Multi-step Reaction Mechanism Research Articles

Analyzing multi-step reaction mechanisms: Unveiling non-linear dynamics with advanced reduction techniques

This study aims to achieve the computational results for the oxidation of carbon monoxide using the spectral quasi-equilibrium manifold and the intrinsic low-dimensional manifold techniques, enabling the identification of the slow invariant manifold and subsequent simulation of the solutions. In addition, the application of Gibbs’ rule facilitates the reduction of the system, thereby effectively transforming higher dimensions into lower dimensions, ultimately revealing the underlying 1D manifold dynamics. This research serves to elucidate the intricacies of phase-shifting behaviors in the context of key species within the overarching and interconnected multi-step reaction mechanisms, contributing significantly to the advancement of understanding in this complex field.

Molecular Mechanism for Converting Carbon Dioxide Surrounding Water Microdroplets Containing 1,2,3-Triazole to Formic Acid.

Spraying water microdroplets containing 1,2,3-triazole (Tz) has been found to effectively convert gas-phase carbon dioxide (CO2), but not predissolved CO2, into formic acid (FA). Herein, we elucidate the reaction mechanism at the molecular level through quantum chemistry calculations and ab initio molecular dynamics (AIMD) simulations. Computations suggest a multistep reaction mechanism that initiates from the adsorption of CO2 by Tz to form a CO2-Tz complex (named reactant complex (RC)). Then, the RC either is reduced by electrons that were generated at the air-liquid interface of the water microdroplet and then undergoes intramolecular proton transfer (PT) or switches the reduction and PT steps to form a [HCO2-(Tz-H)]- complex (named PC-). Subsequently, PC- undergoes reduction and the C-N bond dissociates to generate COOH- and [Tz-H]- (m/z = 69). COOH- easily converts to HCOOH and is captured at m/z = 45 in mass spectroscopy. Notably, the intramolecular PT step can be significantly lowered by the oriented electric field at the interface and a water-bridge mechanism. The mechanism is further confirmed by testing multiple azoles. The AIMD simulations reveal a novel proton transfer mechanism where water serves as a transporter and is shown to play an important role dynamically. Moreover, the transient •COOH captured by the experiment is proposed to be partly formed by the reaction with H•, pointing again to the importance of the air-water interface. This work provides valuable insight into the important mechanistic, kinetic, and dynamic features of converting gas-phase CO2 to valuable products by azoles or amines dissolved in water microdroplets.

PH-dependent reaction triggering in PmHMGR crystals for time-resolved crystallography

Serial crystallography and time-resolved data collection can readily be employed to investigate the catalytic mechanism of Pseudomonas mevalonii 3-hydroxy-3-methylglutaryl (HMG)-coenzyme-A (CoA) reductase (PmHMGR) by changing the environmental conditions in the crystal and so manipulating the reaction rate. This enzyme uses a complex mechanism to convert mevalonate to HMG-CoA using the co-substrate CoA and cofactor NAD+. The multi-step reaction mechanism involves an exchange of bound NAD+ and large conformational changes by a 50-residue subdomain. The enzymatic reaction can be run in both forward and reverse directions in solution and is catalytically active in the crystal for multiple reaction steps. Initially, the enzyme was found to be inactive in the crystal starting with bound mevalonate, CoA, and NAD+. To observe the reaction from this direction, we examined the effects of crystallization buffer constituents and pH on enzyme turnover, discovering a strong inhibition in the crystallization buffer and a controllable increase in enzyme turnover as a function of pH. The inhibition is dependent on ionic concentration of the crystallization precipitant ammonium sulfate but independent of its ionic composition. Crystallographic studies show that the observed inhibition only affects the oxidation of mevalonate but not the subsequent reactions of the intermediate mevaldehyde. Calculations of the pKa values for the enzyme active site residues suggest that the effect of pH on turnover is due to the changing protonation state of His381. We have now exploited the changes in ionic inhibition in combination with the pH-dependent increase in turnover as a novel approach for triggering the PmHMGR reaction in crystals and capturing information about its intermediate states along the reaction pathway.

Metal-Free Photocatalytic CO2 Reduction to CH4 and H2 O2 under Non-sacrificial Ambient Conditions.

