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.

Adiabatic density surface,neutral density surface, potential density surface,and mixing path

In this paper,adiabatic density surface,neutral density surface and potential density surface are compared.The adiabatic density surface is defined as the surface on which a water parcel can move adiabatically,without changing its potential temperature and salinity.For a water parcel taken at a given station and pressure level,the corresponding adiabatic density surface can be determined through simple calculations.This family of surface is neutrally buoyant in the world ocean,and different from other surfaces that are not truly neutrally buoyant.In order to explore mixing path in the ocean,a mixing ratio m is introduced,which is defined as the portion of potential temperature and salinity of a water parcel that has exchanged with the environment during a segment of migration in the ocean.Two extreme situations of mixing path in the ocean are m=0(no mixing),which is represented by the adiabatic density curve,and m=1,where the original information is completely lost through mixing.The latter is represented by the neutral density curve.The reality lies in between,namely,0<m<1.In the turbulent ocean,there are potentially infinite mixing paths,some of which may be identified by using different tracers(or their combinations)and different mixing criteria.Searching for mixing paths in the real ocean presents a great challenge for further research.

Surface-sensitive electronic structure of kagome superconductor CsV_(3)Sb_(5)

We systematically study the electronic structure of a kagome superconductor CsV_(3)Sb_(5)at different temperatures coveringboth its charge density wave state and normal state with angle-resolved photoemission spectroscopy.We observe thatthe V-shaped band aroundГshows three different behaviors,referred to as a/a',βandγ,mainly at different temperatures.Detailed investigations confirm that these bands are all from the same bulk Sb-p_(z)origin,but they are quite sensitiveto the sample surface conditions mainly modulated by temperature.Thus,the intriguing temperature dependent electronicbehavior of the band nearГis affected by the sample surface condition,rather than intrinsic electronic behavior originatingfrom the phase transition.Our result systematically reveals the confusing electronic structure behavior of the energy bandsaroundГ,facilitating further exploration of the novel properties in this material.

Nonlinear change of ion-induced secondary electron emission in theκ-Al_(2)O_(3) surface charging from first-principle modelling

Secondary electron emission(SEE)induced by the positive ion is an essential physical process to influence the dynamics of gas discharge which relies on the specific surface material.Surface charging has a significant impact on the material properties,thereby affecting the SEE in the plasma-surface interactions.However,it does not attract enough attention in the previous studies.In this paper,SEE dependent on the charged surface of specific materials is described with the computational method combining a density functional theory(DFT)model from the first-principle theory and the theory of Auger neutralization.The effect ofκ-Al2O3 surface charge,as an example,on the ion-induced secondary electron emission coefficient(SEEC)is investigated by analyzing the defect energy level and band structure on the charged surface.Simulation results indicate that,with the surface charge from negative to positive,the SEEC of a part of low ionization energy ions(such as Ei=12.6 eV)increases first and then decreases,exhibiting a nonlinear changing trend.This is quite different from the monotonic decreasing tendency observed in the previous model which simplifies the electronic structure.This irregular increase of the SEEC can be attributed to the lower escaped probability of orbital energy.The results further illustrate that the excessive charge could cause the bottom of the conduction band close to the valence band,thus leading to the decrease of the orbital energy occupied by the excited electrons.The nonlinear change of SEEC demonstrates a more realistic situation of how the electronic structure of material surface influences the SEE process.This work provides an accurate method of calculating SEEC from specific materials,which is urgent in widespread physical scenarios sensitive to surface materials,such as increasingly growing practical applications concerning plasma-surface interactions.

Chemical composition and surface charge properties of montmorillonite

The effects of the cell parameter and chemical composition on the surface charge properties of five kinds of different colour montmorillonites were studied. The results indicate that the surface isoelectric point（IEP） of the montmorillonite shows positive correlation with the mass fractions of Fe203 and K20, but it has little relation to the mass fractions of other chemical compositions. At around pH=6.8, the surface zeta potential of the montmorillonite shows the negative relationship with the mass fractions of Fe203 and MgO, but it does not linearly correlate to the mass fractions of other chemical compositions. Cell parameter（bo） of the montmorillonite expresses negative linear relationship with mass fractions of K2O and Na2O, so does cosinβ with mass fractions of SlOE and Fe2O3. And there is no specific relationship between bo and IEP of different montmorillonites, but there is positive correlation between cosinβ and IEP of different montmorillonite samples.

