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
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
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
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
The influences of particle size,shape,and catalyst distribution on the reactivity and hydrocarbon product selectivity of a cobalt-based catalyst for Fischer-Tropsch synthesis were investigated in the present work.A se...The influences of particle size,shape,and catalyst distribution on the reactivity and hydrocarbon product selectivity of a cobalt-based catalyst for Fischer-Tropsch synthesis were investigated in the present work.A self-consistent kinetic model for Fischer-Tropsch reaction proposed here was found to correlate experimental data well and hence was used to describe the consumption rates of reactants and formation rates of hydrocarbon products.The perturbed-chain statistical associating fluid theory equation of state was used to describe vapor-liquid equilibrium behavior associated with Fischer-Tropsch reaction.Local interaction between intraparticle diffusion and Fischer-Tropsch reaction was investigated in detail.Results showed that in order to avoid the adverse influence of intraparticle diffusional limitations on catalyst reactivity and product selectivity,the use of small particles is necessary.Large eggshell spherical particles are shown to keep the original catalyst reactivity and enhance the selectivity of heavy hydrocarbon products.The suitable layer thickness for a spherical particle with a diameter of 2 mm is nearly 0.15 mm.With the same outer diameter of 2 mm,the catalyst reactivity and heavy product selectivity of hollow cylindrical particles with a layer thickness of 0.25 mm are found to be larger than eggshell spherical particles.From the viewpoint of catalytic performance,hollow cylindrical particles are a better choice for industrial applications.展开更多
Undoubtedly,the enormous progress observed in recent years in the Ni-rich layered cathode materials has been crucial in terms of pushing boundaries of the Li-ion battery(LIB)technology.The achieved improvements in the...Undoubtedly,the enormous progress observed in recent years in the Ni-rich layered cathode materials has been crucial in terms of pushing boundaries of the Li-ion battery(LIB)technology.The achieved improvements in the energy density,cyclability,charging speed,reduced costs,as well as safety and stability,already contribute to the wider adoption of LIBs,which extends nowadays beyond mobile electronics,power tools,and electric vehicles,to the new range of applications,including grid storage solutions.With numerous published papers and broad reviews already available on the subject of Ni-rich oxides,this review focuses more on the most recent progress and new ideas presented in the literature references.The covered topics include doping and composition optimization,advanced coating,concentration gradient and single crystal materials,as well as innovations concerning new electrolytes and their modification,with the application of Ni-rich cathodes in solid-state batteries also discussed.Related cathode materials are briefly mentioned,with the high-entropy approach and zero-strain concept presented as well.A critical overview of the still unresolved issues is given,with perspectives on the further directions of studies and the expected gains provided.展开更多
Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(te...Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.展开更多
In recent decades,the importance of surface acoustic waves,as a biocompatible tool to integrate with microfluidics,has been proven in various medical and biological applications.The numerical modeling of acoustic stre...In recent decades,the importance of surface acoustic waves,as a biocompatible tool to integrate with microfluidics,has been proven in various medical and biological applications.The numerical modeling of acoustic streaming caused by surface acoustic waves in microchannels requires the effect of viscosity to be considered in the equations which complicates the solution.In this paper,it is shown that the major contribution of viscosity and the horizontal component of actuation is concentrated in a narrow region alongside the actuation boundary.Since the inviscid equations are considerably easier to solve,a division into the viscous and inviscid domains would alleviate the computational load significantly.The particles'traces calculated by this approximation are excellently alongside their counterparts from the completely viscous model.It is also shown that the optimum thickness for the viscous strip is about 9-fold the acoustic boundary layer thickness for various flow patterns and amplitudes of actuation.展开更多
Inspired by the function of crucial components in photosystemⅡ(PSⅡ),electrochemical and dyesensitized photoelectrochemical(DSPEC)water oxidation devices were constructed by the selfassembly of well-designed amphipat...Inspired by the function of crucial components in photosystemⅡ(PSⅡ),electrochemical and dyesensitized photoelectrochemical(DSPEC)water oxidation devices were constructed by the selfassembly of well-designed amphipathic Ru(bda)-based catalysts(bda=2,2'-bipyrdine-6,6'-dicarbonoxyl acid)and aliphatic chain decorated electrode surfaces,forming lipid bilayer membrane(LBM)-like structures.The Ru(bda)catalysts on electrode-supported LBM films demonstrated remarkable water oxidation performance with different O-O formation mechanisms.However,compared to the slow charge transfer process,the O-O formation pathways did not determine the PEC water oxidation efficiency of the dyesensitized photoanodes,and the different reaction rates for similar catalysts with different catalytic paths did not determine the PEC performance of the DSPECs.Instead,charge transfer plays a decisive role in the PEC water oxidation rate.When an indolo[3,2-b]carbazole derivative was introduced between the Ru(bda)catalysts and aliphatic chain-modified photosensitizer in LBM films,serving as a charge transfer mediator for the tyrosine-histidine pair in PSⅡ,the PEC water oxidation performance of the corresponding photoanodes was dramatically enhanced.展开更多
