Chemical Engineering Journal最新文献

{"title":"Critical role of RO radicals in autocatalytic decomposition of nitrate esters","authors":"Guangda Luo, Shiyao Niu, Mengqi Wu, Xiaoqing Wu, Wengang Qu, Huijun Jiang, Igor Ying Zhang, Feng Zhang","doi":"10.1016/j.cej.2025.169477","DOIUrl":"https://doi.org/10.1016/j.cej.2025.169477","url":null,"abstract":"Nitrate esters (R–ONO₂) have long served as essential constituents in solid propellants owing to their excellent energetic performance. However, their intrinsic tendency toward autocatalytic decomposition undermines storage and operational safety. Although NO₂ radicals—formed by initial RO–NO₂ bond cleavage—are acknowledged to drive low-temperature autocatalysis, the exact mechanism is disputed. Here, we integrate molecular dynamics simulations with quantum chemical calculations to elucidate the early decomposition events and key bimolecular reactions that sustain autocatalysis. We select isopropyl nitrate (iPN) and nitroglycerin (NG) as model mono- and polynitrate esters, respectively. The results indicate that, in condensed-phase thermal decomposition of iPN, RO radicals—rather than NO₂-mediated H-abstraction or acid-hydrolysis pathways—exhibit the lowest free energy barriers and greatest exothermicity. For NG, RO radicals preferentially undergo unimolecular dissociation or react with NO₂, thereby propagating radical chain pathways. These findings refine our mechanistic understanding of nitrate ester autocatalysis and highlight the hitherto underappreciated role of RO radicals. Such insights may inform the rational design of more effective stabilizers for nitrate ester-based energetic materials.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"10 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255007","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unraveling competitive cation-melamine complexation for efficient wet-process phosphoric acid purification via precipitation and gradient alkaline extraction","authors":"Jing Guo, Bing Li, Guochan Zheng, Wentao Li, Shuangli Xi, Ting Yang, Qian Zhang, Jun Du, Changyuan Tao, Zuohua Liu","doi":"10.1016/j.cej.2025.169357","DOIUrl":"https://doi.org/10.1016/j.cej.2025.169357","url":null,"abstract":"The purification of wet-process phosphoric acid (WPA) was essential for producing high-value phosphate products. Metal impurities (Fe³⁺, Al³⁺, Mg²⁺) in WPA compromised downstream processes, while conventional purification methods suffered from low phosphorus recovery efficiency, inadequate impurity removal, and generation of intractable raffinate streams. Herein, we proposed an integrated strategy combining melamine-induced precipitation with pH-gradient alkaline extraction for selective metal removal and WPA purification. Under optimal conditions (n(ME): n(P) = 1.20, 30 °C, 50 min, liquid-solid ratio = 4 mL/g), phosphate precipitation efficiency reached 90.46 %. Subsequent alkaline extraction (pH 7.8, 25 °C, 20 min) achieved 80.41 % overall phosphorus recovery, with Fe³⁺, Al³⁺, Mg²⁺ removal efficiencies of 93.74 %, 98.56 %, and 99.78 %, respectively. Density functional theory (DFT) calculations established the binding energy hierarchy (Fe³⁺ > Al³⁺ > Mg²⁺), elucidating the selective removal mechanism. Moreover, regeneration experiments demonstrated melamine's recyclability, and the short-flow design minimized waste and energy consumption. This integrated approach provides a sustainable and scalable pathway for high-purity phosphate production, enabling dual valorization of phosphorus and strategic metals from complex raffinate acids.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"20 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255008","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Humidity-compatible chemiresistive hydrogel sensor for real-time breath CO2 monitoring","authors":"Tianyi Wang, Longqi Wu, Chao Zhang, Guozhu Zhang, Yang Chen, Chengze Gao, Zeyu Wang, Yiming Wang, Yang Gao, Fuzhen Xuan","doi":"10.1016/j.cej.2025.169155","DOIUrl":"https://doi.org/10.1016/j.cej.2025.169155","url":null,"abstract":"Real-time monitoring of exhaled carbon dioxide (CO₂) is essential for assessing metabolic status and tracking disease progression. However, the high moisture content of exhaled breath poses a significant challenge to the accuracy and stability of CO₂ detection. Here, we present a flexible chemiresistive CO₂ sensor based on a dimethylamine-functionalized hydrogel, in which water molecules critically facilitate the CO₂-induced reversible protonation of tertiary amine groups, thereby modulating the hydrogel's ionic conductivity for real-time breath analysis. As a result, the hydrogel synthesized from <em>N</em>-[3-(dimethylamino) propyl] methacrylamide (DMAPMA) exhibits a high CO₂ response of 37.3 % at 10,000 ppm and a low detection limit of 100 ppm. To further enhance mechanical durability under respiratory-induced stress, <em>N</em>,<em>N</em>-Dimethylacrylamide (DMAA) was incorporated into the hydrogel, increasing the tensile strain limit from 34.2 % to 51.0 % without compromising CO₂ sensing performance. In addition, we demonstrate the integration of the hydrogel sensor into a wireless smart mask system, enabling multimodal monitoring of respiratory CO₂ patterns, physical activity, and postprandial metabolic changes. This platform offers a scalable, low-power solution for wearable CO₂ sensing in personalized health monitoring.