Chemical Engineering Science最新文献_第7页

Kinetic insights into process optimization of peracetic acid oxidative degradation of cured epoxy resins 过氧乙酸氧化降解固化环氧树脂工艺优化动力学研究

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-01-26 DOI: 10.1016/j.ces.2026.123453

Xiao-Sa Liu , Qi Zeng , Zi-Bin Huang , Zhan-Quan Zhang , Pei-Qing Yuan

To address the challenge of green recycling of carbon-fiber-reinforced polymer composites (CFRPs) imposed by highly crosslinked epoxy matrices, this study investigates peracetic-acid (PAA) oxidative degradation of a cured epoxy resin (cEP) based on diglycidyl ether of bisphenol A cured with 4,4′-diaminodiphenylmethane. Under representative conditions, PAA removes 99.8% of the epoxy matrix from CFRP laminates while retaining about 95% of the original single-filament tensile strength. To elucidate the controlling mechanisms and enable process optimization, a factorial evaluation of stirring speed, solid–liquid ratio, and temperature was performed using cEP particles as a model system. Guided by the experimentally observed “swollen reactive shell–unreacted core” morphology, a coupled swelling–intraparticle diffusion–chemical reaction–oxidant self-decay kinetic model was developed to quantitatively predict both cEP degradation and the time evolution of liquid-phase PAA concentration. Parameter estimation yields an apparent activation energy of 148.92 kJ·mol⁻¹ for PAA-driven cEP oxidation. Although increasing temperature accelerates degradation, it also intensifies oxidant self-decay and non-productive oxidation of liquid-phase intermediates. Model-guided operation shows that stepwise PAA feeding can suppress non-target consumption and improve terminal conversion. At 353 K, using only 1.025 times the theoretical PAA requirement, stepwise feeding raises the resin degradation degree from 0.93 (single-shot) to 0.99 within 3 h, thereby minimizing oxidant cost. The demonstrated laminate-scale feasibility, together with the particle-scale kinetic framework, provides a quantitative basis for designing PAA-based CFRP recycling processes that balance resin removal, fiber integrity, and oxidant efficiency.

为了解决高交联环氧树脂基体对碳纤维增强聚合物复合材料（CFRPs）绿色回收的挑战，本研究研究了4,4 ' -二氨基二苯甲烷固化的双酚a二甘油酯固化环氧树脂（cEP）的过乙酸（PAA）氧化降解。在具有代表性的条件下，PAA从CFRP层压板中去除99.8%的环氧基，同时保留约95%的原始单丝拉伸强度。为了阐明控制机理并实现工艺优化，以cEP颗粒为模型系统，对搅拌速度、料液比和温度进行了析因评价。以实验观察到的“膨胀反应壳-未反应核”形态为指导，建立了膨胀-颗粒内扩散-化学反应-氧化剂自衰减耦合动力学模型，定量预测了cEP降解和液相PAA浓度的时间演变。参数估计表明paa驱动cEP氧化的表观活化能为148.92 kJ·mol−1。虽然温度升高加速了降解，但也加剧了氧化剂的自腐和液相中间体的非生产性氧化。模型引导运算表明，PAA分步进料可以抑制非目标消耗，提高终端转化率。在353 K时，仅使用理论PAA用量的1.025倍，逐步加料在3 h内将树脂降解度从0.93（单次）提高到0.99，从而最大限度地降低了氧化剂成本。所证明的层压尺度可行性，以及颗粒尺度的动力学框架，为设计基于paa的CFRP回收工艺提供了定量基础，以平衡树脂去除，纤维完整性和氧化剂效率。

{"title":"Kinetic insights into process optimization of peracetic acid oxidative degradation of cured epoxy resins","authors":"Xiao-Sa Liu , Qi Zeng , Zi-Bin Huang , Zhan-Quan Zhang , Pei-Qing Yuan","doi":"10.1016/j.ces.2026.123453","DOIUrl":"10.1016/j.ces.2026.123453","url":null,"abstract":"<div><div>To address the challenge of green recycling of carbon-fiber-reinforced polymer composites (CFRPs) imposed by highly crosslinked epoxy matrices, this study investigates peracetic-acid (PAA) oxidative degradation of a cured epoxy resin (cEP) based on diglycidyl ether of bisphenol A cured with 4,4′-diaminodiphenylmethane. Under representative conditions, PAA removes 99.8% of the epoxy matrix from CFRP laminates while retaining about 95% of the original single-filament tensile strength. To elucidate the controlling mechanisms and enable process optimization, a factorial evaluation of stirring speed, solid–liquid ratio, and temperature was performed using cEP particles as a model system. Guided by the experimentally observed “swollen reactive shell–unreacted core” morphology, a coupled swelling–intraparticle diffusion–chemical reaction–oxidant self-decay kinetic model was developed to quantitatively predict both cEP degradation and the time evolution of liquid-phase PAA concentration. Parameter estimation yields an apparent activation energy of 148.92 kJ·mol<sup>−1</sup> for PAA-driven cEP oxidation. Although increasing temperature accelerates degradation, it also intensifies oxidant self-decay and non-productive oxidation of liquid-phase intermediates. Model-guided operation shows that stepwise PAA feeding can suppress non-target consumption and improve terminal conversion. At 353 K, using only 1.025 times the theoretical PAA requirement, stepwise feeding raises the resin degradation degree from 0.93 (single-shot) to 0.99 within 3 h, thereby minimizing oxidant cost. The demonstrated laminate-scale feasibility, together with the particle-scale kinetic framework, provides a quantitative basis for designing PAA-based CFRP recycling processes that balance resin removal, fiber integrity, and oxidant efficiency.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"325 ","pages":"Article 123453"},"PeriodicalIF":4.3,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

From dispersion to powder: Monitoring PMMA latex coagulation with Photon density Wave Spectroscopy (PDWS) 从分散到粉末：用光子密度波光谱（PDWS）监测PMMA乳胶凝固

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-01-26 DOI: 10.1016/j.ces.2026.123450

Sara González-González, Miren Aguirre

This study explores the use of Photon Density Wave Spectroscopy (PDWS) as an in-line technique to monitor coagulation experiments of polymethyl methacrylate (PMMA) latexes. The coagulation process was induced by the addition of monovalent (NaCl) and divalent (CaCl₂) salts under varying conditions of temperature and salt addition speed. PDWS effectively tracked the evolution of the reduced scattering coefficient, enabling real-time detection of coagulation. The results were validated against conventional off-line techniques such as laser diffraction (Mastersizer) and Scanning Electron Microscopy (SEM). The study demonstrates that PDWS can accurately detect early coagulation events, although limitations exist in calculating the average particle size of the aggregates. The influence of temperature, salt type, and salt addition rate on particle size, morphology, and bulk density was systematically analysed, offering insights into optimizing coagulation processes for industrial applications.