Photocatalytic CO2 reduction to CH4 requires photosensitizers and sacrificial agents to provide sufficient electrons and protons through metal-based photocatalysts, and the separation of CH4 from by-product O2 has poor applications. Herein, we successfully synthesize a metal-free photocatalyst of a novel electron-acceptor 4,5,9,10-pyrenetetrone (PT), to our best knowledge, this is the first time that metal-free catalyst achieves non-sacrificial photocatalytic CO2 to CH4 and easily separable H2 O2 . This photocatalyst offers CH4 product of 10.6 μmol ⋅ g-1 ⋅ h-1 under non-sacrificial ambient conditions (room temperature, and only water), which is two orders of magnitude higher than that of the reported metal-free photocatalysts. Comprehensive in situ characterizations and calculations reveal a multi-step reaction mechanism, in which the long-lived oxygen-centered radical in the excited PT provides as a site for CO2 activation, resulting in a stabilized cyclic carbonate intermediate with a lower formation energy. This key intermediate is thermodynamically crucial for the subsequent reduction to CH4 product with the electronic selectivity of up to 90 %. The work provides fresh insights on the economic viability of photocatalytic CO2 reduction to easily separable CH4 in non-sacrificial and metal-free conditions.

Ab Initio Study of Glycine Formation in the Condensed Phase: Carbon Monoxide, Formaldimine, and Water Are Enough

Glycine is considered to be crucial in the formation of proteins and prebiotic substances. Nevertheless, the mechanism of spontaneous glycine formation under prebiotic Earth conditions or within the interstellar medium (ISM) remains a topic of debate, given the changing geochemical environment over Earth’s history and the difficulty of detecting it within the ISM. Yet it is believed that its formation could be possible in interstellar water-rich ice. In this study, using molecular dynamics (MD) simulations at the ab initio level of theory enhanced with modern free energy calculations, we modeled the chemical reaction between carbon monoxide, formaldimine, and water to produce glycine. We estimated under what conditions, in condensed phase at 50, 70, 100, and 300 K, glycine is formed. We also explored the effect of different electric fields on this process. Our results show that glycine could be formed with energy barriers as low as 0.5 kcal mol−1 at 50 K. We discuss whether this reaction could be a suitable candidate for explaining the mechanism of glycine formation under conditions that resemble various astrophysical environments, such as planets, exoplanets, and Earth. This study is relevant to finding a consensus among various proposals for glycine formation. Moreover, it highlights the importance of metadynamics and Car–Parrinello MD methods as tools in finding unknown complex, multistep reaction mechanism pathways, possibly important to the astronomical phenomena.

Preparation and Use of Iron on Carbon Foam for Removal of Organic Dye from Water: Batch Studies.

The presence of dyes in effluents from textile industries has a detrimental effect on aquatic ecosystems as it hinders the process of photosynthesis by reducing the penetration of sunlight. The adsorption capacity of a carbon foam-based iron oxide sorbent obtained from natural sources for the removal of organic methylene blue (MB) dye from water was investigated. The adsorption capacities were examined by batch experiments, wherein the impacts of varying iron content, sorbent dosage, contact time, dye concentration, and characterization were assessed. The physical characteristics and surface morphology of the synthesized carbon foam were also investigated. The carbon precursor and iron oxide precursor were coalesced within a singular container and subjected to carbonization process. This resulted in the formation of a porous structure that is capable of effectively providing support to the iron oxide particles. The carbon foam produced is a self-assembled formation that possesses the characteristic shape and underlying network structure reminiscent of bread. As the number of nanoparticles went up, so did the number of active sites. At elevated temperatures, the interactions between the dye molecules were enhanced, resulting in a more efficient process of dye removal. The magnetite sample exhibited endothermic adsorption, and all other samples exhibited exothermic adsorption. The adsorption of MB onto iron supported by carbon foam did not exhibit intraparticle diffusion as the only rate-limiting step for all samples. The adsorption rate was governed by a multistep elementary reaction mechanism in which multiple processes occurred simultaneously. The experimental data in this study may be accurately modeled by the pseudo-second-order kinetic model (R2 > 0.96). Additionally, the Freundlich isotherm best describes the adsorption equilibrium, which is supported by the outstanding fit of data to the model (R2 > 0.999). The findings suggest that the utilization of a natural carbon foam as a support for an immobilized iron oxide sorbent demonstrates considerable effectiveness in the removal of methylene dye from industrial effluent.