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"8 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255066","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Marine polysaccharide-derived multifunctional Fe single-atom catalysts and temperature-tolerant gel electrolyte for sustainable hydrogen production across a wide temperature range","authors":"Chenglong Qiu, Zhaowei Ji, Zongyan Li, Chunliu Zhu, Yafei Zhang, Weiqian Tian, Jingwei Chen, Kaisheng Xia, Lei Zhang, Minghua Huang, Zhi Li, Huanlei Wang","doi":"10.1016/j.cej.2025.169499","DOIUrl":"https://doi.org/10.1016/j.cej.2025.169499","url":null,"abstract":"Advanced green hydrogen production systems typically rely on costly catalysts and face operational challenges in off-grid regions and extreme temperature environments. Herein, we propose a dual-purpose material strategy that synchronously converts marine polysaccharides into low-cost tri-functional electrocatalysts and weather-resistant gel electrolytes, enabling decarbonized hydrogen production in remote areas and under harsh temperature conditions. The constructed system demonstrated robust performance across temperatures ranging from −40 °C to 60 °C. A multiscale optimization approach modulates charge density at Fe active sites and metal-support interactions in Fe-based catalysts, achieving trifunctional activity (ORR: E_1/2 = 0.90 V; OER/HER: η = 261/172 mV@10 mA cm⁻²). Concurrently, hydrogen bond engineering transforms electrochemically inert agarose into highly compatible electrochemical interface gel electrolytes, enabling quasi-solid-state Zn-air batteries with extended operational temperature tolerance. This approach eliminates dependence on petroleum-derived materials while achieving carbon-neutral hydrogen production. Our work provides a mild, economical, and sustainable pathway for multidimensional marine biomass utilization and green hydrogen production.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"19 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255069","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A general pyrolysis strategy to construct rare-earth oxide-stabilized high-density Ru single atom catalysts for efficient thermocatalytic CO2 methanation","authors":"Yunxiang Tang, Yanan Zhang, Aihuan Sun, Hao Wang, Yawei Miao, Zhengyi Yang, Yunqian Tang, Qun Li, Shujiao Wang, Lingheng Kong, Yinfeng Han","doi":"10.1016/j.cej.2025.169471","DOIUrl":"https://doi.org/10.1016/j.cej.2025.169471","url":null,"abstract":"Single atom catalysts possess great potential for CO₂ conversion applications; however, their practical performance is often limited by low metal loadings, weak metal-support interactions and insufficient thermal stability. Herein, we propose a general pyrolysis strategy to construct high-density Ru single atom (<em>ca.</em> 5.4 wt%) on a rare earth element modified Al₂O₃ support. The as-prepared Ru_SA/Nd-Al₂O₃ exhibits superior catalytic performance, achieving a CH₄ production rate of 90.3 mmol g_cat⁻¹ h⁻¹, with a CO₂ conversion efficiency of 44.9 % and near-100 % CH₄ selectivity at 300 °C. A combination of detailed experimental characterization and density functional theory (DFT) calculations reveals the synergistic interaction between Ru single atoms and Nd modification. The presence of Nd₂O₃ not only facilitates the anchoring of high-density Ru species, thereby increasing the number of active sites, but also promotes the formation of reaction intermediates through its abundant oxygen vacancies and surface Lewis acid-base sites, ultimately leading to enhanced catalytic performance. This work elucidates the underlying interaction between single atom sites and the support, and provides a versatile strategy for constructing high-density single atom catalysts.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"31 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255113","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Na₂SO₄·10H₂O hydrogel for thermal management via synergistic phase change and evaporative cooling","authors":"Xiaopeng Liu, Yaoqi Huang, Xiaomin Cheng, Youchong Hu, Shuai Luo, Yuanyuan Li, Xusheng Xia","doi":"10.1016/j.cej.2025.169438","DOIUrl":"https://doi.org/10.1016/j.cej.2025.169438","url":null,"abstract":"With the increasing power density of integrated circuits challenging traditional passive heat dissipation, novel materials such as phase change hydrogel are often required. In this work, a biomimetic sweating phase change composite hydrogel is presented where a Co-N/O coordination structure is fabricated via the coordination reaction of CoSO₄·7H₂O and ethanolamine. The hydrated salt phase change material, Na₂SO₄·10H₂O, is embedded in a polyacrylamide