Thermochemical Analysis Research Articles

Thermochemical analysis of premixed ammonia/biogas flames in a model gas turbine swirl combustion system

This study examined the premixed NH3/biogas combustion at near stoichiometric using an experimentally validated numerical method. Raising the NH3 wt.% in NH3/CH4 combustion at φ = 0.8 brought up the average reaction temperature (Tavg) due to heat retention. Intensified by CO2 addition, Tavg in NH3/biogas increased by a factor of 1.2 compared to NH3/CH4. At φ = 1.1, higher NH3 and CO2 wt.% reduced Tavg. The local Damköhler number (Da) was reduced marginally in the absence of CO2 as φ increased from 0.8 to 1.1. Conversely, local Da grew considerably in the presence of CO2 and was particularly sensitive to variations in the excess air ratio. Increased NH3 wt.% promoted NO emission, primarily via N + OH → NO + H and H + HCNO → CH2 + NO pathways. NH3/biogas produced more NO than NH3/CH4 from φ = 0.9 to 1.1, but as φ approached 1.1, NO is generally lowered. N2O is produced mainly by NH + NO → N2O + H. Fuel-lean operation generally results in a higher N2O than fuel-rich operation. The NH3/biogas combustion at φ = 0.8 is a potential clean fuel solution in lowering NO emissions, as compared to NH3/CH4 combustion.

Enhanced Electrocatalysis on Copper Nanostructures: Role of the Oxidation State in Sulfite Oxidation.

The influence of surface morphology and the oxidation state on the electrocatalytic activity of nanostructured electrodes is well recognized, yet disentangling their individual roles in specific reactions remains challenging. Here, we investigated the electrooxidation of sulfite ions in an alkaline environment using cyclic voltammetry on copper oxide nanostructured electrodes with different oxidation states and morphologies but with similar active areas. To this aim, we synthesized nanostructured Cu films made of nanoparticles or nanorods on top of glassy carbon electrodes. Our findings showed an enhanced sensitivity and a lower detection threshold when utilizing Cu(I) over Cu(II). Density functional theory-based thermochemical analysis revealed the underlying oxidation mechanism, indicating that while the energy gain associated with the process is comparable for both oxide surfaces, the desorption energy barrier for the resulting sulfate molecules is three times higher on Cu(II). This becomes the limiting step of the reaction kinetics and diminishes the overall electrooxidation efficiency. Our proposed mechanism relies on the tautomerization of hydroxyl groups confined on the surface of Cu-based electrodes. This mechanism might be applicable to electrochemical reactions involving other sulfur compounds that hold technological significance.

Utilizing the Perfluoronaphthalene Radical Cation as a Selective Deelectronator to Access a Variety of Strongly Oxidizing Reactive Cations.

A selective deelectronation reagent with very high potential of +2.00 (solution)/+2.41 V (solid-state) vs. Fc+/0 and based on a room temperature stable perfluoronaphthalene (naphthaleneF) radical cation salt was developed and applied. The solid-state deelectronation of commercial naphthaleneF with [NO]+[F{Al(ORF)3}2]- generates [naphthaleneF]+⋅[F{Al(ORF)3}2]- (ORF=OC(CF3)3) in gram scale. Thermochemical analysis unravels the solid-state deelectronation potential of the starting [NO]+-reagent to be +2.34 V vs. Fc+/0 with [F{Al(ORF)3}2]- counterion, but only +1.14 V vs. Fc+/0 with the small [SbF6]- ion. Selective reactions demonstrate the selectivity of [naphthaleneF]+⋅ for deelectronation of a multitude of organ(ometall)ic molecules and elements in solution: providing the molecular structures of the acene dications [tetracene]2+, [pentacene]2+ or spectroscopic evidence for the carbonyl complex of the ferrocene dication [Fc(CO)]2+, the [P9]+ cation from white phosphorus, the solvent-free copper(I) salt starting from copper metal and the dicationic Fe(IV)-scorpionate complex [Fe(sc)2]2+.

