Buckypapers(BPs)consist of carbon nanotube(CNT)membranes with good mechanical,thermal and elec-trical properties.We report the modification of CNT buckypapers by the surface deposition of a thin layer of ti-tanium dio...Buckypapers(BPs)consist of carbon nanotube(CNT)membranes with good mechanical,thermal and elec-trical properties.We report the modification of CNT buckypapers by the surface deposition of a thin layer of ti-tanium dioxide and their subsequent photocatalytic use for the removal of three wastewater pollutants:diclofenac(DF),carbofuran(CB)and methylene blue(MB).The results show the following decreases(RE)in the initial concentrations of these pollutants,REDF=99.5%,REMB=96%and RECB=90%after 90 min of exposure to UV-Vis radiation using~0.6 mg of photocatalyst.Experiments also showed that the degradation rate of diclofenac(k=0.1028 min^(−1))is respectively 3.5 and 6 times faster than the values for CB(k=0.0298 min^(−1))and MB(k=0.0174 min^(−1)),probably due to the easier bond cleavage in DF.UV-Vis irradiated solutions of these pollutants were then analyzed by mass spectrometry to identify the species formed during photocatalysis and suggest possible degradation paths for MB,DF,and CB.Data showed that the degradation of DF involves the formation of a photocyclization product through loss of HCl molecule,clearly consuming less energy than that needed for the opening of the central aromatic ring in MB,or the loss of the N-methyl amide functional group for CB.展开更多
A strategy for the green synthesis of heterocyclicβ-ketosulfides via nucleophilic substitution ofα-halogenated ketone with het-eroaryl thiols in water media is presented.Compared with the available literature report...A strategy for the green synthesis of heterocyclicβ-ketosulfides via nucleophilic substitution ofα-halogenated ketone with het-eroaryl thiols in water media is presented.Compared with the available literature reports,this new method had the advantages of base-free,additives-free,simple operation,mild condition,greenness,high efficiency,tolerance of a broad scope of substrates.Furth-more,the reaction could easily be scaled up in gram scale and the products also could easily transformed to other useful organic compounds.Mechanism investigation indicated that the tautomerism of pyrimidine-2-thiol to pyrimidine-2(1H)-thione and the hy-drogen bonds played important roles in the reaction.展开更多
In sub nanometer carbon nanotubes,water exhibits unique dynamic characteristics,and in the high-frequency region of the infrared spectrum,where the stretching vibrations of the internal oxygen-hydrogen(O-H)bonds are c...In sub nanometer carbon nanotubes,water exhibits unique dynamic characteristics,and in the high-frequency region of the infrared spectrum,where the stretching vibrations of the internal oxygen-hydrogen(O-H)bonds are closely related to the hydrogen bonds(H-bonds)network between water molecules.Therefore,it is crucial to analyze the relationship between these two aspects.In this paper,the infrared spectrum and motion characteristics of the stretching vibrations of the O-H bonds in one-dimensional confined water(1DCW)and bulk water(BW)in(6,6)single-walled carbon nanotubes(SWNT)are studied by molecular dynamics simulations.The results show that the stretching vibrations of the two O-H bonds in 1DCW exhibit different frequencies in the infrared spectrum,while the O-H bonds in BW display two identical main frequency peaks.Further analysis using the spring oscillator model reveals that the difference in the stretching amplitude of the O-H bonds is the main factor causing the change in vibration frequency,where an increase in stretching amplitude leads to a decrease in spring stiffness and,consequently,a lower vibration frequency.A more in-depth study found that the interaction of H-bonds between water molecules is the fundamental cause of the increased stretching amplitude and decreased vibration frequency of the O-H bonds.Finally,by analyzing the motion trajectory of the H atoms,the dynamic differences between 1DCW and BW are clearly revealed.These findings provide a new perspective for understanding the behavior of water molecules at the nanoscale and are of significant importance in advancing the development of infrared spectroscopy detection technology.展开更多
Hanyu Xu 1,Xuedan Song 1,*,Qing Zhang 1,Chang Yu 1,Jieshan Qiu 1,2,*1 Liaoning Key Lab for Energy Materials and Chemical Engineering,State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian Univers...Hanyu Xu 1,Xuedan Song 1,*,Qing Zhang 1,Chang Yu 1,Jieshan Qiu 1,2,*1 Liaoning Key Lab for Energy Materials and Chemical Engineering,State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,Liaoning Province,China.展开更多
Coal seam water injection in tunnels is an effective technical measure for preventing coal mine rock bursts.This study used the improved split Hopkinson pressure bar(SHPB)to apply three equal static stresses to water-...Coal seam water injection in tunnels is an effective technical measure for preventing coal mine rock bursts.This study used the improved split Hopkinson pressure bar(SHPB)to apply three equal static stresses to water-saturated coal to simulate the initial stress environment of coal at different depths.Then,dynamic mechanical experiments were conducted on the saturated coal at different depths to investigate the effects of water saturation and depth on the coal samples’dynamic mechanical properties.Under uniaxial compression and without lateral compression,the strength of coal samples decreased to varying degrees in the saturated state;under different depth conditions,the dynamic strength of coal in the saturated state decreased compared with that in the natural state.However,compared with that at 0 m,the reduction in the strength of coal under the saturated condition at 200,400,600,and 800 m was significantly reduced.The findings of this study provide a basic theoretical foundation for the prevention and control of dynamic coal mine disasters.展开更多
While the moisture content of soil affects significantly the blast impulse of shallow buried explosives,the role of surface-covering water(SCW)on soil in such blast impulse remains elusive.A combined experimental and ...While the moisture content of soil affects significantly the blast impulse of shallow buried explosives,the role of surface-covering water(SCW)on soil in such blast impulse remains elusive.A combined experimental and numerical study has been carried out to characterize the effect of SCW on transferred impulse and loading magnitude of shallow buried explosives.Firstly,blast tests of shallow buried explosives were conducted,with and without the SCW,to quantitatively assess the blast loading impulse.Subsequently,finite element(FE)simulations were performed and validated against experimental measurement,with good agreement achieved.The validated FE model was then employed to predict the dynamic response of a fully-clamped metallic circular target,subjected to the explosive impact of shallow buried explosives with SCW,and explore the corresponding physical mechanisms.It was demonstrated that shallow buried explosives in saturated soil generate a greater impulse transferred towards the target relative to those in dry soil.The deformation displacement of the target plate is doubled.Increasing the height of SCW results in enhanced center peak deflection of the loaded target,accompanied by subsequent fall,due to the variation of deformation pattern of the loaded target from concentrated load to uniform load.Meanwhile,the presence of SCW increases the blast impulse transferred towards the target by three times.In addition,there exists a threshold value of the burial depth that maximizes the impact impulse.This threshold exhibits a strong sensitivity to SCW height,decreasing with increasing SCW height.An empirical formula for predicting threshold has been provided.Similar conclusions can be drawn for different explosive masses.The results provide technical guidance on blast loading intensity and its spatial distribution considering shallow buried explosives in coast-land battlefields,which can ultimately contribute to better protective designs.展开更多
