Kinetic Reaction Mechanism Research Articles

In-depth exploration of waste printed circuit boards pyrolysis: Real-time products characteristics, kinetics parameter optimization and reaction mechanism

Pyrolysis is a promising technology for recycling waste printed circuit boards (WPCBs). This study delves into a real-time examination of the volatiles emitted from WPCBs during pyrolysis using thermogravimetric analysis coupled with Fourier transform infrared spectroscopy/mass spectrometry (TG-FTIR/MS), offering an in-depth analysis of the entire pyrolysis mechanism. An optimized kinetic model for printed circuit board (PCB) pyrolysis is developed by the shuffled complex evolution (SCE) algorithm. Results indicate that the main pyrolysis products are phenol and alkyl-substituted phenols, along with hydrogen bromide (HBr) and bromophenols. Bromides exhibit an earlier onset and peak temperature compared to phenolic products. The pyrolysis process can be divided into two stages: initial depolymerization of the resin body into macromonomers, followed by prevalent alkyl removal, homolytic reactions, and isomerization. The apparent activation energy (E) is 155.32 kJ/mol, the pre-exponential factor (ln(A)) is 29.77 min−1, and the kinetic mechanism function is described by (1‐α)2.02. This study provides crucial knowledge to advance the technology of WPCBs pyrolysis.

A Novelly Hierarchical LDHs−Based Cathode with Reduced Deprotonation Barrier Toward High−Performance Alkaline Energy Storage

AbstractLayered double hydroxides (LDHs) are promising electrode materials for alkaline electrochemical energy storage (EES). However, their low capacity, sluggish rate performance, and limited cycle life significantly hinder practical applications. This study unlocks the direct deprotonation reaction pathway for LDH materials through theoretical calculations. Guided by this insight, a novelly hierarchical composite (LDH−TPA) with various dimensions and components is fabricated by introducing terephthalic acid (TPA), serving as a superior cathode material for alkaline EES devices. Experimental results and theoretical investigations reveal the transformation process for metal–organic framework quantum dots (MOF−QDs) and the enhanced mechanism of reaction kinetics in the LDH−TPA electrode. Benefiting from the reduced deprotonation barrier, optimized electronic structure, and fast electrons/ions transport rates, the LDH−TPA1 electrode demonstrates a high specific capacity of 267 mAh g−1 at 1 A g−1 and retains 167 mAh g−1 even at 20 A g−1, along with excellent cycling stability. Furthermore, an alkaline nickel−zinc battery (AZB) with LDH−TPA1 cathode is assembled, achieving a lifespan exceeding 3400 cycles, and a high energy density of 341.3 Wh kg−1 at a power density of 1640.9 W kg−1. This study is expected to provide new insight into the modification of LDHs and the advancement of alkaline energy systems.

Kinetic research of red mud waste oxidative pyrolysis and comparison under different atmospheres

Red mud, as a solid waste with high alkalinity, had a detrimental impact on the environment and required urgent attention. Currently, the mass processing and consumption of red mud were typically conducted under thermal conditions, so it was essential to gain a comprehensive understanding of the oxidative pyrolysis process. The thermogravimetric experiments were conducted at multiple heating rates in air and exhibited three obvious stages. The activation energy and reaction mechanism of three oxidative pyrolysis stages were explored using model-free and model-fitting methods, revealing the activation energies of 162.2, 265.8, 214.1 kJ/mol and the most suitable reaction mechanisms of g(α)=[-ln(1-α)]³, g(α)=1-(1-α)1/⁴, g(α)=[-ln(1-α)]1/2 for each stage, respectively. Furthermore, the estimated kinetic parameters and reaction mechanisms were applied to extra heating rate to verify the accuracy. More important, the effect of air on the pyrolysis process of red mud was examined by comparing the results with those obtained from pure nitrogen pyrolysis. The obtained oxidative pyrolysis characteristics of red mud could provide valuable insights of its co-pyrolysis or combustion for resources recycling.