本研究探讨了利用光子密度波光谱（PDWS）作为在线技术监测聚甲基丙烯酸甲酯（PMMA）乳液的混凝实验。在不同的温度和加盐速度条件下，一价盐（NaCl）和二价盐（CaCl2）的加入诱导了混凝过程。PDWS有效地跟踪了降低的散射系数的演变，实现了凝血的实时检测。结果通过传统的离线技术，如激光衍射（母粒机）和扫描电子显微镜（SEM）进行了验证。该研究表明，PDWS可以准确地检测早期凝血事件，尽管在计算聚集体的平均粒径方面存在局限性。系统分析了温度、盐类型和盐添加速率对颗粒大小、形态和堆积密度的影响，为优化工业应用的混凝工艺提供了见解。

引用次数: 0

Synergistic effects of hydrogen spillover and oxygen vacancies on efficient CO2 methanation over Fe–Co alloy catalyst 氢溢出和氧空位对Fe-Co合金催化剂上CO2高效甲烷化的协同效应

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-01-26 DOI: 10.1016/j.ces.2026.123454

Zekai Liu , Xiaolin Pi , Gege Wang , Peng Du , Linfeng Zhang , Jia Guo , Huadong Wu

The massive emission of CO₂ poses a huge challenge to global environmental protection. Both oxygen vacancies (OVs) and hydrogen spillover effect are critical to CO₂ hydrogenation, but their synergistic mechanism over transition metal alloys remains insufficiently explored. In this work, a facile one-pot liquid-phase reduction method for synthesizing Fe–Co alloy catalysts with tunable Fe/Co ratios (7:1–1:13) without pre-activation, avoiding rare metals to realize cost advantage. The physico-chemical properties of catalysts were systematically characterized by XRD, XPS, SEM/TEM, BET, EPR, H₂-TPR, CO₂-TPD, in-situ DRIFTS. It was found that Fe incorporation promotes OV formation by inducing surface oxidation, while Co enrichment enhances hydrogen spillover via increased exposed metallic Co sites. The optimal Fe₁Co₉ catalyst exhibits superior performance: >99% CH₄ selectivity, and a CH₄ space–time yield of 57.9 mmol·g_cat⁻¹·h⁻¹ at 280 ℃ and 6.0 MPa, meanwhile Fe₁Co₉ favors the direct *CO-mediated pathway (CO₂ → *CO→ *CH → CH₄) instead of the formate pathway, with *CO as the key intermediate. DFT calculations further confirm that Fe₁Co₉ has a CO₂ adsorption energy of 1.68 eV, and a low Gibbs free energy difference (ΔG) of 0.95 eV for the rate-limiting step (*CH → *CH₂). This work innovatively realizes the synergistic regulation of OVs and hydrogen spillover via Fe/Co ratio tuning, providing a new strategy for constructing low-cost, high-performance transition metal alloy catalysts.

二氧化碳的大量排放给全球环境保护带来了巨大挑战。氧空位（OVs）和氢溢出效应都是CO2加氢的关键因素，但它们在过渡金属合金中的协同作用机制尚未得到充分探讨。本研究采用简单的一锅液相还原法合成Fe/Co比可调（7:1 ~ 1:13）的Fe - Co合金催化剂，无需预活化，避免使用稀有金属，实现成本优势。采用XRD、XPS、SEM/TEM、BET、EPR、H2-TPR、CO2-TPD、原位漂移等方法对催化剂的理化性质进行了系统表征。研究发现，Fe的掺入通过诱导表面氧化促进OV的形成，而Co的富集通过增加暴露的金属Co位促进氢的溢出。优化后的Fe1Co9催化剂表现出优异的CH4选择性：>；99%，在280℃、6.0 MPa条件下，CH4时空产率为57.9 mmol·gcat−1·h−1，且Fe1Co9更倾向于以*CO为关键中间体的*CO直接介导途径（CO2→*CO→*CH → CH4），而不是甲酸途径。DFT计算进一步证实，Fe1Co9对CO2的吸附能为1.68 eV，在*CH→*CH2这一限制反应步骤中，其Gibbs自由能差（ΔG）为0.95 eV。本研究创新性地实现了Fe/Co比调控对OVs和氢溢出的协同调控，为构建低成本、高性能的过渡金属合金催化剂提供了新思路。