To investigate the explosion load characteristics and structural response law in a water mist environment in a cabin,explosion experiments are carried out.The weakening rates of the initial peak overpressure,quasistat...To investigate the explosion load characteristics and structural response law in a water mist environment in a cabin,explosion experiments are carried out.The weakening rates of the initial peak overpressure,quasistatic pressure and structural residual deflection increase with increasing working pressure of the water mist nozzle.Specifically,the weakening rate of the initial peak overpressure ranges from 7.8%to 31.0%,the quasistatic pressure weakening rate ranges from 29.2%to 41.0%,and the weakening rate of the center of the plate residual deflection ranges from 10.8%to 34.4%under the various working pressures of the nozzles.To further explore the effect of water mist explosion suppression,a method for three-dimensional numerical simulations of water mist weakening the explosion shock wave is established to explore the explosion load characteristics of the compartment and the bulkhead response law.On the basis of the dimension analysis method,empirical formulas are derived to predict the residual deflection thickness in the center of the bulkheads.These findings provide the fundamental basis for the appli-cation of water mist in anti-explosive protection.展开更多
As the proton transport channel and binder within the catalytic layer(CL),the physicochemical properties of the ionomer can affect the CL microstructure and performance of the membrane electrode assembly.In this paper...As the proton transport channel and binder within the catalytic layer(CL),the physicochemical properties of the ionomer can affect the CL microstructure and performance of the membrane electrode assembly.In this paper,we select ionomers with different side-chain lengths and investigate the effects of the side-chain structure and content of the ionomers on the performance of membrane electrode assembly(MEA).Electrochemical tests show that at a mass ratio of 10 wt.%of ionomer/Ir(I/Ir),long-side-chain(LSC)ionomer exhibits the best performance(2.141 V@2.00 A/cm^(2),while short-side-chain(SSC)ionomer is 2.208 V@2.00 A/cm^(2)).The MEA containing LSC ionomer shows better electrochemical performance than the SSC at the same I/Ir mass ratio,especially at high current density.The MEA containing LSC ionomer has a larger average pore size and porosity,which indicates that it may have better mass-transfer properties.From the analysis of voltage loss,it can be seen that LSC ionomers have a smaller ohmic impedance and mass transfer resistance than SSC ionomers.In conclusion,LSC ionomers are more conducive to water-gas transport,which can provide excellent water electrolysis performance.This article focuses on the optimization of ionomer side chains and content,which can enhance PEM water electrolysis performance at lower cost.展开更多
This study investigates the application of Gurney and flight of fragment equations,typically used to predict metal fragment velocities,in modeling the water jet behavior.Three shotgun cartridge sizes were used as the ...This study investigates the application of Gurney and flight of fragment equations,typically used to predict metal fragment velocities,in modeling the water jet behavior.Three shotgun cartridge sizes were used as the energy source:2.59 g,5.83 g,and 7.13 g.Two configurations were tested:standard(full-barrel water load)and"negative 8"(partial water load).High-speed footage captured water column velocities,and Gurney models,including infinitely tamped and open-faced configurations,combined with the flight of fragment model were used to assess prediction accuracy.Results showed charge strength significantly affects water column velocity,with higher strengths yielding greater stability and velocity retention over distance.The infinitely tamped Gurney model closely predicted experimental velocities,deviating by as little as 1.4%for standard charges and 2.8% for negative 8 charges.Additionally,interesting dynamics such as a 1-2°rise in jet height and the rear overtaking the front was observed.These findings have significant implications for optimizing PAN disruptors and enhancing performance in high-velocity fluid applications and explosive breaching systems.展开更多
Because of actual requirement,shield machine always excavates with an inclined angle in longitudinal direction.Since many previous studies mainly focus on the face stability of the horizontal shield tunnel,the effects...Because of actual requirement,shield machine always excavates with an inclined angle in longitudinal direction.Since many previous studies mainly focus on the face stability of the horizontal shield tunnel,the effects of tensile strength cut-off and pore water pressure on the face stability of the longitudinally inclined shield tunnel are not well investigated.A failure mechanism of a longitudinally inclined shield tunnel face is constructed based on the spatial discretization technique and the tensile strength cut-off criterion is introduced to modify the constructed failure mechanism.The pore water pressure is introduced as an external force into the equation of virtual work and the objective function of the chamber pressure of the shield machine is obtained.Moreover,the critical chamber pressure of the longitudinally inclined shield tunnel is computed by optimal calculation.Parametric analysis indicates that both tensile strength cut-off and pore water pressure have a significant impact on the chamber pressure and the range of the collapse block.Finally,the theoretical results are compared with the numerical results calculated by FLAC3D software which proves that the proposed approach is effective.展开更多
The maneuverability and stealth of aerial-aquatic vehicles(AAVs)is of significant importance for future integrated air-sea combat missions.To improve the maneuverability and stealth of AAVs near the water surface,this...The maneuverability and stealth of aerial-aquatic vehicles(AAVs)is of significant importance for future integrated air-sea combat missions.To improve the maneuverability and stealth of AAVs near the water surface,this paper proposed a high-maneuverability skipping motion strategy for the tandem twin-rotor AAV,inspired by the motion behavior of the flying fish to avoid aquatic and aerial predators near the water surface.The novel tandem twin-rotor AAV was employed as the research subject and a strategybased ADRC control method for validation,comparing it with a strategy-based PID control method.The results indicate that both control methods enable the designed AAV to achieve high stealth and maneuverability near the water surface with robust control stability.The strategy-based ADRC control method exhibits a certain advantage in controlling height,pitch angle,and reducing impact force.This motion strategy will offer an inspiring approach for the practical application of AAVs to some extent.展开更多