Numerical Investigation of Hydrogen Role on Detonation of CH4/H2/air Mixtures

ABSTRACT Steady one-dimensional Zeldovich-von Neumann-Dӧring (ZND) calculation and thermo-chemical analysis are performed to investigate the hydrogen role on ZND detonation of CH4/H2/air mixtures. Different hydrogen blend ratios (i.e. Hbr) ranging from 0% to 100% are selected in this paper. The results show that hydrogen blend ratio has a significant impact on the ZND detonation reaction pathway of stoichiometric CH4-air mixtures. When Hbr ≤ 20%, CH4 is converted to CO2 by route 1: CH4 => CH3 => C2H6 => … => CO2 and route 2: CH4 => CH3 => CH3O => CH2O => HCO => CO => CO2. When Hbr ≥ 50%, CH3 in route 2 is directly converted to CH2O through R97 (CH3 + O <=> CH2O + H). This causes different ZND detonation structures. The induction length decreases with hydrogen addition. This is because R0 (H + O2 <=> O + OH) governs the heat release during the induction stage, enhancing the energy absorption in induction stage and the molecular thermal decomposition after leading shock wave. Finally, the effect of hydrogen blend ratio on the detonation cell size is explored, and a prediction model of detonation cell size incorporated with detonation stability parameter and induction length is developed for CH4/H2/air mixtures.

Adsorption of 2-4-6.trichlorophenol on montmorillonite surface: ONIOM study

The wastewater contains several chemicals, organic and inorganic molecules, among themolecules, 2.4.6-trichlorophenol, which is a source of contamination. The main aim of this work is to distinguish the process of 2.4.6-trichlorophenol retention with montmorillonite using QM: MM-ONIOM approach and applying local and global reactivity parametersthatare an excellent key for identifying adsorption sites. A weak hydrogen bond between the hydroxyl proton of 2,4,6-trichlorophenol molecule and oxygen atom on the montmorillonite surface, with a specific distance, Hb = 2.66 Å using M06-2X functional) has proved the physical adsorption. Thermochemical analysis reveals the exothermic nature of adsorption process. Negative ΔH values signify heat release and negative ΔG values indicating spontaneity under standard conditions.Theobtained results have proved an agreement with other experimental and theoretical data.

Development of biocompatible packaging material: starch/PVA-based bio-composite enhanced with hydroxypropyl methylcellulose

ABSTRACT Hydroxypropyl methylcellulose (HPMC) incorporated bio-composite films (unplasticized and plasticized) were prepared from pregelatinized maize starch/polyvinyl alcohol (PMS/PVA) blends by solution casting method. 10% boric acid (BA) was used as crosslinker. The physico-mechanical properties (tensile strength (TS), elongation at break (%EB), water solubility and moisture uptake) of the bio-composite films were studied. The thermo-chemical stability of the biofilms was studied by FT-IR, TGA and DSC analysis. TS, %EB, water solubility and moisture absorbency of 10% HPMC containing unplasticized films were found 38.1 MPa, 8.5%, 61% and 32.3%, respectively, however, the films were hard and brittle. On the contrary, TS, %EB, water solubility and moisture absorbency of 10% HPMC plasticized films were found 19.2 MPa, 28.5%, 62.2% and 57.3%. The biofilms exhibited relatively low water solubility and moisture uptake compared to higher HPMC containing composite. The thermo-chemical analysis revealed that the HPMC incorporated plasticized film was more thermally stable compared to pure PMS, PVA, HPMC and other bio composite films due to strong hydrogen bonding interaction with BA. The biodegradability of HPMC incorporated plasticized films was confirmed by soil burial test (anaerobic condition, RH 98%, 3 months). Therefore, the plasticized biofilm would be considered an alternative approach for biocompatible packaging material.

Numerical investigation on critical ignition in shock tube with controlled expansion rate

To evaluate the potential of studying the competition between chemical heat release and expansion-induced cooling in shock tube facilities, one-dimensional numerical simulations using Stanshock were performed with focus on two approaches to obtain controlled expansion rate in the post-reflected shock region. A first approach is through the utilization of driver insert, and a second approach relies on the utilization of the reflected expansion head. Auto-ignition in hydrogen-oxygen-argon mixtures in the driven section was studied. Numerical simulations for the first approach were performed for various expansion rates induced by the driver insert, for two Ar dilutions of 99 % and 95 %, and for various target temperatures in two shock tubes with different lengths. For the second approach, numerical simulations were performed for various target temperatures, and for two Ar dilutions of 95 % and 90 %. Depending on the expansion rate, either ignition or chemical quenching could be effectively observed, which is consistent with the critical decay rate concept. To further investigate the mechanisms responsible for ignition and quenching, quantitative thermo-chemical analyses were performed for quenching and successful ignition conditions. Because of the lower expansion rates generated by using driver inserts, the first strategy is limited to the low-temperature regime, with dominant pathways at critical conditions related to the chemical dynamics of HO2. For the second strategy, the much higher expansion rate enables to access the high-temperature regime, for which successful ignition is driven by chain-branching chemistry.

