Pub Date : 2025-01-17DOI: 10.1021/acs.langmuir.4c04011
Anindita Bhattacharya, Suman Chakraborty
Electrorheological fluids are suspensions that are characterized by a strong functional dependence of their constitutive behavior on the local electric field. While such fluids are known to be promising in different applications of microfluidics including electrokinetic flows, their capabilities of controlling ion transport and preferential solute segregation in confined fluidic systems remain to be explored. In this work, we bring out the unique role of electrorheological fluids in orchestrating the selective enrichment and depletion of charged species in variable area microfluidic channels. Our reported phenomenon is fundamentally distinctive from other types of nonlinear electrokinetic effects previously reported, in a sense that here the dependence of the flow rheology on the electric field turns out to be the central mechanism toward orchestrating the observed nonlinear ion transport. Our results indicate exclusive features of the resulting ion concentration polarization, such as more pronounced ion concentration polarization, controlled largely by the influence of the variations in the channel cross section on the driving electrokinetic forces and the resistive viscous interactions. The underlying physical mechanism is captured aptly by a simple one-dimensional area-averaged model, and validated by full-scale three-dimensional simulations. Our illustrative case study for a converging-diverging microchannel with cross-sectionally uniform solute concentrations reveals that electrorheological effect with greater contrast between the deep and shallow region depths, greater solute concentration, and larger applied axial electric field, all acting in tandem, magnifies the solute enrichment and depletion in the respective segregation zones, bearing significant implications in analytical chemistry, bioanalysis, and beyond.
{"title":"Modulating the Selective Enrichment and Depletion of Ions Using Electrorheological Fluids in Variable-Area Microchannels","authors":"Anindita Bhattacharya, Suman Chakraborty","doi":"10.1021/acs.langmuir.4c04011","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04011","url":null,"abstract":"Electrorheological fluids are suspensions that are characterized by a strong functional dependence of their constitutive behavior on the local electric field. While such fluids are known to be promising in different applications of microfluidics including electrokinetic flows, their capabilities of controlling ion transport and preferential solute segregation in confined fluidic systems remain to be explored. In this work, we bring out the unique role of electrorheological fluids in orchestrating the selective enrichment and depletion of charged species in variable area microfluidic channels. Our reported phenomenon is fundamentally distinctive from other types of nonlinear electrokinetic effects previously reported, in a sense that here the dependence of the flow rheology on the electric field turns out to be the central mechanism toward orchestrating the observed nonlinear ion transport. Our results indicate exclusive features of the resulting ion concentration polarization, such as more pronounced ion concentration polarization, controlled largely by the influence of the variations in the channel cross section on the driving electrokinetic forces and the resistive viscous interactions. The underlying physical mechanism is captured aptly by a simple one-dimensional area-averaged model, and validated by full-scale three-dimensional simulations. Our illustrative case study for a converging-diverging microchannel with cross-sectionally uniform solute concentrations reveals that electrorheological effect with greater contrast between the deep and shallow region depths, greater solute concentration, and larger applied axial electric field, all acting in tandem, magnifies the solute enrichment and depletion in the respective segregation zones, bearing significant implications in analytical chemistry, bioanalysis, and beyond.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"30 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-17DOI: 10.1021/acs.langmuir.4c04434
Hong Liu, Wenzhuang Wang, Qinghua Chuai, Wenling Xu, Feng Guo
The pervasive presence of toluene in aquatic environments, primarily due to oil spills and industrial effluents, necessitates the development of effective and sustainable remediation strategies. This study introduces ZIF-8@DES-treated loofah sponge (ZIF-8@DLS), a novel adsorbent composite material, synthesized via an in situ process that integrates the high surface area of ZIF-8 with the natural loofah sponge. The composite was characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR), confirming the successful loading of ZIF-8 onto the loofah substrate. The adsorption capacity of ZIF-8@DLS for toluene was evaluated, achieving a maximum of 145.3 mg/g with an efficiency of 72% under standard conditions. Kinetic studies revealed that the adsorption process predominantly followed a pseudo-second-order model, indicative of chemisorption. The adsorption isotherm data were found to align more closely with the Freundlich model, suggesting a multilayer adsorption mechanism on the composite’s heterogeneous surface. The ZIF-8@DLS composite demonstrates a promising synergy of high adsorption performance, cost-effectiveness, facile synthesis, and environmental benignity, positioning it as a candidate for practical applications in wastewater treatment and adsorptive separation processes.
