Model Reaction System Research Articles

Enhancing selectivity through forced dynamic operation with intraparticle diffusion limitations: Ethane oxidative dehydrogenation

During steady state operation (SSO) of industrial fixed-bed reactors diffusion limitations are often present. Well-known impacts include the reduced rate of a positive order reaction and reduced selectivity of the desired intermediate product in a sequential reaction system. This work presents an approach for circumventing diffusion limitations through forced dynamic operation (FDO) of metal oxide catalyzed partial oxidation reactions. Through coupled experiments and modeling, we examine the use of FDO to mitigate selectivity losses of the intermediate product in a parallel-consecutive reaction. With the oxidative dehydrogenation (ODH) of ethane (C2H6) to ethylene (C2H4) over an Al2O3 supported VOx catalyst as the model reaction system, FDO is shown to mitigate undesired C2H4 overoxidation to COx that predominates in steady state diffusion-limited pellets, resulting in C2H4 selectivities that are 15 % (absolute) higher compared to SSO in 2.6 mm catalyst pellets. A kinetic model reveals that FDO beneficially alters the distribution of chemisorbed (O*) and lattice (OL) oxygen, which respectively primarily participate in reactions consuming C2H4 and C2H6. FDO is shown to lead to less detrimental impact of diffusion on the ethylene selectivity and yield compared to SSO. During FDO, generated C2H4 reacts with unselective O*, leaving behind selective OL. The reduced bulk phase O2 in the reductive half cycle leads to accumulation of OL, suppressing C2H4 overoxidation. This effect is amplified via C2H4 trapping in the catalyst pellet. Thus, larger catalyst pellets exhibit selectivities that more rapidly increase with reduction time, inducing higher FDO cycle averages compared to SSO. The findings raise the prospect of applying FDO through feed switching or chemical looping as a way to increase intermediate yield in the class of partial oxidation reactions.

Uncovering Factors Controlling Reactivity of Metal-TEMPO Reaction Systems in the Solid State and Solution.

Nitroxides find application in various areas of chemistry, and a more in-depth understanding of factors controlling their reactivity with metal complexes is warranted to promote further developments. Here, we report on the effect of the metal centre Lewis acidity on both the distribution of the O- and N-centered spin density in 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and turning TEMPO from the O- to N-radical mode scavenger in metal-TEMPO systems. We use Et(Cl)Zn/TEMPO model reaction system with tuneable reactivity in the solid state and solution. Among various products, a unique Lewis acid-base adduct of Cl2Zn with the N-ethylated TEMPO was isolated and structurally characterised, and the so-called solid-state 'slow chemistry' reaction led to a higher yield of the N-alkylated product. The revealed structure-activity/selectivity correlations are exceptional yet are entirely rationalised by the mechanistic underpinning supported by theoretical calculations of studied model systems. This work lays a foundation and mechanistic blueprint for future metal/nitroxide systems exploration.

Molecular modeling of reactive systems with REACTER

From batteries to biology, many important technologies and physical phenomena operate as out-of-equilibrium reactive systems. Accurately modeling the nanoscale dynamics of non-equilibrium reactive systems and how they respond to external stimuli is challenging, especially if both atomistic resolution and large scales (>105 atoms) are required. REACTER is a protocol for modeling chemical reactions during classical molecular dynamics (MD) simulations. Coupling traditional fixed-valence force fields with heuristic reactive MD is advantageous for large-scale simulations of dynamic systems that can include the complex reaction mechanisms common in organic chemistry. This paper details the current features of the LAMMPS implementation of REACTER, known as fix bond/react, and surveys recent applications of the protocol in a variety of fields, including photopolymers, high-performance composites, and membranes. Conceived as a tool for modeling polymerization processes, the scope of REACTER is expanding as it is applied to new materials and supporting features are implemented. Three new case studies are presented that highlight the capabilities of REACTER, including modeling hierarchical materials, the mechanics of molecular machines, and large-scale dynamics of heterogeneous catalysis.

Probabilistic and maximum entropy modeling of chemical reaction systems: Characteristics and comparisons to mass action kinetic models.

We demonstrate and characterize a first-principles approach to modeling the mass action dynamics of metabolism. Starting from a basic definition of entropy expressed as a multinomial probability density using Boltzmann probabilities with standard chemical potentials, we derive and compare the free energy dissipation and the entropy production rates. We express the relation between entropy production and the chemical master equation for modeling metabolism, which unifies chemical kinetics and chemical thermodynamics. Because prediction uncertainty with respect to parameter variability is frequently a concern with mass action models utilizing rate constants, we compare and contrast the maximum entropy model, which has its own set of rate parameters, to a population of standard mass action models in which the rate constants are randomly chosen. We show that a maximum entropy model is characterized by a high probability of free energy dissipation rate and likewise entropy production rate, relative to other models. We then characterize the variability of the maximum entropy model predictions with respect to uncertainties in parameters (standard free energies of formation) and with respect to ionic strengths typically found in a cell.

