One‑Step Gas-Solid‑Phase Diffusion‑Induced Elemental Reaction for Bandgap‑Tunable Cu_(a)Agm_(1)Bim_(2)I_(n)/CuI Thin Film Solar Cells

Lead-free inorganic copper-silver-bismuth-halide materials have attracted more and more attention due to their environmental friendliness,high element abundance,and low cost.Here,we developed a strategy of one-step gas-solid-phase diffusioninduced reaction to fabricate a series of bandgap-tunable Cu_(a)Agm_(1)Bim_(2)I_(n)/CuI bilayer films due to the atomic diffusion effect for the first time.By designing and regulating the sputtered Cu/Ag/Bi metal film thickness,the bandgap of Cu_(a)Agm_(1)Bim_(2)I_(n)/CuI could be reduced from 2.06 to 1.78 eV.Solar cells with the structure of FTO/TiO_(2)/Cu_(a)Agm_(1)Bim_(2)I_(n)/CuI/carbon were constructed,yielding a champion power conversion efficiency of 2.76%,which is the highest reported for this class of materials owing to the bandgap reduction and the peculiar bilayer structure.The current work provides a practical path for developing the next generation of efficient,stable,and environmentally friendly photovoltaic materials.

Gas-solid catalytic reactions over ruthenium-based catalysts

Ruthenium （Ru）‐based catalysts are widely employed in several types of gas‐solid reactions because of their high catalytic activities. This review provides theoretical research on Ru‐based catalysts and an analysis of their basic properties and oxidation behavior. There is particular emphasis on Ru‐catalyzed gas‐solid catalytic reactions, including the catalytic oxidation of VOCs, preferential oxidation of CO, synthesis of ammonia, oxidation of HCl and partial oxidation of CH4. Recent litera‐ture on catalysis is summarized and compared. Finally, we describe current challenges in the field and propose approaches for future development of Ru‐based catalysts.

Preparation of ultrafine WC-Co powder via fluidized bed

In this study,the effects of reaction parameters on the deep-reduction and carbonization process of WO_(2)-Co to WC-Co were studied.The results indicate that the oxygen loss rate of WO_(2) is positively correlated with temperature and methane partial pressure.The partial pressure of methane has no significant effect on the formation rate of WC.The carbon content and particle size of the product increase with the increase of CH_(4) partial pressure.By synergistically regulating the reaction temperature to 950℃,the CH_(4) partial pressure to 1.25%,and the reaction time to 60 min,ultrafine WC-Co powder without h phase can be obtained.The particle size of the composite powder is 128 nm,with total carbon content of 6.16%,free carbon content of 0.4%,and residual oxygen content of 0.05%,respectively.The growth rate relationship of tungsten carbide is as follows:δ(t)=1.21×10^(-13)exp(-12809.72/T)√t.

A generalized mathematical model for non-catalytic gas-solid reactions

Based on a general classification and characteristic comparison of the existing models, a new model for non-catalytic gas-solid reactions is proposed and a general formulation for the model in terms of the solid conversion, X, is presented in mis paper. The model, referred to the generalized model, is demonstrated to be applicable to any solid reactant of general structure ranging from highly porous to nonporous materials. It is shown that the generalized model incorporates the grain and pore structure for a solid pellet and can be reduced to the grain and random pore models as extreme cases.

Fluidized-bed chlorination thermodynamics and kinetics of Kenya natural rutile ore

Natural rutile and gaseous chlorine with carbon as reductant were used to prepare titanium tetrachloride. Thermodynamics and kinetics of chlorination of Kenya natural rutile particles in a batch-type fluidized bed were studied at 1173-1273 K. Thermodynamic analysis of this system revealed that the equation of producing CO was dominant at high temperatures. Based on the gas-solid multi-phase reaction theory and a two-phase model for the fluidized bed, the mathematical description for the chlorination reaction of rutile was proposed. The reaction parameters and the average concentration of gaseous chlorine in the emulsion phase were estimated. The average concentration of emulsion phase in the range of fluidized bed was calculated as 0.3 mol/m^3. The results showed that the chlorination of natural rutile proceeded principally in the emulsion phase, and the reaction rate was mainly controlled by the surface reaction.

