Solution chemistry back‐contact FTO/hematite interface engineering for efficient photocatalytic water oxidation

This work describes a simple yet powerful scalable solution chemistry strategy to create back‐contact rich interfaces between substrates such as commercial transparent conducting fluorine‐doped tin oxide coated glass(FTO)and photoactive thin films such as hematite for low‐cost water oxidation reaction.High‐resolution electron microscopy(SEM,TEM,STEM),atomic force microscopy(AFM),elemental chemical mapping(EELS,EDS)and photoelectrochemical(PEC)investigations reveal that the mechanical stress,lattice mismatch,electron energy barrier,and voids between FTO and hematite at the back‐contact interface as well as short‐circuit and detrimental reaction between FTO and the electrolyte can be alleviated by engineering the chemical composition of the precursor solutions,thus increasing the overall efficiency of these low‐cost photoanodes for water oxidation reaction for a clean and sustainable generation of hydrogen from PEC water‐splitting.These findings are of significant importance to improve the charge collection efficiency by minimizing electron‐hole recombination observed at back‐contact interfaces and grain boundaries in mesoporous electrodes,thus improving the overall efficiency and scalability of low‐cost PEC water splitting devices.

Discovering Cathodic Biocompatibility for Aqueous Zn–MnO_(2) Battery:An Integrating Biomass Carbon Strategy

Developing high-performance aqueous Zn-ion batteries from sustainable biomass becomes increasingly vital for large-scale energy storage in the foreseeable future.Therefore,γ-MnO_(2) uniformly loaded on N-doped carbon derived from grapefruit peel is successfully fabricated in this work,and particularly the composite cathode with carbon carrier quality percentage of 20 wt%delivers the specific capacity of 391.2 mAh g^(−1)at 0.1 A g^(−1),outstanding cyclic stability of 92.17%after 3000 cycles at 5 A g^(−1),and remarkable energy density of 553.12 Wh kg^(−1) together with superior coulombic efficiency of~100%.Additionally,the cathodic biosafety is further explored specifically through in vitro cell toxicity experiments,which verifies its tremendous potential in the application of clinical medicine.Besides,Zinc ion energy storage mechanism of the cathode is mainly discussed from the aspects of Jahn–Teller effect and Mn domains distribution combined with theoretical analysis and experimental data.Thus,a novel perspective of the conversion from biomass waste to biocompatible Mn-based cathode is successfully developed.

Tackling the proton limit under industrial electrochemical CO_(2)reduction by a local proton shuttle

Industrial CO_(2)electroreduction has received tremendous attentions for resolution of the current energy and environmental crisis,but its performance is greatly limited by mass transport at high current density.In this work,an ion‐polymer‐modified gas‐diffusion electrode is used to tackle this proton limit.It is found that gas diffusion electrode‐Nafion shows an impressive performance of 75.2%Faradaic efficiency in multicarbon products at an industrial current density of 1.16 A/cm^(2).Significantly,in‐depth electrochemical characterizations combined with in situ Raman have been used to determine the full workflow of protons,and it is found that HCO_(3)^(−)acts as a proton pool near the reaction environment,and HCO_(3)^(−)and H_(3)O^(+)are local proton donors that interact with the proton shuttle−SO_(3)^(−)from Nafion.With rich proton hopping sites that decrease the activation energy,a“Grotthuss”mechanism for proton transport in the above system has been identified rather than the“Vehicle”mechanism with a higher energy barrier.Therefore,this work could be very useful in terms of the achievement of industrial CO_(2)reduction fundamentally and practically.

