Langmuir最新文献

{"title":"Regulating the Performance of CO2 Adsorbents Based on the Pyrolysis Mechanism of Self-Sacrificial Templating Agents","authors":"Su Dan Bao, Agula Bao","doi":"10.1021/acs.langmuir.4c03844","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03844","url":null,"abstract":"Previous research has proven that the pore shape and nitrogen group content of adsorbents play essential roles in determining their carbon dioxide (CO₂) adsorption performance. In this article, a series of nitrogen-doped porous carbon materials were prepared for CO₂ adsorption by varying the proportion of carbon nitride, the pyrolysis temperature, and the activation ratio of KOH, using chitosan as the carbon source, carbon nitride (g-C₃N₄ and g-C₃N₅) as self-sacrificing templating agents, and KOH as the activator. Among the prepared materials, T6-850-1 has the highest specific surface area (<i>S</i>_BET) of 2336 m²/g, and T6-750-1 has the highest microporous area (<i>S</i>_micro) and CO₂ adsorption capacity (1 bar, 298 K) of 1969 m²/g and 3.49 mmol/g, respectively. The thermal decomposition temperature and products of carbon nitride templates were characterized and tested by thermogravimetric infrared gas chromatography-mass spectrometry (TG-IR-GC-MS), and the thermal decomposition mechanisms of the two carbon nitride templates were investigated. We found that the thermal stability of the template directly affects the pore structure of the final sample as well as the type and quantity of nitrogen species.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589137","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}

{"title":"Glycoside-Mediated Enhancement of Stability in Aluminum Oxyhydroxide Nanoadjuvants during Freeze-Drying","authors":"Mudasira Bhurt, Xin Li, Nan Zhang, Wenqi Yang, Muzhe Xu, Yang Liu, Yejiong Yu, Bingbing Sun","doi":"10.1021/acs.langmuir.4c03474","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03474","url":null,"abstract":"Aluminum-based adjuvants have been indispensable to vaccine potency. However, their effectiveness is difficult to maintain after freeze-drying, which limits the storage and application of aluminum-adjuvanted vaccines. In this study, the impact of freeze-drying on aluminum oxyhydroxide nanorods (AlOOH NRs) was investigated. Freeze-drying led to aggregation and resulted in the loss of the surface hydroxyl content of aluminum adjuvants. To alleviate freeze-drying-induced damage, the potency of different alkyl glycosides as protectants was further evaluated. It was demonstrated that the structural balance of the head and tail of a glycoside was more conducive to protecting AlOOH NRs from aggregation and loss of surface hydroxyl groups. These results underline the proper selection of protectants to protect adjuvants against functional defects caused by freeze-drying, which is important for the stability and efficacy of vaccines and biopharmaceutical products.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589134","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}

{"title":"Effects of Thermal Energy on the Formation of Lattice Strain in VO₂ Thin Films Grown on TiO₂(001).","authors":"Reki Nakamoto, Hiroyuki Okazaki, Takanori Wakita, Takayoshi Yokoya, Yuji Muraoka","doi":"10.1021/acs.langmuir.4c03004","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03004","url":null,"abstract":"<p><p>Film thickness is a well-known experimental parameter for controlling lattice strain in oxide films. However, due to environmental and resource conservation considerations, films need to be as thin as possible, increasing the need to find alternative factors for strain management. Herein, we present the importance of thermal energy as a factor for the formation of lattice strain in the oxide films, specifically focusing on the effects of laser fluence during pulsed laser deposition (PLD) on the in-plane lattice strain of vanadium dioxide (VO₂) thin films grown on titanium dioxide (TiO₂) (001). VO₂ thin films were deposited using a KrF excimer laser (λ = 248 nm) at laser fluences ranging from 0.88 to 1.70 J/cm². The film thickness ranged from 10-15 nm, below the critical thickness. Films grown at higher laser fluences exhibited smooth surfaces and completely strained in-plane lattices. In contrast, films grown at lower laser fluences displayed numerous small islands and relaxed in-plane lattice strain. The metal-insulator transition (MIT) temperature was lower for films grown at higher laser fluencies compared to those grown at lower laser fluences. It was also revealed that Ti-V interdiffusion occurs, forming a solid solution (V_1-<i>x</i>Ti_<i>x</i>O₂) near the interface. These observations suggest that the thermal energy of the particles, influenced by laser fluence, is a critical factor in the formation of lattice strain in metal oxide films and also that laser fluence in PLD is an effective experimental parameter for strain management in oxide films. Our findings enhance the understanding of lattice strain formation in metal oxides and offer insights for establishing effective methods for controlling lattice strain in metal oxide films.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589541","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}