A submerged cavitation water jet(SCWJ)is an effective method to recycle solid propellant from obsolete solid engines by the breaking method.Solid propellant's breaking modes and mechanical process under SCWJ impac...A submerged cavitation water jet(SCWJ)is an effective method to recycle solid propellant from obsolete solid engines by the breaking method.Solid propellant's breaking modes and mechanical process under SCWJ impact are unclear.This study aims to understand those impact breaking mechanisms.The hydroxyl-terminated polybutadiene(HTPB)propellant was chosen as the research material,and a self-designed test system was used to conduct impact tests at four different working pressures.The high-speed camera characterized crack propagation,and the DIC method calculated strain change during the impact process.Besides,micro and macro fracture morphologies were characterized by scanning electron microscope(SEM)and computed tomography(CT)scanning.The results reveal that the compressive strain concentration region locates right below the nozzle,and the shear strain region distributes symmetrically with the jet axis,which increases to 4% at first 16th ms,the compressive strain rises to 2% and 6% in the axial and transverse direction,respectively.The two tensile cracks formed first at the compression strain concentrate region,and there generate many shear cracks around the tensile cracks,and those shear cracks that develop and aggregate cause the cracks to become wider and cut through the tensile cracks,forming the tensile-shear cracks and the impact parts eventually fail.The HTPB propellant forms a breaking hole shaped conical after impact 10 s.The mass loss increases by 17 times at maximum,with the working pressure increasing by three times.Meanwhile,the damage value of the breaking hole remaining on the surface increases by 7.8 times while 2.9 times in the depth of the breaking hole.The breaking efficiency is closely affected by working pressures.The failure modes of HTPB impacted by SCWJ are classified as tensile crack-dominated and tensile-shear crack-dominated damage mechanisms.展开更多
Alkaline water electrolysis(AWE)is the most mature technology for hydrogen production by water electrolysis.Alkaline water electrolyzer consists of multiple electrolysis cells,and a single cell consists of a diaphragm...Alkaline water electrolysis(AWE)is the most mature technology for hydrogen production by water electrolysis.Alkaline water electrolyzer consists of multiple electrolysis cells,and a single cell consists of a diaphragm,electrodes,bipolar plates and end plates,etc.The existing industrial bipolar plate channel is concave-convex structure,which is manufactured by complicated and high-cost mold punching.This structure still results in uneven electrolyte flow and low current density in the electrolytic cell,further increasing in energy consumption and cost of AWE.Thereby,in this article,the electrochemical and flow model is firstly constructed,based on the existing industrial concave and convex flow channel structure of bipolar plate,to study the current density,electrolyte flow and bubble distribution in the electrolysis cell.The reliability of the model was verified by comparison with experimental data in literature.Among which,the electrochemical current density affects the bubble yield,on the other hand,the generated bubbles cover the electrode surface,affecting the active specific surface area and ohmic resistance,which in turn affects the electrochemical reaction.The result indicates that the flow velocity near the bottom of the concave ball approaches zero,while the flow velocity on the convex ball surface is significantly higher.Additionally,vortices are observed within the flow channel structure,leading to an uneven distribution of electrolyte.Next,modelling is used to optimize the bipolar plate structure of AWE by simulating the electrochemistry and fluid flow performances of four kinds of structures,namely,concave and convex,rhombus,wedge and expanded mesh,in the bipolar plate of alkaline water electrolyzer.The results show that the expanded mesh channel structure has the largest current density of 3330 A/m^(2)and electrolyte flow velocity of 0.507 m/s in the electrolytic cell.Under the same current density,the electrolytic cell with the expanded mesh runner structure has the smallest potential and energy consumption.This work provides a useful guide for the comprehensive understanding and optimization of channel structures,and a theoretical basis for the design of large-scale electrolyzer.展开更多
Background Water deficit is an important problem in agricultural production in arid regions.With the advent of wholly mechanized technology for cotton planting in Xinjiang,it is important to determine which planting m...Background Water deficit is an important problem in agricultural production in arid regions.With the advent of wholly mechanized technology for cotton planting in Xinjiang,it is important to determine which planting mode could achieve high yield,fiber quality and water use efficiency(WUE).This study aimed to explore if chemical topping affected cotton yield,quality and water use in relation to row configuration and plant densities.Results Experiments were carried out in Xinjiang China,in 2020 and 2021 with two topping method,manual topping and chemical topping,two plant densities,low and high,and two row configurations,i.e.,76 cm equal rows and 10+66 cm narrow-wide rows,which were commonly applied in matching harvest machine.Chemical topping increased seed cotton yield,but did not affect cotton fiber quality comparing to traditional manual topping.Under equal row spacing,the WUE in higher density was 62.4%higher than in the lower one.However,under narrow-wide row spacing,the WUE in lower density was 53.3%higher than in higher one(farmers’practice).For machine-harvest cotton in Xinjiang,the optimal row configuration and plant density for chemical topping was narrow-wide rows with 15 plants m-2 or equal rows with 18 plants m-2.Conclusion The plant density recommended in narrow-wide rows was less than farmers’practice and the density in equal rows was moderate with local practice.Our results provide new knowledge on optimizing agronomic managements of machine-harvested cotton for both high yield and water efficient.展开更多
Electro-copolymerized film containing ruthenium complexes as electron-transfer(or redox)mediators and water-oxidation catalysts by an oxidative copolymerization method is presented.The addition of the redox mediator s...Electro-copolymerized film containing ruthenium complexes as electron-transfer(or redox)mediators and water-oxidation catalysts by an oxidative copolymerization method is presented.The addition of the redox mediator significantly improved the electrocatalytic water-oxidation activity and reduced the overpotential to 220 mV.The prepared electrode showed a water-oxidation catalytic rate constant kobs of 31.7 s^(-1)and an initial turnover frequency of 1.01 s^(-1)in 1000 s by potential electrolysis at 1.7 V applied bias vs NHE(normal hydrogen electrode).The kinetic isotope effect study suggests that the catalytic water oxidation reaction on the electrode surface occurs via a bimolecular coupling mechanism.展开更多
