Journal of Analytical and Applied Pyrolysis最新文献

{"title":"Explosion limit evolution and structure-kinetic correlations of C1–C4 low-carbon alcohols","authors":"Qiang Guo ,&nbsp;Jiaxin Li ,&nbsp;Jie Liu ,&nbsp;Jingkuan Li","doi":"10.1016/j.jaap.2025.107577","DOIUrl":"10.1016/j.jaap.2025.107577","url":null,"abstract":"<div><div>Based on a detailed chemical kinetic mechanism, this study systematically investigates the explosion limit characteristics and reaction pathways of C₁–C₄ low-carbon alcohols, elucidating the intrinsic effects of molecular structure, hydrogen abstraction sites, and chain-branching pathways on fuel reactivity. The results show that the explosion limit curves of C₁–C₃ alcohols shift toward lower pressures with increasing temperature. Methanol exhibits the weakest overall reactivity, while ethanol and n-propanol demonstrate the strongest explosive activity in the high-temperature regime, and isopropanol shows slightly higher reactivity than methanol in the high-temperature region. At low temperatures, n-propanol undergoes α-hydrogen abstraction to form C₃H₆OH-1, followed by efficient radical regeneration through the CH₃/CH₃O₂ cycle, markedly enhancing chain-branching efficiency. The explosion limits of butanol isomers exhibit strong temperature dependence. n-butanol shows a deep and pronounced NTC behavior, whereas t-butanol exhibits only an incipient/mild NTC tendency at low temperatures. In the intermediate-temperature region, the reactivity order transitions to i-butanol &gt; n-butanol &gt; s-butanol ≈ t-butanol, while at high temperatures (<em>T</em> &gt; 958 K) the chemistry is dominated by C–C bond cleavage and CH₃-cycling, with s-butanol and t-butanol showing the highest reactivity and leaving n-butanol as the least reactive isomer. Overall analysis demonstrates that straight-chain alcohols favor RO₂→QOOH→KET chain branching under low-temperature conditions, whereas branched alcohols promote C–C bond cleavage and CH₃ regeneration at high temperatures, thereby enhancing radical recycling. With increasing carbon chain length, the explosion domain expands significantly, especially on the low-temperature side. The constructed explosion limit regime diagram for C₁–C₄ alcohols clearly delineates the dominant explosion regions of each fuel, providing a kinetic basis for assessing reactivity and combustion performance of low-carbon oxygenated fuels, guiding the selection of suitable alcohols as cold-start/HCCI promoters, high-temperature SI additives, or low-reactivity components for explosion mitigation, and complementing octane-number data for practical fuel formulation and knock control.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107577"},"PeriodicalIF":6.2,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880180","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic study of AAEM-catalyzed steam gasification of oxygen-containing functional groups in biomass char based on DFT","authors":"Xun Zou ,&nbsp;Peng Wang ,&nbsp;Miaoyu Cai ,&nbsp;Li Guo ,&nbsp;Yu Zhang ,&nbsp;Guojun Xie ,&nbsp;Ming Zhai","doi":"10.1016/j.jaap.2025.107580","DOIUrl":"10.1016/j.jaap.2025.107580","url":null,"abstract":"<div><div>Steam gasification of biomass represents a promising route for sustainable hydrogen production, offering dual benefits of efficient resource utilization and carbon emission reduction. In this process, biomass reacts with steam at elevated temperatures to generate hydrogen-rich syngas, which provides a renewable alternative to fossil-derived hydrogen and contributes to the development of a low-carbon energy system. The initial stage of gasification is dominated by surface reactions involving oxygen-containing functional groups in biomass char, which serve as the primary active sites for steam activation and hydrogen evolution. Understanding the reactivity and transformation pathways of these functional groups is therefore crucial for optimizing the gasification process and enhancing hydrogen yield. Alkali and alkaline earth metals (AAEMs) are widely recognized as effective catalysts that facilitate bond dissociation and significantly reduce the energy barriers associated with steam-char reactions. In this work, density functional theory (DFT) calculations were carried out to explore the catalytic influence of AAEMs on the steam gasification mechanisms of representative oxygen-containing functional groups in biomass char. The analysis reveals that the