Liuxuan Ren, Tinghao Jia, Mengen Zhang, Xiaoqiang Fan, Congjing Ren, Jingdai Wang, Yongrong Yang, Yao Yang
In high‐pressure free‐radical polymerization, peroxide initiators are routinely blended to improve process performance, yet their synergistic interactions remain insufficiently elucidated. Here, these effects are probed using reaction‐network analysis. Reaction networks of blended initiators were generated with reaction mechanism generator (RMG) and refined through experiments. Network analysis revealed diverse interaction patterns, motivating three complementary metrics to quantify synergy: rate enhancement ( k ‐fold increase), radical generation capacity (GI), and radical persistence. The combined behavior of these metrics distinguishes cooperative synergy from largely independent decomposition. Synergistic enhancement requires meaningful decomposition overlap and the formation of a complementary, stable radical pool. Incorporating the extracted parameters and GI‐corrected radical release into a reactor model enabled formulation optimization. Application to an industrial tubular reactor reduced initiator consumption by over 30% while maintaining conversion and molecular‐weight targets. These findings offer mechanistic insight and practical guidance for initiator design in industrial high‐pressure polymerization.
{"title":"Quantifying synergistic initiator interactions in high‐pressure polymerization through reaction‐network analysis","authors":"Liuxuan Ren, Tinghao Jia, Mengen Zhang, Xiaoqiang Fan, Congjing Ren, Jingdai Wang, Yongrong Yang, Yao Yang","doi":"10.1002/aic.70308","DOIUrl":"https://doi.org/10.1002/aic.70308","url":null,"abstract":"In high‐pressure free‐radical polymerization, peroxide initiators are routinely blended to improve process performance, yet their synergistic interactions remain insufficiently elucidated. Here, these effects are probed using reaction‐network analysis. Reaction networks of blended initiators were generated with reaction mechanism generator (RMG) and refined through experiments. Network analysis revealed diverse interaction patterns, motivating three complementary metrics to quantify synergy: rate enhancement ( <jats:italic>k</jats:italic> ‐fold increase), radical generation capacity (GI), and radical persistence. The combined behavior of these metrics distinguishes cooperative synergy from largely independent decomposition. Synergistic enhancement requires meaningful decomposition overlap and the formation of a complementary, stable radical pool. Incorporating the extracted parameters and GI‐corrected radical release into a reactor model enabled formulation optimization. Application to an industrial tubular reactor reduced initiator consumption by over 30% while maintaining conversion and molecular‐weight targets. These findings offer mechanistic insight and practical guidance for initiator design in industrial high‐pressure polymerization.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"12 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146778869","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
J. Galen Wang, Umesh Dhumal, Monica E. A. Zakhari, Roseanna N. Zia
Monodisperse, purely repulsive hard spheres (MPRHS) are a canonical model for fluid–solid phase behavior in atomic and colloidal systems. Liquid-state theory, free-energy calculations, simulations, and experiments establish a first-order fluid–solid transition in this model, a thermodynamic picture we take as given. Following Alder and Wainwright, we treat explicit fluid–crystal phase separation—coexistence of fluid-and-crystal domains—as an important benchmark for confirming first-order behavior, complementary to demonstrating phase transition between single phases. Against this backdrop, we highlight a specific gap. Decades of simulations have mapped equations of state, coexistence properties, and nucleation rates, forming a foundational body of results, yet spontaneous, long-lived fluid–crystal coexistence has not been reported in unbiased MPRHS simulations. Instead, coexistence appears either when physical/model-level bias is introduced (e.g., seeding, gravity) or under algorithmic bias designed to accelerate barrier crossing. Studies that avoid bias typically observe transient mixed states ultimately overtaken by a single metastable phase, consistent with Frenkel's estimate that a spontaneous coexistence state in even large simulations would require years of sampling. In this Perspective, we focus on why such coexistence is so difficult to realize under pristine conditions, and what that means for testing Frenkel's entropy-exchange mechanism in simulation. We argue that this kinetic difficulty is precisely what one expects from Frenkel's picture of competing vibrational and configurational entropy in hard-sphere crystallization, and that minimal, controlled “hardness” perturbations that directly enhance in-cage vibrational entropy provide the most direct route to making that entropic mechanism dynamically accessible and quantifiable.
