Study on synergistic leaching of potassium and phosphorus from potassium feldspar and solid waste phosphogypsum via coupling reactions

To achieve the resource utilization of solid waste phosphogypsum(PG)and tackle the problem of utilizing potassium feldspar(PF),a coupled synergistic process between PG and PF is proposed in this paper.The study investigates the features of P and F in PG,and explores the decomposition of PF using hydrofluoric acid(HF)in the sulfuric acid system for K leaching and leaching of P and F in PG.The impact factors such as sulfuric acid concentration,reaction temperature,reaction time,material ratio(PG/PF),liquid–solid ratio,PF particle size,and PF calcination temperature on the leaching of P and K is systematically investigated in this paper.The results show that under optimal conditions,the leaching rate of K and P reach more than 93%and 96%,respectively.Kinetics study using shrinking core model(SCM)indicates two significant stages with internal diffusion predominantly controlling the leaching of K.The apparent activation energies of these two stages are 11.92 kJ·mol^(-1)and 11.55 kJ·mol^(-1),respectively.

Light Inducing the Geometric Conversion of NiO_(6) to Trigger a Faster Oxygen Evolution Reaction Pathway:The Coupled Oxygen Evolution Mechanism

Developing highly active and robust oxygen evolution reaction(OER)electrocatalysts is still a critical challenge for water electrolyzers and metal-air batteries.Realizing the dynamic evolution of the intermediate and charge transfer during OER and developing a clear OER mechanism is crucial to design high-performance OER catalysts.Recently in Nature,Xue and colleagues revealed a new OER mechanism,coupled oxygen evolution mechanism(COM),which involves a switchable metal and oxygen redox under light irradiation in nickel oxyhydroxide-based materials.This newly developed mechanism requires a reversible geometric conversion between octahedron(NiO_(6))and square planar(NiO_(4))to achieve electronic states with both“metal redox”and“oxygen redox”during OER.The asymmetric structure endows NR-NiOOH with a nonoverlapping region between the dz^(2) orbitals and a_(1g)^(*)bands,which facilitate the geometric conversion and enact the COM pathway.As a result,NR-NiOOH exhibited better OER activity and stability than the traditional NiOOH.

Transportation of Two Coupled Particles in an Asymmetric Saw-Tooth Potential

Based on a simple model, we theoretically show the transport behaviors of two harmonically coupled Brownian particles in an asymmetric saw-tooth potential with two slopes. The coupled particles are subject to stochastic fluctuations. It is found that when the equilibrium distance of the coupled particles is between the two slopes of the potential, the transport direction of the coupled particles will be reversed with a certain harmonic coupling strength. This current reversal can be easily understood with the near rigid approximation, where the two coupled particles can be regarded as a single particle in an effective potential. Compared with the original saw-tooth potential, the asymmetry of the effective potential could be reversed when the equilibrium distance is between the two slopes of the original potential, which results in the current reversal.

Comparison of the interface reaction behaviors of CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) solid-state systems based on the diffusion couple method

The formation mechanism of calcium vanadate and manganese vanadate and the difference between calcium and manganese in the reaction with vanadium are basic issues in the calcification roasting and manganese roasting process with vanadium slag.In this work,CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples were prepared and roasted for different time periods to illustrate and compare the diffusion reaction mechanisms.Then,the changes in the diffusion product and diffusion coefficient were investigated and calculated based on scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) analysis.Results show that with the extension of the roasting time,the diffusion reaction gradually proceeds among the CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples.The regional boundaries of calcium and vanadium are easily identifiable for the CaO–V_(2)O_(5) diffusion couple.Meanwhile,for the MnO_(2)–V_(2)O_(5) diffusion couple,MnO_(2) gradually decomposes to form Mn_(2)O_(3),and vanadium diffuses into the interior of Mn_(2)O_(3).Only a part of vanadium combines with manganese to form the diffusion production layer.CaV_(2)O_(6) and MnV_(2)O_(6) are the interfacial reaction products of the CaO–V_(2)O_(5) and MnO_(2)–V_(2)O_(5) diffusion couples,respectively,whose thicknesses are 39.85 and 32.13μm when roasted for 16 h.After 16 h,both diffusion couples reach the reaction equilibrium due to the limitation of diffusion.The diffusion coefficient of the CaO–V_(2)O_(5) diffusion couple is higher than that of the MnO_(2)–V_(2)O_(5) diffusion couple for the same roasting time,and the diffusion reaction between vanadium and calcium is easier than that between vanadium and manganese.

