Langmuir最新文献

{"title":"Functionalization of 2H-MoS2 with Pt Nanoclusters for HER in Alkaline Solutions and Supercapacitors","authors":"Zhijun Wang, Yingjing Liu, Yao Deng, Hailei Wang, Shuting Han, Yinfeng Wang, Xiaoxue Zhang, Xuexia Liu","doi":"10.1021/acs.langmuir.5c01328","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c01328","url":null,"abstract":"Noble metals offer a wide range of potential catalysis applications, particularly in fuel cells and supercapacitors. The decoration strategy is a promising efficient strategy to address the limited structural flexibility and enhance the performance of noble metal electrode materials. Herein, we report a facile method to synthesize the nanocomposites with Pt nanoclusters (NCs) decorated on the surface of 2H-MoS₂ nanosheets (Pt NCs@2H-MoS₂). Fortunately, Pt NCs@2H-MoS₂ demonstrates excellent catalytic activity and stability toward the hydrogen evolution reaction (HER) in alkaline solutions, along with satisfactory electrochemical characteristics for supercapacitors (SCs). Specifically, a low overpotential of 61.2 mV at 10 A g^–1 and 98% retention after 10 h can be achieved for the HER, which is comparable to the commercial Pt/C catalysts. When used as electrode materials for supercapacitors, a high specific capacitance of 284 F g^–1 can be achieved at a scan rate of 5 mV s^–1 in 1 M KOH. Consequently, these results demonstrate that the noble metal-decorated transition metal materials strategy offers significant potential for economically and sustainably electrochemical applications.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"37 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144177211","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":"Construction of Ag2WO4/CuBi2O4 S-Scheme Heterojunctions with Enhanced Sonocatalytic Performance for the Removal of Tetracycline: Characterization, Sonocatalytic Mechanism, and Degradation Pathways","authors":"Yangcheng Liu, Yang Han, Haitao Qiu, Maoqi Yang, Meng Zhang, Yang Wang, Zheng Xiang, Wei Liu, Xin Wang","doi":"10.1021/acs.langmuir.5c00744","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c00744","url":null,"abstract":"This study successfully synthesized Ag₂WO₄/CuBi₂O₄ (ACBO) composite materials via a two-step method. Tetracycline (TET) was employed as a model pollutant to evaluate the sonocatalytic performance of Ag₂WO₄/CuBi₂O₄ composite materials. Among all samples, ACBO-30 exhibited the most outstanding sonocatalytic activity. Under optimal experimental conditions, the removal efficiency of TET reached 98.06 ± 1.10%. Based on the results of active species trapping experiments and X-ray photoelectron spectroscopy, it was confirmed that an S-scheme heterojunction formed between Ag₂WO₄ and CuBi₂O₄, which effectively promoted the separation of electron–hole pairs and significantly enhanced the sonocatalytic performance of CuBi₂O₄. Cyclic experiments further demonstrated that the Ag₂WO₄/CuBi₂O₄ composite catalyst possessed excellent reusability and stability. Through high-performance liquid chromatography–mass spectrometry (HPLC-MS) analysis, several plausible conversion pathways of the TET were proposed. Biological toxicity tests verified that the sonocatalytic technology could degrade TET into less toxic byproducts. This study provides valuable insights into the design and development of novel sonocatalysts for the efficient treatment of pharmaceutical wastewater.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"95 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165730","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 Co-Doped In2O3 Hierarchical Porous Nanocubes for High-Performance Hydrogen Sulfide Sensors","authors":"Xiaohua Wang, Yanwei Li, Guang Sun, Jianliang Cao, Yan Wang","doi":"10.1021/acs.langmuir.5c01131","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c01131","url":null,"abstract":"Recently, because of the urgent need for safety and health protection, there has been a growing focus on exploring effective and feasible gas sensors based on metal oxide semiconductors (MOSs) for detecting trace levels of hydrogen sulfide (H₂S). In this context, a cobalt (Co) doping strategy was proposed to improve the H₂S-sensitive properties of In₂O₃ nanomaterials, enabling them to monitor 1 ppm of H₂S at a relatively lower temperature. The Co-doped In₂O₃ hierarchical porous nanocubes (Co–In₂O₃ HPNCs) were prepared through a hydrothermal route using In(OH)₃ as a precursor. When utilized as a sensing material to detect H₂S, the Co–In₂O₃ HPNCs demonstrated significant enhancements compared to pure In₂O₃. These enhancements include a reduction in the operating temperature (260 vs 300 °C), a significant increase in response (36.99 vs 12.28 for 20 ppm of H₂S), and better selectivity (13.21 vs 3.07 times to ethanol). Even to 1 ppm of H₂S, the Co–In₂O₃ sensor can give a response value of 1.86, highlighting its substantial potential for detecting H₂S at the limit of detection (LOD) of 1 ppm. A detailed analysis of the multiple sensitization effects of Co doping reveals that these improved H₂S sensing characteristics of Co–In₂O₃ HPNCs can be primarily traced back to three factors, namely, an increased oxygen vacancy concentration, a narrowing of the bandgap, and an upward shift of the Fermi level.