Pub Date : 2026-03-24DOI: 10.1021/acs.iecr.5c05370
Ananda J. Jadhav,Aniruddha Bhalchandra Pandit
Bulk nanobubbles (BNBs), or ultrafine bubbles, have attracted significant attention due to their unexpected long-term stability and unusual physicochemical behavior. Classical models, including the Epstein–Plesset framework, predict rapid dissolution of nanoscale bubbles; however, numerous studies now confirm that BNBs persist for weeks to months, challenging established theories and stimulating renewed interest in their mechanistic origins. This review provides a comprehensive synthesis of current understanding, beginning with the historical evolution of BNB research and the primary pathways proposed for their formation, including nucleation-driven processes and microbubble shrinkage. Major generation strategies such as cavitation, electrolysis, pressurization–decompression, membrane permeation, and microfluidics are critically evaluated with respect to scalability, efficiency, and gas selectivity. The physicochemical attributes of BNBs, encompassing interfacial charge stabilization, enhanced gas solubility, radical generation, and mass-transfer effects, are discussed alongside recent advances in theoretical, atomistic, and continuum-level modeling that seek to reconcile their anomalous stability. Progress in characterization techniques, from light scattering and acoustic detection to nanopore- and fluorescence-based methods, is also assessed.
{"title":"From Paradox to Practice: A Review on Production Strategies, Stability Mechanisms, and Theoretical Insights of Bulk Nanobubbles","authors":"Ananda J. Jadhav,Aniruddha Bhalchandra Pandit","doi":"10.1021/acs.iecr.5c05370","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c05370","url":null,"abstract":"Bulk nanobubbles (BNBs), or ultrafine bubbles, have attracted significant attention due to their unexpected long-term stability and unusual physicochemical behavior. Classical models, including the Epstein–Plesset framework, predict rapid dissolution of nanoscale bubbles; however, numerous studies now confirm that BNBs persist for weeks to months, challenging established theories and stimulating renewed interest in their mechanistic origins. This review provides a comprehensive synthesis of current understanding, beginning with the historical evolution of BNB research and the primary pathways proposed for their formation, including nucleation-driven processes and microbubble shrinkage. Major generation strategies such as cavitation, electrolysis, pressurization–decompression, membrane permeation, and microfluidics are critically evaluated with respect to scalability, efficiency, and gas selectivity. The physicochemical attributes of BNBs, encompassing interfacial charge stabilization, enhanced gas solubility, radical generation, and mass-transfer effects, are discussed alongside recent advances in theoretical, atomistic, and continuum-level modeling that seek to reconcile their anomalous stability. Progress in characterization techniques, from light scattering and acoustic detection to nanopore- and fluorescence-based methods, is also assessed.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"18 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506372","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}
Pub Date : 2026-03-24DOI: 10.1021/acs.iecr.5c05369
Fuxing Jia,Min Wei,Limin Wang
Droplet impact on superhydrophobic surfaces is central to applications such as self-cleaning, waterproofing, and heat-transfer enhancement. However, the coupled roles of droplet geometric asymmetry and substrate macroscopic curvature in rebound dynamics remain unclear. This study employs the Volume-of-Fluid (VOF) framework to study ellipsoidal droplets impacting a superhydrophobic cylindrical surface, varying rotation angle (φ, defined as the angle between the droplet’s major axis and the cylinder axis), aspect ratio (AR), and Weber number (We). Rotation angle is identified as a dominant control parameter: small φ promotes rebound and shortens contact time, whereas large φ increases residence time. A robust transition from rebound promotion to suppression occurs at φ = 60°–75° across the investigated We and AR ranges. We further show that the rebound height-to-width ratio (Λ) provides a simple visual indicator for contact-time trends. Based on these insights, we propose an empirical model incorporating a geometric asymmetry parameter (P), predicting contact time within ±10% and agreeing well with published data.