Design and implementation of an accelerating rate calorimeter based on Modelica modeling

The safety of self-reactive chemicals has garnered attention due to their immense destructive power. The use of an accelerating rate calorimeter allows for more accurate measurement and understanding of the kinetic parameters and reaction mechanisms of self-reactive chemicals, thereby reducing the occurrence of major accidents. In this study, a new accelerating rate calorimeter is designed and constructed by combining Modelica and a fuzzy Proportional-Integral-Derivative algorithm. The feasibility of the calorimeter data was verified by using two solutions with significantly different reaction rates: 20 % mass fraction di‑tert‑butyl peroxide/toluene and tert-butylperoxy-2-ethylhecanoate. Their thermal hazard characteristic parameters were compared with the literature data. In addition, the risk level of thermal runaway was determined using the Stoessel risk assessment method. These results demonstrate that the accelerating rate calorimeter based on Modelica modeling meets the accuracy of thermal hazard characteristic parameters. It is capable of performing risk assessments for runaway reactions of self-reactive chemicals.

A study on combustion behaviour and reaction kinetics mechanism of some Egean region Turkish lignites

A study on combustion behaviour and reaction kinetics mechanism of some Egean region Turkish lignites

Effects of hydrogen addition on ignition characteristics and engine performance of ammonia-hydrogen blended fuel: A kinetic analysis

To investigate the effects of hydrogen addition on the ignition characteristics and engine performance of ammonia-hydrogen fuel, a reaction kinetics mechanism suitable for high-pressure engine conditions was proposed. The study explores the influence of hydrogen blending ratios on the ignition delay time (IDT) of ammonia-hydrogen fuel, revealing the sensitive reactions and evolution characteristics of reaction pathways during the ignition process of ammonia-hydrogen fuel promoted by hydrogen. The study also investigates the impact of hydrogen blending ratios on the engine performance of ammonia-hydrogen fuel. The results show that the IDT of ammonia significantly decreases with increasing hydrogen blending ratios and temperature. The addition of hydrogen to ammonia significantly lowers the autoignition temperature boundary of the mixture. Under low-temperature and low-pressure conditions, ammonia, which would not ignite originally, ignites due to the addition of hydrogen. The addition of hydrogen shifts the sensitive reactions of the mixture from NH3 and NH2-related reactions to H2/O2-related reactions, without altering the reaction pathway of ammonia, only changing the pathway flux of components such as NH2, H2NN, H2NO, and HONO. In a spark-ignition (SI) engine, maintaining the total fuel heat value and ignition timing constant, an increase in hydrogen blending ratio significantly raises the peak cylinder pressure. However, due to the forward movement of the heat release process, the power performance of engine experiences varying degrees of reduction. Therefore, it is necessary to delay the ignition timing of engine with the increase in hydrogen blending ratio, moving the combustion center beyond the top dead center (TDC). Furthermore, increasing the hydrogen concentration in the blend significantly raises the temperature and pressure during the engine combustion process, leading to an increase in the concentration of thermal NOX in the emissions.

Ammonia pyrolysis oxidation excited by nanosecond pulsed discharge: Global/fluid models hybrid solution

The kinetic characteristics of plasma-assisted oxidative pyrolysis of ammonia are studied by using the global/fluid models hybrid solution method. Firstly, the stable products of plasma-assisted oxidative pyrolysis of ammonia are measured. The results show that the consumption of NH3/O2 and the production of N2/H2 change linearly with the increase of voltage, which indicates the decoupling of non-equilibrium molecular excitation and oxidative pyrolysis of ammonia at low temperatures. Secondly, the detailed reaction kinetics mechanism of ammonia oxidative pyrolysis stimulated by a nanosecond pulse voltage at low pressure and room temperature is established. Based on the reaction path analysis, the simplified mechanism is obtained. The detailed and simplified mechanism simulation results are compared with experimental data to verify the accuracy of the simplified mechanism. Finally, based on the simplified mechanism, the fluid model of ammonia oxidative pyrolysis stimulated by the nanosecond pulse plasma is established to study the pre-sheath/sheath behavior and the resultant consumption and formation of key species. The results show that the generation, development, and propagation of the pre-sheath have a great influence on the formation and consumption of species. The consumption of NH3 by the cathode pre-sheath is greater than that by the anode pre-sheath, but the opposite is true for OH and O(1S). However, within the sheath, almost all reactions do not occur. Further, by changing the parameters of nanosecond pulse power supply voltage, it is found that the electron number density, electron current density, and applied peak voltages are not the direct reasons for the structural changes of the sheath and pre-sheath. Furthermore, the discharge interval has little effect on the sheath structure and gas mixture breakdown. The research results of this paper not only help to understand the kinetic promotion of non-equilibrium excitation in the process of oxidative pyrolysis but also help to explore the influence of transport and chemical reaction kinetics on the oxidative pyrolysis of ammonia.