Pitfalls and Uncertainties of Using Potentiometric Titration for Estimation of Plant Roots Surface Charge and Acid-Base Properties

Amount and properties of roots surface charge are important for nutrient uptake and balance in plants. Roots surface charge markedly varies at different rizosphere conditions (particularly pH and ionic strength), which can markedly alter during vegetation season. Among recently available measuring methods, surface charge-pH dependence of roots (as well as other biological objects) is most easily evaluated by potentiometric titration. Use of this method is also easy at different ionic strengths. Potentiometric titration also allows for estimation of the distribution of charge generating surface groups. However, many applications of this method seem to be based either on incorrect methodical or theoretical approaches. In this paper we discuss the methodical and theoretical backgrounds of the titration method. Basing on experimental titration curves of roots of barley grown in nutrient solution, we show inconsistency of surface charge results obtained at different measuring conditions. Limitations of theoretical interpretations of the results are outlined also.

Theoretical Description of Water from Single-Molecule to Condensed Phase:Recent Progress on Potential Energy Surfaces and Molecular Dynamics

In this work,we review recent progress on the view of potential energy surfaces and molecular dynamics study of water and its related reactions in the last decade or so.Some important gas-phase reactions of water with radicals,chemisorbed dissociative dynamics of water on solid surfaces,and statistical mechanics and vibrational spectrum simulations of water from clusters to the condensed phase have been introduced.The recently developed machine learning techniques,such as the neural networks in a combination of permutational invariant polynomials or fundamental invariants,the atomic neural networks framework,the gaussian approximation potentials with the smooth overlap of atomic position kernel,as well as the many-body expansion framework for the construction of highly accurate potential energy surfaces,have also been discussed.Finally,some suggestions have been provided for further improvement of the potential energy surfaces and dynamics methods of water-related systems.

Review of Global Ocean Intermediate Water Masses: 1.Part A, the Neutral Density Surface (the ‘McDougall Surface’) as a Study Frame for Water-Mass Analysis

This review article commences with a comprehensive historical review of the evolution and application of various density surfaces in atmospheric and oceanic studies. The background provides a basis for the birth of the neutral density idea. Attention is paid to the development of the neutral density surface concept from the nonlinearity of the equation of state of seawater. The definition and properties of neutral density surface are described in detail as developed from the equations of state of seawater and the buoyancy frequency when the squared buoyancy frequency N2 is zero, a neutral state of stability. In order to apply the neutral density surface to intermediate water-mass analysis, this review also describes in detail its practical oceanographic application. The mapping technique is focused for the first time on applying regularly gridded data in this review. It is reviewed how a backbone and ribs framework was designed to flesh out from a reference cast and first mapped the global neutral surfaces in the world’s oceans. Several mapped neutral density surfaces are presented as examples for each world ocean. The water-mass property is analyzed in each ocean at mid-depth. The characteristics of neutral density surfaces are compared with those of potential density surfaces.

Analysis of Potential Energy Surface for Butanone Isomerization

The potential energy surfaces for butanone isomerization have been investigated by density function theory calculation. Six main reaction pathways are confirmed using the intrinsic reaction coordinate method, and the corresponding isomerization products are 1-buten-2-ol, 2-buten-2-ol, butanal or 1-buten-l-ol, methyl 1-propenyl ether, methyl allyl ether, and ethyl vinyl ether, respectively. Among them, there are three pathways through butylene oxide, indicating butylene oxide is an important intermediate product during butanone isomer ization. The calculated vertical ionization energies of the reactant and its products are in a good agreement with the experimental values available. From the consideration for the relative energies Of transition states and the number of high-energy barriers we infer that the reaction pathway butanone-＊l-buten-2-ol---2-buten-2-oi is the most competitive. The obtained results are informative for future studies on isomerization of ketone molecules.