introduction of AAEMs not only reshapes the potential energy surfaces but also directs the reaction toward more favorable pathways. For carbonyl groups, Na and K exhibit superior catalytic effects, with Na providing the lowest overall reaction energy. In contrast, K shows the best catalytic activity in carboxyl group gasification, while Ca and Mg outperform the alkali metals in hydroxyl group gasification, with Ca yielding the most stable reaction route. These findings clarify the structure-activity relationships of different AAEM catalysts and their interactions with functionalized char surfaces. The insights gained offer a theoretical foundation for designing more efficient catalytic gasification systems and promoting high yield hydrogen production from renewable biomass resources.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107580"},"PeriodicalIF":6.2,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880258","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Continuous synthesis of quinolines derivatives from catalytic oxidative depolymerization products of lignin in a micro-manufacturing platform","authors":"Pengfei Lian ,&nbsp;Zengji Yao ,&nbsp;Guangwei Sun ,&nbsp;Yao Li ,&nbsp;Zihao Ma ,&nbsp;Xing Wang ,&nbsp;Ying Han","doi":"10.1016/j.jaap.2025.107579","DOIUrl":"10.1016/j.jaap.2025.107579","url":null,"abstract":"<div><div>The abundant aromatic structures present in lignin render it a potential raw material for quinoline compounds. Consequently, the utilization of the vast reserves of lignin and the exploration of efficient, practical, and sustainable synthetic routes for quinoline compounds will be a significant development direction in the utilization of biomass resources. In this work, with the monomer model compounds of lignin and 2-aminobenzyl alcohol as raw materials, the feasibility of continuous-flow synthesis of quinoline derivatives was explored using a microchannel reactor. The study investigated the influence of various factors on the synthesis process of quinoline derivatives and characterized the product structures, including analyses such as HPLC, TOF-MS, ¹H-NMR, ¹³C-NMR, and 2D-HSQC. The research results indicated that under the optimal conditions, the yields of 2-phenylquinoline, 4-(quinolin-2-yl)phenol, 4-(quinolin-2-yl)guaiacol, and 4-(quinolin-2-yl)syringol were 93.89 %, 64.26 %, 33.98 %, and 41.30 %, respectively. The research results demonstrated that it is feasible to construct the quinoline ring through reactions such as C-N bond condensation and C-C cyclization.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107579"},"PeriodicalIF":6.2,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880260","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Study on plasma pretreatment of lignin to inhibiting pyrolysis intermediate polymerization and promoting Mo/ZSM-5 catalytic pyrolysis","authors":"Jiajun Yu ,&nbsp;Kai Wu ,&nbsp;Longfei Hong ,&nbsp;Liangdong Hu ,&nbsp;Xiujuan Feng ,&nbsp;Huiyan Zhang","doi":"10.1016/j.jaap.2025.107574","DOIUrl":"10.1016/j.jaap.2025.107574","url":null,"abstract":"<div><div>Catalytic pyrolysis of lignin can produce renewable aromatics in one step, but the development of this process is severely constrained by problems such as high-temperature polymerization and catalyst coking. Here, we propose a method combining plasma rapid pretreatment with catalyst modification to efficiently convert lignin into aromatics through catalytic pyrolysis. Pyrolysis tests of lignin derivatives show that large amounts of oligomers form after pyrolysis of guaiacol and syringol, and intramolecular interactions between methoxy and hydroxyl groups are the main factors contributing to lignin intermediate polymerization during pyrolysis. Plasma pretreatment can rapidly break some connecting bonds and methoxy groups, significantly inhibiting secondary polymerization of intermediates and oligomer formation during pyrolysis, thus promoting the generation of lignin pyrolysis monomer phenols. Mo-modified ZSM-5 can enhance catalytic cracking and deoxygenation performance while reducing the formation of coke precursors such as naphthalene (drops from 1.45 to 1.03 wt%). Converting pretreated lignin to aromatics using Mo-modified ZSM-5 increases the yield to 6.0 wt%, while simultaneously suppressing intermediate polymerization and coking. Overall, this work demonstrates the inhibition mechanism of lignin pretreatment combined with Mo modification on polymerization and coking during lignin catalytic pyrolysis, providing a simple and environmentally friendly approach for the efficient pyrolysis of lignin.