{"title":"Greenly Synthesized Conducting Polymer Nanotunnels with Metal-Hydroxide Nanobundles in Single Dais for Unmitigated Water Oxidation.","authors":"Kuppusamy Rajan, Dhanasingh Thiruvengadam, Krishnan Umapathy, Murugan Muthamildevi, Muthukumaran Sangamithirai, Jayaraman Jayabharathi, Manoharan Padmavathy","doi":"10.1021/acs.langmuir.4c02586","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c02586","url":null,"abstract":"<p><p>Electrochemical water splitting required efficient electrocatalysts to produce clean hydrogen fuel. Here, we adopted greenway coprecipitation (GC) method to synthesize conducting polymer (CP) nanotunnel network affixed with luminal-abluminal CoNi hydroxides (GC-CoNiCP), namely, GC-Co₁Ni₂CP, GC-Co_1.5Ni_1.5CP, and GC-Co₂Ni₁CP. The active catalyst, GC-Co₂Ni₁CP/GC, has low oxygen evolution reaction (OER) overpotential (307 mV) and a smaller Tafel slope (47 mV dec^-1) than IrO₂ (125 mV dec^-1). The electrochemical active surface area (EASA) normalized linear sweep voltammetry (LSV) curve exhibited outstanding intrinsic activity of GC-Co₂Ni₁CP, which required 285 mV to attain 10 mA cm^-2. At 1.54 V, the estimated turnover frequency (TOF) of GC-Co₂Ni₁CP/GC (0.017337 s^-1) was found to be 3-fold higher than that of IrO₂ (0.0014 s^-1). Furthermore, the GC-Co₂Ni₁CP/NF consumed a very low overpotential (281 mV) with a small Tafel slope of 121 mV dec^-1. The ultrastability of GC-Co₂Ni₁CP for industrial application was confirmed by durability at 10 and 100 mA cm^-2 for the OER (GC/NF-8 h, 2.0%/100 h, 2.2%) and overall water splitting (100 h, 3.8%), which implies that GC-Co₂Ni₁CP had adequate kinetics to address the elevated rates of water oxidation. The effect of pH and addition of tetramethylammonium cation (TMA⁺) reveal that GC-Co₂Ni₁CP follows the lattice oxygen mechanism (LOM). The solar-powered water electrolysis at 1.55 V supports the efficacy of GC-Co₂Ni₁CP in the solar-to-hydrogen conversion. The environmental impact studies and solar-driven water electrolysis proved that GC-CoNiCP has excellent greenness and efficiency, respectively.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580870","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}

{"title":"Utilizing Waste Biomass from Agricultural and Forestry Sustainable Resources: Biomass Conversion to Functional Adsorbent Material for Efficient Removal of Total Phosphate in Practical Water","authors":"Junjie Yuan, Yao Zhu, Jizhang Wang, Zhigang Liu, Tao Zhang, Pingping Li, Fengxian Qiu","doi":"10.1021/acs.langmuir.4c03289","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03289","url":null,"abstract":"The promotion of the utilization of waste agricultural and forestry resources (AFRs) as a means of combating environmental pollution represents an advanced and necessary development approach with the potential to achieve sustainable development. In this work, an advanced adsorbent with a functional Mg–Al bimetallic layer was prepared using waste sawdust biomass (WSD) as a raw material. The layer serves as the primary active component for adsorbing total phosphate from both simulated and real wastewater. The hierarchical structure of the Mg–Al bimetallic hydroxide-modified waste sawdust biomass (MA@WSD) has an abundance of nanosheets on its surface, providing ample binding sites and an enhanced specific surface area of 175.99 m²/g. Under the optimal conditions, the maximum removal efficiency toward phosphate can reach 99.99%. The adsorption of phosphate by MA@WSD follows the pseudo-second order kinetic (PSOK) model, indicating that chemisorption is the rate-determining step. Moreover, the thermodynamic data demonstrate the spontaneous nature of the adsorption process, indicating the favorable characteristics of the developed material. The adsorption mechanism can be summarized as the collaboration of physical adsorption, electrostatic interaction, and chemical adsorption. The results of the regeneration process indicate that MA@WSD exhibits a retention of 50.3% of its initial adsorption performance following the fifth testing cycle, thereby suggesting its potential for comparable reusability. The MA@WSD performs well in adsorbing total phosphate in real river water, and the removal efficiency of MA@WSD is evidently superior to commercial activated carbon, which is at least 70% higher than that of the commercial activated carbon. Besides, the 5-time average removal efficiency toward total phosphate by MA@WSD is 62.9%, evidently higher than the 29.1% of commercially available activated carbon, indicating its potential as an alternative for treating phosphorus-containing wastewater. The research provides theoretical support for harmless treatment, resource utilization, carbon sequestration, and emission reduction of waste biomass.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589133","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}