Unlock the full potential of carbon cloth-based scaffolds towards magnesium metal storage via regulation on magnesiophilicity and surface geometric structure

The development of rechargeable magnesium(Mg) batteries is of practical significance to upgrade the electric energy storage devices due to exceptional capacity and abundant resources of Mg-metal anode.However,the reversible Mg electrochemistry suffers from unsatisfied rate capability and lifespan,mainly caused by non-uniform distribution of electrodeposits.In this work,a fresh design concept of threedimensional carbon cloths scaffolds is proposed to overcome the uncontrollable Mg growth via homogenizing electric field and improving magnesiophilicity.A microscopic smooth and nitrogen-containing defective carbonaceous layer is constructed through a facile pyrolysis of ZIF8 on carbon cloths.As revealed by finite element simulation and DFT calculation results,the smooth surface endows with uniform electric field distribution and simultaneously the nitrogen-doping species enable good magnesiophilicity of scaffolds.The fine and uniform Mg nucleus as well as the inner electrodeposit behavior are also disclosed.As a result,an exceptional cycle life of 500 cycles at 4.0 mA cm^(-2) and 4.0 mA h cm^(-2) is firstly realized to our best knowledge.Besides,the functional scaffolds can be cycled for over 2200 h at 2.0 mA cm^(-2) under a normalized capacity of 5.0 mA h cm^(-2),far exceeding previous results.This work offers an effective approach to enable the full potential of carbon cloths-based scaffolds towards metal storage for next generation battery applications.

Mathematical model of multistage and multiphase chemical reactions in flash furnace

A mathematical model of multistage and multiphase reactions in flash smelting furnace, which based on the description of chemical reactions and reaction rate, is presented. In this model, main components of copper concentrate are represented as FeS 2 and CuFeS based on experiment, intermediate products are assumed to be S 2 and FeS, and the final products are assumed as FeS, FeO, SO 2, Cu 2S, FeO and FeO(SiO 2) 2. The model incorporates the transport of momentum, heat and mass, reaction kinetics between gas and particles, and reactions between gas and gas. The k-ε model is used to describe gas phase turbulence. The model uses the Eulerian approach for the gas flow equations and the Lagrangian approach for the particles. The coupling of gas and particle equations is performed through the particle source in cell(PSIC) method. Comparison between the model predictions and the plant measurements shows that the model has high reliability and accuracy.

Linear-in-Parameter Models Based on Parsimonious Genetic Programming Algorithm and Its Application to Aero-Engine Start Modeling

A novel Parsimonious Genetic Programming （PGP） algorithm together with a novel aero-engine optimum data-driven dynamic start process model based on PGP is proposed. In application of this method, first, the traditional Genetic Programming（GP） is used to generate the nonlinear input-output models that are represented in a binary tree structure; then, the Orthogonal Least Squares algorithm （OLS） is used to estimate the contribution of the branches of the tree （refer to basic function term that cannot be decomposed anymore according to special rule） to the accuracy of the model, which contributes to eliminate complex redundant subtrees and enhance GP＇s convergence speed; and finally, a simple, reliable and exact linear-in-parameter nonlinear model via GP evolution is obtained. The real aero-engine start process test data simulation and the comparisons with Support Vector Machines （SVM） validate that the proposed method can generate more applicable, interpretable models and achieve comparable, even superior results to SVM.

Br-doping of g-C3N4 towards enhanced photocatalytic performance in Cr(Ⅵ)reduction

Semiconductor photocatalytic technology is widely recognized as one of the most promising technologies to solve current energy and environmental crisis, due to its ability to make effective use of solar energy. In recent years, graphite carbon nitride(g-C3N4), a new type of non-metallic polymer semiconductor photocatalyst, has rapidly become the focus of intense research in the field of photocatalysis because of its suitable bandgap energy, unique structure, and excellent chemical stability. In order to improve its intrinsic shortages of small specific surface area, narrow visible light response range, high electron-hole pair recombination rate, and low photon quantum efficiency, a simple method was utilized to synthesize Br-doped g-C3N4(CN–Br X, X = 5, 10, 20, 30), where X is a percentage mole ratio of NH4 Br to melamine. Experimental results showed that Br atoms were doped into the g-C3N4 lattice by replacing the bonded N atoms in the form of C–N=C, while the derived material retained the original framework of g-C3N4. The interaction of Br element with the g-C3N4 skeleton not only broadened the visible-light response of g-C3N4 to 800 nm with an adjustable band gap, but also greatly promoted the separation efficiency of the photogenerated charge carrier and the surface area. The photocurrent intensity of bare CN and CN–Br X(X = 5, 10, 20, 30) catalysts is calculated to be 1.5, 2.0, 3.1, 6.5, and 1.9 μA, respectively. And their specific surface area is measured to be 9.086, 9.326, 15.137, 13.397, and 6.932 m2/g. As a result, this Br-doped g-C3N4 gives significantly enhanced photocatalytic reduction of Cr(VI), achieving a twice enhancement over g-C3N4, with high stability during prolonged photocatalytic operation compared to bare g-C3N4 under visible light irradiation. Furthermore, an underlying photocatalytic reduction mechanism was proposed based on control experiments using radical scavengers.