Highly energetic formulations of boron and polytetrafluoroethylene for improved ignition and oxidative heat release

Boron (B) is desirable for energetic applications due to high gravimetric and volumetric energy densities. However, their use is limited because the native oxide shells on their surfaces limit oxidation and heat release by acting as a diffusion barrier and dead weight that does not contribute to heat release during oxidation. This paper reports a facile and efficient method of blending B with perfluoro additives to obtain materials with augmented heat release. We use polytetrafluoroethylene (PTFE) as a fluorine source that reacts with the oxide layer exothermally and use thermochemical analysis to identify the optimum composition of PTFE to extract high energy from B as a result of synergistic oxidation and fluorination reactions. The reduction in ignition temperatures of B is also observed due to its blending with PTFE. In this work, we determined B/PTFE blends with lower ignition temperature and higher oxidative heat release. These effects are due to the gasification of native surface oxide by fluorine via exothermic reactions that facilitate the enhanced reactions in the exposed metal core by eliminating the kinetic/thermodynamic barrier in the diffusion of the oxidizer to the B particle core. The study demonstrates the optimized formulation of highly energetic blends of B/PTFE for energetic applications.

Low temperature vaporisation of Cr from fluoride flux reacted at 1350 °C with Al–Cr–Fe powder: Thermochemical analysis of gas phase reactions and nano-strand formation

The submerged arc welding (SAW) process is complex because multi-phase reactions occur simultaneously across a large temperature interval from 2500 °C in the arc cavity, down to the weld pool liquidus temperare at the slag-weld pool interface. This complexity hinders research on specific process metallurgy aspects, such as gas formation from the oxy-fluoride slag. The main objective of this work is to illustrate a low temperature experimental technique as an accurate reaction simulation experiment of SAW flux oxy-fluoride slag behaviour in terms of gas formation and metal powder assimilation reaction mechanisms as observed in the SAW process. The oxy-fluoride slag behaviour was confirmed by identification and analyses of nano-strand formation in the reacted slag formed from the reaction of welding flux with Al-Fe-Cr metal powders at 1350 °C. The observed nano-strand formation agrees with similar observations in SAW post-weld slags used to confirm of oxy-fluoride vaporisation and re-condensation. Element distribution from energy dispersive X-ray spectroscopy (EDS) maps and thermochemical calculations were used to gain insights into the reactions in nano-strand formation. The nano-strands contained chromium patches and spots of less than 1 μm in scale, confirming that added Cr metal powder assimilated via the gas phase. Cr-fluoride formed part of the oxy-fluoride slag and likely formed Cr-fluoride gas. Cr was recovered via re-condensation of Cr vapour formed from the reaction of Cr-fluoride with Al gas. This work presents an accurate low temperature simulation method of gas formation and metal powder assimilation reactions in oxy-fluoride slags as in the SAW process.

Theoretical Insights into the Gas-Phase Oxidation of 3-Methyl-2-butene-1-thiol by the OH Radical: Thermochemical and Kinetic Analysis.

3-Methyl-2-butene-1-thiol ((CH3)2C═CH-CH2-SH; MBT) is a recently identified volatile organosulfur compound emitted from Cannabis sativa and is purported to contribute to its skunky odor. To understand its environmental fate, hydroxyl radical (•OH)-mediated oxidation of MBT was conducted using high-level quantum chemical and theoretical kinetic calculations. Three stable conformers were identified for the title molecule. Abstraction and addition pathways are possible for the MBT + OH radical reaction, and thus, potential energy surfaces involving H-abstraction and •OH addition were computed at the CCSD(T)/aug-cc-pV(T+d)Z//M06-2X/aug-cc-pV(T+d)Z level of theory. The barrier height for the addition of the OH radical to a C atom of the alkene moiety, leading to the formation of a C-centered MBT-OH radical, was computed to be -4.1 kcal mol-1 below the energy of the starting MBT + OH radical-separated reactants. This reaction was found to be dominant compared to other site-specific H-abstraction and addition paths. The kinetics of all the site-specific abstraction and addition reactions associated with the most stable MBT + OH radical reaction were assessed using the MESMER kinetic code between 200 and 320 K. Further, we considered the contributions from two other conformers of MBT to the overall reaction of MBT + OH radical. The estimated global rate coefficient for the oxidation of MBT with respect to its reactions with the OH radical was found to be 6.1 × 10-11 cm3 molecule-1 s-1 at 298 K and 1 atm pressure. The thermodynamic parameters and atmospheric implications of the MBT + OH reaction are discussed.