Hydrogen-based direct reduction of industrial iron ore pellets:Statistically designed experiments and computational simulation

As part of efforts to reduce anthropogenic CO_(2) emissions by the steelmaking industry,this study investigated the direct reduction of industrially produced hematite pellets with H_(2) using the Doehlert experimental design to evaluate the effect of pellet diameter(10.5-16.5 mm),porosity(0.36-0.44),and temperature(600-1200℃).A strong interactive effect between temperature and pellet size was observed,indicating that these variables cannot be considered independently.The increase in temperature and decrease in pellet size considerably favor the reduction rate,while porosity did not show a relevant effect.The change in pellet size during the reduction was negligible,except at elevated temperatures due to crack formation.A considerable decrease in mechanical strength at high temperatures suggests a maximum process operating temperature of 900℃.Good predictive capacity was achieved using the modified grain model to simulate the three consecutive non-catalytic gas-solid reactions,considering different pellet sizes and porosities,changes during the reaction from 800 to 900℃.However,for other temperatures,different mechanisms of structural modifications must be considered in the modeling.These results represent significant contributions to the development of ore pellets for CO_(2)-free steelmaking technology.

Preparation and characteristic research of anhydrous magnesium chloride with dehydrated ammonium carnallite

Taking the saline lake bischofite and NH4Cl that was removed with the ammonia method and continuously followed by filtration as raw materials with a molar ratio of 1∶1 of MgCl2 to NH4Cl, ammonium carnallite was synthesized. And then the ammonium carnallite was dehydrated to some extent at 160℃ for 4 h. Ammonium carnallite reacted with ammonia at 240℃ for 150 min and the ammonation ammonium carnallite was produced. Finally, the ammonation ammonium carnallite was calcined at 750℃ into anhydrous magnesium chloride containing only 0.1%（mass fraction） of MgO. On the other hand, dehydrated ammonium carnallite was mixed with the solid ammonium chloride at mass ratio 1∶4 at high temperature and with the differential pressure of NH3 above 30.5kPa. The dehydrated ammonium carnallite of mixture was dehydrated at 410℃, and then calcined at 700℃ into anhydrous magnesium chloride with only 0.087%（mass fraction） of MgO. X-ray diffraction and electron microscopy analysis results prove that anhydrous magnesium chloride obtained by both methods hasn’t mixed phases, the particle is large and even has good dispersion, which is suitable for preparation of metal magnesium in the electrolysis.

Two Alternative Routes to MS_2 Nanotubes

Inorganic tubular nanostructure MS2 （M=Mo, W, Nb, Ta） were synthesized by two alternative routes. Thermal decomposition method was used for producing fullerence-like MS2 （M=Mo, W） nanotubes on Al2O3 template using ammonium sulfur respectively; NbS2, and TaS2 nanotubes were obtained successfully by reducing corresponding metal trisulfide in a stream of H2 （mixed with N2 in some cases） at elevated temperatures.Detailed experimental procedure, and the characterization of associated results, were evaluated using X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM） and high resolution transmission electron microscopy （HRTEM）. The result reveals that products are composed of high density of MS2 tubular nanostructures with the diameter of 100 nm and length of tens of micrometers. And no mistake, these 1-D （one-dimensional） tubular nanomaterials added quantities and varieties in the growing family of nanotubes of inorganic layered materials.

DIRECT REDUCTION OF GALENA AT MODERATE TEMPERATURES

The direct reduction of galena with hydrogen at 873—973 K could be described by the shrink- ing core model in the chemically controlled region.The reaction was revealed to be of first or- der with respect to hydrogen concentration and the activation energy is 79.0 kJ/mol.Be- cause of the fairly large interface tension between the solid galena and the liquid Pb,the SEM second electron images showed that the liquid Pb film is difficult to be formed on the unreacted galena surface in reaction process.

Heterogeneous reaction of NO_(2) on the surface of NaCl particles

The heterogeneous reaction of NO_(2)on NaCl particles has been investigated with the new sample preparation and the mode of gas-solid free diffusion.Diffuse Reflectance Infrared Fourier Transform Spectroscopy(DRIFTS)is used to characterize the adsorbed products in situ,combined with Ion Chromatographic(IC),X-ray Photoelectron Spectroscopy(XPS)and Scan Electron Micros-copy(SEM).Our results indicate that the reaction is not limited to the surface of the NaCl particles,but penetrated into the upper layers.Surface reactive sites determine the reaction.Kinetic measurements show that nitrate formation on sodium chloride is second order in NO_(2)concentration and reactive uptake coefficient is(1.54±0.70)×10^(-5).

Mechanism of fluidized chlorination reaction of Kenya natural rutile ore

In this paper, the thermodynamics and kinetics of nature rutile carbochlorination in a fluidized-bed were investigated. The thermodynamic calculations of TiO2-C- C12 system show that when C is excess in the solid phase, titanium tetrachloride and carbon monoxide can exist sta- bly. At high temperature, the reaction with CO as the product is the dominant reaction. The appropriate reaction conditions are as follows： reaction temperature of 950 ℃, reaction time of 40 min, carbon ratio of 30 wt% of rutile, natural rutile particle size of -96 μm, petroleum coke size of -150 μm, and chlorine flow of 0.036 m3.h-1. Under the above conditions, the reaction conversion rate of TiO2 can reach about 95 %. This paper proposed a reaction rate model, and got a rutile chlorination rate formula, which is generally consistent with the experimental data. For the TiO2-C-C12 system, the reaction rate is dependent on the initial radius of rutile particle, density, and the partial pressures of C12. From 900 to 1,000 ℃, the apparent activation energy is 10.569 kJ.mo1-1, and the mass diffu- sion is found to be the main reaction-controlling step. The expression for the chlorine reaction rate in the C-C12 sys- tem is obtained, and it depends on the degree of reaction, the partial pressure of C12, and the size of rutile particle.

