Surface Reaction Model Research Articles

Development of Air–Ti Gas-Surface Reaction Mechanisms and Rate Calculations

Gas-surface reaction mechanisms and rates were developed for an air–titanium surface to support finite-rate catalytic surface reaction models used in computational fluid dynamics. For the surface dissociation/recombination reactions, a two-step reaction method was applied based on the assumption that two atoms must be positioned in adjacent cells to recombine. Transition state theory was used to calculate the surface reactions for adsorbed diatomic molecules to dissociate to the adjacent unit cell or atoms located in the adjacent cells to recombine into diatomic molecules. For the second step, atoms located in the adjacent cells are allowed to further dissociate to another cell (total separation), or totally separated atoms recombine into the adjacent cells. A stochastic gas-surface kinetics simulation code, STOKIN, was developed to simulate gas-surface reactions and to calculate the equilibrium constants of second molecular dissociation ⇌ recombination processes. Thermodynamic properties of the adsorbates (enthalpies, entropies, and heat capacities) were calculated using density functional theory along with statistical mechanics assuming no rotational and translational contributions to the entropies and heat capacities due to the adsorbates’ inability to freely move or rotate on the surface.

Significant effect of salinity on zinc adsorption on tropical coastal and floodplain soils

AbstractRising sea levels due to climate change are causing increased salinisation of low‐lying coastal and floodplain soils, and the impact of this process on the bioavailability of plant nutrients needs to be understood as mitigation strategies are adapted. Zinc (Zn) is an element of particular importance due to its function as a micronutrient for plants including rice and other staple foods. In the current study, our aim was to investigate the effects of salinisation on zinc adsorption onto soils representing at‐risk coastal and floodplain environments, addressing in particular our knowledge gap concerning the roles that solution chemistry and soil composition play. To this end, we conducted batch adsorption experiments in the laboratory and ran geochemical models in saline solutions up to 0.7 mol L−1 ion strength incorporating both (i) a multi surface model (MSM) for surface reactions containing three phases, that is iron hydroxides, organic matter and phyllosilicate clays, and (ii) aqueous‐phase complexation to dissolved organic and inorganic ligands. Surface reactions were modelled using the diffuse double layer model, the NICA–Donnan model and an ion exchange model using the Gaines–Thomas convention. We combined the experimentally determined mass composition of surface phases with generic modelling parameters taken from the literature. We first show that increasing salinity enhances the formation of aqueous Zn‐chloride complexes in the presence of dissolved organic matter and bicarbonate, thereby decreasing the availability of free Zn2+ and supressing the partitioning of zinc to the adsorbed phase. We demonstrate using batch adsorption experiments with a calcareous hydraquent and a tropaquept, that salinity decreases zinc adsorption strongly in the pH range between 3 and 6. Satisfactory agreement between experiments and model calculations was achieved with root‐mean‐square errors ranging for different salinities between 2.88% and 2.92% for the hydraquent and between 4.59% and 2.74% for the tropaquept soil. Model predictions of adsorption were slightly inferior at low salinity for the hydraquent soil and at high salinity for the tropaquept soil, pointing possibly to an incomplete geochemical model or to a need to parametrise surface adsorption models at higher ionic strengths. Present surface models have been largely parametrised at lower ionic strength. We lastly apply the MSM to examine zinc adsorption in five endoaquepts soils, representing soil series from Bangladesh. We show that increasing salinity decreases zinc adsorption to the soil organic matter and the clay fractions. We conclude from our findings that increased soil salinity due to rising sea levels and climate change will have a significant impact on zinc cycling and possibly other micronutrients in areas where coastal soils and floodplain soils overlap, such as deltas and estuaries. In particular, we predict a decrease in zinc adsorption in acidic to neutral soils. The availability of zinc for biouptake through the roots of crop plants including rice will be significantly disturbed following salinisation, most likely affecting crop production. Our study demonstrates the potential that geochemical modelling combined with experimental data has to improve our capability to assess the effects of salinity due to rising seawater levels in vulnerable regions of the world.