Enhanced surface-insulating performance of EP composites by doping plasmafluorinated ZnO nanofiller

The surface flashover of epoxy resin(EP) composites is a pivotal problem in the field of highvoltage insulation.The regulation of the interface between the filler and matrix is an effective means to suppress flashover.In this work,nano ZnO was fluorinated and grafted using lowtemperature plasma technology,and the fluorinated filler was doped into EP to study the DC surface flashover performance of the composite.The results show that plasma fluorination can effectively inhibit the agglomeration by grafting –CFxgroups onto the surface of nano-ZnO particles.The fluorine-containing groups at the interface provide higher charge binding traps and enhance the insulation strength at the interface.At the same time,the interface bond cooperation caused by plasma treatment also promoted the accelerating effect of nano ZnO on charge dissipation.The two effects synergistically improve the surface flashover performance of epoxy composites.When the concentration of fluorinated ZnO filler is 20%,the flashover voltage has the highest increase,which is 31.52% higher than that of pure EP.In addition,fluorinated ZnO can effectively reduce the dielectric constant and dielectric loss of epoxy composites.The interface interaction mechanism was further analyzed using molecular dynamics simulation and density functional theory simulation.

Promoted surface charge density from interlayer Zn–N_(4) configuration in carbon nitride for enhanced CO_(2) photoreduction

The solar-driven reduction of CO_(2) into valuable products is a promising method to alleviate global environmental problems and energy crises.However,the low surface charge density limits the photocatalytic conversion performance of CO_(2).Herein,a polymeric carbon nitride(PCN)photocatalyst with Zn single atoms(Zn1/CN)was designed and synthesized for CO_(2) photoreduction.The results of the CO_(2) photoreduction studies show that the CO and CH_(4) yields of Zn1/CN increased fivefold,reaching 76.9 and 22.9μmol/(g·h),respectively,in contrast to the unmodified PCN.Ar+plasma-etched X-ray photoelectron spectroscopy and synchrotron radiation-based X-ray absorption fine structure results reveal that Zn single atom is mainly present in the interlayer space of PCN in the Zn–N_(4) configuration.Photoelectrochemical characterizations indicate that the interlayer Zn–N_(4) configuration can amplify light absorption and establish an interlayer charge transfer channel.Light-assisted Kelvin probe force microscopy confirms that more photogenerated electrons are delivered to the catalyst surface through interlayer Zn–N_(4) configuration,which increases its surface charge density.Further,in-situ infrared spectroscopy combined with density functional theory calculation reveals that promoted surface charge density accelerates key intermediates(*COOH)conversion,thus achieving efficient CO_(2) conversion.This work elucidates the role of internal single atoms in catalytic surface reactions,which provides important implications for the design of single-atom catalysts.

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.

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.

Effects of dielectric decrement on surface potential in a mixed electrolyte solution

Surface potential is an important parameter related to the physical and chemical properties of charged particles. A simple analytical model for the estimation of surface potential is established based on the Poisson–Boltzmann theory with the consideration of the dielectric decrement in mixed electrolyte. The analytical relationships between surface potential and charge density are derived in different mixed electrolytes with monovalent and bivalent ions. The dielectric decrease on the charged surface strongly affects the surface potential at a high charge density with different ion strengths and concentration ratios of counter-ions. The surface potential based on the Gouy–Chapman model is underestimated because of the dielectric decrement on the surface. The diffuse layer can be regarded as a continuous uniform medium only when the surface charge density is lower than 0.3 C·m-2. However, the surface charge densities of many materials in practical applications are higher than 0.3 C·m-2. The new model for the estimation of surface potential can return to the results obtained based on the Gouy–Chapman model at a low charge density. Therefore, it is implied that the established model that considers the dielectric decrement is valid and widely applicable.

Surface charging activated mechanism change: A computational study of O, CO, and CO2 interactions on Ag electrodes

Electrocatalytic and plasma-activated processes receive increasing attention in catalysis. Density functional theory(DFT) calculations are state-of-the-art tools for the fundamental study of reaction mechanisms and predicting the performance of catalytic materials. Proper application of DFT-based methods is crucial when investigating charge-doped electrode surfaces during electrocatalytic and plasma-activated reactions. Here, as a model electrode for plasma-activated CO2 splitting, we studied the interactions of O, CO, and CO2 with the neutral and progressively charged Ag(111) metal surfaces. We show that the application of correction procedures is necessary to obtain accurate adsorption energy profiles of O atoms,CO and CO2 molecules on Ag surfaces that are under the influence of additional electrons. Interestingly,the oxidation of CO is found to shift from a Langmuir–Hinshelwood mechanism on a neutral electrode to an Eley–Rideal mechanism on charged electrodes. Furthermore, we show that the surface charging of Ag(111) electrodes increase their CO2 reduction performance by enhancing the adsorption of O atoms and desorption of CO molecules. A further increase in the absolute charge-state of the electrode surface is expected to waive the thermodynamic barriers for the CO2 splitting reaction.