[Background]As one of the most serious environmental issues in the world,soil erosion causes water pollution,reservoir siltation,soil productivity decline,thus threatens agricultural systems and even affects global cl...[Background]As one of the most serious environmental issues in the world,soil erosion causes water pollution,reservoir siltation,soil productivity decline,thus threatens agricultural systems and even affects global climate.The benefits of ecological soil and water conservation measures(ESWCMs,such as micro basins tillage and contour tillage)are widely understood,including runoff and soil loss reducing to a certain extent when compared with traditional tillage.While few studies have focused on China’s different soil types and erosion characteristics.[Methods]We reviewed literature from Web of Science,Scopus,and China National Knowledge Infrastructure using terms like“Conservation practice”“Contour tillage”“Runoff”“Sediment”“Erosion”and“China”and retained literatures based on criteria such as natural or simulated precipitation,runoff or soil loss data,reported replications and statistics,recorded factors like location and slope,and at least two data pairs per group.Ultimately,49 literatures were selected to quantify the impacts on different ESWCMs and identify the slope and precipitation for the greatest runoff and sediment reduction by calculating the log response ratio(LRR).[Results]The three regions’soil and water conservation benefits varied due to the differences in climate,terrain,and soil properties:1)ESWCMs applied in the black soil region of Northeast China were the most effective in reducing runoff and soil loss(66.65%runoff and 75.83%sediment),followed by those applied in the purple soil region of Southwest China(39.98%runoff and 58.30%sediment)and loess soil region of Northwest China(16.36%runoff and 32.44%sediment).2)Micro basins tillage(MBT)(71.79%runoff and 87.03%sediment)no-tillage with mulch(NTM)(17.30%runoff and 32.51%sediment),collecting soil to form a ridge with no-till(CSNT)(55.78%runoff and 71.36%sediment reduction)were the most efficient soil and water conservation measures in controlling water erosion in the black soil of Northeast China,the loess soil region of Northwest China and the purple soil region of Southwest China,respectively.3)The slope gradients ranged from 0-3°,>3°-5°and>10°-15°(0-3°:97.09%;>3°-5°:74.62%;and>10°-15°:39.41%)caused the largest reduction of runoff in the black soil region of Northeast China,the loess soil region of Northwest China,and the purple soil region of Southwest China.Meanwhile,the effects of sediment reduction were the most obvious,ranging from 0-3°,>10°-15°,and>20°-25°(0-3°:89.32%;>10°-15°:75.94%;and>20°-25°:67.25%).4)The effect of ESWCMs under rainstorms was the most obvious in the black soil region of Northeast China.The effect on runoff reduction under light rain in the purple soil region of Southwest China was the most obvious,but it failed to pass the significance test in sediment reduction.[Conclusions]The results provided optimal conservation tillage measures for three regions,different slopes and different rainfalls,and provided data support for reducing regional soil and water loss in China.展开更多
In this study, a three dimensional(3D) numerical model of six-degrees-of-freedom(6DOF) is applied to simulate the water entries of twin spheres side-by-side at different lateral distances and time intervals.The turbul...In this study, a three dimensional(3D) numerical model of six-degrees-of-freedom(6DOF) is applied to simulate the water entries of twin spheres side-by-side at different lateral distances and time intervals.The turbulence structure is described using the shear-stress transport k-ω(SST k-ω) model, and the volume of fluid(VOF) method is used to track the complex air-liquid interface. The motion of spheres during water entry is simulated using an independent overset grid. The numerical model is verified by comparing the cavity evolution results from simulations and experiments. Numerical results reveal that the time interval between the twin water entries evidently affects cavity expansion and contraction behaviors in the radial direction. However, this influence is significantly weakened by increasing the lateral distance between the two spheres. In synchronous water entries, pressure is reduced on the midline of two cavities during surface closure, which is directly related to the cavity volume. The evolution of vortexes inside the two cavities is analyzed using a velocity vector field, which is affected by the lateral distance and time interval of water entries.展开更多
Crop water stress index(CWSI)is widely used for efficient irrigation management.Precise canopy temperature(T_(c))measurement is necessary to derive a reliable CWSI.The objective of this research was to investigate the...Crop water stress index(CWSI)is widely used for efficient irrigation management.Precise canopy temperature(T_(c))measurement is necessary to derive a reliable CWSI.The objective of this research was to investigate the influences of atmospheric conditions,settled height,view angle of infrared thermography,and investigating time of temperature measuring on the performance of the CWSI.Three irrigation treatments were used to create different soil water conditions during the 2020-2021 and 2021-2022 winter wheat-growing seasons.The CWSI was calculated using the CWSI-E(an empirical approach)and CWSI-T(a theoretical approach)based on the T_(c).Weather conditions were recorded continuously throughout the experimental period.The results showed that atmospheric conditions influenced the estimation of the CWSI;when the vapor pressure deficit(VPD)was>2000 Pa,the estimated CWSI was related to soil water conditions.The height of the installed infrared thermograph influenced the T_(c)values,and the differences among the T_(c)values measured at height of 3,5,and 10 m was smaller in the afternoon than in the morning.However,the lens of the thermometer facing south recorded a higher T_(c)than those facing east or north,especially at a low height,indicating that the direction of the thermometer had a significant influence on T_(c).There was a large variation in CWSI derived at different times of the day,and the midday measurements(12:00-15:00)were the most reliable for estimating CWSI.Negative linear relationships were found between the transpiration rate and CWSI-E(R^(2)of 0.3646-0.5725)and CWSI-T(R^(2)of 0.5407-0.7213).The relations between fraction of available soil water(FASW)with CWSI-T was higher than that with CWSI-E,indicating CWSI-T was more accurate for predicting crop water status.In addition,The R^(2)between CWSI-T and FASW at 14:00 was higher than that at other times,indicating that 14:00 was the optimal time for using the CWSI for crop water status monitoring.Relative higher yield of winter wheat was obtained with average seasonal values of CWSI-E and CWSI-T around 0.23 and 0.25-0.26,respectively.The CWSI-E values were more easily influenced by meteorological factors and the timing of the measurements,and using the theoretical approach to derive the CWSI was recommended for precise irrigation water management.展开更多
Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as ...Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.展开更多
基金MIUR,Italian Ministry for University and Research(EX-60%/2024)。
文摘Buckypapers(BPs)consist of carbon nanotube(CNT)membranes with good mechanical,thermal and elec-trical properties.We report the modification of CNT buckypapers by the surface deposition of a thin layer of ti-tanium dioxide and their subsequent photocatalytic use for the removal of three wastewater pollutants:diclofenac(DF),carbofuran(CB)and methylene blue(MB).The results show the following decreases(RE)in the initial concentrations of these pollutants,REDF=99.5%,REMB=96%and RECB=90%after 90 min of exposure to UV-Vis radiation using~0.6 mg of photocatalyst.Experiments also showed that the degradation rate of diclofenac(k=0.1028 min^(−1))is respectively 3.5 and 6 times faster than the values for CB(k=0.0298 min^(−1))and MB(k=0.0174 min^(−1)),probably due to the easier bond cleavage in DF.UV-Vis irradiated solutions of these pollutants were then analyzed by mass spectrometry to identify the species formed during photocatalysis and suggest possible degradation paths for MB,DF,and CB.Data showed that the degradation of DF involves the formation of a photocyclization product through loss of HCl molecule,clearly consuming less energy than that needed for the opening of the central aromatic ring in MB,or the loss of the N-methyl amide functional group for CB.