Convective dissolution in a fractured porous matrix using multi-component surface reaction lattice Boltzmann method

In this paper, an improved lattice Boltzmann method-based surface reaction model for studying the convective dissolution of a multi-component system in porous matrix is propose. This model treats the generation and the consumption of components as a source term in control equation. The accuracy of the model is validated by comparing it with an analytical solution of a two-dimensional square cavity diffusion problem and achieves a good agreement. Subsequently, this model is applied to simulate the dissolution of porous medium with a triangular fissure on the surface. By investigating the aspect ratio of the fissure, the results reveal that a low base-height ratio can promote the dissolution rate. By investigating the main dimensionless number of Sc and Da, the results show that Schmidt number has a dominant influence on the dissolution process, and Da is positively correlated with the total dissolution time.

The Conundrum of "Pair Sites" in Langmuir-Hinshelwood Reaction Kinetics in Heterogeneous Catalysis.

Understanding reaction kinetics is crucial for designing and applying heterogeneous catalytic processes in chemical and energy conversion. Here, we revisit the Langmuir-Hinshelwood (L-H) kinetic model for bimolecular surface reactions, originally formulated for metal catalysts, assuming immobile adsorbates on neighboring pair sites, with the rate varying linearly with the density of surface sites (sites per unit area); r ∝ [*]o 1. Supported metal oxide catalysts, however, offer systematic control over [*]o through variation of the active two-dimensional metal oxide loading in the submonolayer region. Various reactions catalyzed by supported metal oxides are analyzed, such as supported VO x catalysts, including methanol oxidation, oxidative dehydrogenation of propane and ethane, SO2 oxidation to SO3, propene oxidation to acrolein, n-butane oxidation to maleic anhydride, and selective catalytic reduction of nitric oxide with ammonia. The analysis reveals diverse dependencies of reaction rate on [*]o for these surface reactions, with r ∝ [*]o n , where n equals 1 for reactions with a unimolecular rate-determining step and 2 for those with a bimolecular rate-limiting step or exchange of more than 2 electrons. We propose refraining from a priori assumptions about the nature and density of surface sites or adsorbate behavior, advocating instead for data-driven elucidation of kinetics based on the density of surface sites, adsorbate coverage, etc. Additionally, recent studies on catalytic surface mechanisms have shed light on nonadjacent catalytic sites catalyzing surface reactions in contrast to the traditional requirement of adjacent/pair sites. These findings underscore the need for a more nuanced approach in modeling heterogeneous catalysis, especially supported metal oxide catalysts, encouraging reliance on experimental data over idealized assumptions that are often difficult to justify.

Effect of the inlet spatial fluctuation on the gas–solid continuous rotating detonation flow field characteristics

Continuous rotating detonation engines have been extensively studied due to their high thermal efficiency. The utilization of solid particles as fuel can effectively reduce costs and enhance detonation performance. We have constructed a compressible gas–solid multimedium flow combustion numerical method, employing the double flux model coupled with fifth-order weighted essentially non-oscillatory and third-order total variation diminishing Runge–Kutta schemes to solve the unsteady multi-component chemical reaction Eulerian–Eulerian equations. Finite-rate methods and surface reaction models are used to simulate the combustion of gaseous mixtures and carbon particles. The effects of the inlet total pressure spatial fluctuations and particle diameter on the flow field characteristics of the continuous rotating detonation engine are investigated. The results indicate that changing the fluctuation period significantly affects the number, propagation direction, and intensity of gas–solid two-phase continuous rotating detonation waves (CRDW). The variation of fluctuation amplitude noticeably alters the combustion characteristics of the two-phase continuous rotating detonation wave, and excessively high amplitudes cannot form continuous rotating detonation waves. Introducing solid particles into fuel significantly mitigates the impact of inlet total pressure spatial fluctuation and promotes propagation stability on the detonation waves. Moreover, when solid particle diameters reach or exceed the micrometer scale, they contribute more favorably to generating a stable detonation flow field. However, excessive particle sizes result in a low surface reaction rate and inadequate contribution of heat released from particle combustion to the propagation of detonation waves.