Recent advances in paired electrolysis coupling CO_(2) reduction with alternative oxidation reactions

Electrocatalytic CO_(2) reduction reaction(CO_(2)RR)holds great promise in green energy conversion and storage.However,for current CO_(2) electrolyzers that rely on the oxygen evolution reaction,a large portion of the input energy is"wasted"at the anode due to the high overpotential requirement and the recovery of low-value oxygen.To make efficient use of the electricity during electrolysis,coupling CO_(2)RR with anodic alternatives that have low energy demands and/or profitable returns with high-value products is then promising.Herein,we review the latest advances in paired systems for simultaneous CO_(2) reduction and anode valorization.We start with the cases integrating CO_(2)RR with concurrent alternative oxidation,such as inorganic oxidation using chloride,sulfide,ammonia and urea,and organic oxidation using alcohols,aldehydes and primary amines.The paired systems that couple CO_(2)RR with on-site oxidative upgrading of CO_(2)-reduced chemicals are also introduced.The coupling mechanism,electrochemical performance and economic viability of these co-electrolysis systems are discussed.Thereby,we then point out the mismatch issues between the cathodic and anodic reactions regrading catalyst ability,electrolyte solution and reactant supply that will challenge the applications of these paired electrolysis systems.Opportunities to address these issues are further proposed,providing some guidance for future research.

Single photon transport properties in coupled cavity arrays nonlocally coupled to a two-level atom in the presence of dissipation

We discuss the effects of dissipation on the behavior of single photon transport in a system of coupled cavity arrays, with the two nearest cavities nonlocally coupled to a two-level atom. The single photon transmission amplitude is solved exactly by employing the quasi-boson picture. We investigate two different situations of local and nonlocal couplings, respectively. Comparing the dissipative case with the nondissipative one reveals that the dissipation of the system increases the middle dip and lowers the peak of the single photon transmission amplitudes, broadening the line width of the transport spectrum. It should be noted that the influence of the cavity dissipation to the single photon transport spectrum is asymmet- ric. By comparing the nonlocal coupling with the local one, one can find that the enhancement of the middle dip of single photon transmission amplitudes is mostly caused by the atom dissipation and that the reduced peak is mainly caused by the cavity dissipation, no matter whether it is a nonlocal or local coupling case. Whereas in the nonlocal coupling case, when the coupling strength gets stronger, the cavity dissipation has a greater effect on the single photon transport spectrum and the atom dissipation affection becomes weak, so it can be ignored.

Insight into coupled Ni-Co dual-metal atom catalysts for efficient synergistic electrochemical CO_(2)reduction

The development of highly active,selective,and stable electrocatalysts can facilitate the effective implementation of electrocatalytic CO_(2)conversion into fuels or chemicals for mitigating the energy crisis and climate problems.Therefore,it is necessary to achieve the goal through reasonable material design based on the actuality of the operational active site at the molecular scale.Inspired by the stimulating synergistic effect of coupled heteronuclear metal atoms,a novel Ni-Co atomic pairs configuration(denoted as NiN_(3)?CoN_(3)-NC)active site was theoretically screened out for improving electrochemical CO_(2)reduction reaction(CO_(2)RR).The structure of NiN_(3)?CoN_(3)-NC was finely regulated by adjusting Zn content in the precursors Zn/Co/Ni-zeolite imidazolate frameworks(Zn/Co/Ni-ZIFs)and pyrolysis temperature.The structural features of NiN_(3)?CoN_(3)-NC were systematically confirmed by aberration-corrected HAADF-STEM coupled with 3D atom-overlapping Gaussian-function fitting mapping,XAFS,and XRD.The results of theoretical calculations reveal that the synergistic effect of Ni-Co atomic pairs can effectively promote the*COOH intermediate formation and thus the overall CO_(2)RR kinetic was improved,and also restrained the competitive hydrogen evolution reaction.Due to the attributes of Ni-Co atomic pairs configuration,the developed NiN_(3)?CoN_(3)-NC with superior catalytic activity,selectivity,and durability,with a high turnover frequency of 2265 h^(-1)at-1.1 V(vs.RHE)and maximum Faradaic efficiency of 97.7%for CO production.This work demonstrates the great potential of DACs as highly efficient catalysts for CO_(2)RR,provides a useful strategy to design heteronuclear DACs,exploits the synergistic effect of multiple metal sites to facilitate complex CO_(2)RR catalytic reactions,and inspires more efforts to develop the potential of DACs in various fields.