{"title":"Synergistic effects of hydrogen spillover and oxygen vacancies on efficient CO2 methanation over Fe–Co alloy catalyst","authors":"Zekai Liu , Xiaolin Pi , Gege Wang , Peng Du , Linfeng Zhang , Jia Guo , Huadong Wu","doi":"10.1016/j.ces.2026.123454","DOIUrl":"10.1016/j.ces.2026.123454","url":null,"abstract":"<div><div>The massive emission of CO<sub>2</sub> poses a huge challenge to global environmental protection. Both oxygen vacancies (OVs) and hydrogen spillover effect are critical to CO<sub>2</sub> hydrogenation, but their synergistic mechanism over transition metal alloys remains insufficiently explored. In this work, a facile one-pot liquid-phase reduction method for synthesizing Fe–Co alloy catalysts with tunable Fe/Co ratios (7:1–1:13) without pre-activation, avoiding rare metals to realize cost advantage. The physico-chemical properties of catalysts were systematically characterized by XRD, XPS, SEM/TEM, BET, EPR, H<sub>2</sub>-TPR, CO<sub>2</sub>-TPD, in-situ DRIFTS. It was found that Fe incorporation promotes OV formation by inducing surface oxidation, while Co enrichment enhances hydrogen spillover via increased exposed metallic Co sites. The optimal Fe<sub>1</sub>Co<sub>9</sub> catalyst exhibits superior performance: >99% CH<sub>4</sub> selectivity, and a CH<sub>4</sub> space–time yield of 57.9 mmol·g<sub>cat</sub><sup>−1</sup>·h<sup>−1</sup> at 280 ℃ and 6.0 MPa, meanwhile Fe<sub>1</sub>Co<sub>9</sub> favors the direct *CO-mediated pathway (CO<sub>2</sub> → *CO→ *CH → CH<sub>4</sub>) instead of the formate pathway, with *CO as the key intermediate. DFT calculations further confirm that Fe<sub>1</sub>Co<sub>9</sub> has a CO<sub>2</sub> adsorption energy of 1.68 eV, and a low Gibbs free energy difference (ΔG) of 0.95 eV for the rate-limiting step (*CH → *CH<sub>2</sub>). This work innovatively realizes the synergistic regulation of OVs and hydrogen spillover via Fe/Co ratio tuning, providing a new strategy for constructing low-cost, high-performance transition metal alloy catalysts.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"325 ","pages":"Article 123454"},"PeriodicalIF":4.3,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044724","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mechanistic insights into morphological control of energetic cocrystals: Critical factors and underlying mechanisms in CL-20/HMX systems 高能共晶形态控制的机理：CL-20/HMX系统中的关键因素和潜在机制

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-01-26 DOI: 10.1016/j.ces.2026.123448

Shifan Xu , Hongtu Zhao , Hui Wang , Wenbo Wu , Na Wang , Ting Wang , Xin Huang , Hongxun Hao

Crystal morphology manipulation and prediction of energetic materials is essential for their production and application, as it profoundly influences performance of weapons. This study focuses on investigating the factors and mechanisms influencing the energetic cocrystals morphology using CL-20/HMX cocrystal as model compound, by combining statistical and molecular simulation methods. The molecular simulation results demonstrate that the morphologically predominant (1 0 0) crystal facet exhibits relatively low competitive adsorption for solvents, mainly caused by the distinct behavior of hydrogen atoms contributing to the differential adsorption capabilities of various solvents on the facet. Furthermore, Spearman correlation coefficient was used to assess the effects of factors on the morphology, such as the Hansen solubility parameters, molecular polarity index (MPI), Flory-Huggins interaction parameters, and various DFT descriptors. The results indicate that the MPI of solvent plays a crucial role in determining the CL-20/HMX cocrystal morphology. Notably, the MPI value (0.72 < r < 0.87) emerges as a powerful predictive parameter for evaluating the solvent’s influence on crystal morphology, outperforming the widely used Hansen solubility parameters (0.68 < r < 0.81). Moreover, experimental results confirmed the validation of the prediction. This work offers both theoretical support and practical guidance for the crystal engineering of energetic materials, contributing to the improvement of intelligent design of crystallization processes.

含能材料的晶体形态控制和预测对其生产和应用至关重要，因为它深刻影响着武器的性能。本研究以CL-20/HMX共晶为模型化合物，采用统计和分子模拟相结合的方法，重点研究影响含能共晶形态的因素和机理。分子模拟结果表明，形态学上占优势的（1 0 0）晶面对溶剂的竞争吸附能力相对较低，这主要是由于氢原子的不同行为导致了不同溶剂在晶面上的不同吸附能力。此外，Spearman相关系数用于评估汉森溶解度参数、分子极性指数（MPI）、Flory-Huggins相互作用参数和各种DFT描述符等因素对形貌的影响。结果表明，溶剂的MPI对CL-20/HMX共晶形貌的影响至关重要。值得注意的是，MPI值（0.72 < r < 0.87）成为评估溶剂对晶体形态影响的强大预测参数，优于广泛使用的Hansen溶解度参数（0.68 < r < 0.81）。实验结果证实了预测的正确性。本研究为含能材料的晶体工程提供了理论支持和实践指导，有助于提高结晶过程的智能化设计。

{"title":"Mechanistic insights into morphological control of energetic cocrystals: Critical factors and underlying mechanisms in CL-20/HMX systems","authors":"Shifan Xu , Hongtu Zhao , Hui Wang , Wenbo Wu , Na Wang , Ting Wang , Xin Huang , Hongxun Hao","doi":"10.1016/j.ces.2026.123448","DOIUrl":"10.1016/j.ces.2026.123448","url":null,"abstract":"<div><div>Crystal morphology manipulation and prediction of energetic materials is essential for their production and application, as it profoundly influences performance of weapons. This study focuses on investigating the factors and mechanisms influencing the energetic cocrystals morphology using CL-20/HMX cocrystal as model compound, by combining statistical and molecular simulation methods. The molecular simulation results demonstrate that the morphologically predominant (1 0 0) crystal facet exhibits relatively low competitive adsorption for solvents, mainly caused by the distinct behavior of hydrogen atoms contributing to the differential adsorption capabilities of various solvents on the facet. Furthermore, Spearman correlation coefficient was used to assess the effects of factors on the morphology, such as the Hansen solubility parameters, molecular polarity index (MPI), Flory-Huggins interaction parameters, and various DFT descriptors. The results indicate that the MPI of solvent plays a crucial role in determining the CL-20/HMX cocrystal morphology. Notably, the MPI value (0.72 < <em>r</em> < 0.87) emerges as a powerful predictive parameter for evaluating the solvent’s influence on crystal morphology, outperforming the widely used Hansen solubility parameters (0.68 < <em>r</em> < 0.81). Moreover, experimental results confirmed the validation of the prediction. This work offers both theoretical support and practical guidance for the crystal engineering of energetic materials, contributing to the improvement of intelligent design of crystallization processes.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"325 ","pages":"Article 123448"},"PeriodicalIF":4.3,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075587","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