{"title":"The elusive fluid-and-crystal coexistence state in simulations of monodisperse, hard-sphere colloids","authors":"J. Galen Wang, Umesh Dhumal, Monica E. A. Zakhari, Roseanna N. Zia","doi":"10.1002/aic.70275","DOIUrl":"https://doi.org/10.1002/aic.70275","url":null,"abstract":"Monodisperse, purely repulsive hard spheres (MPRHS) are a canonical model for fluid–solid phase behavior in atomic and colloidal systems. Liquid-state theory, free-energy calculations, simulations, and experiments establish a first-order fluid–solid transition in this model, a thermodynamic picture we take as given. Following Alder and Wainwright, we treat explicit fluid–crystal phase separation—coexistence of fluid-and-crystal domains—as an important benchmark for confirming first-order behavior, complementary to demonstrating phase transition between single phases. Against this backdrop, we highlight a specific gap. Decades of simulations have mapped equations of state, coexistence properties, and nucleation rates, forming a foundational body of results, yet spontaneous, long-lived fluid–crystal coexistence has not been reported in unbiased MPRHS simulations. Instead, coexistence appears either when physical/model-level bias is introduced (e.g., seeding, gravity) or under algorithmic bias designed to accelerate barrier crossing. Studies that avoid bias typically observe transient mixed states ultimately overtaken by a single metastable phase, consistent with Frenkel's estimate that a spontaneous coexistence state in even large simulations would require <span data-altimg=\"/cms/asset/3a475d24-c618-4349-bc61-2b31aa1624d3/aic70275-math-0001.png\"></span><math altimg=\"urn:x-wiley:00011541:media:aic70275:aic70275-math-0001\" display=\"inline\" location=\"graphic/aic70275-math-0001.png\">\u0000<semantics>\u0000<mrow>\u0000<mo>∼</mo>\u0000<mn>3</mn>\u0000<mo>.</mo>\u0000<mn>17</mn>\u0000<mo form=\"prefix\">×</mo>\u0000<mn>1</mn>\u0000<msup>\u0000<mrow>\u0000<mn>0</mn>\u0000</mrow>\u0000<mrow>\u0000<mn>8</mn>\u0000</mrow>\u0000</msup>\u0000</mrow>\u0000$$ sim 3.17times 1{0}^8 $$</annotation>\u0000</semantics></math> years of sampling. In this Perspective, we focus on why such coexistence is so difficult to realize under pristine conditions, and what that means for testing Frenkel's entropy-exchange mechanism in simulation. We argue that this kinetic difficulty is precisely what one expects from Frenkel's picture of competing vibrational and configurational entropy in hard-sphere crystallization, and that minimal, controlled “hardness” perturbations that directly enhance in-cage vibrational entropy provide the most direct route to making that entropic mechanism dynamically accessible and quantifiable.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"8 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146223231","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
This study builds on the DLV‐SAR micromixer proposed by our research team and uses water as the working fluid to investigate the effects of microchannel dimensional scaling and channel‐length extension (by connecting micro‐mixer units) on flow velocity, mixing performance, and pressure drop. Experimental measurements are used to quantitatively validate the pressure drop. One‐dimensional scaling increases the hydraulic diameter to 0.96 mm 2 , reducing pressure loss but lowering the mixing index to below 85%, while a channel depth of 1200 μm yields the highest overall index of 1.42. Two‐dimensional scaling significantly increases volumetric flow but degrades mixing efficiency, with a peak flow rate of 175 mm 3 /s at a channel diameter of 1000 μm. By connecting five micromixing units with an 800 μm diameter in series, a volumetric flow of 234 mm 3 /s and a maximum mixing index of 99.61% are achieved. These results provide theoretical support for the design of high‐throughput industrial micromixers.