{"title":"Integrating Zeolitic Imidazolate Framework-8 with DES-Treated Loofah Sponge for Enhanced Toluene Adsorption","authors":"Hong Liu, Wenzhuang Wang, Qinghua Chuai, Wenling Xu, Feng Guo","doi":"10.1021/acs.langmuir.4c04434","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04434","url":null,"abstract":"The pervasive presence of toluene in aquatic environments, primarily due to oil spills and industrial effluents, necessitates the development of effective and sustainable remediation strategies. This study introduces ZIF-8@DES-treated loofah sponge (ZIF-8@DLS), a novel adsorbent composite material, synthesized via an in situ process that integrates the high surface area of ZIF-8 with the natural loofah sponge. The composite was characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR), confirming the successful loading of ZIF-8 onto the loofah substrate. The adsorption capacity of ZIF-8@DLS for toluene was evaluated, achieving a maximum of 145.3 mg/g with an efficiency of 72% under standard conditions. Kinetic studies revealed that the adsorption process predominantly followed a pseudo-second-order model, indicative of chemisorption. The adsorption isotherm data were found to align more closely with the Freundlich model, suggesting a multilayer adsorption mechanism on the composite’s heterogeneous surface. The ZIF-8@DLS composite demonstrates a promising synergy of high adsorption performance, cost-effectiveness, facile synthesis, and environmental benignity, positioning it as a candidate for practical applications in wastewater treatment and adsorptive separation processes.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"5 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-17DOI: 10.1021/acs.langmuir.4c04464
Xuewei Gao, Linxi Hou, Weijun Yang, Liangliang Dong, Xin Ge
The development of green and easily regulated amphiphilic particles is crucial for advancing Pickering emulsion catalysis. In this study, lignin particles modified via sulfobutylation were employed as solid emulsifiers to support Pd nanoparticles (NPs), thereby enhancing the catalytic efficiency of biphasic reactions. Sulfobutylation of lignin effectively adjusted the hydrophilic–hydrophobic balance, resulting in controlled emulsion types and droplet sizes. Pd NPs were loaded onto lignin with a 50% sulfobutylation ratio through the in situ reduction of active functional groups, further stabilized by the cross-linked network structure of lignin. In the hydrogenation of nitrobenzene, the Lig-50S-0.6Pd catalyst exhibited superior activity compared to traditional Pd/C catalysts, which is attributed to the high retention of active sites and increased interfacial area. This work underscores the potential for designing lignin-based amphiphilic particles and developing Pickering emulsion-enhanced reactions.
{"title":"Lignin-Based Nanoparticles Stabilized Pickering Emulsion for Enhanced Catalytic Hydrogenation","authors":"Xuewei Gao, Linxi Hou, Weijun Yang, Liangliang Dong, Xin Ge","doi":"10.1021/acs.langmuir.4c04464","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04464","url":null,"abstract":"The development of green and easily regulated amphiphilic particles is crucial for advancing Pickering emulsion catalysis. In this study, lignin particles modified via sulfobutylation were employed as solid emulsifiers to support Pd nanoparticles (NPs), thereby enhancing the catalytic efficiency of biphasic reactions. Sulfobutylation of lignin effectively adjusted the hydrophilic–hydrophobic balance, resulting in controlled emulsion types and droplet sizes. Pd NPs were loaded onto lignin with a 50% sulfobutylation ratio through the in situ reduction of active functional groups, further stabilized by the cross-linked network structure of lignin. In the hydrogenation of nitrobenzene, the Lig-50S-0.6Pd catalyst exhibited superior activity compared to traditional Pd/C catalysts, which is attributed to the high retention of active sites and increased interfacial area. This work underscores the potential for designing lignin-based amphiphilic particles and developing Pickering emulsion-enhanced reactions.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"37 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987343","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-17DOI: 10.1021/acs.langmuir.4c04088
Fengfei Chen, Hongguang Zhou, Xiaohui Yu, Yunpeng Zhao, Chenchen Wang, Bin Dai, Sheng Han
The widespread application of metal–organic frameworks (MOFs) in wastewater and gas treatment has created an increasing demand for accurate and rapid assessment of their BET specific surface area. However, experimental methods for acquiring sufficient statistical data are often costly and time-consuming. Therefore, this study proposes a dual-stage stacking model with Gaussian mixture model-virtual sample generation (GMM-VSG) technology for the BET specific surface area prediction. In this study, 90 real samples were selected from the MOF database and 300 virtual samples were generated. The performance on both real and virtual samples was evaluated by using four machine learning models, including Bayesian regression (Bayes), adaptive boosting (AdaBoost), random forest (RF), and extreme gradient boosting (XGBoost). Subsequently, three best-performing models and a linear regression model were selected for constructing a two-stage stacking model, with R2 value of 0.974. Finally, experimental conditions were adjusted based on feature importance analysis during the validation process, and the result shows that the prediction accuracy of the BET specific surface area is 0.943. This study contributes to the development of more efficient and accurate evaluation methods.
