Potential-dependent insights into the origin of high ammonia yield rate on copper surface via nitrate reduction:A computational and experimental study

Focusing on revealing the origin of high ammonia yield rate on Cu via nitrate reduction(NO3RR),we herein applied constant potential method via grand-canonical density functional theory(GC-DFT)with implicit continuum solvation model to predict the reaction energetics of NO3RR on pure copper surface in alkaline media.The potential-dependent mechanism on the most prevailing Cu(111)and the minor(100)and(110)facets were established,in consideration of NO_(2)_(−),NO,NH_(3),NH_(2)OH,N_(2),and N_(2)O as the main products.The computational results show that the major Cu(111)is the ideal surface to produce ammonia with the highest onset potential at 0.06 V(until−0.37 V)and the highest optimal potential at−0.31 V for ammonia production without kinetic obstacles in activation energies at critical steps.For other minor facets,the secondary Cu(100)shows activity to ammonia from−0.03 to−0.54 V with the ideal potential at−0.50 V,which requires larger overpotential to overcome kinetic activation energy barriers.The least Cu(110)possesses the longest potential range for ammonia yield from−0.27 to−1.12 V due to the higher adsorption coverage of nitrate,but also with higher tendency to generate di-nitrogen species.Experimental evaluations on commercial Cu/C electrocatalyst validated the accuracy of our proposed mechanism.The most influential(111)surface with highest percentage in electrocatalyst determined the trend of ammonia production.In specific,the onset potential of ammonia production at 0.1 V and emergence of yield rate peak at−0.3 V in experiments precisely located in the predicted potentials on Cu(111).Four critical factors for the high ammonia yield and selectivity on Cu surface via NO3RR are summarized,including high NO3RR activity towards ammonia on the dominant Cu(111)facet,more possibilities to produce ammonia along different pathways on each facet,excellent ability for HER inhibition and suitable surface size to suppress di-nitrogen species formation at high nitrate coverage.Overall,our work provides comprehensive potential-dependent insights into the reaction details of NO3RR to ammonia,which can serve as references for the future development of NO3RR electrocatalysts,achieving higher activity and selectivity by maximizing these characteristics of copper-based materials.

Vertical plane depth-resolved surface potential and carrier separation characteristics in flexible CZTSSe solar cells with over 12% efficiency

Cu2ZnSn(S,Se)4(CZTSSe)solar cells have resource distribution and economic advantages.The main cause of their low efficiency is carrier loss resulting from recombination of photo-generated electron and hole.To overcome this,it is important to understand their electron-hole behavior characteristics.To determine the carrier separation characteristics,we measured the surface potential and the local current in terms of the absorber depth.The elemental variation in the intragrains(IGs)and at the grain boundaries(GBs)caused a band edge shift and bandgap(Eg)change.At the absorber surface and subsurface,an upward Ec and Ev band bending structure was observed at the GBs,and the carrier separation was improved.At the absorber center,both upward Ec and Ev and downward Ec-upward Ev band bending structures were observed at the GBs,and the carrier separation was degraded.To improve the carrier separation and suppress carrier recombination,an upward Ec and Ev band bending structure at the GBs is desirable.

Ab initio potential energy surface and anharmonic vibration spectrum of NF_(3)^(+)

Potential energy surfaces(PESs), vibrational frequencies, and infrared spectra are calculated for NF_(3)^(+) using ab initio calculations, based on UCCSD(T)/cc-p VTZ combined with vibrational configuration interaction(VCI). Based on an iterative algorithm, the surfaces(SURF) program adds automatic points to the lattice representation of the potential function, the one-dimensional and two-dimensional PESs are calculated after reaching a convergence threshold, finally the smooth image of the potential energy surface is fitted. The PESs accurately account for the interaction between the different modes, with the mode q_(6) symmetrical stretching vibrations having the greatest effect on the potential energy change of the whole system throughout the potential energy surface shift. The anharmonic frequencies are obtained when the VCI matrix is diagonalized. Fundamental frequencies, overtones, and combination bands of NF_(3)^(+) are calculated, which generate the degenerate phenomenon between their frequencies. Finally, the calculated anharmonic frequency is used to plot the infrared spectra.Modal antisymmetric stretching ν_(5) and symmetric stretching ν_(6) exhibit a phenomenon of large-intensity borrowing. This study can provide data to support the characterization in the laboratory.