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"172 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165736","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":"Design and Tuning of Photocatalytic Properties in MoC2N4/WC2N4 van der Waals Heterostructure: A DFT Investigation","authors":"Mengya Huang, Yuannong Ye, Yue Gao, Zhao Ding, Yi Wang, Xiang Guo, Qizhi Lang, Jiang Yan, Xuefei Liu","doi":"10.1021/acs.langmuir.5c00993","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c00993","url":null,"abstract":"Humanity is currently confronted with significant challenges including energy shortages and limited access to clean energy sources. Photocatalytic water splitting for hydrogen production, utilizing two-dimensional van der Waals heterostructures, offers a promising solution to these pressing issues. In this study, we constructed a type-II van der Waals heterostructure of MoC₂N₄/WC₂N₄, with a lattice mismatch of 0.76%, composed of monolayers of MoC₂N₄ and WC₂N₄. After conducting a thorough thermodynamic stability screening, we identified the most stable stacking configuration. Subsequent calculations of the optical and electronic properties demonstrate that this heterostructure is a highly promising candidate for the overall water splitting photocatalysis. Its stability was further confirmed through phonon dispersion spectroscopy and ab initio molecular dynamics (AIMD) simulations. Then, the electronic properties of the MoC₂N₄/WC₂N₄ heterostructure were calculated using HSE functional. The results show that it is a type-II van der Waals heterostructure with appropriate band edge positions. The photogenerated electrons and holes in the heterostructure are efficiently separated, which significantly enhances photocatalytic activity. Furthermore, the carrier mobility and optical absorption efficiency of the heterostructure are significantly improved compared to those of the monolayer materials. Additionally, we computed the band structure, optical absorption spectra, and hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances under biaxial strain ranging from −5 to +5%. Our findings indicate that biaxial strain substantially influences the band structure and optical absorption efficiency. In particular, under 1% tensile biaxial strain, the heterostructure exhibits enhanced catalytic activity, making it a promising candidate for water splitting photocatalysis.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"2 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144177145","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":"Achieving CNTs Growth by Inducing Nanoparticle Nucleation via Non-Active Fe2O3 Clusters Anchored on the α-Al2O3 Surface","authors":"Peng Wang, Qianpeng Dong, Chenyu Gao, Lianlian Wang, Ruiliang Wang, Dianming Chu, Wenjuan Bai, Yan He","doi":"10.1021/acs.langmuir.5c01539","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c01539","url":null,"abstract":"This research presents a regulation strategy of constructing a heterogeneous bilayer catalyst of Fe and Al₂O₃, namely, Fe–Al₂O₃, through interfacial interaction and particle nucleation, in order to modulate the size and catalytic activity of Fe sites and achieve the growth of carbon nanotubes (CNTs). Through temperature control, the noncatalytically active Fe₂O₃ clusters on the surface of Al₂O₃ are exposed, inducing multiple nucleation of Fe clusters on its surface. Under the synergistic effect of the confinement at the Fe–Al₂O₃ interface, the fabrication of small Fe nanoparticles is accomplished. The results indicate that the catalytically active Fe nanoparticles have a diameter of approximately 10 nm, and the grown CNTs have a diameter of approximately 15 nm. Based on the systematic characterization results, the nonactive Fe₂O₃ clusters confined by strong interfacial interaction induce multiple nucleation of Fe on their surface during multiple loading processes, facilitating the formation of nanoparticles. Additionally, the strong interaction between Al₂O₃ and Fe induces the formation of FeAl₄O₈, thereby enhancing the thermal stability of the nanoparticles. In conclusion, the targeted regulation of the interfacial interaction of the catalyst active sites offers guidance for the low-cost and large-scale preparation of small nanoparticle catalyst particles.