Journal of Analytical and Applied Pyrolysis最新文献

{"title":"Products characteristics and pyrolysis mechanism of oil shale via sub-critical FeCl₃ solution extraction with glycerol/methanol as hydrogen donor","authors":"Huafei Fu ,&nbsp;Sunhua Deng ,&nbsp;Huilin Cao ,&nbsp;Weidong Tang ,&nbsp;Xuanming Zhang ,&nbsp;Yonghong Sun ,&nbsp;Wei Guo","doi":"10.1016/j.jaap.2025.107564","DOIUrl":"10.1016/j.jaap.2025.107564","url":null,"abstract":"<div><div>This study investigated the extraction performance, product characteristics, and pyrolysis mechanism of oil shale treated in a sub-critical FeCl₃ solution containing glycerol or methanol. The extraction process was divided into Stage I, corresponding to initial pyrolysis of immature kerogen, and Stage II, corresponding to subsequent kerogen pyrolysis. Experimental results indicate that glycerol's hydrogen-donating effect diminishes after Stage I, whereas methanol enhances hydrogen-donating effect beyond Stage I, even inducing a third stage of kerogen pyrolysis (Stage III). Addition of glycerol during the initial phase of Stage I resulted in an approximately 90 % increase in shale oil yield, whereas methanol raised the maximum shale oil yield by approximately 30 %. In Stage I, glycerol effectively inhibits Fe³ ⁺ complexation with polar organic compounds, while methanol exhibits this effect mainly in Stages II and III. During the initial pyrolysis of immature kerogen, glycerol promotes the secondary pyrolysis of preasphaltene to generate additional maltenes, which act as solvents to depolymerize residual bitumen and thereby enhance their migration. Both additives facilitate hydrogenation of alkenes to alkanes. In Stage II, glycerol continues to favor the formation of naphthalene and alkylbenzene, whereas methanol markedly accelerates kerogen pyrolysis and promotes alkylbenzene formation, with subsequent Stage III yielding additional naphthalenes. These results provide a reference for optimizing the in-situ exploitation of oil shale via sub-critical water extraction technology.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107564"},"PeriodicalIF":6.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787397","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":"2026-03-01","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":"Hierarchical porous self-supporting carbon modified with carbon nanospheres for high-performance supercapacitors","authors":"Kaiming Dong ,&nbsp;Zhenjie Sun ,&nbsp;Chen Yang ,&nbsp;Ge Jing ,&nbsp;Zhenming Li ,&nbsp;Jialong Chen ,&nbsp;Mingjie Xiong ,&nbsp;Hui Li ,&nbsp;Yunpu Wang ,&nbsp;Feiqiang Guo","doi":"10.1016/j.jaap.2025.107545","DOIUrl":"10.1016/j.jaap.2025.107545","url":null,"abstract":"<div><div>Carbon-based electrode materials with controllable microstructure and rationalized pore distribution are the key to improve the transport and diffusion efficiency of electrolyte ions. In this paper, a new process of carbon nanosphere deposition integrating hydrothermal carbonization and thermochemical conversion was developed using natural porous pine as precursor, and a carbon nano-sphere modified porous capacitive carbon material (CW-H-6) without conductive agent and binder was successfully prepared. The surface and channel walls of CW-H-6 are uniformly modified with carbon nanospheres with a diameter of about 200–300 nm, forming a hierarchical pore structure of microporous-mesoporous-macroporous multi-stage synergy, which substantially enhances both volumetric efficiency and electrochemical storage capability of self-supporting capacitive carbon. CW-H-6 demonstrates an areal specific capacitance of 6.36 F cm⁻² at a current density of 2 mA cm⁻², which is 66.4 % higher than the self-supporting capacitive carbon of unmodified carbon nanospheres. A symmetric supercapacitor was constructed based on the CW-H-6 electrodes, which exhibited an energy density of 236.10 μWh cm⁻² at a power density of 1 mW cm⁻². Furthermore, the symmetric supercapacitor demonstrates exceptional cycling durability, retaining 107.3 % of its original capacitance after 8000 consecutive charge-discharge cycles.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107545"},"PeriodicalIF":6.