An excellent energy-amplified effect between CL-20 and Al/MoO3 nano-thermites with high gas production and combustion properties CL-20与Al/MoO3纳米铝热剂之间具有良好的能量放大效应，具有较高的产气和燃烧性能

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-01-26 DOI: 10.1016/j.ces.2026.123452

Linyan Shen , Zehua Zhang , Jianbing Xu , Qian Wang , Yuan Lai , Yinghua Ye , Ruiqi Shen

Nano thermites have become hotspots because of their outstanding performances such as high energy density, reaction activity, and adiabatic reaction temperatures. However, the inherent low gas production of nano-thermites limits their application in propulsion systems. To address this challenge and enhance gas production, a series of nAl/MoO₃/CL-20 energetic composite materials were designed and prepared by ultrasonic mixing. 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) was added at mass fractions of 0%, 10%, 20%, 30%, 40%, and 50%. The composite materials were characterized, and their combustion reaction performances were systematically studied through rapid temperature rise and ignition experiment, semi-open environment combustion experiment, confined combustion tests and open-environment combustion tests. The peak pressure and pressurization rate of the composite materials were the highest when the addition of 30% CL-20, which were 1210.7 kPa and 71.2 kPa·μs⁻¹, and 2.1 times and 2.6 times than Al/MoO₃ respectively. Compared to the materials without CL-20, the sample with 30% CL-20 exhibited the lowest ignition temperature of 667.1 °C, representing a decrease of 68.2 °C. The open environment test showed a “floating-up flame” effect. Additionally, the samples with 20% and 30% CL-20 demonstrated the most vigorous combustion, with the maximum flame area (MFA) appearing 0.2 ms earlier than the pure Al/MoO₃, and the MFAs were 22.8 cm² and 20.8 cm², respectively. This work demonstrates a novel synergy between CL-20 and Al/MoO₃, achieving a 23.6% increase in exothermic capacity and a 4.4-fold enhancement in peak pressure compared to pure thermites, while maintaining low electrostatic sensitivity.

纳米热剂以其高能量密度、反应活性和绝热反应温度等优异性能成为研究的热点。然而，其固有的低产气量限制了其在推进系统中的应用。为了应对这一挑战并提高产气量，通过超声波混合设计并制备了一系列nAl/MoO3/CL-20含能复合材料。分别以0%、10%、20%、30%、40%和50%的质量分数加入2、4、6、8、10、12-己硝基-2、4、6、8、10、12-己氮杂索乌尔齐坦（CL-20）。对复合材料进行了表征，并通过快速升温点火实验、半开放环境燃烧实验、密闭燃烧实验和开放环境燃烧实验，系统地研究了复合材料的燃烧反应性能。当添加30% CL-20时，复合材料的峰值压力和加压率最高，分别为1210.7 kPa和71.2 kPa·μs−1，分别是Al/MoO3的2.1倍和2.6倍。与不含CL-20的材料相比，含30% CL-20的样品的最低着火温度为667.1℃，降低了68.2℃。开放环境试验显示出“浮焰”效应。此外，添加20%和30% CL-20的样品燃烧最剧烈，最大火焰面积（MFA）比纯Al/MoO3早0.2 ms，分别为22.8 cm2和20.8 cm2。这项工作证明了CL-20和Al/MoO3之间的新型协同作用，与纯铝热剂相比，放热容量增加了23.6%，峰值压力提高了4.4倍，同时保持了较低的静电灵敏度。

{"title":"An excellent energy-amplified effect between CL-20 and Al/MoO3 nano-thermites with high gas production and combustion properties","authors":"Linyan Shen , Zehua Zhang , Jianbing Xu , Qian Wang , Yuan Lai , Yinghua Ye , Ruiqi Shen","doi":"10.1016/j.ces.2026.123452","DOIUrl":"10.1016/j.ces.2026.123452","url":null,"abstract":"<div><div>Nano thermites have become hotspots because of their outstanding performances such as high energy density, reaction activity, and adiabatic reaction temperatures. However, the inherent low gas production of nano-thermites limits their application in propulsion systems. To address this challenge and enhance gas production, a series of nAl/MoO<sub>3</sub>/CL-20 energetic composite materials were designed and prepared by ultrasonic mixing. 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) was added at mass fractions of 0%, 10%, 20%, 30%, 40%, and 50%. The composite materials were characterized, and their combustion reaction performances were systematically studied through rapid temperature rise and ignition experiment, semi-open environment combustion experiment, confined combustion tests and open-environment combustion tests. The peak pressure and pressurization rate of the composite materials were the highest when the addition of 30% CL-20, which were 1210.7 kPa and 71.2 kPa·μs<sup>−1</sup>, and 2.1 times and 2.6 times than Al/MoO<sub>3</sub> respectively. Compared to the materials without CL-20, the sample with 30% CL-20 exhibited the lowest ignition temperature of 667.1 °C, representing a decrease of 68.2 °C. The open environment test showed a “floating-up flame” effect. Additionally, the samples with 20% and 30% CL-20 demonstrated the most vigorous combustion, with the maximum flame area (MFA) appearing 0.2 ms earlier than the pure Al/MoO<sub>3</sub>, and the MFAs were 22.8 cm<sup>2</sup> and 20.8 cm<sup>2</sup>, respectively. This work demonstrates a novel synergy between CL-20 and Al/MoO<sub>3</sub>, achieving a 23.6% increase in exothermic capacity and a 4.4-fold enhancement in peak pressure compared to pure thermites, while maintaining low electrostatic sensitivity.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"325 ","pages":"Article 123452"},"PeriodicalIF":4.3,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075500","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Asphalt − derived nitrogen, boron co − doped porous carbon for promoted lithium storage property 沥青衍生的氮、硼共掺杂多孔碳提高了锂的储存性能

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-01-26 DOI: 10.1016/j.ces.2026.123451