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"58 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165737","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":"Designing Highly Efficient Z-Scheme BiOCl/BiOI Heterojunctions and Oxygen Vacancy-Rich BiO(Cl,I) Solid Solutions for Visible-Light-Driven Mineralization of Aqueous Pollutants","authors":"Meiting Li, Bingxin Yuan, Chi Zhang, Jia Li, Xuejiao Wang","doi":"10.1021/acs.langmuir.5c01503","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c01503","url":null,"abstract":"Hierarchical BiOCl/BiOI and BiO(Cl,I) photocatalysts were obtained via a solution-phase reaction for visible-light-driven elimination of aqueous pollutants, where the phase/morphology evolution, relationship between energy band/microstructure structure and photocatalytic properties, and photoreaction mechanism can be deciphered in detail. It was well-documented that the <i>R</i> = 8:1 BiOCl/BiOI heterojunctions with a coherent interface of Bi and O atoms showed a relatively strong redox capacity owing to their rapid Z-scheme charge transfer and large interfacial contact and eventually degraded ∼92.52% and 96.57% of rhodamine B (RhB) and tetracycline (TC) molecules under 10 min of visible light irradiation, which was larger than those of bare BiOCl and BiOI. However, their poor photocatalytic stability was proved to be unfavorable to practical applications. The best BiOCl_0.88I_0.12 solid solutions separately elucidated the optimal RhB and TC removal efficiency of ∼99.97% and 97.54% after 10 and 6 min of illumination, and it still maintained a high photodegradation efficiency toward RhB after five consecutive runs. The exceptional photocatalytic performance is cogoverned by the characteristics of in situ generated oxygen vacancies and defect energy levels.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"29 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144177147","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":"Protein Denaturation at the Air–Water Interface in the Context of Nanoparticle Soft Corona Studies","authors":"Mahima Unnikrishnan, Martin Gruebele, Catherine J. Murphy","doi":"10.1021/acs.langmuir.5c00761","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c00761","url":null,"abstract":"The interaction of proteins with surfaces can involve both protein binding and unfolding and has been investigated since the 1960s. Proteins in solution can adsorb onto and denature at both solid–liquid and gas–liquid interfaces, and the spontaneous adsorption of proteins on a nanoparticle (NP) surface to form a corona can be described as a specific case of adsorption at the solid–liquid interface, where the surface curvature also becomes important. While nanoparticles offer a large surface area, they are not the only surface in the sample with which the proteins interact due to the creation of other interfaces in an experimental setup. In this work, we examine the role of the air–water interface in protein denaturation via soft corona studies with citrate-capped gold nanoparticles. Chymotrypsin (ChT) protein in the soft corona was observed to exhibit an inverse relationship between concentration and denaturation, an air–water interface-mediated trend that, without the right control experiments, can be misinterpreted to be caused by protein–NP interactions. We show that any protein denaturation observed comes from the synergistic effect of the air–water interface and agitation and that NPs did not denature ChT in the “soft corona” in the absence of these two factors. While the propensity to adsorb and denature at hydrophobic interfaces varies among proteins with different structural properties, it is important to use simplified procedures that minimize interfacial areas other than the nanoparticle surface in corona studies to prevent misattribution of the observed effects.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"2 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165733","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":"DFOB-Induced Dissolution of Anatase, Rutile, and Food-Grade TiO2 Nanoparticles","authors":"Md Imdadul Haque, Matas Simukaitis, Qilin Wei, Ann M. Valentine","doi":"10.1021/acs.langmuir.5c01096","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c01096","url":null,"abstract":"Titanium dioxide nanoparticles (TiO₂ NPs) are prevalent in products of everyday use, especially in food additives, paints, and consumer products. Their favorable properties include inertness in an aqueous environment. In this study, nanosized anatase, rutile, and food-grade TiO₂ particles were investigated with the treatment of the siderophore desferrioxamine B (DFOB), and their physicochemical, spectroscopic, and microscopic natures were revealed under different pH conditions. The formation of a Ti(IV)-DFOB complex in solution is evident from electrospray ionization mass spectroscopy. Dissolved Ti was analyzed by UV/visible and inductively coupled plasma optical emission spectroscopy and was found in the micromolar range (ca. 1–60 μM) over days. At all pH values, dissolution is more extensive for food-grade NP than for anatase and rutile. Near neutral pH, Fourier transform infrared spectroscopy (FTIR) data suggest that siderophore adsorption is more prominent than Ti dissolution. Scanning electron microscopy data reveals erosion of the TiO₂ surface with DFOB. A comprehensive kinetic profile supports multiple dissolution steps associated with anatase and rutile, with fewer steps for food-grade NPs. The addition of small organic acids shows mostly synergistic effects toward dissolution. This study will be helpful for considering TiO₂ applications in the food processing industry and for predicting its environmental fate in the presence of avid ligands.