Flame Surface Density and Artificially Thickened Flame Combustion Models Applied to a Turbulent Partially-Premixed Flame

The Sydney Flame provides an excellent framework for systematic analysis of premixed, partially premixed and non-premixed methane/air combustion. It represents (depending on the axial position from the fuel inlet) non-premixed, partially premixed and fully premixed combustion. We simulate the test case FJ200-5GP-Lr75-57, which represents the partially premixed mode. Large-eddy simulations (LES) are conducted using a flame surface density combustion model (FSD) using one-step chemistry and an artificially thickened flame model (ATF) with a global two-step and an analytically reduced multi-step chemistry reaction mechanism. Unity Lewis numbers are assumed (Le=1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$Le=1$$\\end{document}) at first. The FSD and ATF models are compared using the same computational mesh, numerical scheme and boundary conditions. Both models will be analysed regarding their accuracy and computational efficiency in the regime of partially premixed combustion. A comparison of the results points out the strengths and weaknesses of the FSD models. The FSD model with inclusion of flame stretch effects yields good agreement with mean experimental temperature, CO2 and H2O mass fraction distributions in contrast to the ATF model using the global two-step mechanism, which overestimates downstream temperature, CO2 and H2O mass fractions. The FSD model performs well in all regions, which are dominated first by premixed, then partially premixed and finally non-premixed combustion along the flame. The ATF multi-step chemistry shows good results only in the premixed mode region, while mean temperature, CO2 and mass fractions are overestimated in the non-premixed mode regions at higher mixture fraction values. Including differential diffusion into the transport equations improved the ATF model results in comparison with experiments. A mesh study revealed, that the ATF model performs only after mesh refinement. In particular results are improved in the non-premixed combustion region. In contrast, the FSD model is less resolution sensitive and performs very well for both meshes. An evaluation of the Wasserstein metric provides a quantitative assessment of different ATF model setups on simulation accuracy. Finally, computational times for all simulation setups are compared.

Electrocatalytic reduction of Cr(VI) on gold-based electrodes in acidic medium: A systematic approach to chromium detection

In the present research, gold immobilized on different substrates (Au, GC, Pt) was examined to fabricate a Cr(VI) sensor in an acidic medium via reduction reactions. Comparative analysis revealed that Au-Pt electrode exhibited better electrocatalytic activity towards the reduction of Cr(VI) compared to Au, Au-Au or Au-GC electrode, which is emphatically discussed in this article. Specifically, the inner α-Au2O3 species of Au matrix on the catalytic surface played a key role in catalyzing Cr(VI) in the acidic medium. Voltammetric investigations revealed that the concerned electrode process is proton-dependent. From hydrodynamic voltammetric studies, it was found that the reduction reaction follows a multistep reaction mechanism with a single electron transfer rate-determining step over the Au-Pt surface. The Cr(VI) reduction reaction follows 1st order kinetics at the Au-Pt electrode surface, where the standard rate constant (k) was found to be 1.4×10−2 cm−1. The excellent improvement of reduction current over the Au-Pt surface was exploited in the fabrication of the Cr(VI) sensor. The developed sensor detects Cr(VI) ions with a linear dynamic range of 10 to 130 μM, whereas the sensitivity and limit of detection values are 3.21 μAμM−1cm−2 and 2.97 μM, respectively. Overall, the findings highlight the promising performance of the Au-Pt electrode in detecting Cr(VI) ions and provide valuable insights into the underlying catalytic diagnosis.

Chemical kinetics of two-step thermochemical decomposition of hydrogen sulfide over nickel sulfide

The study develops a multistep reaction mechanism for a two-step thermochemical cycle that produces hydrogen from H2S decomposition, using nickel sulfide as a catalyst. Two mechanisms were investigated: 1) a gas-phase mechanism that occurs without a Ni catalyst to determine the contribution of thermal decomposition to the overall reaction without a catalyst, and 2) a microkinetic model of the catalytic Ni surface phase to examine the key parameters affecting the overall cycling process and H2S conversion efficiency. Both mechanisms were validated using CHEMKIN-Pro software to analyze the experimental data and trends. The study showed that gas-phase H2S conversion was not kinetically significant below 850 °C. The microkinetic model showed that most H2S was transformed into H2 and NiS products when the sulfurization temperature reached 500 °C. Additionally, the site fraction of NiS decreased while the number of free active nickel sites increased as the regeneration temperature increased from 500 °C to 800 °C. A temperature limit of 700 °C was set for the regeneration step due to the agglomeration behavior of nickel sulfide particles.