Turning noncovalent interactions via halogen substituents for improving activity and enantioselectivity of Candida antarctica lipase B

Noncovalent interactions associated with the enzyme, enzyme-substrate complexes, and transition states have profound influences on varying the biocatalytical activity and enantioselectivity. The recent rediscovery of halogen bonds incorporating in biocatalysis has induced our motivation on introducing halogen substituents into the substrate for improving the enzyme performance. By selecting Candida antarctica lipase B (CALB)-catalyzed kinetic hydrolysis (or butanolysis) of trans-2-(p-halophenyl)cyclopropyl 1,2,4-triazolide in methyl tert-butyl ether (MTBE) as the model reaction system, (R, R)-2-(p-halophenyl)cyclopropane-1-carboxylic acid (or ester) of high-optical purity that acts as the key building block for synthesizing the corresponding (1 R, 2S)-2-(p-halophenyl)cyclopropylamine derivatives was obtainable. The thermodynamic and kinetic analysis was then employed for elucidating effects of the halogen substituent and acyl acceptor on enhancing the noncovalent interactions of the rate-limiting tetrahedral intermediate and hence CALB activity and enantioselectivity. A putative model was moreover proposed for interpreting the possible hydrogen and halogen bonding involving the halogen substituent in turning the noncovalent interactions.

Active model learning of stochastic reactive systems (extended version)

AbstractBlack-box systems are inherently hard to verify. Many verification techniques, like model checking, require formal models as a basis. However, such models often do not exist, or they might be outdated. Active automata learning helps to address this issue by offering to automatically infer formal models from system interactions. Hence, automata learning has been receiving much attention in the verification community in recent years. This led to various efficiency improvements, paving the way toward industrial applications. Most research, however, has been focusing on deterministic systems. In this article, we present an approach to efficiently learn models of stochastic reactive systems. Our approach adapts $$L^*$$ L ∗ -based learning for Markov decision processes, which we improve and extend to stochastic Mealy machines. When compared with previous work, our evaluation demonstrates that the proposed optimizations and adaptations to stochastic Mealy machines can reduce learning costs by an order of magnitude while improving the accuracy of learned models.

Automata-based Software Engineering for Control System Design and Verification

The automata composition is defined as the basic language construct of automata programming. Incorporating automata composition into an arbitrary programming language allows the development of automata programs in that language. Methods for specification and verification of reactive systems are defined in detail. All kinds of correctness formulas for a reactive system with respect to its specification are defined. In addition, correctness formulas for verification using the full invariant of the reactive system are developed. The Event-B manual begins with a brilliant illustration of the basic Event-B methods using the example of a car traffic control problem on a narrow bridge. However, the latter refinement in this illustration generates a complex cumbersome program. A simpler and shorter solution to this problem was presented in our work [7] using automata programming approach. Our solution was not easy because 4 non-trivial bugs were found by verification in Event-B. This paper describes our third attempt to construct a short simple automata program to solve this problem. Verification of the automata program in Event-B and Why3 systems was carried out. No errors were found. For verification, a reactive system model is built on Why3, which is simpler and more universal than the why3-do model.

Solvent-induced dual nucleophiles and the α-effect in the SN2 versus E2 competition.

We have quantum chemically investigated how microsolvation affects the various E2 and SN2 pathways, their mutual competition, and the α-effect of the model reaction system HOO-(H2O)n + CH3CH2Cl, at the CCSD(T) level. Interestingly, we identify the dual nature of the α-nucleophile HOO- which, upon solvation, is in equilibrium with HO-. This solvent-induced dual appearance gives rise to a rich network of competing reaction channels. Among both nucleophiles, SN2 is always favored over E2, and this preference increases upon increasing microsolvation. Furthermore, we found a pronounced α-effect, not only for SN2 substitution but also for E2 elimination, i.e., HOO- is more reactive than HO- in both cases. Our activation strain and quantitative molecular orbital analyses reveal the physical mechanisms behind the various computed trends. In particular, we demonstrate that two recently proposed criteria, required for solvent-free nucleophiles to display the α-effect, must also be satisfied by microsolvated HOO-(H2O)n nucleophiles.