Impressive strides in amelioration of corrosion behavior of Mg-based alloys through the PEO process combined with surface laser process: A review

The unsatisfactory corrosion properties of Mg-based alloys pose a significant obstacle to their widespread application. Plasma electrolytic oxidation(PEO) is a prevalent and effective coating method that produces a ceramic-like oxide coating on the surface of Mg-based alloys,enhancing their resistance to corrosion. Research has demonstrated that PEO treatment can substantially improve the corrosion performance of alloys based on magnesium in the short term. In an effort to enhance the corrosion resistance of PEO coatings over an extended period of time, researchers have turned their attention to the use of laser processes as both pre-and post-treatments in conjunction with the PEO process. Various laser processes, such as laser shock melting(LSM), laser shock adhesion(LSA), laser shock texturing(LST), and laser shock peening(LSP), have been investigated for their potential to improve PEO coatings on Mg substrates and their alloys. These laser melting processes can homogenize and alter the microstructure of Mg-based alloys while leaving the bulk material unchanged, thereby modifying the substrate surface. However, the porous and rough structure of PEO coatings, with their open and interconnected pore structure, can reduce their long-term corrosion resistance. As such, various laser processes are well-suited for surface modification of these coatings. This study will first examine the PEO process and the various types of laser processes used in this process, before investigating the corrosion behavior of PEO coatings in conjunction with laser pre-and post-treatment processes.

Path-Following Control With Obstacle Avoidance of Autonomous Surface Vehicles Subject to Actuator Faults

This paper investigates the path-following control problem with obstacle avoidance of autonomous surface vehicles in the presence of actuator faults,uncertainty and external disturbances.Autonomous surface vehicles inevitably suffer from actuator faults in complex sea environments,which may cause existing obstacle avoidance strategies to fail.To reduce the influence of actuator faults,an improved artificial potential function is constructed by introducing the lower bound of actuator efficiency factors.The nonlinear state observer,which only depends on measurable position information of the autonomous surface vehicle,is used to address uncertainties and external disturbances.By using a backstepping technique and adaptive mechanism,a path-following control strategy with obstacle avoidance and fault tolerance is designed which can ensure that the tracking errors converge to a small neighborhood of zero.Compared with existing results,the proposed control strategy has the capability of obstacle avoidance and fault tolerance simultaneously.Finally,the comparison results through simulations are given to verify the effectiveness of the proposed method.

Sensitivity impacts owing to the variations in the type of zero-range pairing forces on the fission properties using the density functional theory

Using the Skyrme density functional theory,potential energy surfaces of^(240)Pu with constraints on the axial quadrupole and octupole deformations(q_(20)and q_(30))were calculated.The volume-like and surface-like pairing forces,as well as a combination of these two forces,were used for the Hartree–Fock–Bogoliubov approximation.Variations in the least-energy fission path,fission barrier,pairing energy,total kinetic energy,scission line,and mass distribution of the fission fragments based on the different forms of the pairing forces were analyzed and discussed.The fission dynamics were studied based on the timedependent generator coordinate method plus the Gaussian overlap approximation.The results demonstrated a sensitivity of the mass and charge distributions of the fission fragments on the form of the pairing force.Based on the investigation of the neutron-induced fission of^(239)Pu,among the volume,mixed,and surface pairing forces,the mixed pairing force presented a good reproduction of the experimental data.