Atmospheric photo-oxidation of acetic anhydride: Kinetic study and reaction mechanism. Products distribution and fate of CH3C(O)OC(O)CH2O· radical

The rate coefficient for the gas-phase reaction of acetic anhydride (Ac2O) with chlorine atoms at 298 K and atmospheric pressure was experimentally determined (kAc2O+Cl= (1.3 ± 0.4) × 10-12 cm3molec−1s−1), while the rate coefficient for the reaction with the hydroxyl radical was estimated (kAc2O+OH=1.9 x 10-13 cm3molec−1s−1). For the Structure-Activity Relationship method, a value of 0.02 was determined for the −C(O)OC(O) group. The mechanism of photo-oxidation of acetic anhydride initiated by chlorine atoms was determined and CO, CO2, CH3C(O)OH (32 %), CH3C(O)OC(O)C(O)H, and 3-hydroxy-1,4-dioxane-2,6-dione (20 %) were identified as products by infrared spectroscopy. Here we determined for the first time the relative energies of the primary reaction pathways for the CH3C(O)OC(O)CH2O· radical using computational methods, which confirmed our experimental data. Finally, the environmental implications of acetic anhydride emissions were calculated, showing an atmospheric lifetime between 31 and 220 days for the reaction with atmospheric radicals, while its wet deposition lifetime is 1.5 years.

Development of laminar burning velocity prediction model and correlation of iso-octane air mixtures using artificial neural network

Surrogate fuels provide an economical alternative for forecasting the combustion properties of transportation fuels like diesel, gasoline, and kerosene. Iso-octane (2,2,4-trimethylpentane), a primary reference fuel for gasoline, is extensively used as a surrogate component. This study utilizes a Feed-Forward Artificial Neural Network (FFANN) with back-propagation (BP) to predict the laminar burning velocity (LBV) of iso-octane/air mixtures. The ANN model was developed using a dataset of 6339 data points, including 3788 experimental data points from literature since 2004 and 2551 simulation data points from reduced kinetic reaction mechanism (RKM) CHEMKIN simulations. The grid search cross-validation (CV) method was employed to optimize the ANN hyperparameters. Implemented in Python using Keras, the ANN model addresses research gaps by forecasting LBV for hydrocarbons beyond n-heptane and modelling LBV under conditions reflective of actual engine operations. Unlike prior studies, we optimized various ML models, their complexity, size, and hyperparameters to achieve high prediction accuracy. We also integrated a hybrid model combining Particle Swarm Optimization (PSO) with Genetic Algorithms (GA) for hyperparameter optimization, ensuring efficient configuration of the ANN. The constructed ANN model was compared to other ML models, including generalized linear regression (GLR), support vector machine (SVM), random forest (RF), and XGBoost regression. For the testing set (20 % of the total dataset), the ANN model outperformed all other ML models and empirical correlations, achieving a coefficient of determination (R2) of 0.9903, root mean square error (RMSE) of 1.911, and mean absolute error (MAE) of 1.206. Optimizing the ANN model with PSO further enhanced prediction accuracy, achieving a correlation coefficient of 0.9973 and a reduced mean absolute error of 0.753. To evaluate the ANN model's predictive ability, a reduced mechanism from the Lawrence Livermore National Laboratory (LLNL) was used. Compared to the LLNL RKM, the ANN predicted values showed lower percentage deviation from experimental data. Additionally, computation cost comparisons revealed that while RKM simulations in CHEMKIN took 244.2 s per case, the PSO-optimized ANN model required only 900 s for 150 cases. A 16-term correlation for laminar burning velocity (LBV) was derived from ANN predictions, serving as a practical tool to predict LBV based on pressure, temperature, and equivalence ratio. Unlike existing literature correlations, this newly developed correlation is valid across a wide range of operating conditions, offering a fundamental database for real-time combustion applications.