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107574"},"PeriodicalIF":6.2,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837371","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"PVC dechlorination-microwave catalysed pyrolysis for the preparation of carbon nanocomposites: Dechlorination kinetics, process and mechanism","authors":"Guangxiong Ji ,&nbsp;Bingguo Liu ,&nbsp;Guolin Luo ,&nbsp;Chao Yuwen ,&nbsp;Fang Peng ,&nbsp;Siyu Gong ,&nbsp;Wang Chen ,&nbsp;Keren Hou ,&nbsp;Zhenxing Yang ,&nbsp;Yuhao Jin","doi":"10.1016/j.jaap.2025.107576","DOIUrl":"10.1016/j.jaap.2025.107576","url":null,"abstract":"<div><div>The chlorine content in PVC has a significant impact on the preparation of carbon nanocomposites through its pyrolysis. In this study, PVC was dechlorinated to different degrees, and Pre-treated PVC was mixed with a self-made FeTiO_x catalyst, and then subjected to catalytic pyrolysis in a microwave field, and FeTi/C nanomaterials with different carbon morphologic profiles were successfully prepared. Firstly, the kinetics of dechlorination during PVC pyrolysis was studied to reveal the nature of the dechlorination reaction and provide a scientific basis for the preparation of Pre-treated PVC with different chlorine content. The results show that the dechlorination process of PVC follows the first-order reaction model, and the average value of activation energy <em>E</em>_<em>a</em> of dechlorination stage is 142.70 kJ·mol⁻¹, and the average value of prefactor <em>A</em> is 1.67 × 10¹⁶ s⁻¹. Secondly, during the pyrolysis process, it was found that FeTiO_x catalyst containing low-valent iron oxides after hydrogen reduction had better microwave absorption and heating performance than FeTiO_x catalyst containing only high-valent iron oxides, which was more likely to promote the microwave pyrolysis process. When the chlorine content of Pre-treated PVC was 0.41 wt%, the carbon material in FeTi/C was mainly carbon nanotubes, and the carbon yield was 33 wt%. As the chlorine content increased to 6.7 wt% and 13.78 wt%, the aromatization during pyrolysis was greater than the dehydrogenation of polyolefins, and the surface of the FeTiO_x catalyst was passivated by an FeClₓ layer. The carbon material in FeTi/C was transformed into spheroidal amorphous carbon with a lower degree of graphitization, and the carbon yield was reduced to 20.69 wt% and 12.39 wt%, respectively. This paper proposes a method to prepare FeTi/C nanomaterials with different carbon morphologies by controlling the chlorine content in PVC under microwave catalytic pyrolysis conditions, providing a new idea for the efficient and harmless recycling of PVC.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107576"},"PeriodicalIF":6.2,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chemical recycling of mixed thermoplastics via pyrolysis: A comparative study of feedstock influence and reactor impact","authors":"Niklas Netsch ,&nbsp;Aljoscha Tauber ,&nbsp;Orhan Keskin ,&nbsp;Britta Bergfeldt ,&nbsp;Harald Wehner ,&nbsp;Dirk Eidam ,&nbsp;Salar Tavakkol ,&nbsp;Dieter Stapf","doi":"10.1016/j.jaap.2025.107575","DOIUrl":"10.1016/j.jaap.2025.107575","url":null,"abstract":"<div><div>Pyrolysis represents a promising solution for increasing plastic waste recycling rates in a circular economy. The thermal decomposition behavior of pure polymers is well investigated. However, the diverse composition and complex technical reactor conditions pose challenges for the pyrolysis of heterogeneous plastic waste. Therefore, this study examines the pyrolysis of virgin polymers, defined reference mixtures, and post-consumer waste in a scalable stirred tank reactor (STR) compared to an auger-type screw reactor (ASR) at pilot-scale. The results of the STR confirm that simple polymer blends of polyolefins and polystyrene degrade following the decomposition mechanisms of the pure polymer, while heteroatom-containing mixtures exhibit interaction effects. These interactions shift the products from the condensable to the gaseous fraction by up to 22 wt.