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787384","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":"Microwave-assisted catalytic pyrolysis of waste cooking oil into hydrocarbon-rich bio-oil: Optimization of dual-stage catalysis and techno-economic assessment","authors":"Qiuhao Wu ,&nbsp;Anqi Dai ,&nbsp;Tianyu Wang ,&nbsp;Linyao Ke ,&nbsp;Liangliang Fan ,&nbsp;Hui Li ,&nbsp;Roger Ruan ,&nbsp;Yunpu Wang","doi":"10.1016/j.jaap.2026.107604","DOIUrl":"10.1016/j.jaap.2026.107604","url":null,"abstract":"<div><div>This study addresses the need for sustainable waste cooking oil valorization by developing a continuous catalytic pyrolysis system to produce hydrocarbon-rich bio-oil. The research focuses on optimizing both the pyrolysis process and catalytic upgrading to maximize bio-oil yield and hydrocarbon content while ensuring process stability. The pyrolysis system demonstrated excellent thermal stability across the pyrolysis process at all bed heights, with a maximum heating rate of 224.0 °C/min. The maximum catalytic bed heating rate was 322.5 °C/min. Temperature overshooting was observed when the CaMg-to-CS ratio reached 1.4 mol/20 g. Average bio-oil yield reached its peak yield of 63.23 wt% at a CaMg-to-CS ratio of 1.0 mol/20 g. Significantly, the hydrocarbon content in bio-oil peaked at 91.37 % when using a ratio of 0.6 mol/20 g. Comparative analysis revealed distinct performance characteristics between single-stage and dual-stage catalysis. While HZSM-5-CS single-stage catalysis showed higher initial activity, but the catalyst deactivated more quickly. In contrast, the dual-stage catalysis demonstrated superior initial activity and more stable catalytic performance. Catalyst characterization showed that the dual-stage catalysis helps mitigate coke-induced deactivation of the HZSM-5-CS catalyst. Microwave radiation had a positive effect on promoting deoxygenation of pyrolysis vapors and aromatization. Catalyst characterization showed that microwave radiation slowed the deactivation of the catalytic bed by reducing coke deposition. Aspen Plus simulate results showed that producing hydrocarbon-rich bio-oil through catalytic pyrolysis of waste cooking oil, especially bio-oil with high benzene, toluene, and xylene content and low oxygen-containing compounds content, is economically feasible.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107604"},"PeriodicalIF":6.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145921191","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":"Furans-enriched biofuel and NH3-rich gas from catalytic fast pyrolysis of tobacco biomass over metal-organic framework materials catalyst","authors":"Ning Shao ,&nbsp;Siyang Liu ,&nbsp;Shuo Song ,&nbsp;Shaolin Ge ,&nbsp;Xiaolan Zhu","doi":"10.1016/j.jaap.2025.107571","DOIUrl":"10.1016/j.jaap.2025.107571","url":null,"abstract":"<div><div>Catalytic pyrolysis offers a viable approach to harness the potential of renewable carbon feedstocks for the production of valuable products like biofuels and chemicals. In this study, three metal-organic framework (MOF) derived catalysts (Zn/MOF, Ce/MOF, and Ca/MOF) were successfully synthesized via modified methods, and their effects on regulating the three-phase distribution of tobacco biomass pyrolysis products were systematically investigated. FTIR analysis showed that all three MOF catalysts promoted the yield of gas phase products and Ce/MOF, Zn/MOF, and Ca/MOF increased the release of NH₃ by 80.6, 194.0, and 90.6 % respectively. The GC-MS analysis of catalytic pyrolysis showed that all three MOF catalysts decreased the yield of nitrogen heterocycles, with the Ce/MOF catalyst exhibiting the highest yields of furans in the liquid phase products. Compared to the control group, the furans content in the tobacco stem pyrolysis products increased by approximately 82 %, with the yield of 5-methylfurfural particularly rising by 240 % under Ce/MOF pyrolysis conditions optimized using response surface methodology. The Ce/MOF derived catalysts presented the favorable synergistic catalysis effect of dual functional acidic sites for the cleavage of the C-O bond to selectively generate furans. This study revealed the potential of metal-based MOF-derived catalysts for the targeted synthesis of oxygen-containing high-value chemicals during the pyrolysis of tobacco biomass.