Chenxi Xu , Yun Peng , Lanyun Yang , Liang Chen , Jiale Sun , Shuangshuang Ren , Binbin Zhou , Zhaohui Hou

Heteroatom doping is widely recognized as an effective strategy for tuning the performance of carbon materials for lithium − ion batteries (LIBs). Till now, most studies have focused on doping single heteroatom into the carbon skeleton, while researches on multiple heteroatoms co − doping remain relatively limited, and the corresponding lithium storage mechanism has not been fully elucidated. In this study, nitrogen, boron co − doped porous carbon (NBPC) is synthesized by multi − step annealing procedures using asphalt as the carbon precursor. The physicochemical properties of the resulting NBPC are systematically analyzed, and its lithium storage performance is comprehensively evaluated. The experimental results indicate that NBPC possesses a hierarchically mesoporous/microporous architecture. Compared with undoped and singly doped carbon samples, NBPC exhibits more structural defects, higher conductivity, larger specific surface area and greater N/B doping levels. Moreover, theoretical calculations uncover that the Li⁺ adsorption capability of the samples abides by the order: boron − doped porous carbon (BPC) > NBPC > nitrogen − doped porous carbon (NPC) > porous carbon (PC). Although BPC shows the strongest theoretical Li⁺ adsorption capability, NBPC with a significantly higher total doping content (N + B: 5.83 at.%) than BPC (B: only 0.39 at.%) offers a substantially larger number of active sites for Li⁺ storage. Benefiting from these features, the NBPC anode delivers markedly enhanced electrochemical performance. These findings not only provide deeper insight into the lithium storage mechanism of multiple heteroatoms co − doped carbon, but also offer valuable insights for the reasonable construction of advanced heteroatom − doped carbon anodes for LIBs.

杂原子掺杂是锂离子电池碳材料性能调整的一种有效方法。到目前为止，大多数研究都集中在单杂原子掺杂到碳骨架上，而多杂原子co−掺杂的研究相对有限，其锂的储存机制也没有完全阐明。本研究以沥青为碳前驱体，采用多步退火法制备了氮硼共掺杂多孔碳（NBPC）。系统分析了制备的NBPC的理化性质，并对其储锂性能进行了综合评价。实验结果表明，NBPC具有中孔/微孔结构。与未掺杂和单掺杂碳样品相比，NBPC具有更多的结构缺陷、更高的电导率、更大的比表面积和更高的N/B掺杂水平。此外，理论计算表明，样品的Li+吸附能力依次为：硼掺杂多孔碳（BPC） > NBPC >；氮掺杂多孔碳（NPC） >；多孔碳（PC）。虽然BPC对Li+的理论吸附能力最强，但NBPC的总掺杂含量（N + B: 5.83 at）明显高于BPC。%)比BPC （B：仅0.39 at）高。%)为Li+存储提供了大量的活性位点。得益于这些特性，NBPC阳极提供了显著增强的电化学性能。这些发现不仅对多杂原子共掺杂碳的锂存储机制有了更深入的了解，也为合理构建先进的杂原子共掺杂碳阳极提供了有价值的见解。

{"title":"Asphalt − derived nitrogen, boron co − doped porous carbon for promoted lithium storage property","authors":"Chenxi Xu , Yun Peng , Lanyun Yang , Liang Chen , Jiale Sun , Shuangshuang Ren , Binbin Zhou , Zhaohui Hou","doi":"10.1016/j.ces.2026.123451","DOIUrl":"10.1016/j.ces.2026.123451","url":null,"abstract":"<div><div>Heteroatom doping is widely recognized as an effective strategy for tuning the performance of carbon materials for lithium − ion batteries (LIBs). Till now, most studies have focused on doping single heteroatom into the carbon skeleton, while researches on multiple heteroatoms co − doping remain relatively limited, and the corresponding lithium storage mechanism has not been fully elucidated. In this study, nitrogen, boron co − doped porous carbon (NBPC) is synthesized by multi − step annealing procedures using asphalt as the carbon precursor. The physicochemical properties of the resulting NBPC are systematically analyzed, and its lithium storage performance is comprehensively evaluated. The experimental results indicate that NBPC possesses a hierarchically mesoporous/microporous architecture. Compared with undoped and singly doped carbon samples, NBPC exhibits more structural defects, higher conductivity, larger specific surface area and greater N/B doping levels. Moreover, theoretical calculations uncover that the Li<sup>+</sup> adsorption capability of the samples abides by the order: boron − doped porous carbon (BPC) > NBPC > nitrogen − doped porous carbon (NPC) > porous carbon (PC). Although BPC shows the strongest theoretical Li<sup>+</sup> adsorption capability, NBPC with a significantly higher total doping content (N + B: 5.83 at.%) than BPC (B: only 0.39 at.%) offers a substantially larger number of active sites for Li<sup>+</sup> storage. Benefiting from these features, the NBPC anode delivers markedly enhanced electrochemical performance. These findings not only provide deeper insight into the lithium storage mechanism of multiple heteroatoms co − doped carbon, but also offer valuable insights for the reasonable construction of advanced heteroatom − doped carbon anodes for LIBs.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"325 ","pages":"Article 123451"},"PeriodicalIF":4.3,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075626","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ionic transport behavior in pH-responsive heterojunction nanofluidic membranes ph响应异质结纳米流体膜中的离子输运行为

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-01-26 DOI: 10.1016/j.ces.2026.123446

Parmida Shahhoseini, Mahdi Khatibi, Seyed Nezameddin Ashrafizadeh

Nanofluidic membranes with charged nanochannels enable selective ionic transport by amplifying interfacial electrostatic effects. In this work, a fully coupled Poisson–Nernst–Planck/Navier–Stokes (PNP–NS) model is developed to quantify how pH-regulated surface chemistry and oxide heterojunction composition govern ionic current rectification (ICR), conductivity, and electroosmotic flow (EOF) in cylindrical nanochannels connecting symmetric KCl reservoirs. Surface charge densities are determined via acid–base equilibria over pH 3–11, allowing a systematic comparison between Al₂O₃/SiO₂ and ZnO/SiO₂ heterojunctions, followed by a composition study of ZnO/SiO₂ (30/70–70/30). The simulations reveal that ZnO/SiO₂ heterojunctions exhibit stronger rectification and higher conductivity under acidic conditions, with peak currents occurring at pH ≈ 3 and a pronounced bias asymmetry relative to Al₂O₃/SiO₂. Varying the ZnO/SiO₂ ratio modulates charge mismatch at the junction, leading to clear trade-offs between rectification strength, conductivity, and EOF magnitude. These results establish quantitative links between oxide composition, pH, and electrokinetic performance, providing design guidelines for heterojunction nanofluidic membranes in separation, sensing, and energy-harvesting applications.