%. Furthermore, product yields and compositions strongly depend on reactor design and process parameters. The gas residence time and the time-dependent polymer pyrolysis temperature are identified as the main influencing parameters. In this study, interaction effects between different polymers overlap the reactor-specific impact in complex feedstock mixtures, dominating the product yields. The condensate yield in the STR exceeds the results obtained in the ASR by 10–24 wt.% for LDPE, PP, PS, and a mixture of them. In contrast, the STR system yields only up to 6 wt.% more condensates than the ASR system for mixtures containing oxygen, nitrogen, and chlorine. The reactor type has a major impact on condensate quality. The H/C ratio, heteroatom content, and proportion of distillation cuts in the light and middle distillate range vary significantly.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107575"},"PeriodicalIF":6.2,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effects of lignin, hemicellulose, and cellulose of feedstock and pyrolytic temperature on the composition and properties of biochar-derived dissolved organic matter","authors":"Manrong Yu ,&nbsp;Yining Gao ,&nbsp;Ruiyi Wang ,&nbsp;Weijia Wu ,&nbsp;Jiao Qiu ,&nbsp;Yuping Huang ,&nbsp;Jingzi Beiyuan ,&nbsp;Hu Cheng ,&nbsp;Yan-ping Zhao ,&nbsp;Zihang Cheng ,&nbsp;Hailong Wang","doi":"10.1016/j.jaap.2025.107572","DOIUrl":"10.1016/j.jaap.2025.107572","url":null,"abstract":"<div><div>Biochar has been widely applied across diverse fields, and its derived dissolved organic matter (BDOM) is attracting growing research interest, particularly concerning the environmental fate and transport of various contaminants. However, systematic studies on BDOM produced from feedstocks with varying lignin, hemicellulose, and cellulose contents under different pyrolysis temperatures are still limited. Differences in the pyrolysis behaviors of these components may lead to significant variations in the BDOM properties, thereby influencing its environmental behaviors and application. To address this knowledge gap, six types of agricultural waste—walnut shell (WAS), corn cob (CC), peanut shell (PS), rice husk (RH), wheat husk (WHS), and corn stalk (CS) with distinct lignocellulosic components—were selected as raw materials to produce biochars at 300°C, 400°C, and 500°C. BDOM was extracted and comprehensively characterized. The results indicate that in addition to pyrolysis temperature, lignocellulosic components also significantly affect the quantity, aromaticity, and composition of BDOM, particularly in biochars produced at lower temperature (≤400°C). A higher cellulose content promoted the release of more BDOM in biochars pyrolyzed at 400°C, as confirmed by the detection of fulvic-like and humic-like substances through fluorescence spectroscopy and three-dimensional fluorescence spectroscopy coupled with parallel factor analysis. Additionally, two-dimensional correlation spectroscopy highlighted oxygen-containing functional groups as the most temperature-sensitive structural features. This study not only provides systematic evidence of the importance of lignocellulosic components on the properties and composition of BDOM, but also offers new insights into the potential applications of biochar in environmental remediation.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107572"},"PeriodicalIF":6.2,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880255","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanism insight into the role of hydrogen on xylan hydropyrolysis by the combination of experiments and ReaxFF-MD simulation","authors":"Wenhao Xu ,&nbsp;Hong Xian ,&nbsp;Tan Li ,&nbsp;Linjia Yin ,&nbsp;Zhongqing Ma ,&nbsp;Chuang Xing ,&nbsp;Muye Feng ,&nbsp;Heping Li ,&nbsp;Kaige Wang","doi":"10.1016/j.jaap.2025.107573","DOIUrl":"10.1016/j.jaap.2025.107573","url":null,"abstract":"<div><div>Hydropyrolysis represented a crucial method in the conversion of biomass into high-value chemical derivatives. The pyrolysis products distribution of xylan, a typical model compound of hemicellulose, under different temperatures, pressures and atmospheres were investigated using a high-pressure micro-pyrolyzer combined with ReaxFF Molecular Dynamics (ReaxFF-MD) simulation to clarify the hydropyrolysis mechanism. The addition of hydrogen changed the pyrolysis reaction path of xylan, and the carbon yield of the condensable product mainly consisted of ketones, furans, and acids at 500 °C and 2 MPa increased by 7.71 wt% to 30.55 wt% compared with inert atmosphere. The ReaxFF-MD simulation results indicated that hydrogen enhanced the HDO and cyclization reactions of xylan and intermediates mainly by combining sidechain OH· to generate a large amount of H·, resulting in increased yield of furans and methane products. The utilization of ReaxFF-MD method offered a valuable approach for elucidating the intricate mechanisms underlying biomass hydropyrolysis.