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"19 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165734","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":"Anisotropic Subsurface Inter- and Intramolecular Properties of Heterogeneous Polymers Revealed by Torsional Force Spectroscopy","authors":"Marvin Hoffer, Felix Petersein, Martin Dehnert, Tobias A. Lintner, Christian Dietz","doi":"10.1021/acs.langmuir.5c01423","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c01423","url":null,"abstract":"Atomic force microscopy (AFM) is widely recognized as an essential technique for the nanomechanical surface characterization of polymers. However, probing subsurface inter- and intramolecular properties of polymers remains a significant challenge with conventional AFM techniques, such as tapping mode. In this study, we utilized torsional force spectroscopy on annealed polystyrene-<i>block</i>-polybutadiene (SB) diblock copolymer films, which consist of rigid polystyrene (PS) cylinders embedded in a softer polybutadiene (PB) matrix, to analyze their inter- and intramolecular interactions as a function of the AFM tip indentation depth. The slow cantilever dynamics in torsional force spectroscopy along the <i>z</i>-direction allows for greater indentation depths compared to tapping mode, facilitating deeper tip penetration into the SB polymer films. This approach enables a precise analysis of the molecular interactions between the AFM tip and the PS and PB polymer blocks. By converting the available observables, such as torsional frequency shift and torsional excitation amplitude, into mechanical quantities, specifically in-plane tip–sample force, shear stress, and the dissipated energy between the lateral tip motion and the polymer blocks, we determined their dependence on the block alignment relative to the tip trajectory. We found that PS cylinders exhibit considerable rigidity when subjected to shear along their length axis with an AFM tip. In contrast, when shear stress is applied perpendicular to the length axis, the PS cylinders can wobble in the softer PB matrix. Additionally, we observed that the molecular interactions of individual molecules within the PS cylinders are approximately 0.22 pN. Our findings highlight the capability of torsional force spectroscopy to visualize local nanomechanical properties and to reveal the differences in inter- and intramolecular interactions within polymeric films. This insight can significantly contribute to the design of functional nanomaterials by providing a deeper understanding of molecular interactions on the nanometer scale.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"3 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144177146","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":"Modulation of Proteinoid Electrical Spiking Activity with Magnetic Nanoparticles","authors":"Panagiotis Mougkogiannis, Andrew Adamatzky","doi":"10.1021/acs.langmuir.5c00932","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c00932","url":null,"abstract":"This study looks at how proteinoid microspheres and their magnetic polystyrene (PS) hybrids behave electrochemically. It also explores their computational abilities. These systems show complex membrane potential dynamics. Pure proteinoids spike without external influence, ranging from 5.39 to 9.81 mV. In contrast, PS-modified variants exhibit sinusoidal oscillations. Their behavior can be described by the equation <i>V</i>(<i>t</i>) = <i>A</i> sin(2π<i>ft</i>) + <i>V</i>_offset, where <i>A</i> is about 1.5 mV and <i>f</i> is around 0.05 Hz. Electrochemical impedance spectroscopy shows key differences in charge transport. The PS-modified systems have better conductivity: |<i>Z</i>|_PS = 7.22 × 10⁴ Ω compared to |<i>Z</i>|_prot = 2.03 × 10⁵ Ω. The systems can perform Boolean logic operations with a 5 mV threshold. They show time-dependent gate behavior, making them suitable for unconventional computing applications. Doping with Fe(NO₃)₃ changes the electrical response. This happens through redox processes where Fe³⁺ gains an electron to become Fe²⁺. As a result, there are greater potential differences and more complex timing behaviors. These findings help us understand proteinoid-based bioelectricity better. They also show how these building blocks can be used in biomolecular computing systems.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"4 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144177255","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}