带电荷纳米通道的纳米流控膜通过放大界面静电效应来实现选择性离子传输。在这项工作中，建立了一个完全耦合的泊松-能斯特-普朗克/纳维-斯托克斯（PNP-NS）模型，以量化ph调节的表面化学和氧化物异质结组成如何控制连接对称KCl储层的圆柱形纳米通道中的离子电流整流（ICR）、电导率和电渗透流动（EOF）。表面电荷密度通过pH值为3-11的酸碱平衡来确定，允许系统地比较Al2O3/SiO2和ZnO/SiO2异质结，然后研究ZnO/SiO2的组成（30/70-70/30）。模拟结果表明，ZnO/SiO2异质结在酸性条件下表现出更强的整流和更高的导电性，在pH≈3时出现峰值电流，相对于Al2O3/SiO2具有明显的偏置不对称性。改变ZnO/SiO2的比例可以调节结处的电荷失配，从而在整流强度、电导率和EOF量级之间进行明确的权衡。这些结果建立了氧化物组成、pH值和电动性能之间的定量联系，为分离、传感和能量收集应用中的异质结纳米流体膜的设计提供了指导。

{"title":"Ionic transport behavior in pH-responsive heterojunction nanofluidic membranes","authors":"Parmida Shahhoseini, Mahdi Khatibi, Seyed Nezameddin Ashrafizadeh","doi":"10.1016/j.ces.2026.123446","DOIUrl":"10.1016/j.ces.2026.123446","url":null,"abstract":"<div><div>Nanofluidic membranes with charged nanochannels enable selective ionic transport by amplifying interfacial electrostatic effects. In this work, a fully coupled Poisson–Nernst–Planck/Navier–Stokes (PNP–NS) model is developed to quantify how pH-regulated surface chemistry and oxide heterojunction composition govern ionic current rectification (ICR), conductivity, and electroosmotic flow (EOF) in cylindrical nanochannels connecting symmetric KCl reservoirs. Surface charge densities are determined via acid–base equilibria over pH 3–11, allowing a systematic comparison between Al<sub>2</sub>O<sub>3</sub>/SiO<sub>2</sub> and ZnO/SiO<sub>2</sub> heterojunctions, followed by a composition study of ZnO/SiO<sub>2</sub> (30/70–70/30). The simulations reveal that ZnO/SiO<sub>2</sub> heterojunctions exhibit stronger rectification and higher conductivity under acidic conditions, with peak currents occurring at pH ≈ 3 and a pronounced bias asymmetry relative to Al<sub>2</sub>O<sub>3</sub>/SiO<sub>2</sub>. Varying the ZnO/SiO<sub>2</sub> ratio modulates charge mismatch at the junction, leading to clear trade-offs between rectification strength, conductivity, and EOF magnitude. These results establish quantitative links between oxide composition, pH, and electrokinetic performance, providing design guidelines for heterojunction nanofluidic membranes in separation, sensing, and energy-harvesting applications.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"325 ","pages":"Article 123446"},"PeriodicalIF":4.3,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Parameter estimation of a size-exclusion simulated moving bed for protein purification via meta-heuristic methods with estimability analysis and uncertainty evaluation 基于可估计性分析和不确定度评估的元启发式蛋白质净化尺寸排除模拟移动床参数估计

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-01-25 DOI: 10.1016/j.ces.2026.123447

Guilherme C. Amaral , Albertina G. Rios , Alírio E. Rodrigues , Ana M. Ribeiro , Diogo Rodrigues , Idelfonso B.R. Nogueira , Alexandre F.P. Ferreira

This study aims to enhance the modelling of myoglobin (Mb) and bovine serum albumin (BSA) separation in size-exclusion gel systems by leveraging experimental data and computational methods. The objective is to estimate the parameters of a mathematical model that accurately represents this separation process. To achieve this, optimization problems with adequate objective functions are solved via Particle Swarm Optimization (PSO), which has been shown to be more efficient than comparable deterministic methods Comprehensive estimability and uncertainty analyses were also conducted to thoroughly assess the model’s reliability and accuracy. The initial phase of the study involved estimating parameters for a fixed bed system. During this phase, it was discerned through estimability analysis that the mass transfer coefficient parameters, denoted as

k_{h}

, had minimal impact on the model’s outputs, leading to their exclusion from subsequent estimations. The focus then shifted to refining the model parameters to simultaneously fit both the fixed bed and Simulated Moving Bed (SMB) experimental data. The comparative analysis between these parameters and the fixed bed parameters highlighted notable differences, particularly in the axial dispersion parameter (

D_{ax}

) and the BSA size exclusion constant (

K_{SEC, B S A}

). An uncertainty evaluation was successfully executed after completing this study, providing confidence intervals for each parameter, and propagating the uncertainty to the prediction of the developed model. This comprehensive approach ensures a more accurate and reliable understanding of the separation dynamics in size-exclusion gel processes for Mb and BSA.