{"title":"Rotation Angle-Controlled Asymmetric Rebound and Contact Time of Ellipsoidal Droplets on Superhydrophobic Cylinder","authors":"Fuxing Jia,Min Wei,Limin Wang","doi":"10.1021/acs.iecr.5c05369","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c05369","url":null,"abstract":"Droplet impact on superhydrophobic surfaces is central to applications such as self-cleaning, waterproofing, and heat-transfer enhancement. However, the coupled roles of droplet geometric asymmetry and substrate macroscopic curvature in rebound dynamics remain unclear. This study employs the Volume-of-Fluid (VOF) framework to study ellipsoidal droplets impacting a superhydrophobic cylindrical surface, varying rotation angle (φ, defined as the angle between the droplet’s major axis and the cylinder axis), aspect ratio (AR), and Weber number (We). Rotation angle is identified as a dominant control parameter: small φ promotes rebound and shortens contact time, whereas large φ increases residence time. A robust transition from rebound promotion to suppression occurs at φ = 60°–75° across the investigated We and AR ranges. We further show that the rebound height-to-width ratio (Λ) provides a simple visual indicator for contact-time trends. Based on these insights, we propose an empirical model incorporating a geometric asymmetry parameter (P), predicting contact time within ±10% and agreeing well with published data.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"22 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506374","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}
Pub Date : 2026-03-24DOI: 10.1021/acs.iecr.6c00581
Kapil Dhotre,Komal P. Tarade,Sanjay P. Kamble
Bisguaiacol-E (BGE) has emerged as a biobased and sustainable alternative to bisphenol-A (BPA) for the production of materials intended for direct contact with humans and animals, including baby feeding bottles and food packaging. In the present study, BGE was synthesized from bioderived guaiacol and acetaldehyde via acid-catalyzed condensation using a highly efficient and reusable ion-exchange resin, Purolite C124SH. Under optimized conditions, the process achieved 96% guaiacol conversion with 100% selectivity toward BGE. The crude product was purified to obtain BGE in 95% isolated yield and 100% purity. The reusability of Purolite C124SH was evaluated over multiple reaction cycles. After five consecutive reuse cycles, guaiacol conversion and BGE selectivity declined by approximately 25–26% and 20–22%, respectively. However, after regeneration by methanol treatment, the catalyst recovered its activity and maintained a consistent performance over the subsequent three cycles. These results demonstrate the catalyst’s regenerability, robustness, and resistance to deactivation, highlighting its potential for cost-effective industrial application. The kinetic study indicates that the condensation of acetaldehyde with guaiacol to form BGE over the Purolite C124SH resin catalyst can be described by a pseudohomogeneous kinetic model. The reaction follows apparent pseudo-first-order behavior, with an activation energy of 43.5 kJ mol–1, suggesting a minimal contribution from external mass-transfer limitations under the investigated conditions. Moreover, at the optimized reaction conditions, the estimated space-time yield (STY) was 0.42 kg L–1 h–1, corresponding to an apparent reaction rate constant of 0.5 h–1. Furthermore, the physicochemical properties of the synthesized BGE were compared with those of reported BGF (Bisguaiacol-F) and BPA, showing strong alignment and confirming its applicability as a safer substitute. The environmental performance of the process was assessed using green chemistry metrics. The calculated E-factor (0.2) and Process Mass Intensity (PMI - 1.27) indicate low waste generation, high material efficiency, and improved sustainability. Overall, the developed methodology offers a clean, efficient, and scalable route for producing BGE as a viable biobased replacement for BPA.