Kinetic Aspects of Esterification and Transesterification in Microstructured Reactors.

Microstructured reactors offer fast chemical engineering transfer and precise microfluidic control, enabling the determination of reactions' kinetic parameters. This review examines recent advancements in measuring microreaction kinetics. It explores kinetic modeling, reaction mechanisms, and intrinsic kinetic equations pertaining to two types of microreaction: esterification and transesterification reactions involving acids, bases, or biocatalysts. The utilization of a micro packed-bed reactor successfully achieves a harmonious combination of the micro-dispersion state and the reaction kinetic characteristics. Additionally, this review presents micro-process simulation software and explores the advanced integration of microreactors with spectroscopic analyses for reaction monitoring and data acquisition. Furthermore, it elaborates on the control principles of the micro platform. The superiority of online measurement, automation, and the digitalization of the microreaction process for kinetic measurements is highlighted, showcasing the vast prospects of artificial intelligence applications.

Defect-engineered TiNOx catalyst targeted to activate rate-determining step for highly efficient K-SeS2 batteries

SeS2 material is attracting intensive attention in the potassium ion storage system due to its high theoretic capacity and compensated physicochemical properties. However, the actual capacity (usually below 400 mAh g−1) in practical studies is far below its theoretical value. This is mainly due to the notorious “shuttle effect” of soluble intermediates and some unknown sluggish conversion steps involved in the SeS2 cathode. In this work, the whole kinetic reaction mechanism is revealed for the first time by in situ Raman and DFT calculations, and the rate-determining step also is identified as the conversion step from K2S2 to K2S. Based on this insight, we synthesized an electrocatalyst (labeled as TiNOx) to maximize the conversion of the SeS2 cathode. The regulated Fermi level and d-band center of the Ti atoms can greatly enhance the adsorption of dissolvable intermediates and especially can be targeted to accelerate the rate-determining step. Consequently, the resultant K-SeS2@TiNOx battery displays a high capacity of 806.6 mAh g−1, two times that of the raw K-SeS2 battery, and achieves a stable capacity retention after 800 cycles. Moreover, the whole smooth conversion process on SeS2@TiNOx is reasonably explained by in situ monitoring techniques and DFT calculations.

The impact of struvite presence on the thermal decomposition of sewage sludge, including formation of NOx emissions

Monoincineration of sewage sludge (SS) is becoming a prevailing type of SS treatment due to its contamination and the ability to achieve enriched concentration of valuable inorganics in the end ash. In order to improve the recovery potential, particularly of inorganic, phosphorous (P) bearing species, thermal transformations of organic as well as inorganic SS compounds have to be considered. While important gains in predictive capability have already been made through extensive description of organic part decomposition, P is mostly present in the inorganic part of SS, together with notable amount of nitrogen (N). Current models consider these species in a simplified manner, making the ability to predict P and N fate during thermal treatment limited. The present work focuses on development and implementation of a one step reaction kinetics mechanism for struvite, a common P and N bearing compound in SS, which also presents an important route for P and N recovery. The new mechanism is implemented into an existing SS organic fraction decomposition mechanism and validated using 0D multiphase reactor simulations in Chemkin software. Results reveal up to 10 s faster temperature increase and decomposition of SS with the presence of struvite due to emission of NH3 and H2O occurring already from 350 °C onwards. The NH3 emissions are especially important as they lead to higher NOx formation. The work presents large potential for improving thermal decomposition prediction as well as emission mitigation strategies if struvite is included in the thermal decomposition models of SS. The developed methodology allows efficient implementation of also other P and N bearing species in the inorganic part of kinetic mechanism.

Kinetic Study and Reaction Mechanism of the Gas-Phase Thermolysis Reaction of Methyl Derivatives of 1,2,4,5-Tetroxane.