LSDA-APF:A Local Obstacle Avoidance Algorithm for Unmanned Surface Vehicles Based on 5G Communication Environment

In view of the complex marine environment of navigation,especially in the case of multiple static and dynamic obstacles,the traditional obstacle avoidance algorithms applied to unmanned surface vehicles(USV)are prone to fall into the trap of local optimization.Therefore,this paper proposes an improved artificial potential field(APF)algorithm,which uses 5G communication technology to communicate between the USV and the control center.The algorithm introduces the USV discrimination mechanism to avoid the USV falling into local optimization when the USV encounter different obstacles in different scenarios.Considering the various scenarios between the USV and other dynamic obstacles such as vessels in the process of performing tasks,the algorithm introduces the concept of dynamic artificial potential field.For the multiple obstacles encountered in the process of USV sailing,based on the International Regulations for Preventing Collisions at Sea(COLREGS),the USV determines whether the next step will fall into local optimization through the discriminationmechanism.The local potential field of the USV will dynamically adjust,and the reverse virtual gravitational potential field will be added to prevent it from falling into the local optimization and avoid collisions.The objective function and cost function are designed at the same time,so that the USV can smoothly switch between the global path and the local obstacle avoidance.The simulation results show that the improved APF algorithm proposed in this paper can successfully avoid various obstacles in the complex marine environment,and take navigation time and economic cost into account.

Experimental investigation of the effects of oil asphaltene content on CO_(2) foam stability in the presence of nanoparticles and sodium dodecyl sulfate

Foam stability tests were performed using sodium dodecyl sulfate(SDS)surfactant and SiO2 nanoparticles as foaming system at different asphaltene concentrations,and the half-life of CO_(2) foam was measured.The mechanism of foam stability reduction in the presence of asphaltene was analyzed by scanning electron microscope(SEM),UV adsorption spectrophotometric concentration measurement and Zeta potential measurement.When the mass ratio of synthetic oil to foam-formation suspension was 1:9 and the asphaltene mass fraction increased from 0 to 15%,the half-life of SDS-stabilized foams decreased from 751 s to 239 s,and the half-life of SDS/silica-stabilized foams decreased from 912 s to 298 s.When the mass ratio of synthetic oil to foam-formation suspension was 2:8 and the asphaltene mass fraction increased from 0 to 15%,the half-life of SDS-stabilized foams decreased from 526 s to 171 s,and the half-life of SDS/silica-stabilized foams decreased from 660 s to 205 s.In addition,due to asphaltene-SDS/silica interaction in the aqueous phase,the absolute value of Zeta potential decreases,and the surface charges of particles reduce,leading to the reduction of repulsive forces between two interfaces of thin liquid film,which in turn,damages the foam stability.

Wind dynamic environment and wind-sand erosion and deposition processes on different surfaces along the Dunhuang–Golmud railway,China

The Dunhuang–Golmud railway passes through different deserts in arid areas,especially drifting-sand desert and sandy-gravel Gobi.The near-surface wind environment and wind-sand transport process vary due to different external factors,such as topography,vegetation,and regional climate,resulting in evident spatial differences in surface erosion and deposition.Consequently,the measures for preventing wind-sand hazards will differ.However,the mechanism and control theory of sand damage remain poorly understood.In this study,we used meteorological observation,three-dimensional(3D)laser scanning,and grain-size analysis to compare and evaluate the spatial distribution of wind conditions,sand erosion and deposition patterns,and grain composition in the drifting-sand desert and sandy-gravel Gobi along the Dunhuang–Golmud railway in China.Results show that the annual mean wind speed,the frequency of sand-driving wind,and the drift potential of sandy-gravel Gobi are higher than those of drifting-sand desert,indicating a greater wind strength in the sandy-gravel Gobi,which exhibits spatial heterogeneity in wind conditions.The major sediment components in sandy-gravel Gobi are very fine sand,fine sand,and medium sand,and that in drifting-sand desert are very fine sand and fine sand.We found that the sediment in the sandy-gravel Gobi is coarser than that in the drifting-sand desert based on mean grain size and sediment component.The spatial distributions of sand erosion and deposition in the sandy-gravel Gobi and drifting-sand desert are consistent,with sand deposition mainly on the west side of the railway and sand erosion on the east side of the railway.The area of sand deposition in the drifting-sand desert accounts for 75.83%of the total area,with a mean deposition thickness of 0.032 m;while the area of sand deposition in the sandy-gravel Gobi accounts for 65.31%of the total area,with a mean deposition thickness of 0.028 m,indicating greater deposition amounts in the drifting-sand desert due to the presence of more fine sediment components.However,the sand deposition is more concentrated with a greater thickness on the embankment and track in the sandy-gravel Gobi and is dispersed with a uniform thickness in the drifting-sand desert.The sand deposition on the track of the sandy-gravel Gobi mainly comes from the east side of the railway.The results of this study are helpful in developing the preventive measures and determining appropriate selection and layout measures for sand control.