Direct seawater electrolysis for hydrogen production has been regarded as a viable route to utilize surplus renewable energy and address the climate crisis.However,the harsh electrochemical environment of seawater,par...Direct seawater electrolysis for hydrogen production has been regarded as a viable route to utilize surplus renewable energy and address the climate crisis.However,the harsh electrochemical environment of seawater,particularly the presence of aggressive Cl^(-),has been proven to be prone to parasitic chloride ion oxidation and corrosion reactions,thus restricting seawater electrolyzer lifetime.Herein,hierarchical structure(Ni,Fe)O(OH)@NiCoS nanorod arrays(NAs)catalysts with heterointerfaces and localized oxygen vacancies were synthesized at nickel foam substrates via the combination of hydrothermal and annealing methods to boost seawater dissociation.The hiera rchical nanostructure of NiCoS NAs enhanced electrode charge transfer rate and active surface area to accelerate oxygen evolution reaction(OER)and generated sulfate gradient layers to repulsive aggressive Cl^(-).The fabricated heterostructure and vacancies of(Ni,Fe)O(OH)tuned catalyst electronic structure into an electrophilic state to enhance the binding affinity of hydroxyl intermediates and facilitate the structural transformation into amorphousγ-NiFeOOH for promoting OER.Furthermore,through operando electrochemistry techniques,we found that theγ-NiFeOOH possessing an unsaturated coordination environment and lattice-oxygen-participated OER mechanism can minimize electrode Cl^(-)corrosion enabled by stabilizing the adsorption of OH*intermediates,making it one of the best OER catalysts in the seawater medium reported to date.Consequently,these catalysts can deliver current densities of 100 and 500 mA cm-2for boosting OER at minimal overpotentials of 245and 316 mV,respectively,and thus prevent chloride ion oxidation simultaneously.Impressively,a highly stable anion exchange membrane(AEM)seawater electrolyzer based on the non-noble metal heterostructure electrodes reached a record low degradation rate under 100μV h-1at constant industrial current densities of 400 and 600 mA cm-2over 300 h,which exhibits a promising future for the nonprecious and stable AEMWE in the direct seawater electrolysis industry.展开更多
Platinum-based alloy nanoparticles are the most attractive catalysts for the oxygen reduction reaction at present,but an in-depth understanding of the relationship between their short-range structural information and ...Platinum-based alloy nanoparticles are the most attractive catalysts for the oxygen reduction reaction at present,but an in-depth understanding of the relationship between their short-range structural information and catalytic performance is still lacking.Herein,we present a synthetic strategy that uses transition-metal oxide-assisted thermal diffusion.PtCo/C catalysts with localized tetragonal distortion were obtained by controlling the thermal diffusion process of transition-metal elements.This localized structural distortion induced a significant strain effect on the nanoparticle surface,which further shortened the length of the Pt-Pt bond,improved the electronic state of the Pt surface,and enhanced the performance of the catalyst.PtCo/C catalysts with special short-range structures achieved excellent mass activity(2.27 Amg_(Pt)^(-1))and specific activity(3.34 A cm^(-2)).In addition,the localized tetragonal distortion-induced surface compression of the Pt skin improved the stability of the catalyst.The mass activity decreased by only 13%after 30,000 cycles.Enhanced catalyst activity and excellent durability have also been demonstrated in the proton exchange membrane fuel cell configuration.This study provides valuable insights into the development of advanced Pt-based nanocatalysts and paves the way for reducing noble-metal loading and increasing the catalytic activity and catalyst stability.展开更多
The catalysis technology of propylene dimerization to form 4-methyl-1-pentene(4MP1)using a Cu-K/K_(2)CO_(3) solid base catalyst is a well-known heterogeneous catalytic reaction.In this study,the intrinsic kinetics of ...The catalysis technology of propylene dimerization to form 4-methyl-1-pentene(4MP1)using a Cu-K/K_(2)CO_(3) solid base catalyst is a well-known heterogeneous catalytic reaction.In this study,the intrinsic kinetics of propylene dimerization were studied in a fixed-bed continuous reactor.Internal and external diffusion during the dimerization reaction experiments were eliminated by adjusting the flow rate of the carrier gas and the particle size of the catalyst support.Then,the concentration changes of each substance at the outlet of the catalyst bed under different residence times were investigated.Moreover,the suitable reaction kinetics equations was derived using the Langmuir Hinshelwood-Hougen-Watson kinetic model.Finally,the activation energy for each reaction involved in the dimerization reaction was calculated.The activation energies of 4MP1,branched by-products,and 1-hexene were 115.0,150.8,and 177.4 kJ/mol,respectively.The effect of process conditions on propylene dimerization with solid base catalysts was studied through kinetic model simulation.By comparing the theoretical values obtained from the simulation with the experimental results,the applicability and accuracy of the kinetic model were verified.展开更多
Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Here...Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N_(2)-bidentate(note that N_(2)-bidentate site=N^N-bidentate site;N_(2)≠dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N_(2)-bidentate site,a Cu SAC with isolated undercoordinated Cu-N_(2) sites(Cu1.0/N_(2)-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N_(2)-GDY exhibits the highest Faradaic efficiency(FE)of 80.6% for CH_(4) in electrocatalytic reduction of CO_(2) at-0.96 V vs.RHE,and the partial current density of CH_(4) is 160 mA cm^(-2).The selectivity for CH_(4) is maintained above 70% when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N_(2)-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N_(2) sites are more favorable in generating key ^(*)COOH and ^(*)CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N_(2) sites toward efficient electrocatalysis.展开更多
As a natural organic polymer,xanthan gum(XG)can alleviate the plastic deformation of gel ink under strong stress and realize the reasonable regulation of the rheological properties of gel ink.However,as the double-hel...As a natural organic polymer,xanthan gum(XG)can alleviate the plastic deformation of gel ink under strong stress and realize the reasonable regulation of the rheological properties of gel ink.However,as the double-helix structure connected by hydrogen bonds cannot resist the mechanical environment of strong stress,XG shows poor shear resistance.In this study,a polymer gel with interpenetrating polymer network structure was prepared by esterifying XG,taking polystyrene maleic anhydride(SMA)as the modifier.In addition to retaining the excellent rheological properties of XG,the generated polymer gel also exhibited high shear resistance.The optimal addition amount of the esterification reaction modifier was determined as mXG:mSMA=5:3 according to the gel ink standard.With this amount,the viscosity of the modified xanthan gum(SXG)gel increased to 1578.8 mPa·s and 100.7 mPa·s at shear rates of 4 s1 and 383 s1,respectively,and the shear resistance increased more than 2 times compared to the unmodified one.It is because of the ester bond formed by esterification that the reaction strengthens the interaction between molecular segments,enabling the new gel to resist to strong mechanical stress.The new polymer gel studied in this paper and the proposed mechanism of action provide new insights for the development of high-end gel ink and also provide theoretical support for the study of rheological properties of non-Newtonian fluids.展开更多
Melamine formaldehyde foam(MFF)generates many poisonous chemicals through the traditional recycling methods for organic resin wastes.Herein,a high MFF degradation ratio of ca.97 wt.%was achieved under the mild conditi...Melamine formaldehyde foam(MFF)generates many poisonous chemicals through the traditional recycling methods for organic resin wastes.Herein,a high MFF degradation ratio of ca.97 wt.%was achieved under the mild conditions(160℃)in a NaOH–H2O system with ammelide and ammeline as the main degradation products.The alkaline solvent had an obvious corrosion effect for MFF,as indicated by scanning electron microscopy(SEM).The reaction process and products distribution were studied by Fourier-transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS),and ^(13)C nuclear magnetic resonance(NMR).Besides,the MFF degradation products that have the similar chemical structures and bonding performances to those of melamine can be directly used as the raw material for synthesis of melamine urea-formaldehyde resins(MUFs).Moreover,the degradation system demonstrated here showed the high degradation efficiency after reusing for 7 times.The degradation process generated few harmful pollutants and no pre-or post-treatments were required,which proves its feasibility in the safe removal or recovery of waste MFF.展开更多
Single zinc oxide nanowires(ZnO NWs)are promising for nanogenerators because of their excellent semiconducting and piezoelectric properties,but characterizing the latter efficiently is challenging.As reported here,an ...Single zinc oxide nanowires(ZnO NWs)are promising for nanogenerators because of their excellent semiconducting and piezoelectric properties,but characterizing the latter efficiently is challenging.As reported here,an electrical breakdown strategy was used to construct single ZnO NWs with a specific length.With the high operability of a nanomanipulator in a scanning electron microscope,ZnO-NW-based twoprobe and three-probe structures were constructed for fabricating AC/DC nanogenerators,respectively.For a ZnO NW,an AC output of between−15.31 mV and 5.82 mV was achieved,while for a DC nanogenerator,an output of24.3 mV was realized.Also,the three-probe structure’s output method was changed to verify the distribution of piezoelectric charges when a single ZnO NW is bent by a probe,and DC outputs of different amplitudes were achieved.This study provides a low-cost,highly convenient,and operational method for studying the AC/DC output characteristics of single NWs,which is beneficial for the further development of nanogenerators.展开更多