Tetroxane derivatives are interesting drugs for antileishmaniasis and antimalaric treatments. The gas-phase thermal decomposition of 3,6,-dimethyl-1,2,4,5-tetroxane (DMT) and 3,3,6,6,-tetramethyl-1,2,4,5-tetroxane (acetone diperoxide (ACDP)) was studied at 493-543 K by direct gas chromatography by means of a flow reactor. The reaction is produced in the injector chamber at different temperatures. The resulting kinetics Arrhenius equations were calculated for both tetroxanes. Including the parent compound of the series 1,2,4,5-tetroxane (formaldehyde diperoxide (FDP)), the activation energy and frequency factors decrease linearly with the number of methyl groups. The reaction mechanisms of ACDP and 3,6,6-trimethyl-1,2,4,5-tetroxane (TMT) decomposition have been studied by means of the DFT method with the BHANDHLYP functional. Our calculations confirm that the concerted mechanism should be discarded and that only the stepwise mechanism occurs. The critical points of the singlet and triplet state potential energy surfaces (S- and T-PES) of the thermolysis reaction of both compounds have been determined. The calculated activation energies of the different steps vary linearly with the number of methyl groups of the methyl-tetroxanes series. The mechanism for the S-PES leads to a diradical O···O open structure, which leads to a C···O dissociation in the second step and the production of the first acetaldehyde/acetone molecule. This last one yields a second C···O dissociation, producing O2 and another acetone/acetaldehyde molecule. The O2 molecule is in the singlet state. A quasi-parallel mechanism for the T-PES from the open diradical to products is also found. Most of the critical points of both PES are linear with the number of methyl groups. Reaction in the triplet state is much more exothermic than the singlet state mechanism. Transitions from the singlet ground state, S0 and low-lying singlet states S1-3, to the low-lying triplet excited states, T1-4, (chemical excitation) in the family of methyl tetroxanes are also studied at the CASSCF/CASPT2 level. Two possible mechanisms are possible here: (i) from S0 to T3 by strong spin orbit coupling (SOC) and subsequent fast internal conversion to the excited T1 state and (ii) from S0 to S2 from internal conversion and subsequent S2 to T1 by SOC. From these experimental and theoretical results, the additivity effect of the methyl groups in the thermolysis reaction of the methyl tetroxane derivatives is clearly highlighted. This information will have a great impact for controlling these processes in the laboratory and chemical industries.

Automated Skeleton Network Generation for ReaxFF Molecular Dynamics Simulations of Hydrocarbon Fuel Pyrolysis and Oxidation via a Rate-Based Algorithm.

In this study, we present an automated approach of rate-based skeleton network generation for ReaxFF MD simulation (RxMD-SN) for deriving the reaction kinetic mechanism of large hydrocarbon fuels in pyrolysis and oxidation from large-scale ReaxFF MD simulations. The approach contains the statistical calculation of reaction rate constants and the generation of skeleton reaction networks using a rate-based algorithm. The RxMD-SN method takes advantage of reaction flux ranking at a small time interval in terms of temporal reaction rate to extract the core reaction networks, which allows for keeping the rare reaction events that may be dominant in a certain period of the reaction network. The kinetic models derived from ReaxFF MD simulation in CH4 oxidation can reproduce what was obtained in the ReaxFF MD simulation, which demonstrates the capability of RxMD-SN in capturing the global reaction kinetics. An evaluation of reaction rate constants indicates that close kinetic parameters are shared for n-octane oxidation of similar reaction classes, shared oxidation reactions of CH4 against n-heptane, and shared pyrolysis reactions of the RP-3 surrogate fuel against n-heptane. This capability of RxMD-SN is particularly beneficial in meeting the challenges in characterizing the oxidation reaction kinetics of large hydrocarbon molecules. RxMD-SN approach is potentially a general approach in chemical kinetics modeling on the basis of ReaxFF MD simulations.

Flame stabilization and pollutant emissions of turbulent ammonia and blended ammonia flames: A review of the recent experimental and numerical advances