Growth behavior and resource potential evaluation of gas hydrate in core fractures in Qilian Mountain permafrost area, Qinghai-Tibet Plateau

The Qilian Mountain permafrost area located in the northern of Qinghai-Tibet Plateau is a favorable place for natural gas hydrate formation and enrichment,due to its well-developed fractures and abundant gas sources.Understanding the formation and distribution of multi-component gas hydrates in fractures is crucial in accurately evaluating the hydrate reservoir resources in this area.The hydrate formation experiments were carried out using the core samples drilled from hydrate-bearing sediments in Qilian Mountain permafrost area and the multi-component gas with similar composition to natural gas hydrates in Qilian Mountain permafrost area.The formation and distribution characteristics of multi-component gas hydrates in core samples were observed in situ by X-ray Computed Tomography(X-CT)under high pressure and low temperature conditions.Results show that hydrates are mainly formed and distributed in the fractures with good connectivity.The ratios of volume of hydrates formed in fractures to the volume of fractures are about 96.8%and 60.67%in two different core samples.This indicates that the fracture surface may act as a favorable reaction site for hydrate formation in core samples.Based on the field geological data and the experimental results,it is preliminarily estimated that the inventory of methane stored in the fractured gas hydrate in Qilian Mountain permafrost area is about 8.67×1013 m3,with a resource abundance of 8.67×108 m3/km2.This study demonstrates the great resource potential of fractured gas hydrate and also provides a new way to further understand the prospect of natural gas hydrate and other oil and gas resources in Qilian Mountain permafrost area.

Surface Characterization and Tribology Behavior of PMMA Processed by Excimer Laser

Polyoxymethylene methacrylate (PMMA) is widely used in ophthalmic biomaterials. Misuse of PMMA in extreme environments is likely to damage the ocular surface and intraocular structures. The surface characterization and tribological behavior of PMMA processed using an excimer laser were investigated in this study by contrasting diferent lubrication conditions and friction cycles. The results show that the roughness of the material surface increases with laser processing, which changes its physical structure. Under lubrication, the laser-treated PMMA exhibits better hydrophilicity, especially during the use of eye drops. No obvious relationship exists between the laser-processing time and friction behavior. However, the laser treatment may contribute to the formation of friction and wear mechanisms of PMMA materials. Laser-treated PMMA in saline solution exhibits better abrasive resistance by showing a lower wear rate than that in eye drops, although it has a higher friction coefcient. In this study, the diferent friction stages in laser-treated PMMA were clarifed under two lubrication conditions. The wear rates of the laser-treated PMMA were found to decrease with the number of cycles, and the friction coefcient has a similar variation tendency. The wear behavior of the laser-treated PMMA is dominated by the main abrasive wear and secondary transferred flm formation. This study provides a theoretical basis for the development and application of ophthalmic biomaterials in complex environments by examining the material surface interface behavior and wear mechanism after laser processing using PMMA as the research matrix.

An accurate analytical surface potential model of heterojunction tunnel FET

Based on the accurate and efficient thermal injection method, we develop a fully analytical surface potential model for the heterojunction tunnel field-effect transistor(H-TFET). This model accounts for both the effects of source depletion and inversion charge, which are the key factors influencing the charge, capacitance and current in H-TFET. The accuracy of the model is validated against TCAD simulation and is greatly improved in comparison with the conventional model based on Maxwell–Boltzmann approximation. Furthermore, the dependences of the surface potential and electric field on biases are well predicted and thoroughly analyzed.