{"title":"Dual-Stage Stacking Machine Learning Method Considering Virtual Sample Generation for the Prediction of ZIF-8′ BET Specific Surface Area with Experimental Validation","authors":"Fengfei Chen, Hongguang Zhou, Xiaohui Yu, Yunpeng Zhao, Chenchen Wang, Bin Dai, Sheng Han","doi":"10.1021/acs.langmuir.4c04088","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04088","url":null,"abstract":"The widespread application of metal–organic frameworks (MOFs) in wastewater and gas treatment has created an increasing demand for accurate and rapid assessment of their BET specific surface area. However, experimental methods for acquiring sufficient statistical data are often costly and time-consuming. Therefore, this study proposes a dual-stage stacking model with Gaussian mixture model-virtual sample generation (GMM-VSG) technology for the BET specific surface area prediction. In this study, 90 real samples were selected from the MOF database and 300 virtual samples were generated. The performance on both real and virtual samples was evaluated by using four machine learning models, including Bayesian regression (Bayes), adaptive boosting (AdaBoost), random forest (RF), and extreme gradient boosting (XGBoost). Subsequently, three best-performing models and a linear regression model were selected for constructing a two-stage stacking model, with <i>R</i><sup>2</sup> value of 0.974. Finally, experimental conditions were adjusted based on feature importance analysis during the validation process, and the result shows that the prediction accuracy of the BET specific surface area is 0.943. This study contributes to the development of more efficient and accurate evaluation methods.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"14 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987341","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-17DOI: 10.1021/acs.langmuir.4c04509
Shankarrao V. Avhad, Sugam Kumar, Ashootosh V. Ambade
2,2-Bis-(methylol)propionic acid-based second-generation polyester dendron amphiphile (T-D) containing visible light-responsive donor–acceptor Stenhouse adduct (DASA) as hydrophobic tails is synthesized. Micelles of T-D amphiphile and its mixed micelles of varying compositions with nonresponsive dendron amphiphile containing lauryl groups are prepared in aqueous solution. In transmission electron microscopy and atomic force microscopy analyses, T-D amphiphiles show rice grain-like ellipsoidal micelles as the predominant morphology. Mixed micelles display a composition-dependent morphology gradient such that the morphology changes from rice grain like to mixed to completely spherical with decreasing content of the T-D amphiphile. Complete morphology change to spherical micelles and partial reversal to ellipsoidal micelles, finally leading to ill-defined aggregates, are observed when the T-D amphiphile micelles are subjected to visible light-dark storage photoswitching cycles. Small-angle neutron scattering (SANS) analysis of 1 wt.% micellar solution in THF:water (10:90) reveals only a minor change in shape and size upon photoirradiation, and the data could be fitted to spherical or ellipsoidal model. Release of hydrophobic dye from mixed micelles is tuned by the content of the photoresponsive amphiphile. Cellular uptake and visible light-triggered release of hydrophobic drug from mixed micelles are demonstrated using MDA-MB-231 cells, suggesting their applicability for photoresponsive drug delivery.