Development and validation of the code COUPLE3.0 for the coupled analysis of neutron transport and burnup in ADS

The analysis of the fuel depletion behavior is critical for maintaining the safety of accelerator-driven subcritical systems(ADSs). The code COUPLE2.0 coupling 3-D neutron transport and point burnup calculation was developed by Tsinghua University. A Monte Carlo method is used for the neutron transport analysis, and the burnup calculation is based on a deterministic method. The code can be used for the analysis of targets coupled with a reactor in ADSs. In response to additional ADS analysis requirements at the Institute of Modern Physics at the Chinese Academy of Sciences, the COUPLE3.0 version was developed to include the new functions of(1) a module for the calculation of proton irradiation for the analysis of cumulative behavior using the residual radionuclide operating history,(2) a fixed-flux radiation module for hazard assessment and analysis of the burnable poison, and(3) a module for multi-kernel parallel calculation, which improves the radionuclide replacement for the burnup analysis to balance the precision level and computational efficiency of the program. This paper introduces thevalidation of the COUPLE3.0 code using a fast reactor benchmark and ADS benchmark calculations. Moreover,the proton irradiation module was verified by a comparison with the analytic method of calculating the210 Po accumulation results. The results demonstrate that COUPLE3.0 is suitable for the analysis of neutron transport and the burnup of nuclides for ADSs.

Mathematical model for coupled reactive flow and solute transport during heap bioleaching of copper sulfide

Based on the momentum and mass conservation equations,a comprehensive model of heap bioleaching process is developed to investigate the interaction between chemical reactions,solution flow,gas flow,and solute transport within the leaching system.The governing equations are solved numerically using the COMSOL Multiphysics software for the coupled reactive flow and solute transport at micro-scale,meso-scale and macro-scale levels.At or near the surface of ore particle,the acid concentration is relatively higher than that in the central area,while the concentration gradient decreases after 72 d of leaching.The flow simulation between ore particles by combining X-ray CT technology shows that the highest velocity in narrow pore reaches 0.375 m/s.The air velocity within the dump shows that the velocity near the top and side surface is relatively high,which leads to the high oxygen concentration in that area.The coupled heat transfer and liquid flow process shows that the solution can act as an effective remover from the heap,dropping the highest temperature from 60 to 38 °C.The reagent transfer coupled with solution flow is also analyzed.The results obtained allow us to obtain a better understanding of the fundamental physical phenomenon of the bioleaching process.

d-d Orbital coupling induced by crystal-phase engineering assists acetonitrile electroreduction to ethylamine

The d-d orbital coupling induced by crystal-phase engineering can effectively adjust the electronic structure of electrocatalysts,thus showing significant catalytic performance,while it has been rarely explored in electrochemical acetonitrile reduction reaction(ARR)to date.Herein,we successfully realize the structural transformation of Pd Cu metallic aerogels(MAs)from face-centered cubic(FCC)to body-centered cubic(BCC)through annealing treatment.Specifically,the BCC Pd Cu MAs exhibit excellent ARR performance with high ethylamine selectivity of 90.91%,Faradaic efficiency of 88.60%,yield rate of 316.0 mmol h^(-1)g^(-1)_(Pd+Cu)and long-term stability for consecutive electrolysis within 20 h at-0.55 V vs.reversible hydrogen electrode,outperforming than those of FCC Pd Cu MAs.Under the membrane electrode assembly system,BCC Pd Cu MAs also demonstrate excellent ethylamine yield rate of 389.5 mmol h^(-1)g^(-1)_(Pd+Cu).Density functional theory calculation reveals that the d-d orbital coupling in BCC Pd Cu MAs results in an evident correlation effect for the interaction of Pd and Cu sites,which boosts up the Cu sites electronic activities to enhance ARR performance.Our work opens a new route to develop efficient ARR electrocatalysts from the perspective of crystalline structure transformation.

Coupling Au with BO_(x) matrix induced by Closo-boron cluster for electrochemical synthesis of ammonia

Au is considered as one of the most promising catalysts for nitrogen reduction reaction(NRR),however maximizing the activity utilization rate of Au and understanding the synergistic effects between Au and carriers pose ongoing challenges.Herein,we systematically explore the synergistic catalytic effect of incorporating Au with boron clusters for accelerating NRR kinetics.An in-situ abinitio strategy is employed to construct B-doped Au nanoparticles(2-6 nm in diameter)loaded on BO_(x) substrates(AuBO_(x)),in which B not only modulates the surface electronic structure of Au but also forms strong coupling interactions to stabilize the nanoparticles.The electrochemical results show that Au-BO_(x) possesses excellent NRR activity(NH_(3) yield of 48.52μg h^(-1)mg_(cat)^(-1),Faraday efficiency of 56.18%),and exhibits high stability and reproducibility throughout the electrocatalytic NRR process.Theoretical calculations reveal that the introduction of B induces the formation of both Au dangling bond and Au-B coupling bond.which considerably facilitates the hydrogenation of~*N_(2)^(-)~*NH_(3).The present work provides a new avenue for the preparation of metal-boron materials achieved by one-step reduction and doping process,utilizing boron clusters as reducing and stabilizing agents.