Analytic Solution for Steady Slip Flow between Parallel Plates with Micro-Scale Spacing

The Navier-Stokes equations for slip flow between two very closely spaced parallel plates are transformed to an ordinary differential equation based on the pressure gradient along the flow direction using a new similarity transformation. A powerful easy-to-use homotopy analysis method was used to obtain an analytical solution. The convergence theorem for the homotopy analysis method is presented. The solutions show that the second-order homotopy analysis method solution is accurate enough for the current problem.

Revealing the unexpected promotion effect of EuO_x on Pt/CeO_2 catalysts for catalytic combustion of toluene

Pt/Eu2O3-CeO2 materials with different Eu concentrations were prepared and applied to toluene destruction,and the remarkable promotion impact of EuOx on Pt/CeO2 can be observed.The characterization results reveal that the presence of EuOx significantly enhances the redox property,lattice O concentration,and Ce3+ ratio of the Pt/CeO2 material,which facilitates the dispersion and activity of Pt active sites and thus accelerates the decomposition process of toluene.Among all catalysts,a sample with an Eu content of 2.5 at.%(Pt/EC-2.5)possesses the best catalytic activity with 0.09 vol% of toluene completely destructed at 200 ℃ under a relatively high GHSV of 50000 h^-1.The possible reaction pathway and mechanism of toluene combustion over Pt/Eu2O3-CeO2 samples are presented according to in-situ DRIFTS,which confirms that the toluene oxidation process obeys the Mars-van Krevelen mechanism with aldehydes and ketones as primary organic intermediates.

Accelerated methane storage in clathrate hydrates using surfactantstabilized suspension with graphite nanoparticles

In this study,enhanced kinetics of methane hydrate formation in the sodium dodecyl sulfate(SDS)solution with different concentrations of suspended graphite nanoparticles(GNPs)were investigated at 6.1-9.0 MPa and 274.15 K.The GNPs with rough surfaces and excellent thermal conductivity not only provided a considerable number of microsites for hydrate nucleation but also facilitated the fast hydrate heat transfer in the suspension system.At a relatively low pressure of 6.1 MPa,the suspension with 0.4 wt%of GNPs exhibited the minimum induction time of 22 min and maximum methane uptake of 126.1 cm3·cm-3.However,the methane storage performances of the suspensions with higher and lower concentrations of GNPs were not satisfactory.At the applied pressure,the temperature increase arising from the hydrate heat in the suspension system with the optimized concentration(0.4 wt%)of GNPs was more significant than that in the traditional SDS solution.Furthermore,compared with those of the system without GNPs,enhanced hydration rate and storage capacity were achieved in the suspensions with GNPs,and the storage capacities were increased by 3.9%-17.0%.The promotion effect of GNPs on gas hydrate formation at low pressure is much more obvious than that at high pressure.