{"title":"Visible Light-Responsive Composition-Dependent Morphology and Cargo Release in Mixed Micelles of Dendron Amphiphiles","authors":"Shankarrao V. Avhad, Sugam Kumar, Ashootosh V. Ambade","doi":"10.1021/acs.langmuir.4c04509","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04509","url":null,"abstract":"2,2-Bis-(methylol)propionic acid-based second-generation polyester dendron amphiphile (T-D) containing visible light-responsive donor–acceptor Stenhouse adduct (DASA) as hydrophobic tails is synthesized. Micelles of T-D amphiphile and its mixed micelles of varying compositions with nonresponsive dendron amphiphile containing lauryl groups are prepared in aqueous solution. In transmission electron microscopy and atomic force microscopy analyses, T-D amphiphiles show rice grain-like ellipsoidal micelles as the predominant morphology. Mixed micelles display a composition-dependent morphology gradient such that the morphology changes from rice grain like to mixed to completely spherical with decreasing content of the T-D amphiphile. Complete morphology change to spherical micelles and partial reversal to ellipsoidal micelles, finally leading to ill-defined aggregates, are observed when the T-D amphiphile micelles are subjected to visible light-dark storage photoswitching cycles. Small-angle neutron scattering (SANS) analysis of 1 wt.% micellar solution in THF:water (10:90) reveals only a minor change in shape and size upon photoirradiation, and the data could be fitted to spherical or ellipsoidal model. Release of hydrophobic dye from mixed micelles is tuned by the content of the photoresponsive amphiphile. Cellular uptake and visible light-triggered release of hydrophobic drug from mixed micelles are demonstrated using MDA-MB-231 cells, suggesting their applicability for photoresponsive drug delivery.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"27 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987344","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-16DOI: 10.1021/acs.langmuir.4c04598
Abebual Molla, Tun Naw Sut, Joshua A. Jackman
Alkylphospholipids are single-chain lipid amphiphiles that possess clinically relevant biological activities driven by membrane-destabilizing interactions. Subtle variations in alkylphospholipid structure can lead to significant differences in their biological effects, yet corresponding membrane interactions remain underexplored. Herein, we employed the quartz crystal microbalance-dissipation (QCM-D) technique to characterize the real-time membrane interactions of three alkylphospholipids–edelfosine, miltefosine, and perifosine–on supported lipid bilayers with varying cholesterol fractions. Our findings reveal that the tested alkylphospholipids had distinct membrane-interaction profiles: (1) edelfosine exhibited irreversible binding and caused weak membrane disruption; (2) miltefosine caused major disruption by affecting membrane packing; and (3) perifosine exhibited reversible binding while triggering structural rearrangements and modest disruption. Overall, alkylphospholipid micelles showed greater activity than monomers, and higher membrane cholesterol fractions resulted in more extensive disruption, highlighting the interplay between membrane stiffness and responsiveness. These results provide biophysical evidence that different alkylphospholipids have distinct membrane-interaction behaviors that align well with reported biological activities. Our supported lipid bilayer approach offers a valuable platform for designing and assessing alkylphospholipids with tailored membrane-interaction profiles.