本研究旨在通过利用实验数据和计算方法，增强肌红蛋白（Mb）和牛血清白蛋白（BSA）在尺寸排除凝胶系统分离的建模。目的是估计精确表示这一分离过程的数学模型的参数。为了实现这一目标，通过粒子群优化（PSO）来解决具有适当目标函数的优化问题，该方法已被证明比同类确定性方法更有效，并进行了全面的可估计性和不确定性分析，以彻底评估模型的可靠性和准确性。研究的初始阶段包括估计固定床系统的参数。在此阶段，通过可估计性分析可以看出，传质系数参数（表示为kh）对模型输出的影响最小，导致其被排除在后续估计之外。然后，重点转移到改进模型参数，以同时适应固定床和模拟移动床（SMB）的实验数据。这些参数与固定床参数的对比分析显示出显著差异，特别是在轴向分散参数（Dax）和BSA粒径排除常数（KSEC，BSA）方面。在完成本研究后，成功地执行了不确定性评估，为每个参数提供了置信区间，并将不确定性传播到所开发模型的预测中。这种全面的方法确保了对Mb和BSA的尺寸排除凝胶过程中分离动力学的更准确和可靠的理解。

{"title":"Parameter estimation of a size-exclusion simulated moving bed for protein purification via meta-heuristic methods with estimability analysis and uncertainty evaluation","authors":"Guilherme C. Amaral , Albertina G. Rios , Alírio E. Rodrigues , Ana M. Ribeiro , Diogo Rodrigues , Idelfonso B.R. Nogueira , Alexandre F.P. Ferreira","doi":"10.1016/j.ces.2026.123447","DOIUrl":"10.1016/j.ces.2026.123447","url":null,"abstract":"<div><div>This study aims to enhance the modelling of myoglobin (Mb) and bovine serum albumin (BSA) separation in size-exclusion gel systems by leveraging experimental data and computational methods. The objective is to estimate the parameters of a mathematical model that accurately represents this separation process. To achieve this, optimization problems with adequate objective functions are solved via Particle Swarm Optimization (PSO), which has been shown to be more efficient than comparable deterministic methods Comprehensive estimability and uncertainty analyses were also conducted to thoroughly assess the model’s reliability and accuracy. The initial phase of the study involved estimating parameters for a fixed bed system. During this phase, it was discerned through estimability analysis that the mass transfer coefficient parameters, denoted as <span><math><msub><mi>k</mi><mi>h</mi></msub></math></span>, had minimal impact on the model’s outputs, leading to their exclusion from subsequent estimations. The focus then shifted to refining the model parameters to simultaneously fit both the fixed bed and Simulated Moving Bed (SMB) experimental data. The comparative analysis between these parameters and the fixed bed parameters highlighted notable differences, particularly in the axial dispersion parameter (<span><math><msub><mi>D</mi><mrow><mi>ax</mi></mrow></msub></math></span>) and the BSA size exclusion constant (<span><math><msub><mi>K</mi><mrow><mi>SEC</mi><mo>,</mo><mi>B</mi><mi>S</mi><mi>A</mi></mrow></msub></math></span>). An uncertainty evaluation was successfully executed after completing this study, providing confidence intervals for each parameter, and propagating the uncertainty to the prediction of the developed model. This comprehensive approach ensures a more accurate and reliable understanding of the separation dynamics in size-exclusion gel processes for Mb and BSA.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"325 ","pages":"Article 123447"},"PeriodicalIF":4.3,"publicationDate":"2026-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075501","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Chitosan-based hydrogel composite membrane for stable and enhanced freshwater production in photothermal membrane distillation system 壳聚糖基水凝胶复合膜用于光热膜蒸馏系统中稳定和提高淡水产量

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-01-25 DOI: 10.1016/j.ces.2026.123425

Jinzhao Wang , Xiantao Zhang , Tingting Ren , Lanyue Zhang , Peng Liu , Xuejiao Hu , Lu Huang

Traditional photothermal membrane distillation (PMD) for seawater desalination suffers from low photothermal conversion efficiency and poor operational stability under high-salinity brine conditions. In response to these limitations, this study reports a hydrogel composite membrane (HCM) mediated photothermal membrane distillation device. The HCM consists of a chitosan/agarose hydrogel (CAH) layer, carbon nanotube (CNT) coating, and polytetrafluoroethylene (PTFE) hydrophobic membrane. The CNT layer significantly improves the photothermal conversion efficiency, achieving 98.5% solar absorption under standard solar irradiation. The CAH modulates intermediate water states by tuning the chitosan-to-agarose ratio, thereby reducing water evaporation enthalpy and enabling stable freshwater production. Under 1 kW m⁻² solar intensity (i.e. 1 sun) for 1.5 h, the water flux of the device increased by 40.7% than pure CNT/PTFE membrane. Simultaneously, CAH employs its three-dimensional porous structure and abundant amino (–NH₂) and hydroxyl (–OH) groups to achieve synergistic salt rejection through electrostatic repulsion. The device achieved continuous and stable freshwater production in a 7 wt% NaCl solution, demonstrating outstanding salt-rejection properties. This study developed hydrogel composite membrane to enhance water flux and system stability in PMD, proposing novel concepts for performance enhancement of PMD.

传统的光热膜蒸馏（PMD）海水淡化存在光热转换效率低、在高盐度盐水条件下运行稳定性差的问题。针对这些局限性，本研究报道了一种水凝胶复合膜（HCM）介导的光热膜蒸馏装置。HCM由壳聚糖/琼脂糖水凝胶（CAH）层、碳纳米管（CNT）涂层和聚四氟乙烯（PTFE）疏水膜组成。碳纳米管层显著提高了光热转换效率，在标准太阳照射下可达到98.5%的太阳吸收率。CAH通过调节壳聚糖与琼脂糖的比例来调节中间水状态，从而降低水蒸发焓，实现稳定的淡水生产。在1 kW m−2太阳强度下（即1个太阳）照射1.5 h，该装置的水通量比纯CNT/PTFE膜提高了40.7%。同时，CAH利用其三维多孔结构和丰富的氨基（-NH2）和羟基（-OH）基团，通过静电斥力实现协同排盐。该装置在7 wt% NaCl溶液中实现了连续稳定的淡水生产，表现出出色的防盐性能。本研究开发了水凝胶复合膜来增强PMD中的水通量和系统稳定性，为PMD的性能增强提出了新的概念。