Exploring the Impact of Surface Functionalization on the Reaction, Magnetophoretic, and Collective Transport Behavior of Nanoscale Zerovalent Iron.

This study provides a systematic analysis of the transport and magnetophoretic behavior of nanoscale zerovalent iron (nZVI) particles, both bare and surface functionalized by poly(ethylene glycol) (PEG) and carboxymethyl cellulose (CMC), after undergoing a chemical reaction. Here, a simple and well-investigated chemical reaction of methyl orange (MO) degradation by nZVI was used as a model reaction system, and the sand column transport and low-gradient magnetophoretic profiles of the nanoparticles were measured before and after the reaction. The results were compared over time and analyzed in the context of extended Derjaguin-Landau-Verwey-Overbeek (DLVO) theory to understand the particle interactions involved. The colloidal stability of both bare and functionalized nZVI particles was enhanced after the reaction due to the consumption of metallic Fe content, resulting in a significant drop in their magnetic properties. As a result, they exhibited improved mobility across the sand column and a slower magnetophoretic collection rate compared to the unreacted particles. Here, the colloidal filtration theory (CFT) was employed to analyze the transport behavior of nZVI particles across the packed sand column. It has been observed that the surface properties of the reacted functionalized particles changed, possibly due to the entrapment of degraded products within the polymer adlayer. Moreover, quartz crystal microbalance with dissipation (QCM-D) measurements were performed to reveal the viscoelastic contribution of the adlayer formed by both bare and functionalized nZVI particles after the reaction on influencing their transport behavior across the sand column. Finally, we proposed the implementation of a high-gradient magnetic trap (HGMT) to reduce the transport distance of the colloidally stable CMC-nZVI, both before and after the reaction. This study sheds light on the behavioral changes of iron nanoparticles after the reaction and highlights environmental concerns regarding the presence of reacted nanoparticles.

Reply to "Comment on 'Validity of path thermodynamic description of reactive systems: Microscopic simulations'".

The Comment's author argues that a correct description of reactive systems should incorporate an explicit interaction with reservoirs, leading to a unified system-reservoir entity. However, this proposition has two major flaws. First, as we will emphasize, this entity inherently follows a thermodynamic equilibrium distribution. In the Comment, no indication is provided on how to maintain such a system-reservoir entity in a nonequilibrium state. Second, contrary to the author's claim, the inclusion of a system-reservoir interaction in the traditional stochastic modeling of reactive systems does not automatically alter the limited applicability of path thermodynamics to problematic reactive systems. We will provide a simple demonstration to illustrate that certain elementary reactions may not involve any changes in reservoir components, which seem to have been overlooked by the author.

Concerted Hydrosilylation Catalysis by Silica-Immobilized Cyclic Carbonates and Surface Silanols.

Developing a method for creating a novel catalysis of organic molecules is essential because of the growing interest in organocatalysis. In this study, we found that cyclic carbonates immobilized on a nonporous or mesoporous silica support showed catalytic activity for hydrosilylation, which was not observed for the free cyclic carbonates, silica supports, or their physical mixture. Analysis of the effects of linker lengths and pore sizes on the catalytic activity and carbonate C=O stretching frequency revealed that the proximity of carbonates and surface silanols was crucial for synergistic hydrosilylation catalysis. A carbonate and silanol concertedly activated the silane and aldehyde for efficient hydride transfer. Density functional theory calculations on a model reaction system demonstrated that both the carbonate and silanol contributed to the stabilization of the transition state of hydride transfer, which resulted in a reasonable barrier height of 16.8 kcal mol-1. Furthermore, SiO2/carbonate(C4) enabled the hydrosilylation of an aldehyde with an amino group without catalyst poisoning, owing to the weak acidity of surface silanols, in sharp contrast to previously developed acid catalysts. This study demonstrates that immobilization on a solid support can convert inactive organic molecules into active and heterogeneous organocatalysts.

Validation of quenching effectiveness and pollutant degradation ability of singlet oxygen through model reaction system

Quenching method is widely used to assess the contribution of specified reactive species through the probe inhibition efficiency (IE) caused by adding excessive quencher. However, for reactive species with weak ability such as singlet oxygen (1O2), the quenching results are prone to ambiguity. In this study, an 1O2 system using furfuryl alcohol (FFA) as a probe was successfully constructed by methylene-blue-N vis-photosensitization, to discuss the quenching, interference elimination and pollutant degradation ability of 1O2. Inhibition of FFA transformation caused by both quenching and interrupting of 1O2 production was found. The quenching is affected by quencher dosage and ability, which depends on the second-order-rate constant (k). A high k means a strong ability, and less dosage is required to achieve the same IE. Comparison between the calculated ratio of reactive species consumed by quencher and experimental IE helps to judge the interruption of 1O2 production. None of the organic-solvents (methanol, ethanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, tetrahydrofuran, acetonitrile, acetone and chloroform) scavenged 1O2, which would be used as screening-agent for other reactive species (e.g., hydroxyl radicals) that would interrupt 1O2 contribution assessment. Besides, 1O2 was powerless to degrade most selected pollutants. These results encourage proper use of quenchers and better experimental design.