{"title":"Unraveling Cholesterol-Dependent Interactions of Alkylphospholipids with Supported Lipid Bilayers","authors":"Abebual Molla, Tun Naw Sut, Joshua A. Jackman","doi":"10.1021/acs.langmuir.4c04598","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04598","url":null,"abstract":"Alkylphospholipids are single-chain lipid amphiphiles that possess clinically relevant biological activities driven by membrane-destabilizing interactions. Subtle variations in alkylphospholipid structure can lead to significant differences in their biological effects, yet corresponding membrane interactions remain underexplored. Herein, we employed the quartz crystal microbalance-dissipation (QCM-D) technique to characterize the real-time membrane interactions of three alkylphospholipids–edelfosine, miltefosine, and perifosine–on supported lipid bilayers with varying cholesterol fractions. Our findings reveal that the tested alkylphospholipids had distinct membrane-interaction profiles: (1) edelfosine exhibited irreversible binding and caused weak membrane disruption; (2) miltefosine caused major disruption by affecting membrane packing; and (3) perifosine exhibited reversible binding while triggering structural rearrangements and modest disruption. Overall, alkylphospholipid micelles showed greater activity than monomers, and higher membrane cholesterol fractions resulted in more extensive disruption, highlighting the interplay between membrane stiffness and responsiveness. These results provide biophysical evidence that different alkylphospholipids have distinct membrane-interaction behaviors that align well with reported biological activities. Our supported lipid bilayer approach offers a valuable platform for designing and assessing alkylphospholipids with tailored membrane-interaction profiles.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"30 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987057","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The high-temperature proton exchange membranes suffer from weak binding strength for phosphoric acid molecules, which seriously reduce the fuel cell efficiency, especially operation stability. Introduction of microporous material in the membrane can effectively reduce the leaching of phosphoric acid. However, due to the poor compatibility between the polymer and fillers, the membrane’s performance significantly reduced at high fillers content. Therefore, in this work, the strategy of micropore confinement was developed; the β-cyclodextrin was carbonylated and introduced into PBI casting solution as solution state rather than dry powder for reducing the interface energy between two phases, thus further reducing interface defects and increasing the content of effective confined micropores within the membrane. By this way, carbonylated β-cyclodextrin/PBI (50 wt %) mixed matrix membranes were obtained, the proton conductivity reached 142 ± 4 mS cm–1, while the conductivity attenuation was only 16.6%.
{"title":"Designing High Content Carbonylated β-Cyclodextrin/PBI Mixed Matrix Membrane as HT-PEM to Reduce H3PO4 Loss","authors":"Yingnan Ma, Juan Chen, Shanshan Xu, Yulu Zhang, Junyi Yan, Zeyun Liao, Zheng Xu, Zhen Xu, Lelin Zeng, Panliang Zhang","doi":"10.1021/acs.langmuir.4c04624","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04624","url":null,"abstract":"The high-temperature proton exchange membranes suffer from weak binding strength for phosphoric acid molecules, which seriously reduce the fuel cell efficiency, especially operation stability. Introduction of microporous material in the membrane can effectively reduce the leaching of phosphoric acid. However, due to the poor compatibility between the polymer and fillers, the membrane’s performance significantly reduced at high fillers content. Therefore, in this work, the strategy of micropore confinement was developed; the β-cyclodextrin was carbonylated and introduced into PBI casting solution as solution state rather than dry powder for reducing the interface energy between two phases, thus further reducing interface defects and increasing the content of effective confined micropores within the membrane. By this way, carbonylated β-cyclodextrin/PBI (50 wt %) mixed matrix membranes were obtained, the proton conductivity reached 142 ± 4 mS cm<sup>–1</sup>, while the conductivity attenuation was only 16.6%.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"77 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987348","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Polyvinylidene fluoride (PVDF) latex nanoparticles serve as a versatile platform for surface modification due to their role as precursors in PVDF manufacturing. However, the strong chemical stability and poor compatibility of PVDF present significant challenges for effective surface modification. To address this, we developed a method that facilitates surface modification through chain entanglement. By employing monomer swelling emulsion polymerization, poly(meth)acrylate (PA) monomers are incorporated into PVDF nanoparticles and subsequently polymerized. Rheological properties and transmission electron microscopy mapping confirmed the chain entanglement between PVDF and PA, indicating a successful integration. This method is efficient, straightforward, and highly adaptable, making it well-suited for large-scale industrial production.