matrix, and carbon nanotubes are introduced to construct a 3D thermal conduction pathway. During the phase change, Na₂SO₄·10H₂O absorbs heat and releases water for evaporative cooling. The Co-N/O structure, acting as a hygroscopic site, adsorbs ambient moisture when the system is inactive, promoting the hydration and regeneration of Na₂SO₄·10H₂O and enabling synergistic optimization. This composite hydrogel features a phase change enthalpy exceeding 130 J·g⁻¹. The addition of carbon nanotubes boosts its thermal conductivity by 107 % to 0.793 W·m⁻¹·K⁻¹. The Co-N/O structure significantly enhances its moisture absorption/desorption capabilities, with a moisture absorption rate of 4.71 g·g⁻¹ at 95 % relative humidity and a maximum water absorption rate of 2.7 g·g⁻¹·h⁻¹. At 30 % relative humidity, over 80 % of water is released within 50 min at 60 °C. In operation, it reduces the heating plate temperature by 8.6 °C and maintains a low temperature for 140 min, offering an efficient and eco - friendly solution for high - density electronic device heat dissipation.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"40 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255116","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Performance analysis of centrifugal compressors in supercritical CO₂ Brayton cycles considering non-equilibrium condensation","authors":"Hongbing Ding, Panpan Zhang, Shiwei Wang, Chuang Wen","doi":"10.1016/j.cej.2025.169521","DOIUrl":"https://doi.org/10.1016/j.cej.2025.169521","url":null,"abstract":"Energy storage technologies play a critical role in balancing energy supply and demand, as well as facilitating large-scale integration of renewable energy sources. The supercritical carbon dioxide (sCO₂) Brayton cycle, known for its high efficiency and compact design, is widely regarded as an ideal solution for large-scale energy storage. However, the dramatic variation in sCO₂ thermodynamic properties near the critical point can induce condensation within compressors, adversely affecting system performance and stability. To address this challenge, this paper presents a novel condensation flow model that integrates the entropy transport equation with real gas thermodynamics, enabling precise prediction of condensation behavior and its impact on compressor performance. The results show that when the inlet temperature decreases from 320 K to 310 K, condensation is significantly intensified, with phase-change entropy generation increasing by 9.16 times and heat transfer entropy generation increasing by 47.2 %, resulting in greater exergy destruction and reduced efficiency. Compared to conventional dry gas models, the proposed model provides a more accurate assessment of compressor efficiency, avoiding overestimation errors of up to 11.6 %. This theoretical tool offers the scientific community a new approach for in-depth analysis of condensation phenomena within compressors, supporting the optimization of sCO₂ energy storage system design, enhancing system stability and efficiency, and addressing engineering challenges such as blade corrosion.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"121 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145261472","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Non-linear dynamics of fluidized beds: Insights from coupled CFD-DEM simulations","authors":"Subi Nath, Shantanu Roy","doi":"10.1016/j.cej.2025.169452","DOIUrl":"https://doi.org/10.1016/j.cej.2025.169452","url":null,"abstract":"Accurately capturing the highly nonlinear gas-solid interactions within fluidized beds remains a formidable challenge, critically hindering their robust design and optimization for industrial applications. Conventional numerical characterization methods often focus only on time-averaged data, failing to resolve the inherent dynamic complexities governing these systems. This study proposes an integrated approach, combining Computational Fluid Dynamics - Discrete Element Method (CFD-DEM) simulations with advanced nonlinear dynamics analysis, to comprehensively elucidate the true dynamic characteristics of both monodisperse and polydisperse gas-solid fluidized beds.We systematically investigated dynamic pressure and solids distribution fluctuations extracted from high-fidelity CFD-DEM simulations across varying superficial gas velocities, compositional variations, probe positions, and aspect ratios. Employing tools from nonlinear dynamics theory, this analysis rigorously unveiled the intrinsic nonlinearity of fluidized beds, confirming their profound sensitivity to initial conditions and complex, unpredictable behavior. Specifically, Kolmogorov Entropy, quantifying information loss and system unpredictability, and Correlation Dimension, measuring system complexity and degrees of freedom, were precisely quantified. These robust metrics provided unprecedented, nuanced insights into fluidization regime transitions, the critical influence of polydispersity on dynamic behavior, the intricate dynamics of bubble formation and interaction, and the precise identification of highly chaotic regions within the bed.This study significantly advances the understanding of fluidized bed dynamic characteristics by introducing a robust methodology that transcends conventional reliance on averaged properties. The integration of CFD–DEM with nonlinear dynamics analysis demonstrates high efficacy, yielding robust, data-driven insights crucial for optimizing reactor design and enhancing operational control. Furthermore, by successfully capturing dynamic profiles, this combined approach establishes a strong foundation for rigorous investigations into the scale-up of fluidized bed reactors, delineating a clear trajectory for future research.