Multiscale modeling of reactive flow in heterogeneous porous microstructures

This paper presents a multiscale reactive flow model to simulate in-situ leaching of copper in heterogeneous porous microstructures. The introduced workflow combines fluid flow simulation with advection-diffusion-reaction simulation, both required to model reactive flow. The proposed workflow can include the fluid flow in resolved and unresolved pore structures and utilizes required parameters from molecular simulation (ionic diffusivity) and reaction databases (reaction rate parameters). The modeling approach is validated by comparing results to other open-source codes for a model calcite dissolution on acid injection. This model is applied to copper mining by leaching to analyze the reactive flow through a fractured digital rock model of a subsurface sample. Results are analyzed by tracking the concentration distribution along the pore space structure and calculating the outlet concentration of copper to conform the leaching path. Several sensitivity studies are performed to show the robustness of the modeling framework as well as to investigate the importance of each of these parameters on copper production. The complexity of the model is systematically increased from a single scale surface reaction model, to consider the influence of competitive bulk solution reactions, and finally to include flow through porous media to model multiscale reactive flow. This study shows that a multi-scale flow model with homogeneous bulk and heterogeneous surface reactions is required to accurately model copper leaching.

Preparation of poly(divinylbenzene-co-methyl acrylate) adsorbent with tunable surface hydrophilicity for atrazine removal

To efficiently remove atrazine, it is crucial to facilitate synergistic adsorption effect between aromatic structure and hydrophilic adsorption sites through tuning surface hydrophilicity. Herein, we reported a polymer adsorbent which was synthesized by copolymerizing divinylbenzene (DVB) and methyl acrylate (MA) with different monomer ratio, and subsequently hydrolyzing the copolymer to obtain carboxyl group on its surface. The surface hydrophilicity could be easily adjusted by changing the ratio of monomer and the optimal feeding ratio was 4:1 (VDVB:VMA) in terms of porosity (specific surface area 712.92 m2/g) and hydrophilicity regarding atrazine adsorption. The adsorption process followed the Langmuir isotherm with a maximum adsorption capacity of 75.75 mg/g. The mixed surface reaction and film diffusion model revealed that the adsorption procedure is dramatically controlled by film diffusion. Atrazine molecules diffusive and bound with porous adsorbent via strong hydrogen bonding between N (triazine and amine) and carboxyl groups introduced by copolymerization. Furthermore, high porosity caused by aromatic crosslinked network provided sufficient adsorption sites through π-stacking interaction. This work not only supplies a highly efficient adsorbent for atrazine removal but also enables a platform for preparation of polymers with tunable porosity and surface hydrophilicity.

Recovery of Cobalt, Nickel, and Lithium from Spent Lithium-Ion Batteries with Gluconic Acid Leaching Process: Kinetics Study

The demand for lithium-ion batteries (LIBs) is driven by environmental concerns and market growth, particularly in the transportation sector. The EU’s push for net-zero emissions and the European Green Deal accentuates the role of battery technologies in sustainable energy supply. Organic acids, like gluconic acid, are explored for the eco-friendly leaching of valuable metals from spent batteries. This study investigates leaching kinetics using gluconic acid (hydrolyzed glucono-1.5-lacton), analyzing factors such as temperature, acid concentration, particle size, and reaction time. Results reveal the temperature’s influence on leaching efficiency for cobalt, nickel, and lithium. The mechanism for Co follows a surface chemical reaction model with an activation energy of 28.2 kJ·mol−1. Nickel, on the contrary, shows a diffusion-controlled regime and an activation energy of 70.1 kJ·mol−1. The reaction of leaching Ni and Co using gluconic acid was determined to be first-order. The process within this environmentally friendly alternative leaching agent shows great potential for sustainable metal recovery.

Models of Protocells Undergoing Asymmetrical Division.

The conditions that allow for the sustained growth of a protocell population are investigated in the case of asymmetrical division. The results are compared to those of previous studies concerning models of symmetrical division, where synchronization (between duplication of the genetic material and fission of the lipid container) was found under a variety of different assumptions about the kinetic equations and about the place where molecular replication takes place. Such synchronization allows a sustained proliferation of the protocell population. In the asymmetrical case, there can be no true synchronization, since the time to duplication may depend upon the initial size, but we introduce a notion of homogeneous growth that actually allows for the sustained reproduction of a population of protocells. We first analyze Surface Reaction Models, defined in the text, and we show that in many cases they undergo homogeneous growth under the same kinetic laws that lead to synchronization in the symmetrical case. This is the case also for Internal Reaction Models (IRMs), which, however, require a deeper understanding of what homogeneous growth actually means, as discussed below.