Thermochemical energy storage analysis of solar driven carbon dioxide reforming of methane in SiC-foam cavity reactor

Solar energy is an abundant renewable energy source, and the use of solar energy for carbon dioxide reforming of methane (CRM) is a promising thermochemical energy storage scheme, but the reactor using the traditional powder catalyst has the disadvantages of complex encapsulation and low energy storage efficiency. In this paper, porous SiC-foam with high thermal conductivity is used to prepare Ni/CeO2–Al2O3/SiC catalyst, and then is loaded into a cavity reactor to achieve highly efficient and stable CRM under solar simulator. After a period of reaction, methane conversion rate remains high. As inlet flow rate decreases and incident energy flux rises, methane conversion rate is improved, and thermochemical energy storage efficiency first rises and then drops with maximum 31.4%. The numerical model of the cavity reactor under concentrated heat flux is established, and the simulation results are in good agreement with the experimental data. The structure of catalyst bed directly influences the heat storage performance, and the optimal bed thickness, radius and porosity are obtained. For thick bed, the reverse reaction appears in the end region of the bed, and then this region expands with bed thickness rising, so the reaction rate first increases and then decreases.

Effect of copper powder addition on the product quality of sintered stainless steels

Abstract Powder metallurgy and selective laser melting (SLM) methods are widely used in producing metal parts. Adding reinforcements can improve the mechanical and physical properties of the parts. This study uses the powder metallurgy method before SLM to investigate the effect of copper reinforcement (0, 0.5, 1, 2, and 5 wt.%) on 316L and MS1 (maraging steel) material. The study started by thermochemical investigating the effects of copper addition on the phases during cooling. According to the thermochemical analysis, experimental sintering processes were carried out with the addition of copper in suitable mixing ratios. The findings show that 316L material is more convenient to the sinter than MS1 due to alloy ratios and powder sizes. Adding up to 2 wt.% copper to 316L results in a 36 wt.% reduction in linear shrinkage and improved mechanical and physical stability. The most satisfactory results were obtained by sintering the samples at 1200 °C for 1 h. This study shows that future research should focus on producing copper-reinforced 316L metal powders using SLM methods and parameter optimization and developing hybrid manufacturing methods that combine SLM with powder metallurgy.

Limits on Ti Element Transfer in Submerged Arc Welding: Thermochemical Analysis

TiO2 inclusion formation in the weld pool is required to produce potent nucleation sites for acicular ferrite microstructure formation. Weld metal oxygen content must be limited to ensure acceptable materials properties, although sufficient oxygen is required for inclusion formation. Weld pool oxygen is sourced from the decomposition of flux oxides. Weld metal oxygen is controlled with flux chemistry formulation by CaF2 dilution of oxides. In conventional submerged arc welding (SAW), the flux is the source of weld metal Ti. Transfer of Ti from the slag appears to be limited to 400 parts per million (ppm). SAW modification by metal powder additions changes the element transfer reactions. Thermochemical analysis is applied to explain the limitations in Ti transfer from the slag, compared to improved reaction conditions for Ti element transfer in the aluminum‐assisted Ti alloying of weld metal. Low TiO2 activity due to low flux TiO2 content from CaF2 dilution and Ti loss from Ti‐fluoride gas formation limits Ti transfer from slag. Aluminum‐assisted alloying of the weld metal shifts the gas composition from Ti‐fluoride formation to Al‐fluoride formation and lowers the system partial oxygen pressure to increase the weld metal Ti content, with acceptable ppm O remaining in the weld metal.

Minimum oxygen supply rate for smouldering propagation: Effect of fuel bulk density and particle size

Smouldering is a low-temperature, flameless, and persistent combustion process driven by heterogeneous oxidations. Oxygen supply is a key parameter of smouldering and is sensitive to fuel density and particle size, but our understanding is still limited. Herein, we explore the oxygen threshold for smouldering propagation under upward internal airflow velocities up to 5 mm/s. Pine needles with different bulk densities (55–120 kg/m3) and wood samples with different particle sizes (1–50 mm) are tested. We found that the minimum airflow velocity for sustaining smouldering propagation increases with the decrease of the bulk density or the increase of the particle size. By increasing the airflow velocity, the smouldering front first propagates unidirectionally (opposed) and then bidirectionally (opposed + forward). Nevertheless, when the pore size is large (the fuel particle size is large or the fuel bulk density is small), bidirectional propagation always occurs, because the oxygen can leak through the opposed smouldering front. A simplified thermochemical analysis is proposed to reveal the influence of interparticle heat transfer on the minimum oxygen supply rate of smouldering propagation. This work advances the fundamental understanding of smouldering on solid fuel particles and their smouldering fire risks and helps optimize the efficiency and safety of smouldering processes.