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"114 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255064","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Critical role of dissolved and particulate phosphorus in controlling the fate of polystyrene nanoplastics in porous media","authors":"Linqing Liu, Pingxiao Wu, Jiayan Wu, Tianming Wang, Leiye Sun, Bo Li, Jieyu Liu, Sheng Liu, Kaiyuan Ma, Quanyun Ye, Nengwu Zhu, Zhi Dang","doi":"10.1016/j.cej.2025.169356","DOIUrl":"https://doi.org/10.1016/j.cej.2025.169356","url":null,"abstract":"The different forms of phosphorus (P) (dissolved P (inorganic P (orthophosphate, PO₄) and organic P (phytic acid, PA)) and particulate P (nanohydroxyapatite, nHAP)) influenced the transport and fate of nanoplastics. This study investigates the fate of polystyrene nanoplastics (PS) in porous media under the individual and combined effects of different forms of P. It was shown that under the effect of different P forms, the migration rate of PS was: PS-PA + nHAP &gt; PS-PA &gt; PS-PO₄ &gt; PS &gt; PS-PO₄ + nHAP &gt; PS-nHAP, which indicated that PO₄ alleviated the inhibitory effect of nHAP on the transport of PS, while coexistence of PA and nHAP produced significant synergistic facilitation effect on the transport of PS. The results of various characterization techniques, classical or extended Derjaguinee-Landauee-Verweyee-Overbeek (DLVO/EDLVO) theory, and density function theory (DFT) calculations revealed that the adsorption of PO₄ increased the negative electronegativity of the heterogeneous aggregates of PS and nHAP, alleviating the inhibitory effect of nHAP on the transport of PS by enhancing electrostatic repulsion. And PA was adsorbed on the surfaces of nHAP and PS, respectively, increasing the electrostatic interaction and steric effect between PS and the media, which synergistically promoted the transport of PS. Among them, the steric effect between PS and nHAP after adsorption of PA was the main factor for synergistic promoted PS transport. This study provides theoretical support for the development of predictive models for nanoplastic transport in phosphorus-rich environments and risk management strategies.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"66 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255117","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Progress on electrochemical preparation of inorganic materials in deep eutectic solvents-mediated organic electrolytes","authors":"Haiyang Jia, Fen Zhang, Jiawei Sun, Fali Chong","doi":"10.1016/j.cej.2025.169516","DOIUrl":"https://doi.org/10.1016/j.cej.2025.169516","url":null,"abstract":"Excellent electrical conductivity, wide potential windows, high solubility, and low vapor pressure are typical of deep eutectic solvents, which endow these newly emerging solvents with significant advantages in electrochemical preparation. Deep eutectic solvents have proven effective for the electrochemical preparation of inorganic materials, either as complete electrolytes or as conductive mediators in electrolyte systems. The related technical route comprises electrodeposition, electro-exfoliation, and electrolytic redox, and the resultant materials have demonstrated impressive functional enhancements. This review begins with a concise overview of compositions, characteristics, and applications of the deep eutectic solvents. Whereafter, progress in electrochemically preparing inorganic materials in deep eutectic solvents-mediated organic electrolytes is retrospectively emphasized. The deep eutectic solvents discussed are limited to those derived from choline quaternary ammonium salts, especially Reline, Ethaline, and Glyceline. The synthesis includes electrodeposition to synthesize elementary substances, bimetallic alloys, trimetallic alloys, and metal-nonmetal compounds. The electrochemical process involves electro-exfoliation to produce two-dimensional materials, exemplified by graphene. The preparation also covers the electrolysis to prepare metallic oxides. Finally, the electrolytic preparation of functional inorganic materials in deep eutectic solvent-mediated organic electrolytes, based on two-electrode systems, is discussed and envisioned.","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"338 1","pages":""},"PeriodicalIF":15.1,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}