本研究以我们的研究团队提出的DLV - SAR微混合器为基础，以水作为工作流体，研究微通道尺寸缩小和通道长度延长（通过连接微混合器单元）对流速、混合性能和压降的影响。实验测量用于定量验证压降。一维结垢使水力直径增加到0.96 mm 2，减少了压力损失，但将混合指数降至85%以下，而通道深度为1200 μm时，总体指数最高，为1.42。二维结垢显著增加了体积流量，但降低了混合效率，在通道直径为1000 μm时，峰值流速为175 mm 3 /s。通过串联5个直径为800 μm的微混合单元，获得了234mm3 /s的体积流量和99.61%的最大混合率。这些结果为高通量工业微混频器的设计提供了理论支持。
{"title":"The study on the size scaling characteristics of DLV ‐ SAR microchannel mixers","authors":"Liyu Xia, Yuanyuan Ma, Tianyi Su, Yankun Zhao, Xiang Li, Yuexiang Zhao","doi":"10.1002/aic.70303","DOIUrl":"https://doi.org/10.1002/aic.70303","url":null,"abstract":"This study builds on the DLV‐SAR micromixer proposed by our research team and uses water as the working fluid to investigate the effects of microchannel dimensional scaling and channel‐length extension (by connecting micro‐mixer units) on flow velocity, mixing performance, and pressure drop. Experimental measurements are used to quantitatively validate the pressure drop. One‐dimensional scaling increases the hydraulic diameter to 0.96 mm <jats:sup>2</jats:sup> , reducing pressure loss but lowering the mixing index to below 85%, while a channel depth of 1200 μm yields the highest overall index of 1.42. Two‐dimensional scaling significantly increases volumetric flow but degrades mixing efficiency, with a peak flow rate of 175 mm <jats:sup>3</jats:sup> /s at a channel diameter of 1000 μm. By connecting five micromixing units with an 800 μm diameter in series, a volumetric flow of 234 mm <jats:sup>3</jats:sup> /s and a maximum mixing index of 99.61% are achieved. These results provide theoretical support for the design of high‐throughput industrial micromixers.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"3 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146215696","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuqi Zhang, Daofan Ma, Taotao Fu, Chunying Zhu, Youguang Ma
Efficient and low‐energy absorbents are always desirable to control the greenhouse effect. In this study, a novel amino polycarboxylate ionic liquid absorbent is constructed by introducing carboxylate groups. The CO 2 absorption‐desorption experiments in microchannel and macroscopic devices are performed to comprehensively investigate the performance of choline iminodiacetate ([Ch] 2 [IDA]). It is found that [Ch] 2 [IDA] could form soluble carbamic acid upon CO 2 absorption, thereby effectively preventing equipment blocking compared to choline glycine ([Ch][Gly]). The dual carboxyl groups in [IDA] 2− could generate a synergistic effect to weaken the negative inductive action of the amino group; consequently, [Ch] 2 [IDA] displays superior CO 2 absorption performance over [Ch][Gly]. Furthermore, [Ch] 2 [IDA] aqueous solution could release more CO 2 in the rapid desorption stage and effectively alleviate the sharp increase of energy consumption during the desorption termination period. Especially, it exhibits excellent cycling stability. Comparatively, [Ch] 2 [IDA] aqueous solution demonstrates great potential as a next‐generation efficient and low‐energy CO 2 absorbent.
{"title":"A high‐efficiency carboxylated choline amino acid ionic liquid for CO 2 capture and its absorption‐desorption performance","authors":"Yuqi Zhang, Daofan Ma, Taotao Fu, Chunying Zhu, Youguang Ma","doi":"10.1002/aic.70301","DOIUrl":"https://doi.org/10.1002/aic.70301","url":null,"abstract":"Efficient and low‐energy absorbents are always desirable to control the greenhouse effect. In this study, a novel amino polycarboxylate ionic liquid absorbent is constructed by introducing carboxylate groups. The CO <jats:sub>2</jats:sub> absorption‐desorption experiments in microchannel and macroscopic devices are performed to comprehensively investigate the performance of choline iminodiacetate ([Ch] <jats:sub>2</jats:sub> [IDA]). It is found that [Ch] <jats:sub>2</jats:sub> [IDA] could form soluble carbamic acid upon CO <jats:sub>2</jats:sub> absorption, thereby effectively preventing equipment blocking compared to choline glycine ([Ch][Gly]). The dual carboxyl groups in [IDA] <jats:sup>2−</jats:sup> could generate a synergistic effect to weaken the negative inductive action of the amino group; consequently, [Ch] <jats:sub>2</jats:sub> [IDA] displays superior CO <jats:sub>2</jats:sub> absorption performance over [Ch][Gly]. Furthermore, [Ch] <jats:sub>2</jats:sub> [IDA] aqueous solution could release more CO <jats:sub>2</jats:sub> in the rapid desorption stage and effectively alleviate the sharp increase of energy consumption during the desorption termination period. Especially, it exhibits excellent cycling stability. Comparatively, [Ch] <jats:sub>2</jats:sub> [IDA] aqueous solution demonstrates great potential as a next‐generation efficient and low‐energy CO <jats:sub>2</jats:sub> absorbent.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"11 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146215739","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuxuan Fu, Wenbo Mu, Iman Bahrabadi Jovein, Biaohua Chen, Christoph Held, Gangqiang Yu