Spectroscopic Study of [Mg, H, N, C, O] Species: Implications for the Astrochemical Magnesium Chemistry.

Magnesium is an abundant metal element in space, and magnesium chemistry has vital importance in the evolution of interstellar medium (ISM) and circumstellar regions, such as the asymptotic giant branch star IRC+10216 where a variety of Mg compounds bearing H, C, N, and O have been detected and proposed as the important components in the gas-phase molecular clouds and solid-state dust grains. Herein, we report the formation and infrared spectroscopic characterization of the Mg-bearing molecules HMg, [Mg, N, C], [Mg, H, N, C], [Mg, N, C, O], and [Mg, H, N, C, O] from the reactions of Mg/Mg+ and the prebiotic isocyanic acid (HNCO) in the solid neon matrix. Based on their thermal diffusion and photochemical behavior, a complex reactivity landscape involving association, decomposition, and isomerization reactions of these Mg-bearing molecules is developed, which can not only help understand the chemical processes of the magnesium (iso)cyanides in astrochemistry but also provide implications on the presence of magnesium (iso)cyanates in the ISM and the chemical model for the dust grain surface reactions. It also provides a new paradigm of the key intermediate nature of the cationic complexes in the formation of neutral interstellar species.

Experimental and numerical analysis of the effects of thermal degradation on carbon monoxide oxidation characteristics of a three-way catalyst

This work investigates oxygen-storage capacity (OSC) changes during thermal degradation in modern three-way catalysts. Two experiments are performed using catalysts with different degradation degrees to evaluate OSC and reaction rates. The CO2 production test, where CO and O2 are supplied at a constant temperature, shows decreased CO2 production with more degraded catalysts and reduced purification. The CO2 production test is conducted using transient temperature increases, showing that the maximum CO2 production temperature increases with catalyst degradation. The results reveal an increase in activation energy in the oxygen desorption reaction caused by thermal degradation progresses and a decrease in OSC, resulting in temperature increases in the oxygen storage reaction. In the surface reaction and mass transport model considering the 30 elementary reactions, the predicted results are well-validated for CO2 production, enabling good oxygen storage predictions based on actual data. These results can be used to predict OSC by formulating the changes in active site density and activation energy due to degradation.

CuO nanostructure-decorated InGaN nanorods for selective H2S gas detection.

Establishing a heterostructure is one of the adequate strategies for enhancing device performance and has been explored in sensing, and energy applications. In this study, we constructed a heterostructure through a two-step process involving hydrothermal synthesis of CuO nanostructures and subsequent spin coating on MBE-grown InGaN NRs. We found that the CuO content on the InGaN NRs has a great impact on carrier injection at the heterojunction and thus the H2S gas sensing performance. Popcorn CuO/InGaN NR shows excellent gas sensing performance towards different concentrations of H2S at room temperature. The highest response is up to 35.54% to a H2S concentration of 100 ppm. Even more significantly, this response is further enhanced significantly (123.70%) under 365 nm UV light. In contrast, this composite structure exhibits negligibly low responses to 100 ppm of NO2, H2, CO, and NH3. The heterostructure band model associated with a surface reaction model is manifested to elucidate the sensing mechanism.

First principle-based rate equation theory for the carbonation kinetics of CaO with CO2 in calcium looping

Calcium oxide (CaO), a CO2 sorbent and key ingredient in the process of making cement, exhibits excellent potential for carbon capture, utilization, and storage (CCUS) applications through calcium looping and integrated carbon capture and utilization, owing to its outstanding kinetic properties and high recyclability. From a fundamental standpoint, it is important to establish a comprehensive and precise carbonation kinetic model for CaO. In the present study, a density functional theory (DFT)-based rate equation was developed to predict the gas–solid reaction kinetics of CaO carbonation with CO2 in calcium looping. The reaction pathway of CaO carbonation, including surface reactions and structural transformations, was obtained by a transition state search of DFT calculations, and the transition state theory was used to calculate the reaction rate constants. The nucleation model was implemented in the mean-field surface reaction model to describe the nucleation of the CaCO3 product at the gas–solid interface. A grain model was developed to couple the surface reaction and CO2 diffusion through the product layer. The developed theory was validated using a wide range of experimental data, and the negative activation energy of CaO carbonation close to equilibrium was accurately predicted. The developed first principle-based rate equation provides a detailed theoretical framework for predicting CaO performance and optimizing the microstructure of Ca-based sorbents.