Single-Nanoparticle-Level Understanding of Oxidase-like Activity of Au Nanoparticles on Polymer Nanobrush-Based Proton Reservoirs.

Enzyme-mimicking nanoparticles play a key role in important catalytic processes, from biosensing to energy conversion. Therefore, understanding and tuning their performance is crucial for making further progress in biological applications. We developed an efficient and sensitive electrochemical method for the real-time monitoring of the glucose oxidase (GOD)-like activity of single nanoparticle through collision events. Using brush-like sulfonate (-SO3-)-doped polyaniline (PANI) decorated on TiO2 nanotube arrays (TiNTs-SPANI) as the electrode, we fabricated a proton reservoir with excellent response and high proton-storage capacity for evaluating the oxidase-like activity of individual Au nanoparticles (AuNPs) via instantaneous collision processes. Using glucose electrocatalysis as a model reaction system, the GOD-like activity of individual AuNPs could be directly monitored via electrochemical tests through the nanoparticle collision-induced proton generation. Furthermore, based on the perturbation of the electrical double layer of SPANI induced by proton injection, we investigated the relationship between the measured GOD-like activities of the plasmonic nanoparticles (NPs) and the localized surface plasmon resonance (LSPR) as well as the environment temperature. This work introduces an efficient platform for understanding and characterizing the catalytic activities of nanozymes at the single-nanoparticle level.

Effects of Surface, Interface, and Defect on Zeolite Catalysis Probed by a 3D Anisotropic Model

Zeolite catalysts are characterized by complex surface, interface, and defect structures, which are tightly related to diffusion and subsequent reaction in these catalysts. Herein, we develop a three-dimensional anisotropic model to describe anisotropic diffusion, surface/interface barriers, and reactions in zeolites with rich defects. Benzene alkylation with ethylene catalyzed by ZSM-5 zeolite is taken as the model reaction system. The results show that diffusion anisotropy largely affects the apparent reaction rate of a zeolite catalyst, indicating that diffusion anisotropy should be accounted for. Surface and interface diffusion barriers play an important role when diffusion limitation is strong in zeolites, and it is necessary to regulate surface and interface structures in these cases. Introducing defects into zeolites is favorable. The optimal size, volume, and spatial distribution of defects are obtained to balance diffusion and reaction. This work provides a powerful model and some useful guidance for the optimal design of zeolite catalysts.

Squeezing Stationary Distributions of Stochastic Chemical Reaction Systems

Stochastic modeling of chemical reaction systems based on master equations has been an indispensable tool in physical sciences. In the long-time limit, the properties of these systems are characterized by stationary distributions of chemical master equations. In this paper, we describe a novel method for computing stationary distributions analytically, based on a parallel formalism between stochastic chemical reaction systems and second quantization. Anderson, Craciun, and Kurtz showed that, when the rate equation for a reaction network admits a complex-balanced steady-state solution, the corresponding stochastic reaction system has a stationary distribution of a product form of Poisson distributions. In a formulation of stochastic reaction systems using the language of second quantization initiated by Doi, product-form Poisson distributions correspond to coherent states. Pursuing this analogy further, we study the counterpart of squeezed states in stochastic reaction systems. Under the action of a squeeze operator, the time-evolution operator of the chemical master equation is transformed, and the resulting system describes a different reaction network, which does not admit a complex-balanced steady state. A squeezed coherent state gives the stationary distribution of the transformed network, for which analytic expression is obtained.