双愈创木酚- e （BGE）已成为一种生物基和可持续的双酚a （BPA）替代品，用于生产与人类和动物直接接触的材料，包括婴儿奶瓶和食品包装。在本研究中，以生物源愈创木酚和乙醛为原料，采用高效、可重复使用的离子交换树脂Purolite C124SH，通过酸催化缩合合成了BGE。在优化条件下，愈创木酚的转化率为96%，对BGE的选择性为100%。对粗产物进行纯化，得到BGE，分离率95%，纯度100%。通过多个反应循环对Purolite C124SH的可重复使用性进行了评价。在连续5次重复使用循环后，愈创木酚转化率和BGE选择性分别下降了约25-26%和20-22%。然而，经过甲醇处理再生后，催化剂恢复了活性，并在随后的三个循环中保持了一致的性能。这些结果证明了催化剂的可再生性、稳健性和抗失活性，突出了其具有成本效益的工业应用潜力。动力学研究表明，乙醛与愈创木酚在Purolite C124SH树脂催化剂上的缩合反应可以用拟均相动力学模型来描述。反应具有明显的准一级行为，活化能为43.5 kJ mol-1，表明在所研究的条件下，外部传质限制的影响很小。在优化反应条件下，时空产率为0.42 kg L-1 h-1，反应表观速率常数为0.5 h-1。此外，将合成的BGE与已有报道的BGF （Bisguaiacol-F）和BPA的理化性质进行了比较，显示出较强的亲和性，证实了其作为更安全的替代品的适用性。使用绿色化学指标对该工艺的环境性能进行了评估。计算的e因子（0.2）和过程质量强度（PMI - 1.27）表明废物产生少，材料效率高，可持续性提高。总的来说，所开发的方法为生产BGE提供了一种清洁、高效、可扩展的途径，作为BPA的可行生物基替代品。
{"title":"Condensation of Bioderived Guaiacol with Acetaldehyde for the Synthesis of Bisguaiacol-E: A Biobased Alternative to Bisphenol-A","authors":"Kapil Dhotre,Komal P. Tarade,Sanjay P. Kamble","doi":"10.1021/acs.iecr.6c00581","DOIUrl":"https://doi.org/10.1021/acs.iecr.6c00581","url":null,"abstract":"Bisguaiacol-E (BGE) has emerged as a biobased and sustainable alternative to bisphenol-A (BPA) for the production of materials intended for direct contact with humans and animals, including baby feeding bottles and food packaging. In the present study, BGE was synthesized from bioderived guaiacol and acetaldehyde via acid-catalyzed condensation using a highly efficient and reusable ion-exchange resin, Purolite C124SH. Under optimized conditions, the process achieved 96% guaiacol conversion with 100% selectivity toward BGE. The crude product was purified to obtain BGE in 95% isolated yield and 100% purity. The reusability of Purolite C124SH was evaluated over multiple reaction cycles. After five consecutive reuse cycles, guaiacol conversion and BGE selectivity declined by approximately 25–26% and 20–22%, respectively. However, after regeneration by methanol treatment, the catalyst recovered its activity and maintained a consistent performance over the subsequent three cycles. These results demonstrate the catalyst’s regenerability, robustness, and resistance to deactivation, highlighting its potential for cost-effective industrial application. The kinetic study indicates that the condensation of acetaldehyde with guaiacol to form BGE over the Purolite C124SH resin catalyst can be described by a pseudohomogeneous kinetic model. The reaction follows apparent pseudo-first-order behavior, with an activation energy of 43.5 kJ mol–1, suggesting a minimal contribution from external mass-transfer limitations under the investigated conditions. Moreover, at the optimized reaction conditions, the estimated space-time yield (STY) was 0.42 kg L–1 h–1, corresponding to an apparent reaction rate constant of 0.5 h–1. Furthermore, the physicochemical properties of the synthesized BGE were compared with those of reported BGF (Bisguaiacol-F) and BPA, showing strong alignment and confirming its applicability as a safer substitute. The environmental performance of the process was assessed using green chemistry metrics. The calculated E-factor (0.2) and Process Mass Intensity (PMI - 1.27) indicate low waste generation, high material efficiency, and improved sustainability. Overall, the developed methodology offers a clean, efficient, and scalable route for producing BGE as a viable biobased replacement for BPA.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"83 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506357","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}
Pub Date : 2026-03-24DOI: 10.1021/acs.iecr.5c04832
John G. B. Churchill,Venu B. Borugadda,Ajay K. Dalai
The impact of acid, steam explosion, and washing pretreatments on seven underutilized Canadian lignocellulosic residues was investigated via noncatalytic and catalytic hydrothermal liquefaction (HTL) for biocrude production. Washing was detrimental to biocrude production as it removed both catalytic components and those necessary for biocrude formation. Acid and steam explosion pretreatments primarily degraded hemicellulose. Acid pretreatment at 50 °C, 1 wt % H2SO4, and 4 h, with Fe+K2CO3 HTL catalyst was determined optimal with pine, observing the largest increase in biocrude yield by 13.7 wt %. While the impact on yield was moderate for lower lignin residues (−2.0 to +2.3 wt %), acid pretreatment with catalyst led to a significant oxygen reduction (up to 5.6 wt %), enhancing biocrude quality across most feedstocks. The effectiveness of steam explosion was reduced due to the loss of desirable volatile compounds during pretreatment (up to 16.0 wt %). Hydrocarbon-precursor phenols, carboxylic acids, and ketones were the major biocrude components across experiments. Although acid pretreatment improved biocrude oil production, the overall advantages were questionable due to complexity, energy, and environmental concerns. This study contributes to enhancing the viability of meeting Canadian low-carbon fuel standards through agro-forestry biocrude integration with refineries.