Fast Gold Recovery from Aqueous Solutions and Assessment of Antimicrobial Activities of Novel Gold Composite

A novel porous gold polymer composite was prepared by the functionalization of a glycidyl methacrylate-based copolymer (pGME) with ethylene diamine (pGME-en), and activation by gold (pGME-en/Au), in a simple batch adsorption procedure in an acid solution, at room temperature. Detailed characterization of the pGME-en before and after activation was performed. The main focuses of this research were the design of a method that can enable the recovery of gold and the reuse of this multipurpose sorbent as an antimicrobial agent. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis pointed out amine groups as the primary binding sites for Au activation, while hydroxyl groups also contributed to the chelation reaction. pGME-en exhibited fast gold adsorption with an adsorption half-time of 5 min and an equilibrium time of 30 min. The maximal adsorption capacity was about 187 mg/g. The analysis of sorption experimental data with a non-linear surface reaction and diffusion-based kinetic models revealed the pseudo-second-order and Avrami model as the best fit, with unambiguous control by liquid film and intra-particle diffusion. The biological activity studies against Staphylococcus aureus, Listeria monocytogenes, Escherichia coli, and Candida albicans revealed moderate activity of pGME-en/Au against different bacterial and fungal species. pGME-en/Au was stable in a saline solution, with a release of approximately 2.3 mg/g after 24 h.

Numerical investigation on the combustion characteristics of powder fuel under different regulation parameters

A comprehensive numerical study is undertaken to investigate the operating feature in a powder fueled scramjet combustor. The effect of regulation parameters on the flow field and combustion mechanism is examined systematically. The numerical simulation method is developed for multi-species gas-solid two-phase turbulent combustion in the Euler-Lagrange frame. The particle surface reaction model and the Eddy-dissipation Concept model are utilized for powder fuel combustion. The combustor flow field, flame structure, and species distribution in the powder fueled scramjet combustor are revealed in detail. The numerical simulation results show that the combustion organization scheme of tandem double-cavity can provide an excellent flame stabilization effect. The powder fuel achieves continuous combustion and sufficient release heat in the supersonic airflow. The combustion flow field features and flame distribution are strongly influenced by the transport solid-gas ratio and the equivalent ratio. The increase of both regulation parameters improves the combustion efficiency of powder fuel in the region from the injection hole to the downstream cavity. Nevertheless, the large equivalent ratio significantly leads to higher total pressure losses in the combustor.

Mechanistic Insights into the Induction Period of Methanol-to-Olefin Conversion over ZSM-5 Catalysts: A Combined Temperature-Programmed Surface Reaction and Microkinetic Modeling Study

Mechanistic Insights into the Induction Period of Methanol-to-Olefin Conversion over ZSM-5 Catalysts: A Combined Temperature-Programmed Surface Reaction and Microkinetic Modeling Study

Numerical study on the effect of carbon particles on flow field characteristics of rotating detonation engine

Rotating detonation engines have high thermal efficiency and thus have been extensively studied. Using solid particles as fuel can reduce costs, and experiments have demonstrated the feasibility of gas-solid two-phase rotating detonation. However, numerical simulation research is required that examines the flow field characteristics of a rotating detonation engine. In order to explore the role of carbon particle fuel in a gas-solid two-phase rotating detonation wave, the weighted essentially non-oscillating scheme and third-order total variation diminishing Runge-Kutta scheme are used to solve the gas-solid unsteady Eulerian–Eulerian equations. Finite rate chemical and surface reaction models are used to simulate the combustion of gaseous substances and carbon particles. The influence of the proportion of carbon particles in the fuel and the diameter of the carbon particles on the rotating detonation flow field characteristics is analyzed. The results indicate that when the size of carbon particles is in the micrometer scale or below, the two-phase rotating detonation waves exhibit double-front or single-front detonation structures, respectively. Adding carbon particles to the fuel enables the rotating detonation engine to achieve a total pressure gain.