Dynamics of Charge Transfer by Surface Electric Discharges in Atmospheric Air

This work reveals essential details of plasma-surface interaction in atmospheric air that are important for a wide range of applications, beginning from airflow control and up to the high-voltage insulation. The paper discusses experimental data characterizing dynamics of development and kinetics of energy coupling in surface dielectric barrier discharge (SDBD), atmospheric air plasmas sustained over dielectric surfaces, over a wide range of time scales. The experiments have been conducted using microsecond pulse voltage waveform of single and alternating polarities. Time-resolved discharge development and mechanisms of coupling with quiescent air are analyzed using nanosecond gate camera imaging, electrical measurements, and original surface charge sensors. The results demonstrate several new, critically important processes overlooked in previous studies. Specifically, it is shown that SDBD plasmas energy release may be significantly increased by using an optimized waveform.

Role of Ion-Surface Interaction at the Entry Surface on the Energy Loss of Highly Charged Slow Ions in Solids

Evidence is obtained from the data of an earlier measurement that the effect of ion-surface interaction on the stopping power of highly charged slow ions is not at all tiny rather remarkably large, even it supersedes the bulk stopping power. The stopping power due to the surface interactions is directly proportional to the charge state of incident ions.

Enhanced oxygen reduction reaction performance over Pd catalysts by oxygen-surface-modified SiC

Obtaining a detailed understanding of the surface modification of supports is crucial;however,it is a challenging task for the development and large-scale fabrication of supported electrocatalysts that can be used as alternatives to Pt-based catalysts for the oxygen reduction reaction(ORR).In this study,commercial silicon carbide(SiC)was modified through surface oxidization(O-SiC)to support the use of Pd nanoparticles(Pd NPs)as electrocatalysts for ORR.The obtained Pd/O-SiC catalysts exhibited better ORR activity,stronger durability,and higher resistance to methanol poisoning than that exhibited by commercial Pt/C.The role of the support in enhancing the ORR performance,especially the oxidization of SiC surfaces,was discussed in detail based on the experimental characterizations and density functional theory calculations.The underlying mechanism of the superior ORR performance of Pd/O-SiC catalysts was attributed to the charge transfer from SiC_(x)O_(y)to Pd NPs on the surfaces of SiC and the strong metal–support interactions(SMSIs)between Pd and SiC_(x)O_(y).The charge transfer enhanced the ORR activity by inducing electron-rich Pd,increased the adsorption of the key intermediate OOH,and decreased the Gibbs free energy of the critical ORR step.Furthermore,SMSIs enhanced the ORR stability of the Pd/O-SiC catalyst.This study provided a facile route for designing and developing highly active Pd-based ORR electrocatalysts.

Surface Hardness as an Indicator of Soil Strength of Agricultural Soils

Soil strength is an important quality of agricultural soils prone to traffic. Surface hardness (SH) measured by the Clegg Impact Tester (CIT) was evaluated as an indicator for assessing soil strength. Proctor tests were performed on a diverse range of soils to examine the relationships between bulk density (BD), penetration resistance (PR), SH and water content. All three indices showed typical response curves with increasing water content, with notable differences among the soils. Maximum dry bulk density (MDBD), peak penetration resistance (PPR) and peak surface hardness (PSH) showed values of 1.98 Mg m-3, 8.2 MPa and 248 Cmax for Piarco, River Estate and Piarco respectively. Corresponding critical moisture contents (CMC) were much greater for MDBD compared to PPR and PSH. SH showed a significant positive correlation with PR, but not BD. Further divulgence into the relationships between SH and other soil properties as well as crop response will facilitate greater use of the CIT.

Three-dimensional potential energy surface for fission of^(236)U within covariant density functional theory

We calculate the three-dimensional potential energy surface(PES)for the fission of the compound nucleus^(236)U using covariant density functional theory with constraints on the axial quadrupole and octupole deformations(β_(2),β_(3))coexistence of the elongated and compact fission modes is predicted for comes shallow across a large range of quadrupole and octupole deformations for small scission line in the(β_(2),β_(3))plane extends to a shallow band,leading to fluctuations of several to ten MeV in the estimated total kinetic energies and of several to approximately ten nucleons in the fragment masses.