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107571"},"PeriodicalIF":6.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145837370","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":"2026-03-01","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":"Unraveling the oxygen-dependent combustion mechanisms of polycarbonate by molecular dynamic simulation","authors":"Zheqing Sang,&nbsp;Yongqing Wan,&nbsp;Ting Zhang,&nbsp;Mengxi Yuan,&nbsp;Mengyan Zhao,&nbsp;Zhuiyue Guo,&nbsp;Qingqing Zheng,&nbsp;Yaxing Li,&nbsp;Yanhua Lan","doi":"10.1016/j.jaap.2025.107578","DOIUrl":"10.1016/j.jaap.2025.107578","url":null,"abstract":"<div><div>Polycarbonate (PC) exhibits flammability that is prone to fire hazards during production and application, making its combustion process crucial for fire prevention and personnel protection. Reactive forcefield simulations were utilized to reveal the mechanism governing PC combustion under variable oxygen concentrations (oxygen-lean, stoichiometry, and oxygen-rich) at the microscopic level. The effects of temperature and oxygen concentration on the combustion process and the distribution of the main products of PC were investigated. The final combustion products are mainly H₂O, CO₂, and CO. The generation of CO₂ includes the oxidation or dehydrogenation reaction of carboxylic acid. The formation of CO mainly depends on the breaking of C-C bonds in small molecules, such as ·C₂O₃ and ·C₂O₂. The generated mechanism of H₂O mainly relies on the ·OH capturing the ·H from other groups. During the simulation, the PC chains undergo pyrolysis followed by combustion reactions, and the process is affected by oxygen concentration. The initial reactions of PC chains are mainly pyrolysis reactions under oxygen-lean conditions, and combustion reactions dominate under stoichiometric and oxygen-rich conditions. As the temperature and oxygen concentration rose, they significantly accelerated the combustion reaction rate of PC and also played a key role in regulating the product distribution. They were beneficial to the decomposition of macromolecules (C₄₀₊) into intermediate products (C_14–40 and C_5–13) and finally into small molecular gas products (C_0–4). Rising oxygen concentration also promoted the conversion process from C-C bonds to C-O bonds. The findings could provide some guidance to selectively regulate the combustion process of the PC composites.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107578"},"PeriodicalIF":6.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880256","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":"Regulation of oil yield and composition analysis from co-hydrothermal liquefaction of Chlorella and oil shale","authors":"Xianglong Meng ,&nbsp;Jingjing Li ,&nbsp;Xiaoli Wang ,&nbsp;Chuandong Li ,&nbsp;Guizhong Deng ,&nbsp;Xiaodong Tang","doi":"10.1016/j.jaap.2025.107583","DOIUrl":"10.1016/j.jaap.2025.107583","url":null,"abstract":"<div><div>The co-hydrothermal liquefaction process of Chlorella and oil shale under subcritical water conditions was investigated. Reaction parameters such as temperature and residence time were optimized, with the highest oil yield obtained at 300 ℃ for 30 min. When the proportion of Chlorella was 50 % or more, a synergistic effect was observed, most notably at 75 %. The addition of metal oxide catalysts promoted hydrodeoxygenation, increasing hydrocarbon content, reducing oxygenated compounds, and improving both the hydrogen-to-carbon and oxygen-to-carbon ratios. The heating value of the oil products was within the typical range for biodiesel. Among all catalysts tested, CeO₂ showed the best performance by increasing hydrocarbon content by 24.73 %, raising the heating value to 36.09 MJ/kg, achieving 74.73 % energy recovery efficiency, and reducing the proportion of heavy oil and residue to 30.66 %.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107583"},"PeriodicalIF":6.