文摘A strategy for the green synthesis of heterocyclicβ-ketosulfides via nucleophilic substitution ofα-halogenated ketone with het-eroaryl thiols in water media is presented.Compared with the available literature reports,this new method had the advantages of base-free,additives-free,simple operation,mild condition,greenness,high efficiency,tolerance of a broad scope of substrates.Furth-more,the reaction could easily be scaled up in gram scale and the products also could easily transformed to other useful organic compounds.Mechanism investigation indicated that the tautomerism of pyrimidine-2-thiol to pyrimidine-2(1H)-thione and the hy-drogen bonds played important roles in the reaction.
基金Supported by the Natural Science Foundation of China(51705326,52075339)。
文摘In sub nanometer carbon nanotubes,water exhibits unique dynamic characteristics,and in the high-frequency region of the infrared spectrum,where the stretching vibrations of the internal oxygen-hydrogen(O-H)bonds are closely related to the hydrogen bonds(H-bonds)network between water molecules.Therefore,it is crucial to analyze the relationship between these two aspects.In this paper,the infrared spectrum and motion characteristics of the stretching vibrations of the O-H bonds in one-dimensional confined water(1DCW)and bulk water(BW)in(6,6)single-walled carbon nanotubes(SWNT)are studied by molecular dynamics simulations.The results show that the stretching vibrations of the two O-H bonds in 1DCW exhibit different frequencies in the infrared spectrum,while the O-H bonds in BW display two identical main frequency peaks.Further analysis using the spring oscillator model reveals that the difference in the stretching amplitude of the O-H bonds is the main factor causing the change in vibration frequency,where an increase in stretching amplitude leads to a decrease in spring stiffness and,consequently,a lower vibration frequency.A more in-depth study found that the interaction of H-bonds between water molecules is the fundamental cause of the increased stretching amplitude and decreased vibration frequency of the O-H bonds.Finally,by analyzing the motion trajectory of the H atoms,the dynamic differences between 1DCW and BW are clearly revealed.These findings provide a new perspective for understanding the behavior of water molecules at the nanoscale and are of significant importance in advancing the development of infrared spectroscopy detection technology.
文摘Hanyu Xu 1,Xuedan Song 1,*,Qing Zhang 1,Chang Yu 1,Jieshan Qiu 1,2,*1 Liaoning Key Lab for Energy Materials and Chemical Engineering,State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,Liaoning Province,China.
基金Projects(52225403,52074112)supported by the National Natural Science Foundation of ChinaProject(2022CFD009)supported by the Hubei Natural Science Foundation Innovation and Development Joint Fund Key Project,China+2 种基金Project(SDGZK2423)supported by the State Key Laboratory of Intelligent Construction and Healthy Operation and Maintenance of Deep Underground Engineering,ChinaProject(HJZKYBKT2024111)supported by the Xiangyang Federation of Social Sciences“Hanjiang Think Tank”Project,ChinaProject supported by the Hubei Superior and Distinctive Discipline Group of“New Energy Vehicle and Smart Transportation”,China。
文摘Coal seam water injection in tunnels is an effective technical measure for preventing coal mine rock bursts.This study used the improved split Hopkinson pressure bar(SHPB)to apply three equal static stresses to water-saturated coal to simulate the initial stress environment of coal at different depths.Then,dynamic mechanical experiments were conducted on the saturated coal at different depths to investigate the effects of water saturation and depth on the coal samples’dynamic mechanical properties.Under uniaxial compression and without lateral compression,the strength of coal samples decreased to varying degrees in the saturated state;under different depth conditions,the dynamic strength of coal in the saturated state decreased compared with that in the natural state.However,compared with that at 0 m,the reduction in the strength of coal under the saturated condition at 200,400,600,and 800 m was significantly reduced.The findings of this study provide a basic theoretical foundation for the prevention and control of dynamic coal mine disasters.
基金supported by the National Natural Science Foundation of China(Grant Nos.12002156,11972185,12372136)Research Fund of State Key Laboratory of Mechanics and Control for Aerospace Structures(Grant No.MCMS-I-0222K01)。
文摘While the moisture content of soil affects significantly the blast impulse of shallow buried explosives,the role of surface-covering water(SCW)on soil in such blast impulse remains elusive.A combined experimental and numerical study has been carried out to characterize the effect of SCW on transferred impulse and loading magnitude of shallow buried explosives.Firstly,blast tests of shallow buried explosives were conducted,with and without the SCW,to quantitatively assess the blast loading impulse.Subsequently,finite element(FE)simulations were performed and validated against experimental measurement,with good agreement achieved.The validated FE model was then employed to predict the dynamic response of a fully-clamped metallic circular target,subjected to the explosive impact of shallow buried explosives with SCW,and explore the corresponding physical mechanisms.It was demonstrated that shallow buried explosives in saturated soil generate a greater impulse transferred towards the target relative to those in dry soil.The deformation displacement of the target plate is doubled.Increasing the height of SCW results in enhanced center peak deflection of the loaded target,accompanied by subsequent fall,due to the variation of deformation pattern of the loaded target from concentrated load to uniform load.Meanwhile,the presence of SCW increases the blast impulse transferred towards the target by three times.In addition,there exists a threshold value of the burial depth that maximizes the impact impulse.This threshold exhibits a strong sensitivity to SCW height,decreasing with increasing SCW height.An empirical formula for predicting threshold has been provided.Similar conclusions can be drawn for different explosive masses.The results provide technical guidance on blast loading intensity and its spatial distribution considering shallow buried explosives in coast-land battlefields,which can ultimately contribute to better protective designs.