Analysis of cure kinetics of CFRP composites molding process using incremental thermochemical information aggregation networks

This work focuses on addressing the pain points of poor generalization performance and difficulty in continuous learning that exist in the phenomenological and neural network surrogate models. Therefore, this study proposes a lightweight adaptive thermochemical information aggregation networks (ATANets) to overcome the gradient conflict challenge, and combines the generative knowledge distillation (GKD) algorithm to compress the model to capture finer-grained and enriched information on kinetics behaviors, which yields a thermochemical feature information extraction networks (FENets) with incremental learning capability. The experimental results demonstrated that as the complexity of the learning task deepened, the FENets models obtained by incremental training with ATANets and GKD still had excellent continuous learning capability, with the relative variations of the coefficients of determination and the mean square error being smaller than 6.7 × 10−3 and 0.3860 × 10−3, respectively. Meanwhile, the accurate characterization of cure kinetics behaviors was achieved in the thermochemical coupling analysis of CFRP, with the maximum values of the average and maximum temperature differences of 0.0176 °C and 0.2538 °C, respectively. Overall results show that our proposed incremental model is remarkably preferable to existing models and is beneficial in promoting the widespread reuse of the existing knowledge of cure kinetics behavior of resins in this domain.

Nano-strand formation in CaF2-SiO2-Al2O3-MgO flux reacted at 1350 °C with Al-Ti-Fe powder: SEM analyses and gas reaction thermochemistry

Nano-strands form in fluoride-based slag during submerged arc welding (SAW) due to the re-condensation of gas species formed at high temperatures in the arc cavity. The SAW process is complex due to gas-slag-metal reactions occurring across several reaction zones and over a wide temperature range. This complicates research on specific process aspects, such as gas formation from the oxy-fluoride slag. The objective of this work is to demonstrate that oxy-fluoride nano-strands form in molten flux reacted with Al-Ti-Fe metal powder, even at the low temperature of 1350 °C, which is much lower than SAW process temperatures of 2000 °C–2500 °C. Energy dispersive X-ray spectroscopy (EDS) analyses and thermochemical calculations provide insights into formation reactions in nano-strand formation. Thermochemical analysis clarifies the role of Al in shifting the gas phase composition to limit Ti-fluoride loss to the gas phase. These results motivate the study of gas phase reactions at relatively lower reaction temperatures to gain insights into SAW flux behaviour.

Structural and thermochemical investigation of 1,3-bis(λ4-boraneyl)-1λ4,3λ4-imidazolidine adduct for chemical hydrogen storage.

The structure, thermochemical properties and reaction pathways of a cyclic amine diborane complex (1,3-bis(λ4-boraneyl)-1λ4,3λ4-imidazolidine) were investigated using quantum chemical calculations. Structural and thermochemical analysis revealed that the simultaneous and spontaneous elimination of both hydrogen molecules from this complex is predicted to occur under thermoneutral conditions. This observation is further supported by the investigation of the BH3-catalysed dehydrogenation pathway. The calculated thermochemical parameters indicate that the energy requirements for hydrogen release from this complex are minimal, suggesting efficient hydrogen release capability under suitable conditions. Additionally, the activation barriers, ∼75 and ∼20 kJ mol-1 for the first and second dihydrogen release from the catalysed dehydrogenation reactions of this compound exhibit moderate kinetics, confirmed by kinetic studies. These findings and the ability of the system to easily release two molecules of dihydrogen emphasize the potential of 1,3-bis(λ4-boraneyl)-1λ4,3λ4-imidazolidine as a highly effective hydrogen storage material.