{"title":"Acid, Steam Explosion, and Washing Pretreatment Impacts on Sustainable Biocrude Production via Hydrothermal Liquefaction of Canadian Lignocellulosic Residues","authors":"John G. B. Churchill,Venu B. Borugadda,Ajay K. Dalai","doi":"10.1021/acs.iecr.5c04832","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04832","url":null,"abstract":"The impact of acid, steam explosion, and washing pretreatments on seven underutilized Canadian lignocellulosic residues was investigated via noncatalytic and catalytic hydrothermal liquefaction (HTL) for biocrude production. Washing was detrimental to biocrude production as it removed both catalytic components and those necessary for biocrude formation. Acid and steam explosion pretreatments primarily degraded hemicellulose. Acid pretreatment at 50 °C, 1 wt % H2SO4, and 4 h, with Fe+K2CO3 HTL catalyst was determined optimal with pine, observing the largest increase in biocrude yield by 13.7 wt %. While the impact on yield was moderate for lower lignin residues (−2.0 to +2.3 wt %), acid pretreatment with catalyst led to a significant oxygen reduction (up to 5.6 wt %), enhancing biocrude quality across most feedstocks. The effectiveness of steam explosion was reduced due to the loss of desirable volatile compounds during pretreatment (up to 16.0 wt %). Hydrocarbon-precursor phenols, carboxylic acids, and ketones were the major biocrude components across experiments. Although acid pretreatment improved biocrude oil production, the overall advantages were questionable due to complexity, energy, and environmental concerns. This study contributes to enhancing the viability of meeting Canadian low-carbon fuel standards through agro-forestry biocrude integration with refineries.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"52 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506379","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}
Natural gas hydrate technology offers a potentially safer, more efficient, and convenient method for storing and transporting gases. However, factors such as slow kinetics, environmental contamination, and high cost of use have severely hindered the development of storage applications. Sodium dodecyl sulfate (SDS) is one of the most widely used additives to promote gas hydrate generation, but the large-scale application of SDS can cause serious environmental damage. In order to reduce the dependence on SDS, several scholars have investigated amino acids, an environmentally friendly additive, and have demonstrated that amino acids have better prospects for promoting methane hydrate generation. In this paper, β-CD was selected to be compounded with amino acids, and its purpose was to further enhance the system’s promotion effect on the kinetics of natural gas hydrate formation by adding β-CD. The results show that the addition of β-CD can effectively enhance the hydrate formation kinetics of the four amino acid systems, in which the final gas consumption of the leucine system was enhanced by 34.88% and the T90 of the methionine system was reduced by 19.51%. Then we found that the addition of β-CD can effectively enhance the dendritic properties of some hydrates by recording the generation process of natural gas hydrates in the system, which achieves the effect of enhancing the kinetics of hydrate generation. In addition, there is an obvious difference between the hydrate properties generated by tryptophan and methionine systems at the gas–liquid interface. Finally, we conducted an in-depth study of the synergistic mechanism of the complex system by combining the hydrate morphological observations and kinetic data.