Spontaneous combustion of coal increases the temperature in adjoining overburden strata of coal seams and poses a challenge when loading blastholes.This condition,known as hot-hole blasting,is dangerous due to the inc...Spontaneous combustion of coal increases the temperature in adjoining overburden strata of coal seams and poses a challenge when loading blastholes.This condition,known as hot-hole blasting,is dangerous due to the increased possibility of premature explosions in loaded blastholes.Thus,it is crucial to load the blastholes with an appropriate amount of explosives within a short period to avoid premature detonation caused by high temperatures of blastholes.Additionally,it will help achieve the desired fragment size.This study tried to ascertain the most influencial variables of mean fragment size and their optimum values adopted for blasting in a fiery seam.Data on blast design,rock mass,and fragmentation of 100 blasts in fiery seams of a coal mine were collected and used to develop mean fragmentation prediction models using soft computational techniques.The coefficient of determination(R^(2)),root mean square error(RMSE),mean absolute error(MAE),mean square error(MSE),variance account for(VAF)and coefficient of efficiency in percentage(CE)were calculated to validate the results.It indicates that the random forest algorithm(RFA)outperforms the artificial neural network(ANN),response surface method(RSM),and decision tree(DT).The values of R^(2),RMSE,MAE,MSE,VAF,and CE for RFA are 0.94,0.034,0.027,0.001,93.58,and 93.01,respectively.Multiple parametric sensitivity analyses(MPSAs)of the input variables showed that the Schmidt hammer rebound number and spacing-to-burden ratio are the most influencial variables for the blast fragment size.The analysis was finally used to define the best blast design variables to achieve optimum fragment size from blasting.The optimum factor values for RFA of S/B,ld/B and ls/ld are 1.03,1.85 and 0.7,respectively.展开更多
The presence of geothermal manifestation in Bangka Island(Southeast Sumatra,Indonesia)with the absence of Quaternary volcanic activity and also relatively low seismicity events has raised intriguing questions on the c...The presence of geothermal manifestation in Bangka Island(Southeast Sumatra,Indonesia)with the absence of Quaternary volcanic activity and also relatively low seismicity events has raised intriguing questions on the control of the geothermal system in this area.As the regional tectonic setting of Indonesia volcanic geothermal systems has been known,that of non-volcanic geothermal systems such as radiogenic system become an issue to be investigated.This study reports the geochemistry and petrography analysis of Triassic granite related to radiogenic production at the vicinity of hot springs in Bangka Island.Surface temperatures of the Bangka hot springs range from 37 to 70.7 and pH values vary between 5.6 and 7.5.These hot springs are discharging either in close to massive granite bodies or occur in between two major NE-SW striking faults zones,i.e.,Pemali fault and Payung fault.Our results indicate the average radiogenic heat production of Late Triassic Klabat granite in the northern area ranges from 28.5 to 38.34μWm^(-3)and the southern area ranges from 28.3 to 49.5μWm^(-3).In comparison to similar granite belt located in Malaysia,heat production of granitoid in Bangka hot springs is four times higher,possibly due to their different granite origins.展开更多
Oxygenated carbon materials exhibit outstanding electrocatalytic performance in the production of hydrogen peroxide(H2O2)through a two-electron oxygen reduction reaction.The nature of the active functional group and u...Oxygenated carbon materials exhibit outstanding electrocatalytic performance in the production of hydrogen peroxide(H2O2)through a two-electron oxygen reduction reaction.The nature of the active functional group and underlying reaction mechanism,however,remain unclear.Here,a comprehensive workflow was established to identify the active sites from the numerous possible structures.The common hydroxyl group at the notched edge demonstrates a key role in the two-electron process.The local chemical environment weakens the binding of OOH intermediate to substrate while enhancing interaction with solution,thereby promoting the H_(2)O_(2)production.With increasing pH,the intramolecular hydrogen bond between OOH intermediate and hydroxyl decreases,facilitating OOH desorption.Furthermore,the rise in selectivity with increasing potential stems from the suppression of the four-electron process.The active site was further validated through experiments.Guided by theoretical understanding,optimal performance was achieved with high selectivity(>95%)and current density(2.06 mA/cm^(2))in experiment.展开更多
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.
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supported by the National Natural Science Foundation of China(21908234)the National Key Research&Development Program of China(2020YFB0606404)+1 种基金the Inner Mongolia Science and Technology Agency Program(2019CG058)Shanxi Province Natural Science Foundation(202103021223063).
文摘The influences of particle size,shape,and catalyst distribution on the reactivity and hydrocarbon product selectivity of a cobalt-based catalyst for Fischer-Tropsch synthesis were investigated in the present work.A self-consistent kinetic model for Fischer-Tropsch reaction proposed here was found to correlate experimental data well and hence was used to describe the consumption rates of reactants and formation rates of hydrocarbon products.The perturbed-chain statistical associating fluid theory equation of state was used to describe vapor-liquid equilibrium behavior associated with Fischer-Tropsch reaction.Local interaction between intraparticle diffusion and Fischer-Tropsch reaction was investigated in detail.Results showed that in order to avoid the adverse influence of intraparticle diffusional limitations on catalyst reactivity and product selectivity,the use of small particles is necessary.Large eggshell spherical particles are shown to keep the original catalyst reactivity and enhance the selectivity of heavy hydrocarbon products.The suitable layer thickness for a spherical particle with a diameter of 2 mm is nearly 0.15 mm.With the same outer diameter of 2 mm,the catalyst reactivity and heavy product selectivity of hollow cylindrical particles with a layer thickness of 0.25 mm are found to be larger than eggshell spherical particles.From the viewpoint of catalytic performance,hollow cylindrical particles are a better choice for industrial applications.