Compared to traditional hydrocarbon fuels, ammonia presents significant challenges as a fuel, including high ignition energy, low reactivity, slow flame propagation, and high NOx emissions, which hinder its use as a renewable fuel. Blending ammonia with fossil fuels like natural gas improves its combustion reactivity and helps mitigate CO2 emissions. However, there is still much to understand about the complex dynamics of ammonia and its blends with hydrocarbons. Key areas such as reaction kinetics mechanisms, ignition properties, flame propagation behaviors, and methods for controlling combustion performance under various conditions require further elucidation. This paper reviews recent advancements in experiments and numerical simulations aimed at developing stable, and low-emission combustors for ammonia-fired power generation. Recent burner and flame configurations, including non-swirling jets, single-stage swirl burners, two-stage burners, and newly developed double-swirl burners are analyzed for their flame stability and pollutant emission potential when firing ammonia and ammonia blends. Chemical kinetic modeling of ammonia and its blends plays a crucial role in understanding combustion behavior and pollutant emissions, particularly for NOx. However, there are challenges in predicting NOx emissions accurately, with significant disparities among different models. High-fidelity numerical simulations using detailed and skeletal mechanisms, direct numerical simulation, and large eddy simulation, have helped uncover crucial operational conditions affecting combustion and pollutant emissions, such as combustor pressure, air dilution, wall cooling, fuel/air mixing, and fuel blending. Nonetheless, the accuracy of chemical kinetic models and their integration into turbulent flow simulations remain critical limitations for numerical simulations of ammonia combustion.

Numerical study of hydrogen ratio effect on detonation initiation characteristics of aviation kerosene with hydrogen addition

Detonation initiation is one of the most important problems in the research of pulse detonation engine (PDE). It is difficult for aviation kerosene to meet the performance requirement of short-distance detonation initiation in PDE. Hydrogen can improve the detonability of fuels. Aviation kerosene with hydrogen addition provides a new method to shorten the detonation initiation distance in PDE. Therefore, hydrogen ratio effect on detonation initiation characteristics of hydrogen-doped aviation kerosene was studied by two-dimensional numerical simulation with the adoption of standard k-ε model, finite rate reaction model and simplified aviation kerosene/hydrogen/air reaction kinetics mechanism. The results indicated that hydrogen-doped aviation kerosene/air mixtures could not be successfully detonated with the minimum hydrogen ratio of 9.73 %, while the detonation was eventually initiated with higher hydrogen ratios, suggesting that the detonability of hydrogen-doped aviation kerosene was improved by increasing hydrogen ratio. The critical hydrogen ratio of 11 % was determined by further research. As the hydrogen ratio increased, the initiation time and distance of the plane detonation wave first increased slowly and then decreased rapidly, while the detonation velocity raised monotonically. The degree of spherical wave decoupling had an influence on the detonation initiation. Specifically, less spherical wave decoupling induced two Mach stems to propagate at the same time, which was conducive to accelerating the initiation of plane detonation.

Research on the Mechanism and Propagation Characteristics of Combustion and Explosion of Natural Gas/Ammonia/Hydrogen Mixed Gas Fuel.

The addition of ammonia and hydrogen into natural gas fuel is an effective method to reduce carbon emissions. This study aims to investigate the effect of adding ammonia and hydrogen on the mechanism of natural gas combustion and emission characteristics. Based on a self-developed mixed gas deflagrate experimental platform, the deflagrate characteristics, emission characteristics, and chemical reaction kinetics mechanism of mixed gas fuels under different composition ratios (natural gas 0-100%, hydrogen 10-85%, and ammonia 0-100%) were studied. The results indicate that the propagation of the deflagration shock wave can be categorized into an initial stage (L < 3 m) and a development stage (L > 3 m) based on the observed trend of shock wave intensity variation with distance. The intensity of the deflagration shock wave for the mixed gases increases monotonically as the hydrogen content ratio rises. In contrast, the impact of the ammonia content ratio on the shock wave intensity exhibits a distinct pattern that varies with changes in the equivalence ratio and hydrogen content ratio. In terms of carbon emissions per unit of heat value produced by the fuel, adding hydrogen to natural gas proves to be more effective at reducing carbon emissions than adding ammonia. When the ammonia content ratio is 50% and the hydrogen content ratio is 40%, the combustion performance of the mixed gas fuel is similar to that of natural gas, but its carbon emissions are lower than 30% of natural gas, making it a new type of mixed fuel with potential application value; the interaction between reflected pressure waves and flames is the main reason for the fluctuation of deflagrate shock wave pressure; ammonia lowers the temperature of the reaction system by reducing the concentration of OH radicals.