Assisting effect of Al_(2)O_(3) on MnO_(x) for NO catalytic oxidation

Various Mn-based catalysts for NO oxidation were prepared using MnO_(x)as active compound,while Ti O_(2)and Al_(2)O_(3)were adopted as catalyst support.The performance of the catalysts was tested to study the effect of support on Mn-based catalyst activity.Performance of the catalysts followed as Mn_(0.4)/Al>Mn_(0.2)/Al>Mn_(0.4)/Ti>Mn_(0.2)/Ti>MnO_(x)>Al_(2)O_(3)on the whole,indicating the synergism of MnO_(x)and Al_(2)O_(3)for NO catalytic oxidation.Results were analyzed according to characterization data.Adsorbed oxygen on catalyst rather than lattice oxygen was detected as the active oxidizer for NO oxidation.As catalyst support,Al_(2)O_(3)provided more sites to carry surface adsorbed oxygen than TiO_(2),resulting in the presence of more active oxygen on Mn O_(x)/Al_(2)O_(3)than on MnO_(x)/TiO_(2).Moreover,MnO_(x)/Al_(2)O_(3)possessed high surface area and pore volume,which greatly benefited the adsorption of NO on catalyst and further favored the oxidation of NO by active oxygen.All these advantages helped Mn_(0.4)/Al exhibited the best catalytic efficiency.

Progress and key challenges in catalytic combustion of lean methane

As a primary type of clean energy,methane is also the second most important greenhouse gas after CO_(2)due to the high global warming potential.Large quantities of lean methane(0.1–1.0 vol%)are emitted into the atmosphere without any treatment during coal mine,oil,and natural gas production,thus leading to energy loss and greenhouse effect.In general,it is challenging to utilize lean methane due to its low concentration and flow instability,while catalytic combustion is a vital pathway to realize an efficient utilization of lean methane owing to the reduced emissions of polluting gases(e.g.,NOxand CO)during the reaction.In particular,to efficiently convert lean methane,it necessitates both the designs of highly active and stable heterogeneous catalysts that accelerate lean methane combustion at low temperatures and smart reactors that enable autothermal operation by optimizing heat management.In this review,we discuss the in-depth development,challenges,and prospects of catalytic lean methane combustion technology in various configurations,with particular emphasis on heat management from the point of view of material design combined with reactor configuration.The target is to describe a framework that can correlate the guiding principles among catalyst design,device innovation and system optimization,inspiring the development of groundbreaking combustion technology for the efficient utilization of lean methane.

Recent advancement and future challenges of photothermal catalysis for VOCs elimination:From catalyst design to applications

Photothermal catalysis realizes the synergistic effect of solar energy and thermochemistry,which also has the potential to improve the reaction rate and optimize the selectivity.In this review,the research progress of photothermal catalytic removal of volatile organic compounds(VOCs)by nano-catalysts in recent years is systematically reviewed.First,the fundamentals of photothermal catalysis and the fabrication of catalysts are described,and the design strategy of optimizing photothermal catalysis performance is proposed.Second,the performance for VOC degradation with photothermal catalysis is evaluated and compared for the batch and continuous systems.Particularly,the catalytic mechanism of VOC oxidation is systematically introduced based on experimental and theoretical study.Finally,the future limitations and challenges have been discussed,and potential research directions and priorities are highlighted.A broad view of recent photothermal catalyst fabrication,applications,challenges,and prospects can be systemically provided by this review.

Comprehensive modeling of frictional pressure drop during carbon dioxide two-phase flow inside channels using intelligent and conventional methods

Environmentally friendly nature of CO_(2),associated with its safety and high efficiency,has made it a widely used working fluid in heat exchangers.Since CO_(2)has strange thermophysical features,specific models are required to estimate its two-phase characteristics,particularly frictional pressure drop(FPD).Herein,a widespread dataset,comprising 1195 experimental samples for two-phase FPD of CO_(2)was adopted from 10 sources to fulfill this requirement.The literature correlations failed to provide satisfactory precisions and exhibited the average absolute relative errors(AAREs)between 29.29% and 67.69% from the analyzed data.By inspiring the theoretical method of Lockhart and Martinelli,three intelligent FPD models were presented,among which the Gaussian process regression approach surpassed the others with AARE and R^(2)values of 5.48% and 98.80%,respectively in the test stage.A novel simple correlation was also derived based on the least square fitting method,which yielded opportune predictions with AARE of 19.76% for all data.The truthfulness of the newly proposed models was assessed through a variety of statistical and visual analyses,and the results affirmed their high reliability over a broad range of conditions,channel sizes and flow patterns.Furthermore,the novel models performed favorably in describing the physical attitudes corresponding to two-phase FPD of CO_(2).Eventually,the importance of operating factors in controlling the FPD was discussed through a sensitivity analysis.

