coordinated production of green energy carriers and value-added products.
基金co-supported by the National Key R&D Program of China(No.2022YFB4002203)Baima Lake Laboratory Joint Funds of the Zhejiang Provincial Natural Science Foundation of China(No.LBMHY24B060003)Ningbo Key R&D Project(No.2023Z155).
文摘This work investigates the transient performance and stability of CO_(2)/H_(2)O co-electrolysis in an air-free environment using a flat-tube solid oxide electrolysis cell(SOEC)stack.The results showed that the transient behavior of the stack with and without blowing gas into the air electrode is almost the same.With a current density of 0.67 A·cm^(-2)@750℃,the stack operated for over 200 h under co-electrolysis conditions without air blowing,and the voltage drop rate of the stack was approximately 0.203%/100 hours.Microstructure analysis revealed a significant loss of nickel particles and an apparent for-mation of an insulating phase strontium chromate(SrCrO4)on the surface of the current collection layer of the air electrode,which are identified as key factors contributing to the performance degradation of the stack.This study provides a reference for development of efficient fuel preparation technology based on SOEC stack in airless environments.
基金supported by The National Key Research and Development Program of China(2021YFB4001204)National Natural Science Foundation of China(22179130,22379143,22479145)。
文摘Liquid phosphoric acid(PA),as the proton carrier for high temperature polymer electrolyte membrane fuel cells(HT-PEMFCs),presents challenges such as catalyst poisoning,high gas transport resistance and electrolyte loss.These issues significantly impede the performance and durability of HT-PEMFCs,thereby limiting their potential for further application.In this study,poly(2,3,5,6-tetrafluorostylene-4-phosphonic acid)(PWN)with intrinsic proton conduction ability was employed as catalyst layer binder to reveal the impacts of the ionomer's molecular structure on mass transport within the catalyst layer.Our findings demonstrated that increasing the phosphorylation degree of PWN could enhance both pore formation at the catalyst layer and electrode acidophilic capability while improving proton conduction ability and reducing cells'internal resistance.However,adverse effects included increased local oxygen transport resistance and decreased catalyst utilization resulting from electrode acidophilic capability.This research offers valuable insights for the relationships between micro-scale molecule structure,mesoscale electrode architecture,and membrane electrode assembly design in HT-PEMFCs.
文摘One of the most important of these emissions is fine particulate matter,which is a harmful emission of diesel engines,leading to the imposition of strict regulations.Biodiesel,with its high oxygen content,is an effective alternative to significantly reduce these emissions.In this study,rapeseed methyl ester(RME)was used as a diesel engine fuel and the emitted particulate matter was comparedwith ultra-lowsulfur diesel(ULSD).Inmost experimental studies,the emission of soot wasmeasured.In this work,the effects of injection timing,injection pressure(IP),and engine load on fine particulate matter in both nucleation and accumulation modes were studied.The results show that IP increases the number of particles in the accumulation mode while the number of particles in the crystallization mode is higher for rapeseed methyl ester(RME)than for ultra-low sulfur diesel(ULSD).Conversely,the formation rates of particles in the accumulationmode are higher for ULSD.Cumulative concentration numbers(CCN)are generally higher for RME in crystallization mode but higher for ULSD in accumulation mode.Increasing the IP reduces the CCN values.The particle size in crystallizationmode reaches a maximum of 22 nm at IPs of 800 and 1000 bar but decreases to 15 nm at 1200 bar.Most fine particles fall in the 5–100 nm diameter range.High engine loads reduce the particle size distribution in nucleationmode for both fuels,with a slight increase in particle size in nucleationmode.Thestudy concluded that the use of rapeseed methyl ester as an engine fuel benefits the environment and improves air quality due to the significant reduction in the size,number,and concentration of nano-soot particles and total particles emitted from the engine.