{"title":"Surface Modification of Polyvinylidene Fluoride Latex Nanoparticles through Chain Entanglement by Poly(meth)acrylate Monomer Swelling Seeded Emulsion Polymerization","authors":"Longben Huo, Hui Feng, Jiwei Cui, Ying Zhu, Lingyun Zhu, Xin Jin, Xinyuan Zhu","doi":"10.1021/acs.langmuir.4c04318","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04318","url":null,"abstract":"Polyvinylidene fluoride (PVDF) latex nanoparticles serve as a versatile platform for surface modification due to their role as precursors in PVDF manufacturing. However, the strong chemical stability and poor compatibility of PVDF present significant challenges for effective surface modification. To address this, we developed a method that facilitates surface modification through chain entanglement. By employing monomer swelling emulsion polymerization, poly(meth)acrylate (PA) monomers are incorporated into PVDF nanoparticles and subsequently polymerized. Rheological properties and transmission electron microscopy mapping confirmed the chain entanglement between PVDF and PA, indicating a successful integration. This method is efficient, straightforward, and highly adaptable, making it well-suited for large-scale industrial production.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"29 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986940","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Black phosphorus (BP), a promising two-dimensional material, faces significant challenges for its applications due to its instability in air and water. Herein, molecular dynamics simulations reveal that a self-assembled ferrocene (FeCp2) molecular layer can form on BP surfaces and remain stable in aqueous environments, predicting its effectiveness for passivation. This theoretical finding is corroborated by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, Raman spectroscopy, and optical microscopy observations. In addition, atomic force microscopy analysis confirms that ferrocene-passivated BP flakes with thicknesses of <10 nm exhibit minimal degradation over 25 days. Density functional theory calculations further show that ferrocene stabilizes BP and modulates its band gap, improving its electronic applicability. Notably, we find that the passivation of BP by metallocenes is universal because other metallocenes (VCp2, MnCp2, and NiCp2) exhibit similar adsorption behaviors. These findings underscore the potential of metallocenes as versatile protective layers for BP and other materials that are not stable in air.
{"title":"Toward Surface Passivation of Black Phosphorus via a Self-Assembled Ferrocene Molecular Layer","authors":"Liuhua Mu, Shiyu Gao, Jie Jiang, Minglei Wang, Liang Chen, Shiqi Sheng","doi":"10.1021/acs.langmuir.4c03999","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03999","url":null,"abstract":"Black phosphorus (BP), a promising two-dimensional material, faces significant challenges for its applications due to its instability in air and water. Herein, molecular dynamics simulations reveal that a self-assembled ferrocene (FeCp<sub>2</sub>) molecular layer can form on BP surfaces and remain stable in aqueous environments, predicting its effectiveness for passivation. This theoretical finding is corroborated by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, Raman spectroscopy, and optical microscopy observations. In addition, atomic force microscopy analysis confirms that ferrocene-passivated BP flakes with thicknesses of <10 nm exhibit minimal degradation over 25 days. Density functional theory calculations further show that ferrocene stabilizes BP and modulates its band gap, improving its electronic applicability. Notably, we find that the passivation of BP by metallocenes is universal because other metallocenes (VCp<sub>2</sub>, MnCp<sub>2</sub>, and NiCp<sub>2</sub>) exhibit similar adsorption behaviors. These findings underscore the potential of metallocenes as versatile protective layers for BP and other materials that are not stable in air.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"96 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987053","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-16DOI: 10.1021/acs.langmuir.4c04641
Xiaolong Huang, Guo Feng, Jun Mu, Yan Li, Weifeng Xie, Fukun Wu, Zhiqi Guo, Yanqiao Xu, Zhongjie Wang, Feng Jiang
High-temperature and long-term sintering of β″-Al2O3 solid electrolyte (Beta″ Alumina Solid Electrolyte, BASE) can easily cause Na2O volatilization. It reduces the solid electrolyte (SE) quality, resulting in low ion conductivity of the electrolyte. It is also difficult to form uniform ionic channels. This work designs a simple nonaqueous precipitation through de-etherification heterogeneous polymerization reaction between optimal sodium source sodium ethoxide and aluminum isopropoxide to synthesize highly active precursor powders with Na–O–Al as the skeleton, effectively reducing the synthesis and sintering temperatures of β″-Al2O3 solid electrolyte and minimizing the Na2O volatilization. Importantly, residual organic groups and a low synthesis temperature of 1150 °C promote the formation of in situ carbon uniformly. In-situ carbon with a mass fraction of about 3.98% will form uniformly distributed ion transport channels with a diameter of 1–3 μm when sintering at 1580 °C. These channels ensure a migration rate of sodium ions and ion conductivity of β″-Al2O3 solid electrolyte of 0.028 S/cm at 300 °C.
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