基金supported by the National Natural Science Foundation of China(grant numbers:52201334)sup-ported by National Key Laboratory of Ship Structural Safety(grant numbers:Naklas2024-KF015-s).
文摘To investigate the explosion load characteristics and structural response law in a water mist environment in a cabin,explosion experiments are carried out.The weakening rates of the initial peak overpressure,quasistatic pressure and structural residual deflection increase with increasing working pressure of the water mist nozzle.Specifically,the weakening rate of the initial peak overpressure ranges from 7.8%to 31.0%,the quasistatic pressure weakening rate ranges from 29.2%to 41.0%,and the weakening rate of the center of the plate residual deflection ranges from 10.8%to 34.4%under the various working pressures of the nozzles.To further explore the effect of water mist explosion suppression,a method for three-dimensional numerical simulations of water mist weakening the explosion shock wave is established to explore the explosion load characteristics of the compartment and the bulkhead response law.On the basis of the dimension analysis method,empirical formulas are derived to predict the residual deflection thickness in the center of the bulkheads.These findings provide the fundamental basis for the appli-cation of water mist in anti-explosive protection.
基金Project(52271013)supported by the National Natural Science Foundation of ChinaProject(23DZ1200600)supported by the Science and Technology Innovation Action Plan of Shanghai,China。
文摘As the proton transport channel and binder within the catalytic layer(CL),the physicochemical properties of the ionomer can affect the CL microstructure and performance of the membrane electrode assembly.In this paper,we select ionomers with different side-chain lengths and investigate the effects of the side-chain structure and content of the ionomers on the performance of membrane electrode assembly(MEA).Electrochemical tests show that at a mass ratio of 10 wt.%of ionomer/Ir(I/Ir),long-side-chain(LSC)ionomer exhibits the best performance(2.141 V@2.00 A/cm^(2),while short-side-chain(SSC)ionomer is 2.208 V@2.00 A/cm^(2)).The MEA containing LSC ionomer shows better electrochemical performance than the SSC at the same I/Ir mass ratio,especially at high current density.The MEA containing LSC ionomer has a larger average pore size and porosity,which indicates that it may have better mass-transfer properties.From the analysis of voltage loss,it can be seen that LSC ionomers have a smaller ohmic impedance and mass transfer resistance than SSC ionomers.In conclusion,LSC ionomers are more conducive to water-gas transport,which can provide excellent water electrolysis performance.This article focuses on the optimization of ionomer side chains and content,which can enhance PEM water electrolysis performance at lower cost.
基金supported and funded internally through Dr. Catherine Johnson's research funds at Missouri S&T
文摘This study investigates the application of Gurney and flight of fragment equations,typically used to predict metal fragment velocities,in modeling the water jet behavior.Three shotgun cartridge sizes were used as the energy source:2.59 g,5.83 g,and 7.13 g.Two configurations were tested:standard(full-barrel water load)and"negative 8"(partial water load).High-speed footage captured water column velocities,and Gurney models,including infinitely tamped and open-faced configurations,combined with the flight of fragment model were used to assess prediction accuracy.Results showed charge strength significantly affects water column velocity,with higher strengths yielding greater stability and velocity retention over distance.The infinitely tamped Gurney model closely predicted experimental velocities,deviating by as little as 1.4%for standard charges and 2.8% for negative 8 charges.Additionally,interesting dynamics such as a 1-2°rise in jet height and the rear overtaking the front was observed.These findings have significant implications for optimizing PAN disruptors and enhancing performance in high-velocity fluid applications and explosive breaching systems.
基金Projects(52278395,52208409) supported by the National Natural Science Foundation of ChinaProject(2022JJ40531) supported by the Natural Science Foundation of Hunan Province,China。
文摘Because of actual requirement,shield machine always excavates with an inclined angle in longitudinal direction.Since many previous studies mainly focus on the face stability of the horizontal shield tunnel,the effects of tensile strength cut-off and pore water pressure on the face stability of the longitudinally inclined shield tunnel are not well investigated.A failure mechanism of a longitudinally inclined shield tunnel face is constructed based on the spatial discretization technique and the tensile strength cut-off criterion is introduced to modify the constructed failure mechanism.The pore water pressure is introduced as an external force into the equation of virtual work and the objective function of the chamber pressure of the shield machine is obtained.Moreover,the critical chamber pressure of the longitudinally inclined shield tunnel is computed by optimal calculation.Parametric analysis indicates that both tensile strength cut-off and pore water pressure have a significant impact on the chamber pressure and the range of the collapse block.Finally,the theoretical results are compared with the numerical results calculated by FLAC3D software which proves that the proposed approach is effective.
基金supported by Southern Marine Science and Guangdong Laboratory(Zhuhai)(Grant No.SML2023SP229)。
文摘The maneuverability and stealth of aerial-aquatic vehicles(AAVs)is of significant importance for future integrated air-sea combat missions.To improve the maneuverability and stealth of AAVs near the water surface,this paper proposed a high-maneuverability skipping motion strategy for the tandem twin-rotor AAV,inspired by the motion behavior of the flying fish to avoid aquatic and aerial predators near the water surface.The novel tandem twin-rotor AAV was employed as the research subject and a strategybased ADRC control method for validation,comparing it with a strategy-based PID control method.The results indicate that both control methods enable the designed AAV to achieve high stealth and maneuverability near the water surface with robust control stability.The strategy-based ADRC control method exhibits a certain advantage in controlling height,pitch angle,and reducing impact force.This motion strategy will offer an inspiring approach for the practical application of AAVs to some extent.