To facilitate the efficient screening of deep eutectic solvents (DESs) for capturing fluorinated gases (F-gases) as extremely severe greenhouse gases, this study developed thermodynamics-informed machine learning (ML) models, based on physical descriptors, that is, distribution of surface shielding charge density (σ-profiles), the molecular surface area and molecular volume, derived from the thermodynamic model COSMO-RS to ultimately predict the solubility of F-gases in DESs. More than 1000 experimental solubility data (6F-gases and 42 DESs) were collected. The support vector regression (SVR) was ultimately selected as the optimal predictive ML model under the comprehensive assessments, and was successfully applied to predict the solubility of R-32 in three DESs (not included in the original dataset), demonstrating a highly predictive accuracy (average absolute relative deviation (AARD) of 17.79%) comparable to physical model PC-SAFT (AARD of 11.75%). This demonstrates that thermodynamics-informed ML model has the strong generalization capability to screen DESs for F-gases capture.
{"title":"Hybrid thermodynamics-informed data-driven models for predicting fluorinated gas solubility in deep eutectic solvents","authors":"Yuxuan Fu, Wenbo Mu, Iman Bahrabadi Jovein, Biaohua Chen, Christoph Held, Gangqiang Yu","doi":"10.1002/aic.70299","DOIUrl":"https://doi.org/10.1002/aic.70299","url":null,"abstract":"To facilitate the efficient screening of deep eutectic solvents (DESs) for capturing fluorinated gases (F-gases) as extremely severe greenhouse gases, this study developed thermodynamics-informed machine learning (ML) models, based on physical descriptors, that is, distribution of surface shielding charge density (<i>σ-profiles</i>), the molecular surface area and molecular volume, derived from the thermodynamic model COSMO-RS to ultimately predict the solubility of F-gases in DESs. More than 1000 experimental solubility data (6F-gases and 42 DESs) were collected. The support vector regression (SVR) was ultimately selected as the optimal predictive ML model under the comprehensive assessments, and was successfully applied to predict the solubility of R-32 in three DESs (not included in the original dataset), demonstrating a highly predictive accuracy (average absolute relative deviation (AARD) of 17.79%) comparable to physical model PC-SAFT (AARD of 11.75%). This demonstrates that thermodynamics-informed ML model has the strong generalization capability to screen DESs for F-gases capture.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"104 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146223307","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yan Hou, Yue Zhang, Shaohui Tao, Lili Wang, Xiaoyan Sun, Shuguang Xiang, Li Xia, Guoxuan Li
Methyldiethanolamine (MDEA), an efficient and environmentally friendly absorbent, has been widely used in CO2 capture. This study prepared and evaluated two novel ternary MDEA-based deep eutectic solvents (DES1 and DES2) for CO2 capture performance. Experimental results show that the maximum CO2 absorption capacities of DES1 and DES2 were 0.1237 and 0.1016 g CO2/g DES, with viscosities of 14 and 9.6 mPa s at 50 wt% water content. After five absorption–desorption cycles, DES1 maintained 82% of its initial absorption efficiency. Nuclear magnetic resonance analysis confirms the successful synthesis of DESs, which effectively absorb CO2. After regeneration, the structure remains unchanged despite chemical absorption, indicating the reversibility of MDEA-based DESs. Molecular-level analysis indicates that the DES1 capture CO2 process involves physical absorption and chemical reactions. Specifically, ethanolamine reacts with CO2 to form carbamate, and the interaction energy between CO2 and MDEA is −2699.40 kJ/mol.