{"title":"Enhanced Kinetics of Natural Gas Hydrate Generation by an Amino Acid-Cyclodextrin Complex System","authors":"Chengming Hao,Zhe Jiang,Wei Jia,Lifan Zhang,Zhen Pan,Xianlong Xie,Xiangwei Xu","doi":"10.1021/acs.iecr.5c05378","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c05378","url":null,"abstract":"Natural gas hydrate technology offers a potentially safer, more efficient, and convenient method for storing and transporting gases. However, factors such as slow kinetics, environmental contamination, and high cost of use have severely hindered the development of storage applications. Sodium dodecyl sulfate (SDS) is one of the most widely used additives to promote gas hydrate generation, but the large-scale application of SDS can cause serious environmental damage. In order to reduce the dependence on SDS, several scholars have investigated amino acids, an environmentally friendly additive, and have demonstrated that amino acids have better prospects for promoting methane hydrate generation. In this paper, β-CD was selected to be compounded with amino acids, and its purpose was to further enhance the system’s promotion effect on the kinetics of natural gas hydrate formation by adding β-CD. The results show that the addition of β-CD can effectively enhance the hydrate formation kinetics of the four amino acid systems, in which the final gas consumption of the leucine system was enhanced by 34.88% and the T90 of the methionine system was reduced by 19.51%. Then we found that the addition of β-CD can effectively enhance the dendritic properties of some hydrates by recording the generation process of natural gas hydrates in the system, which achieves the effect of enhancing the kinetics of hydrate generation. In addition, there is an obvious difference between the hydrate properties generated by tryptophan and methionine systems at the gas–liquid interface. Finally, we conducted an in-depth study of the synergistic mechanism of the complex system by combining the hydrate morphological observations and kinetic data.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"402 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506371","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}
Bioengineered (enzyme-enabled) glutarimide-based polyamides have garnered increasing attention due to their renewable monomer availability, low cost, and high performance. However, their physicochemical aging behavior and the underlying mechanisms under realistic thermo-oxidative conditions remain insufficiently elucidated. In this work, we synthesized bio-based PA514 via melt copolymerization of pentamethylenediamine with tetradecanedioic acid and investigated its thermo-oxidative aging behavior and mechanisms under practical service conditions. Early during thermo-oxidative exposure, physical aging manifested as lamellar thickening predominates, resulting in increased yield strength and reduced elongation at break. With prolonged aging, chemical degradation processes─principally amide bond scission followed by pentamethylenediamine cyclization─reduce the number-average molecular weight and entanglement density, concomitant with a γ–α crystalline phase transition. These findings clarify the coupled physical and chemical aging pathway of bio-based PA514 and provide a mechanistic basis for predicting performance decay and optimizing processing and composite application strategies for pentamethylenediamine monomer-based polyamides.
{"title":"Bio-Based Pentylenediamine Monomer-Based Chemical–Physical Change Mechanism of Thermo-Oxidative Aging of Long-Carbon-Chain Nylon","authors":"Minghui Wu,Wentao Zheng,Kejian Yang,Lu Yang,Yunqi Xu,Jinlian Fan,Mingtao Wu,Rui Chen,Jun Peng,Cheng Wang,Xudong Chen","doi":"10.1021/acs.iecr.5c05104","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c05104","url":null,"abstract":"Bioengineered (enzyme-enabled) glutarimide-based polyamides have garnered increasing attention due to their renewable monomer availability, low cost, and high performance. However, their physicochemical aging behavior and the underlying mechanisms under realistic thermo-oxidative conditions remain insufficiently elucidated. In this work, we synthesized bio-based PA514 via melt copolymerization of pentamethylenediamine with tetradecanedioic acid and investigated its thermo-oxidative aging behavior and mechanisms under practical service conditions. Early during thermo-oxidative exposure, physical aging manifested as lamellar thickening predominates, resulting in increased yield strength and reduced elongation at break. With prolonged aging, chemical degradation processes─principally amide bond scission followed by pentamethylenediamine cyclization─reduce the number-average molecular weight and entanglement density, concomitant with a γ–α crystalline phase transition. These findings clarify the coupled physical and chemical aging pathway of bio-based PA514 and provide a mechanistic basis for predicting performance decay and optimizing processing and composite application strategies for pentamethylenediamine monomer-based polyamides.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"14 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506375","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}
Pub Date : 2026-03-24DOI: 10.1021/acs.iecr.6c00074
Raz Abbasi,Anne Ngo,Jaddie Ho,Philip G. Jessop,Michael F. Cunningham
CO2-switchable surfactants enable surface activity during processing but deactivate later, ideal for latex coatings where charged surfactants are used to stabilize the formulation, but the presence of charged species in the final coating negatively impacts the coating performance. In this study, surfactants with CO2-switchable functional head groups including imidazole (C12Im), tertiary aminoethoxy (C10EDMA), and tertiary amine (C12DMA), were applied in the emulsion copolymerization of butyl acrylate and methyl methacrylate using VA-061 as a CO2-switchable initiator. A lower-basicity surfactant produced larger latex particles, whereas higher-basicity surfactants stabilized smaller latex particles at lower concentrations. ATR-FTIR analysis indicated residual bicarbonate species in dried films, likely from the initiator, the most basic component. Coatings made with CO2-switchable surfactants exhibited improved water resistance, greater hydrophobicity, and enhanced corrosion protection relative to coatings with permanently charged surfactants. These findings highlight the critical role of surfactant basicity in governing both polymerization and coating performance.