{"title":"Chitosan-based hydrogel composite membrane for stable and enhanced freshwater production in photothermal membrane distillation system","authors":"Jinzhao Wang , Xiantao Zhang , Tingting Ren , Lanyue Zhang , Peng Liu , Xuejiao Hu , Lu Huang","doi":"10.1016/j.ces.2026.123425","DOIUrl":"10.1016/j.ces.2026.123425","url":null,"abstract":"<div><div>Traditional photothermal membrane distillation (PMD) for seawater desalination suffers from low photothermal conversion efficiency and poor operational stability under high-salinity brine conditions. In response to these limitations, this study reports a hydrogel composite membrane (HCM) mediated photothermal membrane distillation device. The HCM consists of a chitosan/agarose hydrogel (CAH) layer, carbon nanotube (CNT) coating, and polytetrafluoroethylene (PTFE) hydrophobic membrane. The CNT layer significantly improves the photothermal conversion efficiency, achieving 98.5% solar absorption under standard solar irradiation. The CAH modulates intermediate water states by tuning the chitosan-to-agarose ratio, thereby reducing water evaporation enthalpy and enabling stable freshwater production. Under 1 kW m<sup>−2</sup> solar intensity (i.e. 1 sun) for 1.5 h, the water flux of the device increased by 40.7% than pure CNT/PTFE membrane. Simultaneously, CAH employs its three-dimensional porous structure and abundant amino (–NH<sub>2</sub>) and hydroxyl (–OH) groups to achieve synergistic salt rejection through electrostatic repulsion. The device achieved continuous and stable freshwater production in a 7 wt% NaCl solution, demonstrating outstanding salt-rejection properties. This study developed hydrogel composite membrane to enhance water flux and system stability in PMD, proposing novel concepts for performance enhancement of PMD.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"325 ","pages":"Article 123425"},"PeriodicalIF":4.3,"publicationDate":"2026-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075400","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mechanism-Guided interpretable learning Informed by molecular Dynamics: High-Throughput solvent screening for PEO-Based solid polymer electrolytes 由分子动力学指导的机制导向的可解释学习：peo基固体聚合物电解质的高通量溶剂筛选

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-01-25 DOI: 10.1016/j.ces.2026.123424

Longyu Shi , Caoyuan Ma , Xiao Tang , Yi Song , Xiaomin Liu , Timing Fang

PEO based solid polymer electrolytes promise safer solid-state batteries but suffer from low ionic conductivity and limited Li⁺ transference. Molecular dynamics simulation and interpretable machine learning were combined to reveal transport mechanisms and to discover solvents that merge the advantages of DME (dimethoxyethane) and DMC (dimethyl carbonate). Simulations show that additives regulate transport by reshaping the PEO (polyethylene oxide) solvation cage. DME relaxes PEO conformations and unravels the cage, increasing Li⁺ mobility, while DMC binds more strongly to Li⁺ and can pull ions from PEO, providing a complementary pathway. Guided by these insights, a graph expanded solvent library is modeled; interpretable learning SHAP highlights viscosity and polarity as main factors. Multi criterion screening on compatibility and thermodynamic surrogates selects top candidates, validated by molecular dynamics with a cluster aware Nernst Einstein approach. The workflow yields rules for identifying DME and DMC like solvents and provides certain guiding significance for improving solid polymer electrolytes projects.

基于PEO的固体聚合物电解质有望提供更安全的固态电池，但存在离子电导率低和Li+转移受限的问题。分子动力学模拟和可解释的机器学习相结合，揭示了运输机制，并发现了融合DME（二甲氧基乙烷）和DMC（碳酸二甲基）优点的溶剂。模拟表明，添加剂通过重塑PEO（聚乙烯氧化物）溶剂化笼来调节输送。DME使PEO的构象松弛，打开笼，增加Li+的迁移率，而DMC与Li+的结合更强，可以从PEO中拉离子，提供了一个互补的途径。在这些见解的指导下，对扩展的溶剂库进行了建模；可解释学习SHAP强调粘度和极性是主要因素。对相容性和热力学替代物进行多标准筛选，选择最佳候选物，并通过分子动力学和簇感知能-爱因斯坦方法进行验证。该工作流程提供了识别二甲醚和DMC等溶剂的规则，对改进固体聚合物电解质项目具有一定的指导意义。

{"title":"Mechanism-Guided interpretable learning Informed by molecular Dynamics: High-Throughput solvent screening for PEO-Based solid polymer electrolytes","authors":"Longyu Shi , Caoyuan Ma , Xiao Tang , Yi Song , Xiaomin Liu , Timing Fang","doi":"10.1016/j.ces.2026.123424","DOIUrl":"10.1016/j.ces.2026.123424","url":null,"abstract":"<div><div>PEO based solid polymer electrolytes promise safer solid-state batteries but suffer from low ionic conductivity and limited Li<sup>+</sup> transference. Molecular dynamics simulation and interpretable machine learning were combined to reveal transport mechanisms and to discover solvents that merge the advantages of DME (dimethoxyethane) and DMC (dimethyl carbonate). Simulations show that additives regulate transport by reshaping the PEO (polyethylene oxide) solvation cage. DME relaxes PEO conformations and unravels the cage, increasing Li<sup>+</sup> mobility, while DMC binds more strongly to Li<sup>+</sup> and can pull ions from PEO, providing a complementary pathway. Guided by these insights, a graph expanded solvent library is modeled; interpretable learning SHAP highlights viscosity and polarity as main factors. Multi criterion screening on compatibility and thermodynamic surrogates selects top candidates, validated by molecular dynamics with a cluster aware Nernst Einstein approach. The workflow yields rules for identifying DME and DMC like solvents and provides certain guiding significance for improving solid polymer electrolytes projects.</div></div>","PeriodicalId":271,"journal":{"name":"Chemical Engineering Science","volume":"325 ","pages":"Article 123424"},"PeriodicalIF":4.3,"publicationDate":"2026-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146075399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0