Thermodynamic Two-Site Surface Reaction Model for Predicting Munition Constituent Reduction Kinetics with Iron (Oxyhydr)oxides.

Iron (oxyhydr)oxides comprise a significant portion of the redox-active fraction of soils and are key reductants for remediation of sites contaminated with munition constituents (MCs). Previous studies of MC reduction kinetics with iron oxides have focused on the concentration of sorbed Fe(II) as a key parameter. To build a reaction kinetic model, it is necessary to predict the concentration of sorbed Fe(II) as a function of system conditions and the redox state. A thermodynamic framework is formulated that includes a generalized double-layer model that utilizes surface acidity and surface complexation reactions to predict sorbed Fe(II) concentrations that are used for fitting MC reduction kinetics. Monodentate- and bidentate Fe(II)-binding sites are used with individual oxide sorption characteristics determined through data fitting. Results with four oxides (goethite, hematite, lepidocrocite, and ferrihydrite) and four nitro compounds (NB, CN-NB, Cl-NB, and NTO) from six separate studies have shown good agreement when comparing observed and predicted surface area-normalized rate constants. While both site types are required to reproduce the experimental redox titration, only the monodentate site concentration controls the MC reaction kinetics. This model represents a significant step toward predicting the timescales of MC degradation in the subsurface.

3D modeling of feature-scale fluorocarbon plasma etching in silica

Fluorocarbon dry etching of vertical silica-based structures is essential to the fabrication of advanced complementary metal-oxide-semiconductor and dynamic random access memory devices. However, the development of etching technology is challenged by the lack of understanding of complex surface reaction mechanisms and by the intricacy of etchant flux distribution on the feature-scale. To study these effects, we present a three-dimensional, TCAD-compatible, feature-scale modeling methodology. The methodology combines a level-set topography engine, Langmuir kinetics surface reaction modeling, and a combination of reactant flux evaluation schemes. We calibrate and evaluate our model to a novel, highly selective, etching process of a mathrm {SiO_2} via and a textrm{Ru} hardmask by mathrm {CF_4/C_4F_8}. We adapt our surface reaction model to the novel stack of materials, and we are able to accurately reproduce the etch rates, topography, and critical dimensions of the reported experiments. Our methodology is therefore able to prototype and study novel etching processes and can be integrated into process-aware three-dimensional device simulation workflows.

Ammonia thermal decomposition on quartz and stainless steel walls

Ammonia has been proposed as a promising solution for hydrogen carriers as well as clean fuels. However, the reaction kinetics is still not robust in many engineering applications, where the deviation is mainly caused by the surface reactions of ammonia on the wall. To examine the ammonia surface reaction on engineering materials, in the present study, the thermal decomposition of ammonia is systematically investigated in uniformly heated quartz/SUS304 tubular flow reactors with the prescribed heating length. A decrease in the inner diameter of the quartz tubular reactor leads to an increase in the ammonia thermal decomposition rate, showing that the thermal decomposition reaction occurs even on quartz surfaces, which is usually believed to be inert. The thermal decomposition on the SUS304 reactor surface starts from as low as 700 K, indicating it is much more reactive than the quartz surface. One-step surface reaction models of ammonia for quartz/SUS304 surfaces are proposed, with which the reaction rates are estimated based on the experimental data. The inner surface of the SUS304 tubular reactor after the thermal decomposition experiments is examined by X-ray photoelectron spectroscopy. The formation of iron nitride on SUS304, which in turn facilitates ammonia thermal decomposition, reveals the positive feedback between ammonia decomposition and nitriding. Moreover, the present one-step surface reaction on stainless steel has been validated by measuring ammonia distributions in the preheat zone of NH3/O2/N2 premixed flame impinging on a stainless steel plate through a two-photon absorption laser-induced fluorescence (TALIF) technique.