{"title":"CO2-Switchable Surfactants in the Preparation and Application of Butyl Acrylate and Methyl Methacrylate Copolymer Latexes: Effect of Switchable Group Basicity on Polymerization and Coating Properties","authors":"Raz Abbasi,Anne Ngo,Jaddie Ho,Philip G. Jessop,Michael F. Cunningham","doi":"10.1021/acs.iecr.6c00074","DOIUrl":"https://doi.org/10.1021/acs.iecr.6c00074","url":null,"abstract":"CO2-switchable surfactants enable surface activity during processing but deactivate later, ideal for latex coatings where charged surfactants are used to stabilize the formulation, but the presence of charged species in the final coating negatively impacts the coating performance. In this study, surfactants with CO2-switchable functional head groups including imidazole (C12Im), tertiary aminoethoxy (C10EDMA), and tertiary amine (C12DMA), were applied in the emulsion copolymerization of butyl acrylate and methyl methacrylate using VA-061 as a CO2-switchable initiator. A lower-basicity surfactant produced larger latex particles, whereas higher-basicity surfactants stabilized smaller latex particles at lower concentrations. ATR-FTIR analysis indicated residual bicarbonate species in dried films, likely from the initiator, the most basic component. Coatings made with CO2-switchable surfactants exhibited improved water resistance, greater hydrophobicity, and enhanced corrosion protection relative to coatings with permanently charged surfactants. These findings highlight the critical role of surfactant basicity in governing both polymerization and coating performance.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"20 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506369","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}
Pub Date : 2026-03-24DOI: 10.1021/acs.iecr.5c05069
Akihiro Okada,Daichi Homma,Takatoshi Murakami,Shin R. Mukai,Isao Ogino
In supported metal catalysts, the support plays crucial roles in modulating the electronic structure of metal centers and the physicochemical properties of their surrounding microenvironments. Here, we report that microporous carbon supports derived from ZIF-8, a metal–organic framework (MOF), exert a pronounced influence on the intrinsic activity and selectivity of Fe–N–C catalysts in the oxygen reduction reaction (ORR). The average turnover frequency (TOF) of Fe–Nx sites monotonically increases with increasing surface basicity (quantified by a literature method) and a narrower C 1s X-ray photoelectron spectroscopy (XPS) peak, both of which reflect greater π-electron delocalization and a higher point of zero charge (PZC), thereby indicative of the enhanced electron-donating capability of the carbon support. The inverse relationship between C 1s peak width and TOF observed here contrasts with that reported for Fe–N–C catalysts derived from iron porphyrin complexes on conventional carbons, suggesting that MOF-derived carbons create distinct electrostatic environments for Fe–Nx sites located within their microporous structures and modulated by the π-electron system through thermal activation. Rapid microwave heating offers a strategy to tailor these local environments while preserving the microporous framework, in contrast to conventional furnace heating. Thermal activation at ≥1100 °C under a reductive atmosphere in a single-mode microwave reactor increases the surface basicity while preserving microporosity, simultaneously improving the intrinsic activity of Fe–Nx sites and suppressing H2O2 formation, leading to improved 4e– ORR selectivity.