Energetic and Entropic Changes in Volume Work and Chemical Reactions

In the present study, energetic and entropic changes are investigated on a comparative basis, as they occur in the volume changes of an ideal gas in the Carnot cycle and in the course of the chemical reaction in a lead-acid battery. Differences between reversible and irreversible processes have been worked out, in particular between reversibly exchanged entropy (∆eS) and irreversibly produced entropy (∆iS). In the partially irreversible case, ∆eS and ∆iS add up to the sum ∆S for the volume changes of a gas, and only this function has an exact differential. In a chemical reaction, however, ∆eS is independent on reversibility. It arises from the different intramolecular energy contents between products and reactants. Entropy production in a partially irreversible Carnot cycle is brought about through work-free expansions, whereas in the irreversible battery reaction entropy is produced via activated complexes, whereby a certain, variable fraction of the available chemical energy becomes transformed into electrical energy and the remaining fraction dissipated into heat. The irreversible reaction process via activated complexes has been explained phenomenologically. For a sufficiently high power output of coupled reactions, it is essential that the input energy is not completely reversibly transformed, but rather partially dissipated, because this can increase the process velocity and consequently its power output. A reduction of the counter potential is necessary for this purpose. This is not only important for man-made machines, but also for the viability of cells.

Directed transport of coupled Brownian motors in a two-dimensional traveling-wave potential

Considering an elastically coupled Brownian motors system in a two-dimensional traveling-wave potential, we investigate the effects of the angular frequency of the traveling wave, wavelength, coupling strength, free length of the spring, and the noise intensity on the current of the system. It is found that the traveling wave is the essential condition of the directed transport. The current is dominated by the traveling wave and varies nonmonotonically with both the angular frequency and the wavelength. At an optimal angular frequency or wavelength, the current can be optimized. The coupling strength and the free length of the spring can locally modulate the current, especially at small angular frequencies. Moreover, the current decreases rapidly with the increase of the noise intensity, indicating the interference effect of noise on the directed transport.

Analysis of coupled flow-reaction with heat transfer in heap bioleaching processes

A mathematical model for heap bioleaching is developed to analyze heat transfer, oxygen flow, target ion distribution and oxidation leaching rate in the heap. The model equations are solved with Comsol Multiphysics software. Numerical simulation results show the following facts： Concentration of oxygen is relatively high along the boundary of the slope, and low in the center part where leaching rate is slow. Temper- ature is relatively low along the slope and reaches the highest along the bottom region near the slope, with difference being more than 6℃. Concentration of target mental ions is the highest in the bottom region near the slope. Oxidation leaching rate is relatively large in the bottom and slope part with a fast reaction rate, and small in the other part with low oxygen concentration.

GLOBAL EXISTENCE OF SOLUTIONS FOR A STRONGLY COUPLED REACTION-DIFFUSION SYSTEM

This paper is concerned with an Initial Boundary Value Problem (IBVP) for a strongly coupled semilinear reaction-diffusion system. By using the upper and lower solutions method and Leray-Schauder fixed point theorem and so on, the authors prove the global existence and uniqueness of a. smooth. solution for this IBVP under some appropriate conditions.

The Influence of Convergence Movement on Turbulent Transportation in the Atmospheric Boundary Layer

Classical turbulent K closure theory of the atmospheric boundary layer assumes that the vertical turbulent transport flux of any macroscopic quantity is equivalent to that quantity's vertical gradient transport flux. But a cross coupling between the thermodynamic processes and the dynamic processes in the atmospheric system is demonstrated based on the Curier-Prigogine principle of cross coupling of linear thermodynamics. The vertical turbulent transportation of energy and substance in the atmospheric boundary layer is related not only to their macroscopic gradient but also to the convergence and the divergence movement. The transportation of the convergence or divergence movement is important for the atmospheric boundary layer of the heterogeneous underlying surface and the convection boundary layer. Based on this, the turbulent transportation in the atmospheric boundary layer, the energy budget of the heterogeneous underlying surface and the convection boundary layer, and the boundary layer parameterization of land surface processes over the heterogeneous underlying surface are studied. This research offers clues not only for establishing the atmospheric boundary layer theory about the heterogeneous underlying surface, but also for overcoming the difficulties encountered recently in the application of the atmospheric boundary layer theory.

