This paper presents the catalytic pyrolysis of a constant-composition mixture of zeolite β and polyethylene terephthalate (PET) polymer by thermogravimetric analysis (TGA) at different heating rates (2, 5, 10, and 20 K/min). The thermograms showed only one main reaction and shifted to higher temperatures with increasing heating rate. In addition, at constant heating rate, they moved to lower temperatures of pure PET pyrolysis when a catalyst was added. Four isoconversional models, namely, Kissinger–Akahira–Sunose (KAS), Friedman, Flynn–Wall–Qzawa (FWO), and Starink, were applied to obtain the activation energy (Ea). Values of Ea acquired by these models were very close to each other with average value of Ea = 154.0 kJ/mol, which was much lower than that for pure PET pyrolysis. The Coats–Redfern and Criado methods were employed to set the most convenient solid-state reaction mechanism. These methods revealed that the experimental data matched those obtained by different mechanisms depending on the heating rate. Values of Ea obtained by these two models were within the average values of 157 kJ/mol. An artificial neural network (ANN) was utilized to predict the remaining weight fraction using two input variables (temperature and heating rate). The results proved that ANN could predict the experimental value very efficiently (R2 > 0.999) even with new data.

Polylactic acid (PLA) is a biodegradable polymer and is mainly used in the textile and food packaging fields. The aim of this work is to build knowledge on the kinetics of the pyrolysis of PLA with the help of thermogravimetric analysis (TGA) using four model-free methods, namely Friedman, Flynn–Wall–Qzawa (FWO), Kissinger–Akahira–Sunose (KAS), and Starink. Additionally, two model-fitting methods (the Coats–Redfern and Criado methods) were applied. TGA data at 5, 10, 20, and 30 K/min heating rates were collected. The obtained activation energies of the pyrolysis of PLA at different conversions by the model-free models were in good agreement and the average values were 97, 109, 104, and 104 kJ/mol for Friedman, FWO, KAS, and Starink, respectively. The Criado model was used together with the Coats–Redfern model to identify the most appropriate reaction mechanism. As per this work, the best controlling reaction mechanism of the PLA pyrolysis can be expressed by the geometrical contraction model (R2).

Methanol steam reforming (MSR) is a promising technology for on-board hydrogen production in fuel cell applications. Although traditional Cu-based catalysts demonstrate high catalytic activity and selectivity towards CO2 relative to CO, which is produced via methanol decomposition, they suffer from poor thermal stability and rapid coke formation. Nickel phosphides have been widely investigated in recent years for many different catalytic reactions owing to their remarkable activity and selectivity, as well as their low cost. In this work, we present a mechanistic study of methanol decomposition and MSR pathways on Ni2P using density functional theory (DFT) calculations. DFT-predicted enthalpic barriers indicate that MSR may compete with methanol decomposition on Ni2P, in contrast to other transition metals (e.g., Pt, Pd, and Co) which primarily decompose methanol into CO. The formaldehyde intermediate (CH2O*) can react with co-adsorbed hydroxyl (OH*) from water dissociation to produce H2COOH* which then undergoes subsequent dehydrogenation steps to produce CO2 via H2COOH*→ HCOOH* → HCOO* → CO2. We also examined the conversion of CO into CO2 via the water–gas shift (WGS) reaction, but we ruled out this pathway because it exhibits high activation barriers on Ni2P. These findings suggest that Ni2P is a promising new catalyst for MSR.

The direct catalytic conversion of methane (CH4) to higher hydrocarbons has attracted considerable attention in recent years because of the increasing supply of natural gas. Efficient and selective catalytic conversion of methane to value-added products, however, remains a major challenge. Recent studies have shown that the incorporation of phosphorus atoms in transition metals improves their selectivity and resistance to coke formation for many catalytic reactions. In this work, we report a density function theory-based investigation of methane activation and C2 product formation on Ni2P(001). Our results indicate that, despite the lower reactivity of Ni2P relative to Ni, the addition of phosphorus atoms hinders excessive dehydrogenation of methane to CH* and C* species, thus reducing carbon deposition on the surface. CH3* and CH2* moieties, instead, are more likely to be the most abundant surface intermediates once the initial C–H bond in methane is activated with a barrier of 246 kJ mol−1. The formation of ethylene from 2CH2* on Ni2P is facile with a barrier of 56 kJ mol−1, which is consistent with prior experimental studies. Collectively, these findings suggest that Ni2P may be an attractive catalyst for selective methane conversion to ethylene.

The pyrolysis of polyethylene terephthalate (PET) is a well-known process for producing high fuel value. This paper aims to study the kinetics of PET pyrolysis reactions at 4 different heating rates (2, 5, 10, and 20 K min−1) using thermogravimetric analysis (TGA) data. TGA data show only one kinetic reaction within the temperature ranges of 650 to 750 K. Five different model-free models, namely, the Freidman (FR), Flynn–Wall–Qzawa (FWO), Kissinger–Akahira–Sunose (KAS), Starink (STK), and distributed activation energy model (DAEM), were fitted to the experimental data to obtain the activation energy (Ea) and the pre-exponential factor (A0) of the reaction kinetics. The Coats–Redfern (CR) model equation was fitted with the help of master plot (Criado’s) to identify the most convenient reaction mechanism for this system. Ea’s values were determined by the application of the five aforementioned models and were found to possess an average value of 212 kJ mol−1. The mechanism of PET pyrolysis reaction was best described by first-order reaction kinetics; this was confirmed by the compensation. Further thermodynamic parameter analysis indicated that the reaction was endothermic in nature.