{"title":"Improved Emulsifying Performance of Agarose Microgels by Cross-Interfacial Diffusion of Polyphenols","authors":"Wenxin Jiang, Xinwei Xiong, Hefan Zhang, Fengting Li, Dan Yuan, Zhiming Gao, Wei Lu, Yanlei Li, Yuehan Wu","doi":"10.1021/acs.langmuir.4c03548","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03548","url":null,"abstract":"Noninterface-active polysaccharides can acquire better emulsifying properties through microgelation, yet optimizing their emulsifying performance remains a significant challenge. This study introduces a novel approach to enhance the emulsifying performance of polysaccharide microgels by leveraging the cross-interfacial diffusion of polyphenols, which promotes the interfacial adsorption of microgels. Tannic acid (TA) was predispersed in oil phases and subsequently emulsified with agarose microgel (AM) suspensions, and the impacts of TA diffusion on the emulsifying performance of AMs was investigated. In addition, the transmittance profiles of oil–water biphasic systems were found to innovatively indicate the cross-interfacial diffusion of TA and the interfacial adsorption of AMs. The current results suggest that an appropriate level of TA incorporation can benefit the emulsifying performance of AMs, correlating with decreased droplet sizes and improved physical stability of the emulsion. However, excessive TA might trigger the clustering of AMs before they reach the interfacial layer, adversely affecting the emulsion stability. In conclusion, the cross-interfacial diffusion of polyphenols offers a promising strategy to overcome the stability challenges encountered in polysaccharide microgel-stabilized emulsions.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589136","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}

{"title":"Synthesis of Fe₃O₄ Derived from Acid Mine Drainage (AMD) Sludge and Catalytic Degradation of Tetracycline.","authors":"Si Jin, Huiling Li, Jinyuan Jiang, Dongni Shi, Wei Tan, Haoyang Song, Ling Zhu, Yajun Li, Hongke Qin, Lei He","doi":"10.1021/acs.langmuir.4c02959","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c02959","url":null,"abstract":"<p><p>Acid mine drainage (AMD) sludge is waste generated in the process of acid mine wastewater treatment, and the use of AMD sludge to prepare Fe₃O₄ to activate H₂O₂ degradation pollutants is an effective means of resource utilization. In this study, the heterogeneous catalyst Fe₃O₄-based composites were synthesized by a one-step method using AMD sludge as a raw material, and the Fe₃O₄-based materials before and after catalysis were characterized by powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The effects of several key factors (pH values, H₂O₂ content, TC concentration, and Fe₃O₄ content) of tetracycline (TC) degradation were evaluated. The results revealed that the TC removal rate reached up to 95% within 120 min under optimal conditions (pH 3; H₂O₂, 5 mmol/L; TC concentration, 25 mg/L; Fe₃O₄ content, 1g/L). Moreover, ^•OH and ^•O₂^- radicals were generated during the Fenton-like degradation process, and the plausible degradation mechanism was discussed. Besides, the Fe₃O₄ catalyst exhibited fantastic stability after five cycles. In conclusion, this study is expected to promote the resource utilization of industrial sludge and provide a new material for the treatment of antibiotic-contaminated wastewater.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580874","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}

{"title":"Theoretical Calculation of Dissolved Gas in Transformer Oil Using the Gas Sensitive Properties of Sc- and Ti-Modified ZrS2","authors":"Zhao Wang, Dongbin Wang, Kun Xie, Pei Shi, Ye Shen, Long Lin","doi":"10.1021/acs.langmuir.4c03424","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03424","url":null,"abstract":"To guarantee the secure functioning of the complete power system and minimize the risks associated with oil-filled transformers during their operation, it is greatly important to carry out gas sensing studies of dissolved gases in transformer research. Through the utilization of first-principles density functional theory calculations, the adsorption energy, electronic characteristics, and recuperation duration of ZrS₂ modified with Sc and Ti were examined. The results show that compared to those of the initial ZrS₂ material, the doping of TM atoms Sc and Ti significantly improved the adsorption properties of the material, and the adsorption of CO and C₂H₄ showed chemisorption. The adsorption capacity for gases decrease in the following order: C₂H₄ &gt; CO &gt; H₂. The calculated recovery times indicate that Sc-ZrS₂ and Ti-ZrS₂ were ideal carbon monoxide sensing materials under the specific conditions. The results of this work can establish a fundamental rationale for the use of ZrS₂ in sensing the conditions of oil-immersed transformers.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580668","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}