Study on biofuel efficiency of tropical banana leaf biomass using spectroscopy, kinetic and thermodynamic parameters

Bio-oils and biochar are some of the valuable products, which are usually harnessed through the pyrolysis process. Under the current investigation, three popular edible banana species were subjected to the pyrolysis process in order to decipher their bioenergy potential. Thermo-gravimetric analysis was utilized to determine the kinetic parameters. The levels of Eα were estimated to be 206 kJ/mol for Musa acuminata, 179 kJ/mol Musa chinichampa and 180 kJ/mol for Musa paradisiaca. Values of A in the range of 1012–1015 s−1, 1012–1015 s−1,1013–1015 s-1, and 1013–1015 s−1 were observed under FWO, KAS, Starink, and Tang model, respectively. From the master plot analysis, it was observed that the reaction mechanism involved in the thermal decay of major cell wall polymers was quite complex and followed a multi-step reaction mechanism. Analysis of the thermodynamic parameters, validated the endothermic nature of pyrolysis. Overall, combined with the different physical and chemical characteristics, it is observed that the leaf biomass of tropical banana species Musa chinichampa is a better feed stock for bioenergy production.

Multi-Step Nucleation of A Crystalline Silicate Framework via A Structurally Precise Prenucleation Cluster.

Hierarchical nucleation pathways are ubiquitous in the synthesis of minerals and materials. In the case of open framework lattices such as zeolites and metal-organic frameworks, pre-organized multi-ion "secondary building units" (SBUs) have long been proposed as fundamental building blocks of the forming crystals. However, detailing the progress of multi-step reaction mechanisms in going from monomeric species to stable crystals and defining the structures of the intermediate SBUs remains an unmet challenge. Combining in situ nuclear magnetic resonance, small-angle X-ray scattering, and atomic force microscopy, we show that crystallization of the framework silicate, cyclosilicate hydrate, occurs through an assembly of cubic octameric Q38polyanions formed through cross-linking and polymerization of smaller silicate monomers and other oligomers. These Q38 are stabilized by hydrogen bonds with surrounding H2O and tetramethylammonium ions (TMA+). When Q38 levels reach a threshold of~32% of the total silicate species nucleation within these clathrates occurs. Further growth proceeds through the incorporation of [(TMA)x(Q38)·nH2O](x-8) clathrate complexes into step edges on the crystals. These findings provide a clear picture of the multi-step nucleation process by which SBUs build a framework silicate lattice with implications for the synthesis of both functional materials and natural minerals.

Lead-Free Perovskite Cs2 SnBr6 /rGO Composite for Photocatalytic Selective Oxidation of 5-Hydroxymethylfurfural to 2,5-Diformylfuran.

Severe poisonousness and prolonged instability existing in organic-inorganic lead-based perovskite are two matters seriously hindering its potential future application in photocatalysis. Therefore, it is particularly important to explore ecology-friendly, air-stable and highly active metal-halide perovskites. Herein, a new and stable lead-free perovskite Cs2 SnBr6 decorated with reduced graphene oxide (rGO), is synthesized and employed in the photocatalytic organic conversion. The as-prepared Cs2 SnBr6 is ultrastable, exhibiting no clear changes after being placed in the air for six months. The Cs2 SnBr6 /rGO composite shows excellent photocatalytic activity in photo-driven-oxidation of 5-hydroxymethylfurfural (HMF) to high value enclosed 2,5-diformylfuran (DFF), achieving>99.5 % conversion of HMF and 88 % DFF selectivity in the presence of green oxidant O2 . Comprehensive characterizations disclose a multistep reaction mechanism, demonstrating that the molecular oxygen, photogenerated carriers, ⋅O2 - and 1 O2 altogether synergistically participate in the effective photo-driven conversion of HMF to DFF. This work expands the material gallery towards selective organic conversion and environmentally friendly perovskite options for photocatalytic application.