A microwave plasma etching strategy for preparing oxygen-vacancy-rich NiCoO2 Nanoarrays for high-rate performance supercapacitor

Supercapacitors are vital for industries like automotive and energy storage. Transition metal oxides are promising electrode materials due to their diversity and high capacity. This study uses microwave plasma etching (MPE) to synthesize oxygen-vacancy-rich NiCoO2 nanoarrays (E-NCO) for supercapacitors. The etched NiCoO2 nanoarrays exhibit remarkable performance (1360.7 F g−1 at 1 A g−1) and excellent rate performance (996.7 F g−1 at 50 A g−1) in a three-electrode system. After assembling E-NCO-15 into a hybrid supercapacitor, it demonstrated a high energy density of 48.4 Wh kg−1 at the power density of 387.4 W kg−1, and even at the ultra-high power density of 19377.1 W kg−1, the energy density remains 15.2 Wh kg−1. Through the characterization of the material and an exploration of the reaction kinetics mechanism, it was discovered that MPE as a low-cost and easily controllable material modification method can introduce oxygen vacancies into the material, thereby enhancing both the material’s electrical conductivity and charge storage capacity. In addition, nanoarrays morphology provides more active sites and faster ion transport. These results highlight E-NCO’s potential for high-performance supercapacitors.

The computational molecular technology for complex reaction systems: The Red Moon approach

AbstractFor dealing with complex reaction (CR) systems that show typical chemical phenomena in molecular aggregation states, the Red Moon (RM) approach is introduced based on a new efficient and systematic RM methodology. First, the theoretical background with my motivation to develop the RM approach is presented from the recent necessity to perform ‘atomistic’ molecular simulation of large‐scale and long‐term phenomena of (i) complex chemical reactions, (ii) stereospecificity, and (iii) aggregation structures. The RM methodology uses both the molecular dynamics (MD) method for molecular motions (translation, rotation, and vibration of molecules) that frequently occur on a short‐time scale and the Monte Carlo (MC) method for rare events such as chemical reactions that hardly do on that time scale. Then, under the transition rate using both the potential energy difference before and after a rare event trial and its chemical kinetic probability, it is tested and judged by the MC method whether the trial is possible (Metropolis method). Next, typical applications of the RM approach are reviewed in two main research fields, (i) polymerization and (ii) storage battery (rechargeable battery or secondary cell), with various examples of our successful studies. Finally, we conclude that the RM approach using the RM methodology should become an efficient new‐generation approach as one promising computational molecular strategy (CMT). We believe it will play an essential role in surveying, at the multilevel resolution, various specificities of CR systems in molecular aggregation states.This article is categorized under: Theoretical and Physical Chemistry &gt; Reaction Dynamics and Kinetics Structure and Mechanism &gt; Reaction Mechanisms and Catalysis Molecular and Statistical Mechanics &gt; Molecular Dynamics and Monte‐Carlo Methods

Pyrolysis characteristics and kinetic investigation of waste groundnut shells using thermogravimetric analyzer, Py-FTIR, and Py-GC-MS

The objective of the present study was to investigate the bioenergy and resource recovery potential of groundnut shells (GNS) through pyrolysis. The release of vapours at short time scales and their composition were investigated using analytical pyrolysis coupled with Fourier transform infrared (FTIR) spectroscopy and gas chromatography/mass spectrometry (GC/MS). The thermal decomposition behaviour and kinetic evaluation were carried out using a thermogravimetric analyzer (TGA). Five iso-conversional models and master plots method were utilized to explore the kinetic parameters and reaction mechanism at dynamic heating rates (10, 20, and 30 °C min−1). X-ray fluorescence spectroscopy (XRF) was employed to detect the ash composition, which is essential to evaluate the slagging and fouling potential of the biomass when used for bioenergy. TG data revealed three distinct stages of decomposition, while an immense amount of biomass disruption was observed at a higher heating rate (30 °C min−1). Further, the average apparent activation energy of pyrolysis determined using KAS, ST, DAEM, and VZ were 223.26, 214.57, 207.97, and 117.24 kJ mol−1, respectively. The extreme emission of carbon dioxide and carbonyl compounds was discovered through Py-FTIR. The increased formation of hydrocarbons (14.22–34.26%), alcohols (1.41–9.43%), and reduction in phenols (19.13–18.67%) at different temperatures (450, 550, and 650 °C) were validated by Py-GC-MS. Overall, the findings demonstrate that GNS is a promising feedstock for pyrolysis to produce valuable fuel molecules and chemicals.