Interfacial rheology for probing the in-situ chemical reaction at interfaces of molten polymer systems

The design of new functional materials from immiscible polymers or multi-layered structures using reactive compatibilisation is an efficient approach that has been extensively employed in a wide range of applications. The adhesion/interfacial properties in these multiphase polymeric systems depend on the extent of reaction occurring at the interface. However, probing in-situ interfacial reactions in the molten state has proved challenging. In this study, interfacial shear rheology is used for the first time to directly probe the reaction at the interface between maleic anhydride-grafted polyethylene (PEgMA) and aminopropyl-terminated polydimethylsiloxane (PDMS-(PropNH2)2) used as model reactive polymer systems. Then the reaction at the interface was investigated using interfacial shear rheology based on a newly homemade, lightweight biconical setup. Thereafter, the time evolution of the interfacial tension with the progress of interfacial reaction was assessed using the pendant drop method. First, the extent of reaction was checked using differential scanning calorimetry (DSC) and dynamic rheology coupled with fast-scan FTIR spectroscopy. It has been demonstrated that the molecular weight of the aminated PDMS and the temperature of the medium markedly affect the rate of melt reaction at the interface and related interfacial rheological properties. Interestingly, the ability to assess the reactions at the interface in PEgMA/PDMS-(PropNH2)2 systems, even with low concentrations of reactive functionalities, demonstrates that interfacial rheology is a suitable, sensitive probe that could be applied to other reactive polymer systems, allowing better control of the resulting physical properties.

In Situ Synthesis of CuO/Cu2O Nanoparticle-Coating Nanoporous Alumina Membranes with Photocatalytic Activity under Visible Light Radiation

We report the synthesis and characterization of CuO/Cu2O film supported on nanoporous alumina membranes (NAMs) and the photocatalytic properties in the removal of the organic pollutant methyl orange (MO). For this purpose, transparent nanostructured membranes were fabricated and sequentially modified with APTS ((3-aminopropyl)-trimethoxysilane) and EDTAD (ethylenediaminetetraacetic dianhydride) to form a highly functionalized surface with high density of carboxyl groups, which easily complex with copper cations. The Cu2+-modified membranes were annealed in a chemical vapor deposition (CVD) furnace to form a well-ordered nanostructured coating of CuO/Cu2O with photocatalytic properties. These modifications were followed by characterization with FT-IR and UV–visible spectra, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), and energy dispersive X-ray spectroscopy (EDS). Finally, the photocatalytic performance of the NAM-CuO/Cu2O nanostructured membranes was tested in the aqueous removal of MO dye as a model reaction system. Our results revealed 50% photocatalytic removal of MO under continuous light irradiation for 2 h. The procedure presented in this work provides an adequate approach for the fabrication of nanostructured devices with photocatalytic properties for the degradation of organic compounds.

Validity of path thermodynamic description of reactive systems: Microscopic simulations.

Traditional stochastic modeling of reactive systems limits the domain of applicability of the associated path thermodynamics to systems involving a single elementary reaction at the origin of each observed change in composition. An alternative stochastic modeling has recently been proposed to overcome this limitation. These two ways of modeling reactive systems are in principle incompatible. The question thus arises about choosing the appropriate type of modeling to be used in practical situations. In the absence of sufficiently accurate experimental results, one way to address this issue is through the microscopic simulation of reactive fluids, usually based on hard-sphere dynamics in the Boltzmann limit. In this paper, we show that results obtained through such simulations unambiguously confirm the predictions of traditional stochastic modeling, invalidating a recently proposed alternative.

A Mechanochemically Active Metal‐Organic Framework (MOF) Based on Cu‐Bis‐NHC‐Linkers: Synthesis and Mechano‐Catalytic Activation

Mechanochemical Activation In article 2200207, Wolfgang H. Binder and co-workers demonstrate mechanochemical activation of a Cu-metalorganic framework (MOF), in turn triggering CuAAC of a model reaction system. Activation of the MOF generates free coordination-sites to generate spatial proximity between the azide/alkyne and thus inducing the “click”-reaction.

Oxidation of sulfonamide micropollutants by versatile peroxidase from Bjerkandera adusta

The oxidation of five sulfonamide antibiotics by the versatile peroxidase (VP, EC. 1.11.1.16) from Bjerkandera adusta was quantitatively assessed. The biocatalytic activity of the enzyme was studied by assaying different reaction conditions. Conversion levels were higher than 90 % for all five sulfonamide antibiotics in the model reaction system. In addition, the enzyme performance was also studied in treated wastewater effluents, where three sulfonamide antibiotics were oxidized at a higher level (greater than 85 % oxidation) and two were oxidized at a lower level (up to 50 %). The identified reaction products for two antibiotics, sulfasalazine, and sulfamethoxazole, showed higher antimicrobial activity than the parental compounds. Docking analyses exhibited that the reaction products interacted with the catalytic pocket of the dihydropteroate synthase from Escherichia coli, similar to the parental antibiotics. Though the oxidation is carried out at high velocity and conversion rates, the application of VP in the enzymatic oxidation technology of sulfonamide antibiotics must overcome the production of more toxic products.