{"title":"Intercalation Behavior of a Spiro-bipyrrolidinium Cation into a Graphite Electrode from Dimethyl/Propylene Carbonates.","authors":"Jiaxing Qi, Hongyu Wang, Guobao Xu","doi":"10.1021/acs.langmuir.4c03435","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03435","url":null,"abstract":"<p><p>Quaternary ammonium-graphite intercalation compounds (QA⁺-GICs) are promising negative electrode materials in dual-carbon batteries by virtue of safety, low cost, and environmental friendliness. However, the intercalation behavior of QA⁺ into graphite electrodes in mixed solvents has never been reported. Herein, spiro-(1,1')-bipyrrolidinium tetrafluoroborate dissolved in a dimethyl/propylene carbonate (DMC/PC) binary solvent system was employed in graphite/activated carbon (AC) capacitors. The storage behavior of the spiro-(1,1')-bipyrrolidinium cation into graphite is very related to the solvent composition of the electrolyte solutions. <i>In situ</i> X-ray diffraction tests revealed that the graphite electrodes can form different QA⁺-GICs during cycling, which is a key factor influencing the electrochemical performance of graphite/AC capacitors. Besides, the reversible thickness change of graphite in graphite/AC capacitors with different electrolytes during the charge-discharge process was also addressed. These findings provide sound evidence for the co-intercalation of the solvent with the cation.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142575241","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}

{"title":"Deposition of Nanometric Polymer-Surfactant Complexes Formed by Cationic Dextran: A Path to Sustainable Formulations.","authors":"Hammad A Faizi, Daniel S Miller, Lyndsay Leal, Junsi Gu, Michaeleen L Pacholski, Emmett M Partain Iii, Caroline Nimako-Boateng, Janet R McMillan, Chang Qian, Zuochen Wang, Qian Chen","doi":"10.1021/acs.langmuir.4c02860","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c02860","url":null,"abstract":"<p><p>The home and personal care industry is evolving toward more sustainable and environmentally friendly ingredients. Rinse-off personal care products rely on formation of polymer-surfactant complexes to drive deposition of benefit agents (e.g., conditioning oils, fragrances, etc.) onto the skin or hair. The most used natural polymers for this purpose are cationic guar (catGuar) and cationic hydroxyethyl cellulose (catHEC), and the complexation of these polymers with surfactants has been rigorously characterized. Various gaps still exist with these polymers, specifically low biodegradation and undesirable aquatic toxicity profiles. Modified dextran offers an exciting solution as a biodegradable polysaccharide with a high natural origin content. This paper aims to compare the morphology of polymer-surfactant complexes formed between a cationic dextran (catDex) polymer with mixtures of sodium lauryl ether sulfate (SLES) and cocamidopropyl betaine (CapB) to the morphologies of complexes formed between catGuar or catHEC and the same surfactants. Solutions were designed to mimic industrially relevant shampoos. Through a suite of complementary techniques, unique nanometric sized complexes were observed to form between catDex-SLES/CapB compared to the widely reported micrometer-sized coacervates (liquid-liquid phase separation) or precipitates (liquid-solid) formed in catHEC or catGuar-SLES systems. Using a quartz crystal microbalance with dissipation, the adsorption behavior of the catDex-SLES/CapB is characterized on a silica-coated sensor. The results show deposition throughout the dilution regime for catDex-SLES/CapB where the highest deposition is recorded with the undiluted rinsing formulation. This contrasts with catHEC-SLES/CapB and catGuar-SLES/CapB where the highest deposition is recorded in phase-separated regimes. This result was extended to performance testing on hair, confirming that the unique complexes formed by catDex can drive remarkably high levels of silicone deposition from rinse-off personal care products. This innovative approach of utilizing catDex-SLES/CapB complexes could enable design of more sustainable formulations that rely on polycation-surfactant nanocarriers.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142575178","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}