Characterisation and thermochemical stability analysis of 3D printed porous ceria structures fabricated via composite extrusion Modelling

Composite Extrusion Modelling (CEM) is an advanced additive manufacturing technique that enables rapid, cost-effective production of complex, customisable designs. In this study, CEM 3D printing of porous ceria structures is reported for the first time. First, the ceramic injection molding (CIM) feedstock with thermoplastic properties was prepared and optimised in terms of its rheological properties to ensure good workability for the printing process at 140–150 °C. Subsequently, the thermoplastic feedstock was used to print porous ceria structures for thermochemical splitting. The feasibility of printing various porous structures with different dimensions, geometries, and macropore sizes was investigated, and the printing parameters: extrusion multiplier (EM), extrusion temperature (ET), nozzle velocity (NV), and layer thickness (LT), were optimised to prevent clogging of the printing nozzle and to achieve homogeneous overlap of the printed layers. The optimised printing parameters for ceria structures are EM 1.3, ET 150 °C, LT ∼ 0.13 mm, and NV 50 mm/s, which were determined by multiple response optimisation process. The sintered 3D-printed bars yielded relative densities of ≥ 98 % and a total microporosity of 0.29 %, measured with a Hg porosimeter. Thermogravimetric analysis (TGA) and cyclic stability experiments were performed on the printed porous ceria structures and showed stability over 100-redox cycles.

Modulation of the NLO properties of p-coumaric acid by the solvent effects and proton dissociation

Solute-solvent interactions and deprotonation effects have been related to second-order nonlinear optical response modulators. This work takes advantage of sequential Monte Carlo/Quantum mechanics together with Time-Dependent Density Functional Theory, Coupled Cluster methods, and the hyper-Rayleigh scattering formalism to investigate how these effects influence the stability and optical response of p-coumaric acid (pCA) and its anionic and diionic forms. The solvent influences the chromophores in different ways, inducing bathochromic and hypsochromic solvatochromism so for the neutral pCA molecule as for its deprotonated derivatives. The results indicate a high sensitivity of the nonlinear optics (NLO) parameters with relation to proton dissociation. Ionization of the carboxyl group produces the lowest values of the first frequency-dependent hyperpolarizability (βHRS), while phenolic deprotonation leads to the highest values. The results show that proton removal can be used as a switch that modulates the NLO response within a wide range of values (159.15≤βHRS≤4393.97 au) greater than those reported for reference NLO chromophores like urea (37.3 au) and p-nitroaniline (74.3 au). Thermochemical analysis of enthalpies and Gibbs free energies indicate that both monoionic forms of the pCA molecule are the most stable in gas or water solvents. Furthermore, these structures represent the limits of NLO modulation in the gas and solvent phases. Analysis of the projected density of states and mapping of the molecular electrostatic potential indicate that increased contributions from conduction electrons found in the aromatic ring are the mechanism by which deprotonation enhances the NLO response. All the results show that ionic pCA forms are promising in the functionalization of optoelectronic devices.

The impact of oxygen-clustering on the transformation of electrochemically-derived graphite oxide framework

Oxygen-clustering in graphene oxide is the activated process of diffusion of oxygen functionalities: hydroxyls and epoxides, to form clusters and to trigger sp2 percolation, a key element for electrical conductivity. Impact of oxygen-clustering is thoroughly analyzed in electrochemically-derived graphite oxide (EGO), amine-functionalized frameworks (EGOF), and their pyrolyzed forms. Amine pillars within EGOF were suspected to amplify oxygen-clustering in EGOF as onset temperature of thermal decomposition was smaller in EGOF than in EGO. Thermochemical analysis proves that pillars within EGOF significantly augment oxygen-clustering aiding the reduction mechanism as inferred by the activation energy of thermal decomposition. Defective oxygen-clustering mechanism is evidenced using multiple techniques, including XRD, and is harnessed to enhance nitrogen doping. The pyrolytic morphological transformation from lamellae of EGOF into ravioli is revealed through SEM. A labyrinthic network of array prismatic dislocations provides stability to pyrolyzed EGOF ravioli whilst confining long chains of electron delocalization (localized π-orbitals), as unprecedently confirmed by HR-TEM/EELS and conductive AFM (C-AFM). Oxygen-clustering not only improves nitrogen doping in ravioli, but also improves density of array prismatic dislocations, which ultimately boosts Faradaic redox activity as observed in cyclic voltammetry (CV). Results show that Faradaic response originating from redox-active nitrogen groups predominantly relies on abundance of extended localized π-orbitals, which are geometrically and chemically confined within ravioli array prismatic dislocations. Our first-of-a-kind HR-TEM/EELS, C-AFM, and CV comparative and correlative analysis of pyrolyzed forms of EGO, EGOF, and their oxygen-clustered derivatives, confirms emergent role of confined electron delocalizations in amplifying Faradaic redox activity.