基金supported by the Program for National Defense Science and Technology Foundation Strengtheningthe Youth Foundation of Rocket Force University of Engineering(Grant No.2021QN-B014)。
文摘A submerged cavitation water jet(SCWJ)is an effective method to recycle solid propellant from obsolete solid engines by the breaking method.Solid propellant's breaking modes and mechanical process under SCWJ impact are unclear.This study aims to understand those impact breaking mechanisms.The hydroxyl-terminated polybutadiene(HTPB)propellant was chosen as the research material,and a self-designed test system was used to conduct impact tests at four different working pressures.The high-speed camera characterized crack propagation,and the DIC method calculated strain change during the impact process.Besides,micro and macro fracture morphologies were characterized by scanning electron microscope(SEM)and computed tomography(CT)scanning.The results reveal that the compressive strain concentration region locates right below the nozzle,and the shear strain region distributes symmetrically with the jet axis,which increases to 4% at first 16th ms,the compressive strain rises to 2% and 6% in the axial and transverse direction,respectively.The two tensile cracks formed first at the compression strain concentrate region,and there generate many shear cracks around the tensile cracks,and those shear cracks that develop and aggregate cause the cracks to become wider and cut through the tensile cracks,forming the tensile-shear cracks and the impact parts eventually fail.The HTPB propellant forms a breaking hole shaped conical after impact 10 s.The mass loss increases by 17 times at maximum,with the working pressure increasing by three times.Meanwhile,the damage value of the breaking hole remaining on the surface increases by 7.8 times while 2.9 times in the depth of the breaking hole.The breaking efficiency is closely affected by working pressures.The failure modes of HTPB impacted by SCWJ are classified as tensile crack-dominated and tensile-shear crack-dominated damage mechanisms.
基金financially supported by the National Natural Science Foundation of China(No.52074130)the Engineering Research Center of Resource Utilization of Carbon-containing Waste with Carbon Neutrality,Ministry of Education。
文摘Alkaline water electrolysis(AWE)is the most mature technology for hydrogen production by water electrolysis.Alkaline water electrolyzer consists of multiple electrolysis cells,and a single cell consists of a diaphragm,electrodes,bipolar plates and end plates,etc.The existing industrial bipolar plate channel is concave-convex structure,which is manufactured by complicated and high-cost mold punching.This structure still results in uneven electrolyte flow and low current density in the electrolytic cell,further increasing in energy consumption and cost of AWE.Thereby,in this article,the electrochemical and flow model is firstly constructed,based on the existing industrial concave and convex flow channel structure of bipolar plate,to study the current density,electrolyte flow and bubble distribution in the electrolysis cell.The reliability of the model was verified by comparison with experimental data in literature.Among which,the electrochemical current density affects the bubble yield,on the other hand,the generated bubbles cover the electrode surface,affecting the active specific surface area and ohmic resistance,which in turn affects the electrochemical reaction.The result indicates that the flow velocity near the bottom of the concave ball approaches zero,while the flow velocity on the convex ball surface is significantly higher.Additionally,vortices are observed within the flow channel structure,leading to an uneven distribution of electrolyte.Next,modelling is used to optimize the bipolar plate structure of AWE by simulating the electrochemistry and fluid flow performances of four kinds of structures,namely,concave and convex,rhombus,wedge and expanded mesh,in the bipolar plate of alkaline water electrolyzer.The results show that the expanded mesh channel structure has the largest current density of 3330 A/m^(2)and electrolyte flow velocity of 0.507 m/s in the electrolytic cell.Under the same current density,the electrolytic cell with the expanded mesh runner structure has the smallest potential and energy consumption.This work provides a useful guide for the comprehensive understanding and optimization of channel structures,and a theoretical basis for the design of large-scale electrolyzer.
基金Key Research and Development Program of Xinjiang(2022B02001-1)National Natural Science Foundation of China(42105172,41975146).
文摘Background Water deficit is an important problem in agricultural production in arid regions.With the advent of wholly mechanized technology for cotton planting in Xinjiang,it is important to determine which planting mode could achieve high yield,fiber quality and water use efficiency(WUE).This study aimed to explore if chemical topping affected cotton yield,quality and water use in relation to row configuration and plant densities.Results Experiments were carried out in Xinjiang China,in 2020 and 2021 with two topping method,manual topping and chemical topping,two plant densities,low and high,and two row configurations,i.e.,76 cm equal rows and 10+66 cm narrow-wide rows,which were commonly applied in matching harvest machine.Chemical topping increased seed cotton yield,but did not affect cotton fiber quality comparing to traditional manual topping.Under equal row spacing,the WUE in higher density was 62.4%higher than in the lower one.However,under narrow-wide row spacing,the WUE in lower density was 53.3%higher than in higher one(farmers’practice).For machine-harvest cotton in Xinjiang,the optimal row configuration and plant density for chemical topping was narrow-wide rows with 15 plants m-2 or equal rows with 18 plants m-2.Conclusion The plant density recommended in narrow-wide rows was less than farmers’practice and the density in equal rows was moderate with local practice.Our results provide new knowledge on optimizing agronomic managements of machine-harvested cotton for both high yield and water efficient.
文摘Electro-copolymerized film containing ruthenium complexes as electron-transfer(or redox)mediators and water-oxidation catalysts by an oxidative copolymerization method is presented.The addition of the redox mediator significantly improved the electrocatalytic water-oxidation activity and reduced the overpotential to 220 mV.The prepared electrode showed a water-oxidation catalytic rate constant kobs of 31.7 s^(-1)and an initial turnover frequency of 1.01 s^(-1)in 1000 s by potential electrolysis at 1.7 V applied bias vs NHE(normal hydrogen electrode).The kinetic isotope effect study suggests that the catalytic water oxidation reaction on the electrode surface occurs via a bimolecular coupling mechanism.