Experimental study on prediction model of wet gas pressure drop across single-orifice plate in horizontal pipes in the low gas phase Froude number region

The pressure drop prediction of wet gas across single-orifice plate in horizontal pipes had been solved satisfactorily under an annular-mist flow in the upstream of orifice plates.However,this pressure drop prediction is still not clearly determined when the upstream is in an intermittent flow or stratified flow,which is corresponding to a region of low FrG(gas phase Froude number)in the flow pattern map of wet gases.In this study,the wet gas pressure drop across a single-orifice plate was experimentally investigated in the low FrG region.By the experiment,the flow pattern transition in the downstream of single-orifice plates,as well as the effects of FrG and FrL(liquid phase Froude number)on UG(gas phase multiplier),were determined and compared when the upstream is in the flow pattern transition and the stratified flow region,respectively.Prediction performances were examined on the available pressure drop models.It was found that no model could be capable of jointly predicting the wet gas pressure drop in the low FrG region with an acceptable accuracy.With a new method of correlating FrG and FrL simultaneously,new correlations were proposed for the low FrG region.Among which the modified Chisholm model shows the best prediction accuracies,with the prediction deviations of UG being within 7%and 3%when the upstream is in flow pattern transition and stratified flow region,respectively.

Numerical Stability and Accuracy of Contact Angle Schemes in Pseudopotential Lattice Boltzmann Model for Simulating Static Wetting and Dynamic Wetting

There are five most widely used contact angle schemes in the pseudopotential lattice Boltzmann(LB)model for simulating the wetting phenomenon:The pseudopotential-based scheme(PB scheme),the improved virtualdensity scheme(IVD scheme),the modified pseudopotential-based scheme with a ghost fluid layer constructed by using the fluid layer density above the wall(MPB-C scheme),the modified pseudopotential-based scheme with a ghost fluid layer constructed by using the weighted average density of surrounding fluid nodes(MPB-W scheme)and the geometric formulation scheme(GF scheme).But the numerical stability and accuracy of the schemes for wetting simulation remain unclear in the past.In this paper,the numerical stability and accuracy of these schemes are clarified for the first time,by applying the five widely used contact angle schemes to simulate a two-dimensional(2D)sessile droplet on wall and capillary imbibition in a 2D channel as the examples of static wetting and dynamic wetting simulations respectively.(i)It is shown that the simulated contact angles by the GF scheme are consistent at different density ratios for the same prescribed contact angle,but the simulated contact angles by the PB scheme,IVD scheme,MPB-C scheme and MPB-W scheme change with density ratios for the same fluid-solid interaction strength.The PB scheme is found to be the most unstable scheme for simulating static wetting at increased density ratios.(ii)Although the spurious velocity increases with the increased liquid/vapor density ratio for all the contact angle schemes,the magnitude of the spurious velocity in the PB scheme,IVD scheme and GF scheme are smaller than that in the MPB-C scheme and MPB-W scheme.(iii)The fluid density variation near the wall in the PB scheme is the most significant,and the variation can be diminished in the IVD scheme,MPB-C scheme andMPBWscheme.The variation totally disappeared in the GF scheme.(iv)For the simulation of capillary imbibition,the MPB-C scheme,MPB-Wscheme and GF scheme simulate the dynamics of the liquid-vapor interface well,with the GF scheme being the most accurate.The accuracy of the IVD scheme is low at a small contact angle(44 degrees)but gets high at a large contact angle(60 degrees).However,the PB scheme is the most inaccurate in simulating the dynamics of the liquid-vapor interface.As a whole,it is most suggested to apply the GF scheme to simulate static wetting or dynamic wetting,while it is the least suggested to use the PB scheme to simulate static wetting or dynamic wetting.