甲基二乙醇胺（MDEA）是一种高效环保的吸附剂，在CO2捕集中得到了广泛的应用。本研究制备并评价了两种新型三元mdea基深共晶溶剂DES1和DES2的CO2捕集性能。实验结果表明，在50% wt%含水量下，DES1和DES2的最大CO2吸收量分别为0.1237和0.1016 g CO2/g DES，粘度分别为14和9.6 mPa s。经过5次吸附-解吸循环后，DES1仍保持82%的初始吸收效率。核磁共振分析证实了DESs的成功合成，它能有效地吸收CO2。再生后，尽管化学吸收，结构仍保持不变，表明mdea基DESs的可逆性。分子水平分析表明，DES1捕获CO2过程涉及物理吸收和化学反应。其中，乙醇胺与CO2反应生成氨基甲酸酯，CO2与MDEA的相互作用能为- 2699.40 kJ/mol。
{"title":"Reversible methyldiethanolamine-based deep eutectic solvents capture CO2: Experiments and molecular mechanisms","authors":"Yan Hou, Yue Zhang, Shaohui Tao, Lili Wang, Xiaoyan Sun, Shuguang Xiang, Li Xia, Guoxuan Li","doi":"10.1002/aic.70296","DOIUrl":"https://doi.org/10.1002/aic.70296","url":null,"abstract":"Methyldiethanolamine (MDEA), an efficient and environmentally friendly absorbent, has been widely used in CO<sub>2</sub> capture. This study prepared and evaluated two novel ternary MDEA-based deep eutectic solvents (DES1 and DES2) for CO<sub>2</sub> capture performance. Experimental results show that the maximum CO<sub>2</sub> absorption capacities of DES1 and DES2 were 0.1237 and 0.1016 g CO<sub>2</sub>/g DES, with viscosities of 14 and 9.6 mPa s at 50 wt% water content. After five absorption–desorption cycles, DES1 maintained 82% of its initial absorption efficiency. Nuclear magnetic resonance analysis confirms the successful synthesis of DESs, which effectively absorb CO<sub>2</sub>. After regeneration, the structure remains unchanged despite chemical absorption, indicating the reversibility of MDEA-based DESs. Molecular-level analysis indicates that the DES1 capture CO<sub>2</sub> process involves physical absorption and chemical reactions. Specifically, ethanolamine reacts with CO<sub>2</sub> to form carbamate, and the interaction energy between CO<sub>2</sub> and MDEA is −2699.40 kJ/mol.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"3 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146215697","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Momoko Ishida, Tyler Seung Hun Kwak, Derek M. Richard, Saudagar Dongare, Burcu Gurkan, Panagiotis D. Christofides, Carlos G. Morales-Guio
Understanding the interplay between intrinsic kinetics and transport remains a central challenge in electrocatalysis. Rotating disk electrodes (RDE) are widely used because their transport can be described analytically, but radial concentration gradients complicate analysis of multi-electron processes. Rotating cylinder electrodes (RCE) provide an improved convective transport profile that better separates transport from kinetics. However, multiphysics simulations show that the use of a single flat counter electrode distorts the electric field in low-conductivity electrolytes. We present a third-generation gastight RCE cell (RCE-3) with two flat counter electrodes symmetrically positioned around the cylinder. This configuration doubles the counter electrode area, increases achievable current density, and improves field symmetry while maintaining well-defined hydrodynamics. Electrochemical CO2 reduction experiments demonstrate that asymmetric electric fields bias apparent kinetics in non-aqueous electrolytes, whereas symmetric counter electrode operation minimizes these distortions, enabling reliable extraction of intrinsic kinetic parameters. The RCE-3 cell contributes to advancing the mechanistic understanding of non-aqueous electrocatalytic systems.