{"title":"Revisiting the Activity Descriptor for the Oxygen Reduction Reaction Catalyzed by Fe–N–C Catalysts","authors":"Akihiro Okada,Daichi Homma,Takatoshi Murakami,Shin R. Mukai,Isao Ogino","doi":"10.1021/acs.iecr.5c05069","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c05069","url":null,"abstract":"In supported metal catalysts, the support plays crucial roles in modulating the electronic structure of metal centers and the physicochemical properties of their surrounding microenvironments. Here, we report that microporous carbon supports derived from ZIF-8, a metal–organic framework (MOF), exert a pronounced influence on the intrinsic activity and selectivity of Fe–N–C catalysts in the oxygen reduction reaction (ORR). The average turnover frequency (TOF) of Fe–Nx sites monotonically increases with increasing surface basicity (quantified by a literature method) and a narrower C 1s X-ray photoelectron spectroscopy (XPS) peak, both of which reflect greater π-electron delocalization and a higher point of zero charge (PZC), thereby indicative of the enhanced electron-donating capability of the carbon support. The inverse relationship between C 1s peak width and TOF observed here contrasts with that reported for Fe–N–C catalysts derived from iron porphyrin complexes on conventional carbons, suggesting that MOF-derived carbons create distinct electrostatic environments for Fe–Nx sites located within their microporous structures and modulated by the π-electron system through thermal activation. Rapid microwave heating offers a strategy to tailor these local environments while preserving the microporous framework, in contrast to conventional furnace heating. Thermal activation at ≥1100 °C under a reductive atmosphere in a single-mode microwave reactor increases the surface basicity while preserving microporosity, simultaneously improving the intrinsic activity of Fe–Nx sites and suppressing H2O2 formation, leading to improved 4e– ORR selectivity.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"83 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506377","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}
Conductive hydrogels have attracted much attention in wearable electronic devices, but the poor temperature tolerance limits their potential applications in harsh environments. Ionogels with high ionic conductivity and nonvolatility are ideal candidates, while the poor mechanical properties and hygroscopic swelling behavior hinder their practical applications. Herein, a super stretchable dual-cross-linking semi-interpenetrating network (semi-IPN) ionogel is fabricated via cellulose incorporation with polyacrylamide (PAM). The cellulose-induced semi-IPN with PAM constructs a physicochemical dual cross-linked structure. Benefiting from this favored structure and sacrificial hydrogen bonds, the PAM/cellulose ionogel exhibits enhanced mechanical properties (3109% strain, 4861 kJ m–3 toughness) while maintaining high ionic conductivity (1.76 mS cm–1). The enhanced cross-linking density also improves stability against hygroscopic swelling. Importantly, it demonstrates outstanding wearable sensing performance (GF = 1.08, response time: 19 ms) even in harsh environments from −20 to 45 °C. This work provides new insights into the design and fabrication of high-performance environment-tolerant flexible wearable devices.
导电性水凝胶在可穿戴电子器件中备受关注，但其较差的耐温性限制了其在恶劣环境中的潜在应用。具有高离子电导率和非挥发性的离子凝胶是理想的选择，但较差的机械性能和吸湿膨胀行为阻碍了它们的实际应用。本文通过纤维素与聚丙烯酰胺（PAM）的掺入制备了一种超可拉伸的双交联半互穿网络（semi-IPN）离子凝胶。纤维素诱导的PAM半ipn构建了一个物理化学双交联结构。得益于这种有利的结构和牺牲的氢键，PAM/纤维素离子凝胶在保持高离子电导率（1.76 mS cm-1）的同时，表现出增强的力学性能（应变为3109%，韧性为4861 kJ m-3）。增强的交联密度也提高了抗吸湿膨胀的稳定性。重要的是，即使在- 20至45°C的恶劣环境中，它也表现出出色的可穿戴传感性能（GF = 1.08，响应时间：19 ms）。这项工作为高性能环境耐受柔性可穿戴设备的设计和制造提供了新的见解。
{"title":"Dual-Cross-linking Semi-Interpenetrating Network Ionogels with Ultra-Stretchability and Harsh Environment Tolerance for High-Performance Wearable Sensing","authors":"Ye Feng, Genrui Xu, Shuang Liu, Zhaoming Wu, Binxia Chen, Canhui Lu, Zehang Zhou","doi":"10.1021/acs.iecr.5c04820","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04820","url":null,"abstract":"Conductive hydrogels have attracted much attention in wearable electronic devices, but the poor temperature tolerance limits their potential applications in harsh environments. Ionogels with high ionic conductivity and nonvolatility are ideal candidates, while the poor mechanical properties and hygroscopic swelling behavior hinder their practical applications. Herein, a super stretchable dual-cross-linking semi-interpenetrating network (semi-IPN) ionogel is fabricated via cellulose incorporation with polyacrylamide (PAM). The cellulose-induced semi-IPN with PAM constructs a physicochemical dual cross-linked structure. Benefiting from this favored structure and sacrificial hydrogen bonds, the PAM/cellulose ionogel exhibits enhanced mechanical properties (3109% strain, 4861 kJ m<sup>–3</sup> toughness) while maintaining high ionic conductivity (1.76 mS cm<sup>–1</sup>). The enhanced cross-linking density also improves stability against hygroscopic swelling. Importantly, it demonstrates outstanding wearable sensing performance (GF = 1.08, response time: 19 ms) even in harsh environments from −20 to 45 °C. This work provides new insights into the design and fabrication of high-performance environment-tolerant flexible wearable devices.