The effect of sea surface temperature increase on the potential habitat of Ommastrephes bartramii in the Northwest Pacific Ocean

In the Northwest Pacific Ocean, the squid jigging fisheries from China, Japan and other countries and regions have targeted the west winter-spring cohort of neon flying squid（Ommastrephes bartramii） from August to November since the 1970 s. This squid is a short-lived ecological opportunist with a life-span of about one year,and its population is labile and recruitment variability is driven by the environment or climate change. This variability provides a challenge for ones to forecast the key habitats affected by climate change. The catch data of O. bartramii from Chinese squid jigging fishery and the satellite-derived sea surface temperature（SST） data are used in the Northwest Pacific Ocean from August to November of 1998 to 2004, the SST preferences of O.bartramii corresponding to high values of catch per fishing day（CPUE） are determined and monthly potential habitats are predicted using a histogram analysis of the SST data. The possible changes in the potential habitats of O. bartramii in the Northwest Pacific Ocean are estimated under four climate change scenarios based on the Fourth Assessment Report（AR4） of the Intergovernmental Panel on Climate Change, i.e., 0.5, 1, 2 and 4°C increases in the SST because of the climate change. The results reveal an obvious poleward shift of the potential habitats of O. bartramii in the Northwest Pacific Ocean.

Relationship between the specific surface area of rust and the electrochemical behavior of rusted steel in a wet–dry acid corrosion environment

The relationship between the specific surface area（SSA） of rust and the electrochemical behavior of rusted steel under wet-dry acid corrosion conditions was investigated. The results showed that the corrosion current density first increased and then decreased with increasing SSA of the rust during the corrosion process. The structure of the rust changed from single-layer to double-layer, and the γ-FeOOH content decreased in the inner layer of the rust with increasing corrosion time; by contrast, the γ-FeOOH content in the outer layer was constant. When the SSA of the rust was lower than the critical SSA corresponding to the relative humidity during the drying period, condensed water in the micropores of the rust could evaporate, which prompted the diffusion of O_2 into the rust and the following formation process of γ-FeOOH, leading to an increase of corrosion current density with increasing corrosion time. However, when the SSA of the rust reached or exceeded the critical SSA, condensate water in the micro-pores of the inner layer of the rust could not evaporate which inhibited the diffusion of O_2 and decreased the γ-FeOOH content in the inner rust, leading to a decrease of corrosion current density with increasing corrosion time.

LIMITING BEHAVIOR OF BLOW-UP SOLUTIONS OF THE NLSE WITH A STARK POTENTIAL

This article is concerned with blow-up solutions of the Cauchy problem of critical nonlinear SchrSdinger equation with a Stark potential. By using the variational characterization of corresponding ground state, the limiting behavior of blow-up solutions with critical and small super-critical mass are obtained in the natural energy space ∑ = {u ∈ H^1; fRN ｜x｜^2｜u｜^2dx 〈 ＋∞）}. Moreover, an interesting concentration property of the blow-up solutions with critical mass is gotten, which reads that ｜u（t, x）｜^2→ ｜｜Q｜｜L^2 2 δx=x1 as t → T.

The effect of the attractive well of the potential energy surface for Ne-HC1 on rotationally inelastic partial wave cross sections

An interaction potential of the Ne-HC1 van der Waals complex is obtained by utilizing the Huxley analytic potential function to fit the accurate interaction energy data, which have been computed at the coupled cluster singles and doubles including connected triple excitations level and with the augmented correlation consistent polarized valence quintuple zeta basis set extended with a set of 3s3p2dlflg mid-bond functions [CCSD （T）/aug-cc-pV5Z-33211]. The close coupling calculation of state-to-state partial cross sections for collision of Ne with HC1 is first performed by employing the fitted interaction potential. This calculation is performed at the incident energies： 40, 60, 75 and 100 meV, separately. The effects of the long-range attractive and the short-range anisotropic interactions on the inelastic state-to-state partial cross sections are discussed in detail. Two maxima are present in the rotationally inelastic partial cross sections and they originate from different mechanisms.