Thermal degradation study of natural fibre through thermogravimetric analysis

Thermogravimetric analysis was performed to understand the thermal degradation characteristics of natural fibre (bhimal). The objective of the study was to evaluate the suitability of fibre as an alternative to synthetic fibre for reinforcement in polymer composite synthesis. The thermal degradation study was conducted at three heating rates, 10, 15 and 20 °C/min from room temperature to 800 °C. The highest weight loss (65–71 wt%) was observed in the temperature range of 200–435 °C. Three model-free isoconversional methods, FWO, KAS, and Friedman, were applied to estimate the kinetic parameters (activation energy and pre-exponential factor). Average activation energies of 115.96 ± 30.89, 111.08 ± 33.01, and 112.67 ± 41.87 kJ/mol were calculated by FWO, KAS, and FR methods, respectively. The respective estimated pre-exponential factors were 1.41E + 11, 6.62E + 10, and 4.49E + 13 min−1. The kinetic parameters varied substantially with the conversion level, which shows the multi-step reaction mechanism of bhimal fibre thermal degradation. The present study suggests the apparent activation energy of bhimal fibre in the range of 108–120 kJ/mol for polymer composite synthesis.

Site-Averaged Ab Initio Kinetics: Importance Learning for Multistep Reactions on Amorphous Supports

Single-atom centers on amorphous supports include catalysts for polymerization, partial oxidation, metathesis, hydrogenolysis, and more. The disordered environment makes each site different, and the kinetics exponentially magnifies these differences to make ab initio site-averaged kinetics calculations extremely difficult. This work extends the importance learning algorithm for efficient and precise site-averaged kinetics estimates to ab initio calculations and multistep reaction mechanisms. Specifically, we calculate site-averaged proton transfer relaxation rates on an ensemble of cluster models representing Brønsted acid sites on silica-alumina. We include direct and water-assisted proton transfer pathways and simultaneously estimate the water adsorption and activation enthalpies for forward and backward proton transfers. We use density functional theory (DFT) to obtain a site-averaged rate, somewhat like a turnover frequency, for the proton transfer relaxation rate. Finally, we show that importance learning can provide orders-of-magnitude acceleration over standard sampling methods for site-averaged rate calculations in cases where the rate is dominated by a few highly active sites.

Pyrolysis kinetic study of the thermal degradation of pre-treated empty fruit bunches

Empty fruit bunch (EFB) wastes are a significant source of biomass waste in Malaysia and have the potential to be a high-quality source of energy. This study aims to evaluate the kinetic of EFB biochar degradation and its characteristics under three conditions of washing pre-treatments. Prior to biochar production via slow pyrolysis process, stirring and soaking techniques were utilised as part of the pre-treatment for the washing process, with varying solid-to-liquid (S:L) ratios of 1:50, and 1:50 to 1:70, respectively. The study analysed the higher heating value (HHV), pyrolysis yield and kinetic activation energy of the biochar. The morphology and elemental composition of the biochar samples were determined using ultra-high resolution scanning electron microscopy (UHR-SEM) and energy dispersive X-Ray detector (EDX). The Coats-Redfern model was used to estimate the activation energies of the EFB biochar from thermogravimetric (TGA) data in a temperature range of 30 °C to 800 °C and a constant heating rate of 10 °C/min under a nitrogen atmosphere. The results showed that washing pre-treatment significantly changed the morphology and elemental compositions of the EFB biochar samples. The higher S:L ratio of 1:70 has a more significant impact on the breakdown of the lignocellulosic structure of EFB. The soaked samples had slightly lower biochar and bio-oil yields (22.73 mf wt. % to 24.86 mf wt. % and 27.97 mf wt. % to 39.39 mf wt. %, respectively) than the stirred samples (25.22 mf wt. % and 49.59 mf wt. %). The pre-treatment process improved the carbon content while reducing potassium by 60.7 to 81.39%. The HHVs of EFB-4 (28.24 MJ/kg) and EFB-3 (26.57 MJ/kg) were higher than those of EFB-2 (26.2 MJ/kg) and EFB-1 (23.14 MJ/kg), indicating an improvement in their fuel properties. The higher kinetic activation energies of EFB-4 (43.27 to 48.30 MJ/mol) indicate better thermal stability than the others. Therefore, concerning improved fuel properties, the recommended pre-treatment of EFB for the pyrolysis process is soaking at 90 °C with an S:L ratio of 1:70. The kinetic analysis revealed that the pyrolysis of pre-treated EFBs follows a multi-step reaction mechanism, with different activation energies for each stage. The obtained kinetic parameters can be used to optimize the pyrolysis process and design efficient pyrolysis reactors for the valorization of EFBs. Overall, this study provides valuable insights into the thermal behavior of pre-treated EFBs and their potential for bioenergy production.