基金Science and Technology Major Project of Tibetan Autonomous Region of China(XZ202201ZD0005G02)National Natural Science Foundation of China(42277353)Chengdu Science and Technology Project(2022-YF05-01162-SN)。
文摘[Background]As one of the most serious environmental issues in the world,soil erosion causes water pollution,reservoir siltation,soil productivity decline,thus threatens agricultural systems and even affects global climate.The benefits of ecological soil and water conservation measures(ESWCMs,such as micro basins tillage and contour tillage)are widely understood,including runoff and soil loss reducing to a certain extent when compared with traditional tillage.While few studies have focused on China’s different soil types and erosion characteristics.[Methods]We reviewed literature from Web of Science,Scopus,and China National Knowledge Infrastructure using terms like“Conservation practice”“Contour tillage”“Runoff”“Sediment”“Erosion”and“China”and retained literatures based on criteria such as natural or simulated precipitation,runoff or soil loss data,reported replications and statistics,recorded factors like location and slope,and at least two data pairs per group.Ultimately,49 literatures were selected to quantify the impacts on different ESWCMs and identify the slope and precipitation for the greatest runoff and sediment reduction by calculating the log response ratio(LRR).[Results]The three regions’soil and water conservation benefits varied due to the differences in climate,terrain,and soil properties:1)ESWCMs applied in the black soil region of Northeast China were the most effective in reducing runoff and soil loss(66.65%runoff and 75.83%sediment),followed by those applied in the purple soil region of Southwest China(39.98%runoff and 58.30%sediment)and loess soil region of Northwest China(16.36%runoff and 32.44%sediment).2)Micro basins tillage(MBT)(71.79%runoff and 87.03%sediment)no-tillage with mulch(NTM)(17.30%runoff and 32.51%sediment),collecting soil to form a ridge with no-till(CSNT)(55.78%runoff and 71.36%sediment reduction)were the most efficient soil and water conservation measures in controlling water erosion in the black soil of Northeast China,the loess soil region of Northwest China and the purple soil region of Southwest China,respectively.3)The slope gradients ranged from 0-3°,>3°-5°and>10°-15°(0-3°:97.09%;>3°-5°:74.62%;and>10°-15°:39.41%)caused the largest reduction of runoff in the black soil region of Northeast China,the loess soil region of Northwest China,and the purple soil region of Southwest China.Meanwhile,the effects of sediment reduction were the most obvious,ranging from 0-3°,>10°-15°,and>20°-25°(0-3°:89.32%;>10°-15°:75.94%;and>20°-25°:67.25%).4)The effect of ESWCMs under rainstorms was the most obvious in the black soil region of Northeast China.The effect on runoff reduction under light rain in the purple soil region of Southwest China was the most obvious,but it failed to pass the significance test in sediment reduction.[Conclusions]The results provided optimal conservation tillage measures for three regions,different slopes and different rainfalls,and provided data support for reducing regional soil and water loss in China.
基金China Academy of Launch Vehicle Technology(Grant No.CALT-2022-03)Science and Technology on Underwater Information and Control Laboratory(Grant No.2021-JCJQ-LB-030-05).
文摘In this study, a three dimensional(3D) numerical model of six-degrees-of-freedom(6DOF) is applied to simulate the water entries of twin spheres side-by-side at different lateral distances and time intervals.The turbulence structure is described using the shear-stress transport k-ω(SST k-ω) model, and the volume of fluid(VOF) method is used to track the complex air-liquid interface. The motion of spheres during water entry is simulated using an independent overset grid. The numerical model is verified by comparing the cavity evolution results from simulations and experiments. Numerical results reveal that the time interval between the twin water entries evidently affects cavity expansion and contraction behaviors in the radial direction. However, this influence is significantly weakened by increasing the lateral distance between the two spheres. In synchronous water entries, pressure is reduced on the midline of two cavities during surface closure, which is directly related to the cavity volume. The evolution of vortexes inside the two cavities is analyzed using a velocity vector field, which is affected by the lateral distance and time interval of water entries.
基金supported by the Project of State Grid Hebei Electric Power Co.,Ltd.(SGHEYX00SCJS2100077).
文摘Crop water stress index(CWSI)is widely used for efficient irrigation management.Precise canopy temperature(T_(c))measurement is necessary to derive a reliable CWSI.The objective of this research was to investigate the influences of atmospheric conditions,settled height,view angle of infrared thermography,and investigating time of temperature measuring on the performance of the CWSI.Three irrigation treatments were used to create different soil water conditions during the 2020-2021 and 2021-2022 winter wheat-growing seasons.The CWSI was calculated using the CWSI-E(an empirical approach)and CWSI-T(a theoretical approach)based on the T_(c).Weather conditions were recorded continuously throughout the experimental period.The results showed that atmospheric conditions influenced the estimation of the CWSI;when the vapor pressure deficit(VPD)was>2000 Pa,the estimated CWSI was related to soil water conditions.The height of the installed infrared thermograph influenced the T_(c)values,and the differences among the T_(c)values measured at height of 3,5,and 10 m was smaller in the afternoon than in the morning.However,the lens of the thermometer facing south recorded a higher T_(c)than those facing east or north,especially at a low height,indicating that the direction of the thermometer had a significant influence on T_(c).There was a large variation in CWSI derived at different times of the day,and the midday measurements(12:00-15:00)were the most reliable for estimating CWSI.Negative linear relationships were found between the transpiration rate and CWSI-E(R^(2)of 0.3646-0.5725)and CWSI-T(R^(2)of 0.5407-0.7213).The relations between fraction of available soil water(FASW)with CWSI-T was higher than that with CWSI-E,indicating CWSI-T was more accurate for predicting crop water status.In addition,The R^(2)between CWSI-T and FASW at 14:00 was higher than that at other times,indicating that 14:00 was the optimal time for using the CWSI for crop water status monitoring.Relative higher yield of winter wheat was obtained with average seasonal values of CWSI-E and CWSI-T around 0.23 and 0.25-0.26,respectively.The CWSI-E values were more easily influenced by meteorological factors and the timing of the measurements,and using the theoretical approach to derive the CWSI was recommended for precise irrigation water management.
基金the National Basic Research Development of China(2011CB936003)the National Natural Science Foundation of China(50971116)。
文摘Photocatalytic splitting of water over p-type semiconductors is a promising strategy for production of hydrogen.However,the determination of rate law is rarely reported.To this purpose,copper oxide(CuO)is selected as a model photocathode in this study,and the photogenerated surface charge density,interfacial charge transfer rate constant and their relation to the water reduction rate(in terms of photocurrent)were investigated by a combination of(photo)electrochemical techniques.The results showed that the charge transfer rate constant is exponential-dependent on the surface charge density,and that the photocurrent equals to the product of the charge transfer rate constant and surface charge density.The reaction is first-order in terms of surface charge density.Such an unconventional rate law contrasts with the reports in literature.The charge density-dependent rate constant results from the Fermi level pinning(i.e.,Galvani potential is the main driving force for the reaction)due to accumulation of charge in the surface states and/or Frumkin behavior(i.e.,chemical potential is the main driving force).This study,therefore,may be helpful for further investigation on the mechanism of hydrogen evolution over a CuO photocathode and for designing more efficient CuO-based photocatalysts.