基金supported by the program“Excellence Initiative-Research University”for the AGH University of Krakow(IDUB AGH,No.501.696.7996,Action 4,ID 6354)partially supported by the AGH University of Krakow under No.16.16.210.476.
文摘Undoubtedly,the enormous progress observed in recent years in the Ni-rich layered cathode materials has been crucial in terms of pushing boundaries of the Li-ion battery(LIB)technology.The achieved improvements in the energy density,cyclability,charging speed,reduced costs,as well as safety and stability,already contribute to the wider adoption of LIBs,which extends nowadays beyond mobile electronics,power tools,and electric vehicles,to the new range of applications,including grid storage solutions.With numerous published papers and broad reviews already available on the subject of Ni-rich oxides,this review focuses more on the most recent progress and new ideas presented in the literature references.The covered topics include doping and composition optimization,advanced coating,concentration gradient and single crystal materials,as well as innovations concerning new electrolytes and their modification,with the application of Ni-rich cathodes in solid-state batteries also discussed.Related cathode materials are briefly mentioned,with the high-entropy approach and zero-strain concept presented as well.A critical overview of the still unresolved issues is given,with perspectives on the further directions of studies and the expected gains provided.
基金supported by The National Key Research and Development Program of China(2021YFB4001204)National Natural Science Foundation of China(22379143)。
文摘Acid loss and plasticization of phosphoric acid(PA)-doped high-temperature polymer electrolyte membranes(HT-PEMs)are critical limitations to their practical application in fuel cells.To overcome these barriers,poly(terphenyl piperidinium)s constructed from the m-and p-isomers of terphenyl were synthesized to regulate the microstructure of the membrane.Highly rigid p-terphenyl units prompt the formation of moderate PA aggregates,where the ion-pair interaction between piperidinium and biphosphate is reinforced,leading to a reduction in the plasticizing effect.As a result,there are trade-offs between the proton conductivity,mechanical strength,and PA retention of the membranes with varied m/p-isomer ratios.The designed PA-doped PTP-20m membrane exhibits superior ionic conductivity,good mechanical strength,and excellent PA retention over a wide range of temperature(80–160°C)as well as satisfactory resistance to harsh accelerated aging tests.As a result,the membrane presents a desirable combination of performance(1.462 W cm^(-2) under the H_(2)/O_(2)condition,which is 1.5 times higher than that of PBI-based membrane)and durability(300 h at 160°C and 0.2 A cm^(-2))in the fuel cell.The results of this study provide new insights that will guide molecular design from the perspective of microstructure to improve the performance and robustness of HT-PEMs.
文摘In recent decades,the importance of surface acoustic waves,as a biocompatible tool to integrate with microfluidics,has been proven in various medical and biological applications.The numerical modeling of acoustic streaming caused by surface acoustic waves in microchannels requires the effect of viscosity to be considered in the equations which complicates the solution.In this paper,it is shown that the major contribution of viscosity and the horizontal component of actuation is concentrated in a narrow region alongside the actuation boundary.Since the inviscid equations are considerably easier to solve,a division into the viscous and inviscid domains would alleviate the computational load significantly.The particles'traces calculated by this approximation are excellently alongside their counterparts from the completely viscous model.It is also shown that the optimum thickness for the viscous strip is about 9-fold the acoustic boundary layer thickness for various flow patterns and amplitudes of actuation.
基金conducted by the Fundamental Research Center of Artificial Photosynthesis(FReCAP)financially supported by the National Natural Science Foundation of China(22172011 and 22088102)+1 种基金the National Key R&D Program of China(2022YFA0911904)the Fundamental Research Funds for the Central Universities(DUT22LK06,DUT22QN213 and DUT23LAB611)。
文摘Inspired by the function of crucial components in photosystemⅡ(PSⅡ),electrochemical and dyesensitized photoelectrochemical(DSPEC)water oxidation devices were constructed by the selfassembly of well-designed amphipathic Ru(bda)-based catalysts(bda=2,2'-bipyrdine-6,6'-dicarbonoxyl acid)and aliphatic chain decorated electrode surfaces,forming lipid bilayer membrane(LBM)-like structures.The Ru(bda)catalysts on electrode-supported LBM films demonstrated remarkable water oxidation performance with different O-O formation mechanisms.However,compared to the slow charge transfer process,the O-O formation pathways did not determine the PEC water oxidation efficiency of the dyesensitized photoanodes,and the different reaction rates for similar catalysts with different catalytic paths did not determine the PEC performance of the DSPECs.Instead,charge transfer plays a decisive role in the PEC water oxidation rate.When an indolo[3,2-b]carbazole derivative was introduced between the Ru(bda)catalysts and aliphatic chain-modified photosensitizer in LBM films,serving as a charge transfer mediator for the tyrosine-histidine pair in PSⅡ,the PEC water oxidation performance of the corresponding photoanodes was dramatically enhanced.