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"31 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507227","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}
Pub Date : 2026-03-24DOI: 10.1021/acs.iecr.5c04459
Ikram Boulahya, Anass Sibari, Abdelkabir Elouahlouly, Abdelouahed Dahrouch, Lotfi Rghioui, Hind El Masaoudi, Mohammed Benaissa
Zinc ferrite (ZnFe2O4) is attracting increasing interest due to its advantageous optical properties and remarkable chemical and thermal stability. With its bandgap energy in the visible range, this ferrite is a promising material for the photodegradation of organic pollutants in wastewater, provided that its electronic structure is modified to reduce the rapid recombination of photogenerated electron–hole pair. In this study, an attempt to substitute manganese for zinc in the synthesis of zinc ferrite nanoparticles was successfully carried out using the sonochemistry method. Structural and morphological characterizations confirm the formation of nanoparticles, and optical properties reveal a significant decrease in the bandgap energy, from 2.03 to 1.41 eV with increasing manganese concentration. This ability to tune the bandgap energy allows for optimizing the material composition for a specific type of pollutant. Photocatalytic tests under visible light, focused on the degradation of the rhodamine B dye, demonstrate that the modified ferrite performs better than the initial material, where hydroxyl radicals play a key role in the dye degradation process. This enhanced photocatalytic efficiency is due to a better alignment of the energy bands of the ferrite material with respect to the standard hydrogen electrode, resulting in excellent photocatalytic activity combined with exceptional recyclability and high chemical stability. This control over doping allows for the tailoring of nanoparticles for large-scale wastewater treatment applications under solar visible light.
{"title":"Photocatalytic Properties of MnZnFe2O4 Nanoparticles","authors":"Ikram Boulahya, Anass Sibari, Abdelkabir Elouahlouly, Abdelouahed Dahrouch, Lotfi Rghioui, Hind El Masaoudi, Mohammed Benaissa","doi":"10.1021/acs.iecr.5c04459","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04459","url":null,"abstract":"Zinc ferrite (ZnFe<sub>2</sub>O<sub>4</sub>) is attracting increasing interest due to its advantageous optical properties and remarkable chemical and thermal stability. With its bandgap energy in the visible range, this ferrite is a promising material for the photodegradation of organic pollutants in wastewater, provided that its electronic structure is modified to reduce the rapid recombination of photogenerated electron–hole pair. In this study, an attempt to substitute manganese for zinc in the synthesis of zinc ferrite nanoparticles was successfully carried out using the sonochemistry method. Structural and morphological characterizations confirm the formation of nanoparticles, and optical properties reveal a significant decrease in the bandgap energy, from 2.03 to 1.41 eV with increasing manganese concentration. This ability to tune the bandgap energy allows for optimizing the material composition for a specific type of pollutant. Photocatalytic tests under visible light, focused on the degradation of the rhodamine B dye, demonstrate that the modified ferrite performs better than the initial material, where hydroxyl radicals play a key role in the dye degradation process. This enhanced photocatalytic efficiency is due to a better alignment of the energy bands of the ferrite material with respect to the standard hydrogen electrode, resulting in excellent photocatalytic activity combined with exceptional recyclability and high chemical stability. This control over doping allows for the tailoring of nanoparticles for large-scale wastewater treatment applications under solar visible light.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"17 5 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507226","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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