A new model for predicting the critical liquid-carrying velocity in inclined gas wells

Based on the assumption of gas-liquid stratified flow pattern in inclined gas wells,considering the influence of wettability and surface tension on the circumferential distribution of liquid film along the wellbore wall,the influence of the change of the gas-liquid interface configuration on the potential energy,kinetic energy and surface free energy of the two-phase system per unit length of the tube is investigated,and a new model for calculating the gas-liquid distribution at critical conditions is developed by using the principle of minimum energy.Considering the influence of the inclination angle,the calculation model of interfacial friction factor is established,and finally closed the governing equations.The interface shape is more vulnerable to wettability and surface tension at a low liquid holdup,resulting in a curved interface configuration.The interface is more curved when the smaller is the pipe diameter,or the smaller the liquid holdup,or the smaller the deviation angle,or the greater gas velocity,or the greater the gas density.The critical liquid-carrying velocity increases nonlinearly and then decreases with the increase of inclination angle.The inclination corresponding to the maximum critical liquid-carrying velocity increases with the increase of the diameter of the wellbore,and it is also affected by the fluid properties of the gas phase and liquid phase.The mean relative errors for critical liquid-carrying velocity and critical pressure gradient are 1.19%and 3.02%,respectively,and the misclassification rate is 2.38%in the field trial,implying the new model can provide a valid judgement on the liquid loading in inclined gas wells.

Comparative analysis on gas–solid drag models in MFIX-DEM simulations of bubbling fluidized bed

In this study,the open-source software MFIX-DEM simulations of a bubbling fluidized bed(BFB)are applied to assess nine drag models according to experimental and direct numerical simulation(DNS)results.The influence of superficial gas velocity on gas–solid flow is also examined.The results show that according to the distribution of time-averaged particle axial velocity in y direction,except for Wen–Yu and Tenneti–Garg–Subramaniam(TGS),other drag models are consistent with the experimental and DNS results.For the TGS drag model,the layer-by-layer movement of particles is observed,which indicates the particle velocity is not correctly predicted.The time domain and frequency domain analysis results of pressure drop of each drag model are similar.It is recommended to use the drag model derived from DNS or fine grid computational fluid dynamics–discrete element method(CFD-DEM)data first for CFD-DEM simulations.For the investigated BFB,the superficial gas velocity less than 0.9 m·s^(-1) should be adopted to obtain normal hydrodynamics.

A universal charge-compensating strategy for high-energy-density pseudocapacitors

For pseudocapacitive electrode materials(PseEMs),despite much progress having been made in achieving both high power density and high energy density,a general strategy to guide the enhancement of intrinsic capacitive properties of PseEMs remains lacking.Here,we demonstrate a universal chargecompensating strategy to improve the charge-storage capability of PseEMs intrinsically:ⅰ) in the electrolyte with anion as charge carriers(such as OH-),reducing the multivalent cations of PseEMs into lower valences could create more reversible low-to-high valence redox cou ples to promote the intercalation of the anions;ⅱ) in the electrolytes with cation as charge carriers(such as H^(+),Li^(+),Na^(+)),oxidizing the multivalent cations of PseEMs into higher valences could introduce more reversible high-to-low valence redox couples to promote the intercalation of the cations.And we demonstrated that the improved intrinsic charge-storage capability for PseEMs originates from the increased Faradaic charge storage sites.

AERODYNAMIC DESIGN METHOD OF CASCADEPROFILES BASED ON LOAD AND BLADETHICKNESS DISTRIBUTION

A cascade profile design method was proposed using the aerodynamic load and blade thickness distribution as the design constraints, which were correspondent to the demands from the aerodynamic characteristics and the blade strength. These constraints,together with all the other boundary conditions , were involved in the stationary conditions ofa variational principle , in which the angle-function was employed as the unknown function.The angle-function ( i. e. , the circumferential angular coordinate) was defined in the image plane composed of the stream function coordinate ( circumferential direction ) and streamline coordinate. The solution domain, i.e., the blade-to-blade passage, was transformed into a square in the image plane, while the blade contour was projected to a straight line ; thus, the difficulty of the unknown blade geometry was avoided. The finite element method was employed to establish the calculation code. Applications show that this method can satisfy the design requests on the blade profile from both aerodynamic and strength respects. In addition, quite different from the most inverse-problem approaches that often encounter difficulties in the convergence of iteration, the present method shows a stable and fast convergence tendency. This will be significant for engineering applications.