基金supported by the National Key Research and Development Program of China(2022YFB4002100)the Key Program of the National Natural Science Foundation of China(22090032,22090030)。
文摘Direct seawater electrolysis for hydrogen production has been regarded as a viable route to utilize surplus renewable energy and address the climate crisis.However,the harsh electrochemical environment of seawater,particularly the presence of aggressive Cl^(-),has been proven to be prone to parasitic chloride ion oxidation and corrosion reactions,thus restricting seawater electrolyzer lifetime.Herein,hierarchical structure(Ni,Fe)O(OH)@NiCoS nanorod arrays(NAs)catalysts with heterointerfaces and localized oxygen vacancies were synthesized at nickel foam substrates via the combination of hydrothermal and annealing methods to boost seawater dissociation.The hiera rchical nanostructure of NiCoS NAs enhanced electrode charge transfer rate and active surface area to accelerate oxygen evolution reaction(OER)and generated sulfate gradient layers to repulsive aggressive Cl^(-).The fabricated heterostructure and vacancies of(Ni,Fe)O(OH)tuned catalyst electronic structure into an electrophilic state to enhance the binding affinity of hydroxyl intermediates and facilitate the structural transformation into amorphousγ-NiFeOOH for promoting OER.Furthermore,through operando electrochemistry techniques,we found that theγ-NiFeOOH possessing an unsaturated coordination environment and lattice-oxygen-participated OER mechanism can minimize electrode Cl^(-)corrosion enabled by stabilizing the adsorption of OH*intermediates,making it one of the best OER catalysts in the seawater medium reported to date.Consequently,these catalysts can deliver current densities of 100 and 500 mA cm-2for boosting OER at minimal overpotentials of 245and 316 mV,respectively,and thus prevent chloride ion oxidation simultaneously.Impressively,a highly stable anion exchange membrane(AEM)seawater electrolyzer based on the non-noble metal heterostructure electrodes reached a record low degradation rate under 100μV h-1at constant industrial current densities of 400 and 600 mA cm-2over 300 h,which exhibits a promising future for the nonprecious and stable AEMWE in the direct seawater electrolysis industry.
基金supported by the National Natural Science Foundation of China (Grant No.22278123).
文摘Platinum-based alloy nanoparticles are the most attractive catalysts for the oxygen reduction reaction at present,but an in-depth understanding of the relationship between their short-range structural information and catalytic performance is still lacking.Herein,we present a synthetic strategy that uses transition-metal oxide-assisted thermal diffusion.PtCo/C catalysts with localized tetragonal distortion were obtained by controlling the thermal diffusion process of transition-metal elements.This localized structural distortion induced a significant strain effect on the nanoparticle surface,which further shortened the length of the Pt-Pt bond,improved the electronic state of the Pt surface,and enhanced the performance of the catalyst.PtCo/C catalysts with special short-range structures achieved excellent mass activity(2.27 Amg_(Pt)^(-1))and specific activity(3.34 A cm^(-2)).In addition,the localized tetragonal distortion-induced surface compression of the Pt skin improved the stability of the catalyst.The mass activity decreased by only 13%after 30,000 cycles.Enhanced catalyst activity and excellent durability have also been demonstrated in the proton exchange membrane fuel cell configuration.This study provides valuable insights into the development of advanced Pt-based nanocatalysts and paves the way for reducing noble-metal loading and increasing the catalytic activity and catalyst stability.
基金supported by the National Natural Science Foundation of China under agreement number 22378026the Project of Construction of Innovative Teams and Teacher Career Development for Universities and Colleges under Beijing Municipality(IDHT20180508).
文摘The catalysis technology of propylene dimerization to form 4-methyl-1-pentene(4MP1)using a Cu-K/K_(2)CO_(3) solid base catalyst is a well-known heterogeneous catalytic reaction.In this study,the intrinsic kinetics of propylene dimerization were studied in a fixed-bed continuous reactor.Internal and external diffusion during the dimerization reaction experiments were eliminated by adjusting the flow rate of the carrier gas and the particle size of the catalyst support.Then,the concentration changes of each substance at the outlet of the catalyst bed under different residence times were investigated.Moreover,the suitable reaction kinetics equations was derived using the Langmuir Hinshelwood-Hougen-Watson kinetic model.Finally,the activation energy for each reaction involved in the dimerization reaction was calculated.The activation energies of 4MP1,branched by-products,and 1-hexene were 115.0,150.8,and 177.4 kJ/mol,respectively.The effect of process conditions on propylene dimerization with solid base catalysts was studied through kinetic model simulation.By comparing the theoretical values obtained from the simulation with the experimental results,the applicability and accuracy of the kinetic model were verified.