Thermal performance of MMH/NTO rocket thrust chamber based on pintle injector by using liquid film cooling

A liquid rocket engine needs to be protected against damage of the combustion chamber wall during operation, being exposed to high temperature and pressure gas conditions. It is in urge to design a simple and efficient thermal protection method to cool the wall of the thrust chamber. In present study, a liquid rocket engine CFD model with cooling holes in the upstream side of the thrust chamber wall was established and the propellant combustion performance of monomethylhydrazine (MMH) and nitrogen tetroxide (NTO) was simulated by a simplified multi-step chemical reaction mechanism. The liquid cooling performance of thrust chamber wall was numerically investigated by using the discrete phase model coupled with the wave breakup model and the convection/diffusion controlled model, in which the liquid film coolant is regarded as the discrete phase particles by considering the entrainment and evaporation of liquid coolant droplets in hot combustion gas. The effects of pintle head diameter Dp, oxidant slot height h0 and coolant consumption ratio on liquid cooling performance were discussed. The results demonstrated that smaller Dp and h0 can help to improve the characteristic velocity of the thrust chamber. As the coolant ratio increases from 18% to 24%, the maximum wall temperature of the thrust chamber is reduced by 11% (212 K) with only a 1.3% reduction in characteristic velocity (combustion performance). The present numerical method and results can provide important guidance for liquid film cooling design of the liquid rocket engine based on pintle injector.

Sandwich-type N-C@CoTe2@C anode: a stress-buffer nanostructure for stable sodium-ion storage.

Transition metal tellurides (TMTes) have received extensive attention for high specific energy sodium-ion batteries (SIBs) due to their high volumetric specific capacity. However, the continuous capacity attenuation arising from the huge volumetric strain during sodiation/desodiation impedes practical applications. Here, we report a "sandwich-type" carbon confinement strategy that entraps cobalt ditelluride (CoTe2) nanocrystals between two carbon layers. Porous cellulose-derived fibres were employed as the inner carbon framework to construct fast conductive circuits and provide an abundant site for anchoring CoTe2 nanocrystals. Polyvinylpyrrolidone (PVP)-derived carbon layers act as carbon armour to encapsulate CoTe2 nanocrystals, inhibiting their volume change and structural pulverization during repeated sodium intercalation/deintercalation. Benefiting from the exquisite structural design, the N-C@CoTe2@C electrode exhibits excellent cycling stability for over 3000 cycles at 2.0 A g-1 and rate performance (113.8 mA h g-1 at 5.0 A g-1). Moreover, ex situ XRD/TEM and kinetic tests revealed a multistep conversion reaction mechanism and a battery-capacitive dual-model Na-storage process. This work provides a new perspective on the development of low-cost and straightforward techniques for fabricating long-life commercial SIB anode materials.

Kinetic analysis of complex chemical reactions by coupling model-free and model-fitting analysis

Three different complex multi-step reaction mechanisms of parallel-competing, consecutive and parallel-independent reactions were simulated for two different sets of kinetic parameters. The two sets were chosen in such a way to represent two very different situations. An advanced non-linear isoconversional method (NLN) and a multiple heating rates model-fitting method using nonlinear optimization (NLO) were applied to the data. The errors in kinetic parameters were evaluated for each set of data and for each method. It is shown that analysis of the thermoanalytical curves and of the Eα-dependencies can be used in complementary with the model-fitting approach for the elucidation of the reaction mechanisms and estimation of the kinetic parameters of each step. In most cases, NLO improved the accuracy of the kinetic parameters obtained from NLN method, but only if the mechanism was known. However, selecting the right mechanism is an essential problem of NLO. The study showed that it was possible to accurately fit the mechanism of two consecutive steps with a model of two independent steps that resulted in evaluating invalid kinetic parameters. This example also highlights an important limitation of the so-called deconvolution kinetic analysis which consists in fitting of various multi-step reaction mechanisms with a model of independent steps.