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880259","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":"Waste valorization through synergistic co-pyrolysis of cashew nut shell and HDPE for enhanced liquid fuel production","authors":"Hyeong-jin Kim ,&nbsp;Jong-su Kim ,&nbsp;Su-hyeon Choi ,&nbsp;Sungyeon Heo ,&nbsp;Soo-hwa Jeong","doi":"10.1016/j.jaap.2025.107593","DOIUrl":"10.1016/j.jaap.2025.107593","url":null,"abstract":"<div><div>Co–pyrolysis of cashew nut shell (CNS) and high–density polyethylene (HDPE) waste was conducted in a fixed-bed pyrolysis system. The aim of the study is to produce fuel oil from CNS and to evaluate the synergistic effect between CNS and HDPE during pyrolysis. Co-pyrolysis with a 1:1 (wt./wt.) mixing ratio unexpectedly resulted in a liquid yield of 43.6 wt%, which is lower than the calculated value of 50.6 wt%. In addition, the liquid product consisted exclusively of wax. To enhance the synergistic effect, catalytic co-pyrolysis was conducted using HZSM-5 at catalyst bed temperatures of 510, 610, and 710 °C. The results indicated that the viscous-phase fraction constituted 53 wt% of the pyrolysis oil, and the oxygen content of the oil was 5.8 wt%, representing the lowest value among all runs conducted at a catalyst bed temperature of 610 °C. Furthermore, cashew nut shell liquid (CNSL), which is known to influence the viscous oil yield in previous studies, was investigated to clarify its effect during decomposition. Acetone–pretreated CNS with partially removed CNSL was pyrolyzed, as well as on the two-stage co-pyrolysis of CNS and HDPE. In the acetone-pretreated CNS, the viscous oil fraction accounted for 3 wt%, whereas the aqueous oil fraction accounted for 97 wt%. The characteristics of the viscous oils were quantitatively analyzed using GC-MS analysis. The results revealed that 3-methylphenol decreased from 13.1 wt% to 1.2 wt% in the viscous oil after CNSL removal. This implies that CNSL contributes to the viscous oil yield during CNS pyrolysis because of its chemical structure.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107593"},"PeriodicalIF":6.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920679","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":"Plasma-catalytic methane decomposition: Radical-mediated pathways and controlled CNTs growth over plasma-modified Fe catalyst","authors":"Shizhang Wang,&nbsp;Shaozeng Sun,&nbsp;Dongdong Feng,&nbsp;Jipeng Chen,&nbsp;Guanwei Wang,&nbsp;Qi Shang,&nbsp;Yijun Zhao,&nbsp;Yu Zhang","doi":"10.1016/j.jaap.2025.107591","DOIUrl":"10.1016/j.jaap.2025.107591","url":null,"abstract":"<div><div>Methane decomposition is increasingly recognized as pivotal technology for simultaneous production of H₂ and carbon nanomaterials, yet its industrial implementation is severely constrained by high operating temperatures and rapid deactivation to thermal catalytic systems. By integrating in-situ optical emission spectroscopy with multi-scale characterization, it is demonstrated that plasma serves a four-fold function in the Fe-based catalytic system: (1) excitation of CH₄ into a controllable radical pool, (2) enhancement of radical adsorption energy on Fe surfaces through plasma-induced electronic polarization, (3) implementation of a hydrogen-mediated \"pathway pruning\" mechanism wherein H* abstracts H from CH_x* species, preventing gas-phase polymerization while simultaneously accelerating surface-catalyzed carbon assembly, and (4) in-situ etching of amorphous carbon and promotion of surface hydrogen-assisted dehydrogenation on M-H sites. These coupled mechanisms synergistically suppress electrode carbon deposition, enabling sustained discharge stability and maintaining the plasma discharge in high-efficiency tip-discharge regime. Consequently, at 700 °C, the plasma-catalytic system achieves methane conversion of 42.67 % (compared to 25 % in pure plasma at 700 °C, and 19.25 % in pure thermal catalytic at 750 °C), hydrogen selectivity of 57.88 %, carbon yield of 105 mg·g_cat⁻¹·h⁻¹, and uniform CNTs with enhanced graphitization. This work provides a quantitative mechanistic blueprint for designing next-generation plasma-catalytic systems that overcome the limitations of conventional thermal processes.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107591"},"PeriodicalIF":6.2,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920680","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}