文摘Developing Cu single-atom catalysts(SACs)with well-defined active sites is highly desirable for producing CH4 in the electrochemical CO_(2) reduction reaction and understanding the structure-property relationship.Herein,a new graphdiyne analogue with uniformly distributed N_(2)-bidentate(note that N_(2)-bidentate site=N^N-bidentate site;N_(2)≠dinitrogen gas in this work)sites are synthesized.Due to the strong interaction between Cu and the N_(2)-bidentate site,a Cu SAC with isolated undercoordinated Cu-N_(2) sites(Cu1.0/N_(2)-GDY)is obtained,with the Cu loading of 1.0 wt%.Cu1.0/N_(2)-GDY exhibits the highest Faradaic efficiency(FE)of 80.6% for CH_(4) in electrocatalytic reduction of CO_(2) at-0.96 V vs.RHE,and the partial current density of CH_(4) is 160 mA cm^(-2).The selectivity for CH_(4) is maintained above 70% when the total current density is 100 to 300 mA cm^(-2).More remarkably,the Cu1.0/N_(2)-GDY achieves a mass activity of 53.2 A/mgCu toward CH4 under-1.18 V vs.RHE.In situ electrochemical spectroscopic studies reveal that undercoordinated Cu-N_(2) sites are more favorable in generating key ^(*)COOH and ^(*)CHO intermediate than Cu nanoparticle counterparts.This work provides an effective pathway to produce SACs with undercoordinated Metal-N_(2) sites toward efficient electrocatalysis.
基金supported by Shanxi Provincial Science and Technology Achievement Transformation Guidance Special Program of China(202104021301052)Shanxi Provincial Patent Transformation Special Plan Project(202202054,202306013).
文摘As a natural organic polymer,xanthan gum(XG)can alleviate the plastic deformation of gel ink under strong stress and realize the reasonable regulation of the rheological properties of gel ink.However,as the double-helix structure connected by hydrogen bonds cannot resist the mechanical environment of strong stress,XG shows poor shear resistance.In this study,a polymer gel with interpenetrating polymer network structure was prepared by esterifying XG,taking polystyrene maleic anhydride(SMA)as the modifier.In addition to retaining the excellent rheological properties of XG,the generated polymer gel also exhibited high shear resistance.The optimal addition amount of the esterification reaction modifier was determined as mXG:mSMA=5:3 according to the gel ink standard.With this amount,the viscosity of the modified xanthan gum(SXG)gel increased to 1578.8 mPa·s and 100.7 mPa·s at shear rates of 4 s1 and 383 s1,respectively,and the shear resistance increased more than 2 times compared to the unmodified one.It is because of the ester bond formed by esterification that the reaction strengthens the interaction between molecular segments,enabling the new gel to resist to strong mechanical stress.The new polymer gel studied in this paper and the proposed mechanism of action provide new insights for the development of high-end gel ink and also provide theoretical support for the study of rheological properties of non-Newtonian fluids.
基金supported by the National Natural Science Foundation of China(No.21774139)China,Key Research and Development Program of Shanxi Province,China(No,202102040201009)special fund of Beijing Key Laboratory of Clean Fuels and Efficient Catalytic Emission Reduction Technology and the Fund for Shanxi“1331 Project”.Thanks to Ningbo Kejiang Culture Sci.&Tech.Development Co.,Ltd.for the help in schematic drawing。
文摘Melamine formaldehyde foam(MFF)generates many poisonous chemicals through the traditional recycling methods for organic resin wastes.Herein,a high MFF degradation ratio of ca.97 wt.%was achieved under the mild conditions(160℃)in a NaOH–H2O system with ammelide and ammeline as the main degradation products.The alkaline solvent had an obvious corrosion effect for MFF,as indicated by scanning electron microscopy(SEM).The reaction process and products distribution were studied by Fourier-transform infrared spectroscopy(FTIR),X-ray photoelectron spectroscopy(XPS),and ^(13)C nuclear magnetic resonance(NMR).Besides,the MFF degradation products that have the similar chemical structures and bonding performances to those of melamine can be directly used as the raw material for synthesis of melamine urea-formaldehyde resins(MUFs).Moreover,the degradation system demonstrated here showed the high degradation efficiency after reusing for 7 times.The degradation process generated few harmful pollutants and no pre-or post-treatments were required,which proves its feasibility in the safe removal or recovery of waste MFF.
基金supported by the Research Fund Program of the Guangdong Provincial Key Laboratory of Fuel Cell Technology (Grant No.FC202204).