Thermodynamics of Molten Pool Predicted by Computational Fluid Dynamics in Selective Laser Melting of Ti6Al4V:Surface Morphology Evolution and Densification Behavior

The three-dimensional physical model of the randomly packed powder material irradiated by the laser beam was established,taking into account the transformation of the material phase,the melt spreading and the interaction of the free surface of the molten pool and the recoiling pressure caused by the material evaporation during the selective laser melting.Influence of the processing parameters on the thermal behavior,the material evaporation,the surface morphology and the densification behavior in the connection region of the molten pool and the substrate was studied.It was shown that the powder material underwent the transformation from the partial melting state to the complete melting state and finally to the overheating state with the applied laser energy density increasing from 167 J/mm^(3) to 417 J/mm^(3).Therefore,the solidified track ranged from the discontinuous tracks with the rough surface to the continuous tracks with residual porosities,then to the continuous and dense tracks and terminally to the fluctuated tracks with the increase in the laser energy density.Meanwhile,the laser energy effect depth was maintained the positive relationship with the laser energy density.The vortex velocity obtained in the free surface of the molten pool towards to the rear region in the opposite laser scan direction promoted the melt convection to the edge region of the molten pool as the laser energy density was higher than 277 J/mm^(3),demonstrating the efficient energy dissipation from the center of the irradiation region to the whole part of the molten pool and the attendant production of the sufficient melt volume.Therefore,the efficient spreading of the molten pool and the metallurgical bonding ability of the melt with the substrate was obtained at the optimized laser energy density of 277 J/mm^(3).However,the severe material evaporation would take place as the melt was overheated,resulting in the formation of the residual pores and poor surface quality.

Interannual Influences of the Surface Potential Vorticity Forcing over the Tibetan Plateau on East Asian Summer Rainfall

The influences of interannual surface potential vorticity forcing over the Tibetan Plateau(TP)on East Asian summer rainfall(EASR)and upper-level circulation are explored in this study.The results show that the interannual EASR and associated circulations are closely related to the surface potential vorticity negative uniform leading mode(PVNUM)over the TP.When the PVNUM is in the positive phase,more rainfall occurs in the Yangtze River valley,South Korea,Japan,and part of northern China,less rainfall occurs in southern China,and vice versa.A possible mechanism by which PVNUM affects EASR is proposed.Unstable air induced by the positive phase of PVNUM could stimulate significant upward motion and a lower-level anomalous cyclone over the TP.As a result,a dipole heating mode with anomalous cooling over the southwestern TP and anomalous heating over the southeastern TP is generated.Sensitivity experiment results regarding this dipole heating mode indicate that anomalous cooling over the southwestern TP leads to local and northeastern Asian negative height anomalies,while anomalous heating over the southeastern TP leads to local positive height anomalies.These results greatly resemble the realistic circulation pattern associated with EASR.Further analysis indicates that the anomalous water vapor transport associated with this anomalous circulation pattern is responsible for the anomalous EASR.Consequently,changes in surface potential vorticity forcing over the TP can induce changes in EASR.

Multi-Behavior Fusion Based Potential Field Method for Path Planning of Unmanned Surface Vessel

The problem of the unmanned surface vessel (USV) path planning in static and dynamic obstacle environments is addressed in this paper. Multi-behavior fusion based potential field method is proposed, which contains three behaviors: goal-seeking, boundary-memory following and dynamic-obstacle avoidance. Then, different activation conditions are designed to determine the current behavior. Meanwhile, information on the positions, velocities and the equation of motion for obstacles are detected and calculated by sensor data. Besides, memory information is introduced into the boundary following behavior to enhance cognition capability for the obstacles, and avoid local minima problem caused by the potential field method. Finally, the results of theoretical analysis and simulation show that the collision-free path can be generated for USV within different obstacle environments, and further validated the performance and effectiveness of the presented strategy.

Potential energy surfaces of ozone in the ground state

Equilibrium parameters of ozone, such as equilibrium geometry structure parameters, force constants and dissociation energy are presented by CBS-Q ab initio calculations. The calculated equilibrium geometry structure parameters and energy are in agreement with the corresponding experimental values. The potential energy function of ozone with a C2v symmetry in the ground state is described by the simplified Sorbie-Murrell many-body expansion potential function according to the ozone molecule symmetry. The contour of bond stretching vibration potential of an O3 in the ground state, with a bond angle （θ） fixed, and the contour of O3 potential for O rotating around O1-O （R1）, with O1-O bond length taken as the one at equilibrium, are plotted. Moreover, the potentials are analysed.