Elastic scattering and total reaction cross sections of^(6)Li examined via a microscopic continuum discretized coupled-channels model

We present a systematic study of 6Li elastic scattering and total reaction cross sections at incident energies around the Coulomb barrier within the continuum discretized coupled-channels(CDCC)framework,where 6Li is treated in anα+d two-body model.Collisions with 27Al,64Zn,138Ba,and 208Pa are analyzed.The microscopic optical potentials(MOP)based on Skyrme nucleon-nucleon interaction forαand d are adopted in CDCC calculations and satisfactory agreement with the experimental data is obtained without any adjustment on MOPs.For comparison,αand d global phenomenological optical potentials(GOP)are also used in CDCC analysis and a reduction of no less than 50%on the surface imaginary part of deuteron GOP is required for describing the data.In all cases,the 6Li breakup effect is significant and provides repulsive correction to the folding model potential.The reduction on the surface imaginary part of GOP of deuteron reveals a strong suppression of the reaction probability of deuteron as a component of 6Li when compared with that of a free deuteron.Further investigation is performed by considering the d breakup process equivalently within the dynamic polarization potential approach,and the results show that d behaves in a manner similar to a tightly bound nucleus in 6Li induced reactions.

Theoretical and Experimental Study on Reaction Coupling: Dehydrogenation of Ethylbenzene in the Presence of Carbon Dioxide

Dehydrogenation of ethylbenzene （EB） to styrene （ST） in the presence of CO2, in which EB dehydrogenation is coupled with the reverse water-gas shift （RWGS）, was investigated extensively through both theoretical analysis and experimental characterization. The reaction coupling proved to be superior to the single dehydrogenation in several respects. Thermodynamic analysis suggests that equilibrium conversion of EB can be improved greatly by reaction coupling due to the simultaneous elimination of the hydrogen produced from dehydrogenation. Catalytic tests proved that iron and vanadium supported on activated carbon or Al2O3 with certain promoters are potential catalysts for this coupling process. The catalysts of iron and vanadium are different in the reaction mechanism, although ST yield is always associated with CO2 conversion over various catalysts. The two-step pathway plays an important role in the coupling process over Fe/Al2O3, while the one-step pathway dominates the reaction over V/Al2O3. Coke deposition and deep reduction of active components are the major causes of catalyst deactivation. CO2 can alleviate the catalyst deactivation effectively through preserving the active species at high valence in the coupling process, though it can not suppress the coke deposition.

Principle of Cross Coupling Between Vertical Heat Turbulent Transport and Vertical Velocity and Determination of Cross Coupling Coefficient

It has been proved that there exists a cross coupling between vertical heat turbulent transport and vertical velocity by using linear thermodynamics. This result asserts that the vertical component of heat turbulent transport flux is composed of both the transport of the vertical potential temperature gradient and the coupling transport of the vertical velocity. In this paper, the coupling effect of vertical velocity on vertical heat turbulent transportation is validated by using observed data from the atmospheric boundary layer to determine cross coupling coefficients, and a series of significant properties of turbulent transportation are opened out. These properties indicate that the cross coupling coefficient is a logarithm function of the dimensionless vertical velocity and dimensionless height, and is not only related to the friction velocity u., but also to the coupling roughness height zwo and the coupling temperature Two of the vertical velocity. In addition, the function relations suggest that only when the vertical velocity magnitude conforms to the limitation IW/u. I # 1, and is above the level zwo, then the vertical velocity leads to the cross coupling effect on the vertical heat turbulent transport flux. The cross coupling theory and experimental results provide a challenge to the traditional turbulent K closure theory and the Monin-Obukhov similarity theory.

FLUID-SOLID COUPLING MATHEMATICAL MODEL OF CONTAMINANT TRANSPORT IN UNSATURATED ZONE AND ITS ASYMPTOTICAL SOLUTION

The process of contaminant transport is a problem of multicomponent and multiphase flow in unsaturated zone. Under the presupposition that gas existence affects water transport, a coupled mathematical model of contaminant transport in unsaturated zone has been established based on fluid_solid interaction mechanics theory. The asymptotical solutions to the nonlinear coupling mathematical model were accomplished by the perturbation and integral transformation method. The distribution law of pore pressure, pore water velocity and contaminant concentration in unsaturated zone has been presented under the conditions of with coupling and without coupling gas phase. An example problem was used to provide a quantitative verification and validation of the model. The asymptotical solution was compared with Faust model solution. The comparison results show reasonable agreement between asymptotical solution and Faust solution, and the gas effect and media deformation has a large impact on the contaminant transport. The theoretical basis is provided for forecasting contaminant transport and the determination of the relationship among pressure_saturation_permeability in laboratory.