{"title":"Improved symmetry and current distribution in a gastight rotating cylinder electrode cell: Design and characterization","authors":"Momoko Ishida, Tyler Seung Hun Kwak, Derek M. Richard, Saudagar Dongare, Burcu Gurkan, Panagiotis D. Christofides, Carlos G. Morales-Guio","doi":"10.1002/aic.70294","DOIUrl":"https://doi.org/10.1002/aic.70294","url":null,"abstract":"Understanding the interplay between intrinsic kinetics and transport remains a central challenge in electrocatalysis. Rotating disk electrodes (RDE) are widely used because their transport can be described analytically, but radial concentration gradients complicate analysis of multi-electron processes. Rotating cylinder electrodes (RCE) provide an improved convective transport profile that better separates transport from kinetics. However, multiphysics simulations show that the use of a single flat counter electrode distorts the electric field in low-conductivity electrolytes. We present a third-generation gastight RCE cell (RCE-3) with two flat counter electrodes symmetrically positioned around the cylinder. This configuration doubles the counter electrode area, increases achievable current density, and improves field symmetry while maintaining well-defined hydrodynamics. Electrochemical CO<sub>2</sub> reduction experiments demonstrate that asymmetric electric fields bias apparent kinetics in non-aqueous electrolytes, whereas symmetric counter electrode operation minimizes these distortions, enabling reliable extraction of intrinsic kinetic parameters. The RCE-3 cell contributes to advancing the mechanistic understanding of non-aqueous electrocatalytic systems.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"82 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146215698","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jia‐Hui An, Yu Wang, Jia‐Chen Xing, Yi‐Han Qi, En‐Zhou Liu, Hui‐Yong Chen, Long Xu, Qing‐Qing Hao, Qun‐Xing Luo
Chemical upcycling of polyesters presents a sustainable pathway to mitigate plastic waste accumulation while enabling monomer valorization and recovery. Here, we demonstrate a catalyst‐free ammonolysis of poly(trimethylene terephthalate) and selective recovery of 1,3‐propanediol. Non‐dissociated aqueous ammonia () was identified as the actual reactive species for ester bond cleavage. Essential physical and thermodynamic properties were determined through combined experimental and group‐contribution methods, while phase equilibria were quantified using an integrated electrolyte NRTL and Redlich‐Kwong model. Based on the activity of and kinetic data, a phenomenological semi‐empirical kinetic model was developed and validated. This model captures both induction period and main reaction stage through a power‐law expression coupled with a time‐dependent logistic function, supporting a depolymerization mechanism that proceeds through concurrent heterogeneous shrinking‐core and homogeneous reaction. Furthermore, an integrated extraction‐distillation process was developed to achieve controlled purity and high recovery of 1,3‐propanediol.
{"title":"Catalyst‐free ammonolysis of PTT polyester: Thermodynamics, kinetics, and selective recovery of 1,3‐propanediol","authors":"Jia‐Hui An, Yu Wang, Jia‐Chen Xing, Yi‐Han Qi, En‐Zhou Liu, Hui‐Yong Chen, Long Xu, Qing‐Qing Hao, Qun‐Xing Luo","doi":"10.1002/aic.70298","DOIUrl":"https://doi.org/10.1002/aic.70298","url":null,"abstract":"Chemical upcycling of polyesters presents a sustainable pathway to mitigate plastic waste accumulation while enabling monomer valorization and recovery. Here, we demonstrate a catalyst‐free ammonolysis of poly(trimethylene terephthalate) and selective recovery of 1,3‐propanediol. Non‐dissociated aqueous ammonia () was identified as the actual reactive species for ester bond cleavage. Essential physical and thermodynamic properties were determined through combined experimental and group‐contribution methods, while phase equilibria were quantified using an integrated electrolyte NRTL and Redlich‐Kwong model. Based on the activity of and kinetic data, a phenomenological semi‐empirical kinetic model was developed and validated. This model captures both induction period and main reaction stage through a power‐law expression coupled with a time‐dependent logistic function, supporting a depolymerization mechanism that proceeds through concurrent heterogeneous shrinking‐core and homogeneous reaction. Furthermore, an integrated extraction‐distillation process was developed to achieve controlled purity and high recovery of 1,3‐propanediol.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"334 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146184415","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Conducting incompatible multi‐enzymatic and chemo‐enzymatic cascade reactions concurrently is highly attractive yet remains a persistent challenge. Herein, we demonstrated a diatom‐inspired microreactor, fabricated by armoring polymer‐stabilized water‐in‐oil emulsion with silica membranes for interfacial enzymatic catalysis in organic environments. Optimized interfacial engineering employing bis(trimethoxysilyl)hexane yielded resilient and porous silica membranes, facilitating efficient mass transfer. Crucially, synergistic polymer–enzyme–silica interactions promoted enzyme localization on the microreactors' interface, drastically reducing substrates' diffusion distance. Therefore, the polymer‐stabilized microreactors achieved a 45% higher product and retained 88% more activity after 10 cycles than the control in benzaldehyde lyase‐catalyzed benzoin condensation. Moreover, challenging chemo‐enzymatic cascades and multi‐enzymatic cascade reactions were demonstrated with high reactivity and recyclability in the diatom‐inspired microreactors, which compartmentalize distinct catalytic species to maintain their optimal catalytic conditions with minimum mass transfer resistance. The potential of this powerful platform to accommodate more challenging cascades for advanced synthetic applications is thus envisioned.