Toward Extremely Fast Charging through Boosting Intercalative Redox Pseudocapacitance: A SbCrSe3 Anode for Large and Fast Sodium Storage

AbstractAlloying‐type metals with high theoretical capacity are promising anode materials for sodium ion batteries, but suffer from large volume expansion and sluggish reaction kinetics. Dispersing alloying‐type metal into a buffer matrix with interfacial anionic covalent bonding is an effective method to solve the above issues. Here, this bifunctional structural unit is designed by incorporating high‐capacity Sb metal into a rigid CrSe framework for fast‐charging applications. The high‐capacity and high‐rate sodium storage can be synergistically realized in the bifunctional SbCrSe system, where the rigid CrSe framework endows the SbCrSe3 anodes with superior structural stability and improved intercalative redox pseudocapacitance. Moreover, the volume expansion of Sb during discharge can be buffered by the CrSe chain‐like matrix. The novel SbCrSe3 anode delivers a high charge capacity of 472 mAh g−1 at a current density of 0.4 C and retains ≈100% capacity at 60 C over 10 000 cycles. Further in situ and ex situ characterization reveal the multistep reaction mechanism, and the breakage and formation of reversible SbSe bonds during (dis)charge. The proposed bifunctional structural unit that combines alloying type anodes and intercalative anodes is expected to pave a new road for the development of high capacity and high rate anode materials.

Kinetically consistent detailed surface reaction mechanism for steam reforming of methane over nickel catalyst

A one-dimensional model, LOGEcat is used to develop a detailed surface reaction mechanism for modeling the steam reforming of methane over a nickel-based catalyst. The focus of the paper is to develop a kinetically consistent surface reaction mechanism. The two terms, kinetically and thermodynamically consistent mechanisms, will be used frequently in this article. Note that when the mechanism is thermodynamically consistent then the thermodynamic data or the thermochemistry of the species is not used and all the reactions in the mechanism are forward reactions (no backward reactions included) which need the Arrhenius parameters (pre-exponential factor, A_{r}; activation energy, E_{r}; temperature exponent, beta _r) explicitly for each reaction. The kinetically consistent mechanisms need Arrhenius parameters only for the forward reactions and does not need these parameters for backward reactions making the backward reactions independent of the kinetics. The rate for the backward reactions is calculated with the help of thermochemistry of the intermediate species involved in the reaction mechanism. Since the thermochemistry of the intermediate species are not easily available, this makes such studies much more complex. The original multi-step reaction mechanism consists of 42 reactions which are thermodynamically consistent. In this study we have modified this reaction mechanism from literature and used only 21 (reversible) direct reactions. This aspect is important because by using only 21 reactions, we use the thermochemistry of the species to achieve thermodynamic equilibrium instead of providing the Arrhenius parameters for forward and backward reactions. We use the same A_{r}, E_{r} and beta _r values as used in the reference paper for the considered 21 reactions which are in equilibrium. However, the value of A_{r}, E_{r} and beta _r for the inverse/backward reactions are not given in the mechanism and the reverse rates are calculated by using the equilibrium and forward rate. Therefore, a sensitivity analysis on thermochemistry of the species is performed for a better agreement with the literature data. The method is presented for ensuring kinetic consistency and bringing thermochemistry of species in play while developing a surface reaction mechanism. The applicability of the mechanism is tested for two different simulation set-ups available in literature considering various reactor conditions in terms of parameters given as temperature and steam-to-carbon (S/C) ratio. Several chemical reaction terms, such as, selectivity, conversion and mathrm {H_2}/{text{CO}} ratio are shown for different parameters in comparison with the available reference data. The detailed mechanism developed in this study is able to accurately express the steam reforming of methane over the nickel catalyst for complete ranges of temperature for both the set-ups and within acceptable limit for S/C ratio considered for the analysis.