文摘Single zinc oxide nanowires(ZnO NWs)are promising for nanogenerators because of their excellent semiconducting and piezoelectric properties,but characterizing the latter efficiently is challenging.As reported here,an electrical breakdown strategy was used to construct single ZnO NWs with a specific length.With the high operability of a nanomanipulator in a scanning electron microscope,ZnO-NW-based twoprobe and three-probe structures were constructed for fabricating AC/DC nanogenerators,respectively.For a ZnO NW,an AC output of between−15.31 mV and 5.82 mV was achieved,while for a DC nanogenerator,an output of24.3 mV was realized.Also,the three-probe structure’s output method was changed to verify the distribution of piezoelectric charges when a single ZnO NW is bent by a probe,and DC outputs of different amplitudes were achieved.This study provides a low-cost,highly convenient,and operational method for studying the AC/DC output characteristics of single NWs,which is beneficial for the further development of nanogenerators.
文摘Spontaneous combustion of coal increases the temperature in adjoining overburden strata of coal seams and poses a challenge when loading blastholes.This condition,known as hot-hole blasting,is dangerous due to the increased possibility of premature explosions in loaded blastholes.Thus,it is crucial to load the blastholes with an appropriate amount of explosives within a short period to avoid premature detonation caused by high temperatures of blastholes.Additionally,it will help achieve the desired fragment size.This study tried to ascertain the most influencial variables of mean fragment size and their optimum values adopted for blasting in a fiery seam.Data on blast design,rock mass,and fragmentation of 100 blasts in fiery seams of a coal mine were collected and used to develop mean fragmentation prediction models using soft computational techniques.The coefficient of determination(R^(2)),root mean square error(RMSE),mean absolute error(MAE),mean square error(MSE),variance account for(VAF)and coefficient of efficiency in percentage(CE)were calculated to validate the results.It indicates that the random forest algorithm(RFA)outperforms the artificial neural network(ANN),response surface method(RSM),and decision tree(DT).The values of R^(2),RMSE,MAE,MSE,VAF,and CE for RFA are 0.94,0.034,0.027,0.001,93.58,and 93.01,respectively.Multiple parametric sensitivity analyses(MPSAs)of the input variables showed that the Schmidt hammer rebound number and spacing-to-burden ratio are the most influencial variables for the blast fragment size.The analysis was finally used to define the best blast design variables to achieve optimum fragment size from blasting.The optimum factor values for RFA of S/B,ld/B and ls/ld are 1.03,1.85 and 0.7,respectively.
基金upported by Penelitian Disertasi Doktor grant of Ministry of Education,Culture,Research and Technology of Indonesia(0267/E5/AK.04/2022)scholarship from Institut Teknologi Sumatera.
文摘The presence of geothermal manifestation in Bangka Island(Southeast Sumatra,Indonesia)with the absence of Quaternary volcanic activity and also relatively low seismicity events has raised intriguing questions on the control of the geothermal system in this area.As the regional tectonic setting of Indonesia volcanic geothermal systems has been known,that of non-volcanic geothermal systems such as radiogenic system become an issue to be investigated.This study reports the geochemistry and petrography analysis of Triassic granite related to radiogenic production at the vicinity of hot springs in Bangka Island.Surface temperatures of the Bangka hot springs range from 37 to 70.7 and pH values vary between 5.6 and 7.5.These hot springs are discharging either in close to massive granite bodies or occur in between two major NE-SW striking faults zones,i.e.,Pemali fault and Payung fault.Our results indicate the average radiogenic heat production of Late Triassic Klabat granite in the northern area ranges from 28.5 to 38.34μWm^(-3)and the southern area ranges from 28.3 to 49.5μWm^(-3).In comparison to similar granite belt located in Malaysia,heat production of granitoid in Bangka hot springs is four times higher,possibly due to their different granite origins.
基金supported by the National Natural Science Foundation of China(No.52171022,No.22105214)Zhejiang Provincial Natural Science Foundation of China(Grant No.LXR22B030001)+3 种基金Fujian Institute of Innovation and Chinese Academy of Sciences.K.C.Wong Education Foundation(GJTD-2019-13)the National Key Research and Development Program of China(2019YFB2203400)Ningbo Yongjiang Talent Introduction Programme(2021A-036-B)NingBo S&T Innovation 2025 Major Special Programme(No:2020z059)and the“111 Project”(B20030).
文摘Oxygenated carbon materials exhibit outstanding electrocatalytic performance in the production of hydrogen peroxide(H2O2)through a two-electron oxygen reduction reaction.The nature of the active functional group and underlying reaction mechanism,however,remain unclear.Here,a comprehensive workflow was established to identify the active sites from the numerous possible structures.The common hydroxyl group at the notched edge demonstrates a key role in the two-electron process.The local chemical environment weakens the binding of OOH intermediate to substrate while enhancing interaction with solution,thereby promoting the H_(2)O_(2)production.With increasing pH,the intramolecular hydrogen bond between OOH intermediate and hydroxyl decreases,facilitating OOH desorption.Furthermore,the rise in selectivity with increasing potential stems from the suppression of the four-electron process.The active site was further validated through experiments.Guided by theoretical understanding,optimal performance was achieved with high selectivity(>95%)and current density(2.06 mA/cm^(2))in experiment.