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107573"},"PeriodicalIF":6.2,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880265","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nutrient conversion during the fertilization of rice straw: Pyrolysis versus fermentation","authors":"Lide Liu ,&nbsp;Qing Luo ,&nbsp;Yujiao Wen ,&nbsp;Shangzhi Wei ,&nbsp;Shun Zhang ,&nbsp;Nan Sun ,&nbsp;Rui Qin ,&nbsp;Wenzhi Yang ,&nbsp;Zuoxiang Xiang ,&nbsp;Longxing Hu ,&nbsp;Zhi Zhou ,&nbsp;Nan Zhou","doi":"10.1016/j.jaap.2025.107556","DOIUrl":"10.1016/j.jaap.2025.107556","url":null,"abstract":"<div><div>Pyrolysis and fermentation are the main ways of utilization of straw waste. However, existing studies lack information on the differences in nutrient conversion between the two approaches. This study compared these methods using rice straw, analyzing element retention and product properties. The results showed that fermentation enhanced nutrient retention, doubling total nitrogen (TN) to 18.56 g·kg⁻¹ and available nitrogen (AN) to 953.13 mg·kg⁻¹, up from 9.91 g·kg⁻¹ and 479.15 mg·kg⁻¹ in raw straw. Thermochemical transformation is conducive to the accumulation of total phosphorus (TP) and total potassium (TK) in biomass. Pyrolysis at 550 C for 2 h increased total TP and TK to 3.11 g·kg⁻¹ and 67.97 g·kg⁻¹, respectively, from 0.96 g·kg⁻¹ and 14.87 g·kg⁻¹ in RS. In the pyrolysis range from 350 to 550 C, TP and TK in thermochemical transformation products increased with the increase of pyrolysis temperature. In the soil cultivation experiment, straw biochar can promote the plant height and root length of rice seedlings under the three concentrations. The above results are of great significance for the efficient utilization and sustainable development of straw waste.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107556"},"PeriodicalIF":6.2,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836942","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Integrating kinetics, thermodynamics, and compensation effects of cellulose conversion with bimetallic oxygen carriers","authors":"Zhitong Yao ,&nbsp;Jiayao Tong ,&nbsp;Chongxin Huang ,&nbsp;Sachin Kumar ,&nbsp;Shaodan Xu ,&nbsp;Huanxuan Li ,&nbsp;Haoqi Wang ,&nbsp;Yang Chen ,&nbsp;Nebojša Manić ,&nbsp;Ljiljana Medic Pejic ,&nbsp;Jie Liu ,&nbsp;Wei Qi","doi":"10.1016/j.jaap.2025.107570","DOIUrl":"10.1016/j.jaap.2025.107570","url":null,"abstract":"<div><div>The chemical looping pyrolysis (CLP) of cellulose over NiFe₂O₄ was probed to elucidate the kinetic and thermodynamic mechanisms and compensation effects. The incorporation of oxygen carrier NiFe₂O₄ induced additional decomposition peaks, indicative of altered reaction pathways. Thermogravimetric/Fourier transform infrared spectroscopy (TG-FTIR) and thermogravimetry/gas chromatography-mass spectrometry (TG-GC/MS) analyses revealed a shift in major products from <span>D</span>-glucose in cellulose to furan derivatives and acetic acid in the cellulose/NiFe₂O₄ blend, demonstrating catalytic promotion of secondary conversion pathways. Model-free kinetic analyses showed a decrease in the apparent activation energies from 147.90 kJ mol⁻¹ to 93.99 kJ mol⁻¹ . Master-plots analysis indicated the dominant R3 reaction mechanism, with deviations toward the A2 model at α&gt; 0.60. Thermodynamic parameters revealed a decrease in the enthalpy change from 142.66 kJ mol⁻¹ to 88.50 kJ mol⁻¹ and negative entropy change (−0.088 kJ mol⁻¹K⁻¹) for the blend, while Gibbs free energy change remained nearly constant (∼143.5 kJ mol⁻¹). Kinetic and enthalpy–entropy compensation effects were confirmed, with isokinetic temperatures of 596.50 K and 880.07 K for cellulose and the blend, and corresponding free energy of compensation of 143.81 and 140.05 kJ mol⁻¹ . These findings demonstrated that NiFe₂O₄ lowered energy barriers, reorganized transition states, and enhanced cellulose reactivity, providing a quantitative basis for optimizing CLP processes.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107570"},"PeriodicalIF":6.2,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837372","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}