Characteristic of solid product layer of MgSO in the reaction of MgO with SO2

The microstructure, nucleation and growth of MgSO4 product layer during the reaction of MgO single crystal with SO2 and O2 were investigated with thermo gravity analyzer (TGA) and atomic force microscopy (AFM). The AFM images indicated that three dimensional islands with different sizes were formed during the initial reaction stage. At the initial stage, cone-shaped islands were formed, and most of them appeared at the position with terrace-step-kink. With the reaction time increasing, small islands would grow to large islands, and the coalescent would happen during this growth stage. During the product layer growth stage, the space and surface between islands would be occupied by islands, and continuum islands were formed. With the reaction time increasing in the product layer growth stage, the size of island increased while the number and total surface of all islands decreased.

Hole-growth phenomenon during pyrolysis of a cation-exchange resin particle

A novel central hole-expansion phenomenon is identified, in which the cation-exchange resin is pyrolyzed in a mixed atmosphere of nitrogen and oxygen at 400–500 ℃. In this reaction, the reaction path is predictable and always starts from the center of the resin particle to form a central hole, then continues and expands around the hole, finally forming a uniformly distributed hole group;the particle surface remains intact. Analysis shows that this formation mode is due to the different reaction paths of sulfonic groups between the surface and interior of the particle, caused by the temperature difference. On the surface, transformation reactions happen at high temperatures(410–500 ℃) to form stable organic sulfur structures, while decomposition occurs inside the particle at a relatively low temperature(<410 ℃) and promotes complete pyrolysis of the copolymer matrix to form holes.

Competing effects of surface catalysis and ablation in hypersonic reentry aerothermodynamic environment

Under hypersonic flow conditions, the complicated gas-graphene interactions including surface catalysis and surface ablation would occur concurrently and intervene together with the thermodynamic response induced by spacecraft reentry. In this work, the competing effects of surface heterogeneous catalytic recombination and ablation characteristics at elevated temperatures are investigated using the Reactive Molecular Dynamics(RMD) simulation method. A GasSurface Interaction(GSI) model is established to simulate the collisions of hyper-enthalpy atomic oxygen on graphene films in the temperature range of 500–2500 K. A critical temperature Tcaround900 K is identified to distinguish the graphene responses into two parts: at T < T_(c), the heterogeneous surface catalysis dominates, while the surface ablation plays a leading role at T > T_(c). Contradicting to the traditional Arrhenius expression that the recombination coefficient increases with the increase of surface temperature, the value is found to be relatively uniform at T < T_(c) but declines sharply as the surface temperature increases further due to the competing ablation effect. The occurrence of surface ablation decreases the amounts of active sites on the graphene surface for oxygen adsorption, leading to reduced recombination coefficient from both Langmuir-Hinshelwood(L-H) and Eley-Rideal(E-R) mechanisms. It suggests that the traditional Computational Fluid Dynamics(CFD) simulation method, which relies on the Arrhenius-type catalysis model, would result in large discrepancies in predicting aerodynamic heat for carbon-based materials during reentry into strong aerodynamic thermal environment.

Non-isothermal effectiveness factors in thermo-chemical char conversion

Modeling heterogeneous combustion and gasification at large or industry scale is important in ongoing research and development activities.These simulations rely on comprehensive,accurate,and efficient solid conversion models.Pore diffusion is an important sub-process of gas-solid reactions and is often approximated by effectiveness factors.Analytic expressions for isothermal effectiveness factors are usually used,due to the numerical effort of determining non-isothermal ones.The consequences of this simplification are evaluated by determining non-isothermal effectiveness factors for typical combustion conditions for the reactions of carbon with O_(2),CO_(2),H_(2)O,and H_(2).The results show that exothermal reaction rates are under-estimated,while endothermal are over-estimated at low and intermediate temperatures for Thiele moduli between 0.1 and 100.In addition,the reaction zone relocates towards the outer particle layers under these conditions.Cross-sensitivity effects between the four reactions are neglected in this study.A reasonable approximation is the superposition of the individual reactions,because the oxidation reaction is dominant under typical combustion conditions.