{"title":"Polymeric emulsifier and diatom‐inspired membrane synergistically locate enzymes for interfacial cascade reactions","authors":"Mengyao Wang, Nanxiang Shen, Bozheng Wang, Xiaofei Chen, Jian Xu, Jianming Yu, Zhiyong Sun","doi":"10.1002/aic.70290","DOIUrl":"https://doi.org/10.1002/aic.70290","url":null,"abstract":"Conducting incompatible multi‐enzymatic and chemo‐enzymatic cascade reactions concurrently is highly attractive yet remains a persistent challenge. Herein, we demonstrated a diatom‐inspired microreactor, fabricated by armoring polymer‐stabilized water‐in‐oil emulsion with silica membranes for interfacial enzymatic catalysis in organic environments. Optimized interfacial engineering employing bis(trimethoxysilyl)hexane yielded resilient and porous silica membranes, facilitating efficient mass transfer. Crucially, synergistic polymer–enzyme–silica interactions promoted enzyme localization on the microreactors' interface, drastically reducing substrates' diffusion distance. Therefore, the polymer‐stabilized microreactors achieved a 45% higher product and retained 88% more activity after 10 cycles than the control in benzaldehyde lyase‐catalyzed benzoin condensation. Moreover, challenging chemo‐enzymatic cascades and multi‐enzymatic cascade reactions were demonstrated with high reactivity and recyclability in the diatom‐inspired microreactors, which compartmentalize distinct catalytic species to maintain their optimal catalytic conditions with minimum mass transfer resistance. The potential of this powerful platform to accommodate more challenging cascades for advanced synthetic applications is thus envisioned.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"478 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146169416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Catalytic decomposition of ground‐level ozone is proven to be the most efficient and eco‐friendly method for the ozone treatment. Regulating the structure of Mn‐based catalysts has been the primary research focus. But there remains a lack of effective methods to precisely regulate MnO bonds for ground‐breaking catalytic performance. In this study, a PO 43− modified layered double hydroxides catalyst (PO 4 ‐LDH) is reported, which is featured with an elongated MnO bond and reduced MnO coordination number. The ozone decomposition reaction rate reached 254.29 μmol g −1 min −1 , which is preponderant to the state‐of‐the‐art LDH catalysts. Density functional theory (DFT) calculation indicated that the energy barrier of endothermic sub‐steps can all be reduced, including the catalytic step and desorption step. In situ Raman spectra and diffuse reflectance infrared Fourier transform spectra (DRIFTS) further proved that more atomic oxygen can be generated on the surface of PO 4 ‐LDH, and intermediate peroxides were reduced due to the accelerated desorption.
{"title":"Modulation of MnO bond by phosphate for boosting ozone decomposition efficiency","authors":"Wenyan Liu, Xue Deng, Yu‐quan Zhu, Kaitao Li, Wendi Liu, Yanjun Lin","doi":"10.1002/aic.70292","DOIUrl":"https://doi.org/10.1002/aic.70292","url":null,"abstract":"Catalytic decomposition of ground‐level ozone is proven to be the most efficient and eco‐friendly method for the ozone treatment. Regulating the structure of Mn‐based catalysts has been the primary research focus. But there remains a lack of effective methods to precisely regulate MnO bonds for ground‐breaking catalytic performance. In this study, a PO <jats:sub>4</jats:sub> <jats:sup>3−</jats:sup> modified layered double hydroxides catalyst (PO <jats:sub>4</jats:sub> ‐LDH) is reported, which is featured with an elongated MnO bond and reduced MnO coordination number. The ozone decomposition reaction rate reached 254.29 μmol g <jats:sup>−1</jats:sup> min <jats:sup>−1</jats:sup> , which is preponderant to the state‐of‐the‐art LDH catalysts. Density functional theory (DFT) calculation indicated that the energy barrier of endothermic sub‐steps can all be reduced, including the catalytic step and desorption step. <jats:italic>In situ</jats:italic> Raman spectra and diffuse reflectance infrared Fourier transform spectra (DRIFTS) further proved that more atomic oxygen can be generated on the surface of PO <jats:sub>4</jats:sub> ‐LDH, and intermediate peroxides were reduced due to the accelerated desorption.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"300 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2026-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146169414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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