Langmuir最新文献

{"title":"Single-Atom-Embedded Nitrogen-Doped Graphene as Efficient Electrocatalysts for the CO₂ Reduction Reaction.","authors":"Yucan Tan, Yueheng Niu, Xu Ji, Xiuhua Cui, Haiming Duan, Qun Jing","doi":"10.1021/acs.langmuir.5c00728","DOIUrl":"10.1021/acs.langmuir.5c00728","url":null,"abstract":"<p><p>Single-atom catalysts (SACs) have displayed unprecedented activity and selectivity for electrochemical CO₂ reduction reaction (CO₂RR). Herein, a series of metal single atoms embedded on nitrogen-doped graphene (M-N₄G, where M = In, Tl, Ge, Sn, Pb, Sb, and Bi) is systematically evaluated as CO₂RR electrocatalysts by density functional theory (DFT) calculations. The computational results show that most M-N₄G exhibit better CO₂RR selectivity over the hydrogen evolution reaction (HER). Ge/Pb-N₄G exhibits excellent electrocatalytic performance in the generation of HCOOH from the CO₂RR with low limiting potentials of -0.292 and -0.306 V, which surpass the performance of the vast majority of electrocatalysts. Adsorption energy of the key intermediate *HCOO can be used as an effective reactivity reaction descriptor to screen promising CO₂RR catalysts. The results of this work highlight M-N₄G as an ideal electrochemical for the electrocatalytic CO₂RR.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":"7912-7921"},"PeriodicalIF":3.7,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143595853","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":"Exploring the Sensing Performance of T-Graphene, T-Boron Nitride, and Their Lateral Heterostructure for Toxic CO, NO, NO2, and SO2 Gas Molecules","authors":"Siraj Ud Daula Shamim, Abubakkar Siddique, Bivas Kumar Dash, Tanvir Ahmed, Sajib Shaha, Muhitul Islam, Afiya Akter Piya","doi":"10.1021/acs.langmuir.4c05324","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c05324","url":null,"abstract":"In this observation, density functional theory calculations were carried out to examine the adsorption performance of T-graphene (TG), T-boron nitride (TBN), and their heterostructure (TG-TBN) toward CO, SO₂, NO, and NO₂ gas molecules. To observe the sensing performance of the nanosheets, the adsorption energy with adsorption distance, charge transfer, electronic properties, sensitivity, and recovery time have been investigated. The gas molecules were adsorbed in the tetragonal (T) and octagonal (O) sites of the nanosheets, in which we found that the O site was more favorable. In the case of the interaction between TG and gases, low adsorption behavior has been found, but TBN and TG-TBN exhibit favorable interaction behavior with the gases. Among the four gases, SO₂ and NO₂ interact with the TBN in chemisorption energy, which are −0.911 and −1.75 eV, at the O site, respectively. During their interaction, the gases gain −0.139e and −0.428e charges from the TBN. TG-TBN shows high interaction properties with the NO and NO₂ gases with energies −1.21 and −1.35 eV, respectively. The DOS spectra show that extra electronic states are generated at the Fermi level of NO and NO₂ gas adsorption on the nanosheets. Low recovery times have been observed during the desorption; in the case of TG-TBN, the recovery times are 0.19 and 1.56 s at the T and O sites for NO and 28.32 and 41.04 s at the T and O sites for the NO₂ gas molecule. Therefore, TBN can be used as a gas sensor for SO₂ and NO₂ gases and TG-TBN can be used as a gas sensor for NO and NO₂ gas molecules.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"27 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695602","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":"Pioneers in Applied and Fundamental Interfacial Chemistry (PAFIC): Janet A. W. Elliott","authors":"Chiara Neto","doi":"10.1021/acs.langmuir.5c01092","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c01092","url":null,"abstract":"Published as part of the &lt;i&gt;Langmuir&lt;/i&gt; virtual special issue “2023 Pioneers in Applied and Fundamental Interfacial Chemistry: Janet A. W. Elliott” In its 40th anniversary, &lt;i&gt;Langmuir&lt;/i&gt; has established the annual recognition of Pioneers in Applied and Fundamental Interfacial Chemistry to honor influential scientists who have made significant fundamental contributions in these fields of research. Professor Janet A. W. Elliott has been selected as one of the inaugural Pioneers in Applied and Fundamental Interfacial Chemistry, in light of her outstanding contributions to the areas of thermodynamics, colloids and surfaces, and cryobiology. Professor Janet A. W. Elliott is a University of Alberta Distinguished Professor and Tier 1 Canada Research Chair in Thermodynamics in the Department of Chemical and Materials Engineering and an Adjunct Professor in the Department of Laboratory Medicine and Pathology at the University of Alberta. She received her M.Sc. (1992) and Ph.D. (1997) degrees in Mechanical Engineering from the University of Toronto, having been the first female graduate of the Engineering Physics Option of Engineering Science at the University of Toronto in 1990. Professor Elliott currently serves as Editor-in-Chief of the journal &lt;i&gt;Cryobiology&lt;/i&gt;, on the Editorial Advisory Boards of &lt;i&gt;The Journal of Physical Chemistry A, B, &amp; C&lt;/i&gt; and &lt;i&gt;Langmuir&lt;/i&gt;, and on the Editorial Board of &lt;i&gt;Advances in Colloid and Interface Science&lt;/i&gt;. She has previously served as a member of the Physical Sciences Advisory Committee of the Canadian Space Agency, the Board of Directors of the Canadian Society for Chemical Engineering, and the Executive Committee of the American Chemical Society Division of Colloid and Surface Chemistry. Professor Elliott is a Fellow of the Canadian Academy of Engineering (2023), Engineers Canada (2023), the Royal Society of Canada (2022), the American Institute for Medical and Biological Engineering (2019), the Society for Cryobiology (2018), and the Chemical Institute of Canada (2015). Her research has been recognized by numerous awards, with the most recent being the American Chemical Society &lt;i&gt;Langmuir&lt;/i&gt; Lectureship Award (2022). As one of her students put it: “She could convince rocks to study thermodynamics.” Professor Elliott is a distinguished scholar in the fields of thermodynamics (equilibrium and non-equilibrium), colloids and surfaces, and cryobiology. Her outstanding research has resulted in over 160 peer-reviewed journal articles and 2 U.S. patents. She has supervised more than 130 trainees and staff, including research associates, postdoctoral fellows, Ph.D. students, M.Sc. students, undergraduate research students, research engineers, and technicians. The contributions described below were made in collaboration with her trainees and collaborators, as indicated by authorship of the cited references. Professor Elliott has developed semiempirical equations of state that combine foundational equations wi","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"27 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695605","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":"Q&A with Professor Janet A. W. Elliott","authors":"Greco González Miera*,&nbsp;","doi":"10.1021/acs.langmuir.4c0435310.1021/acs.langmuir.4c04353","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04353https://doi.org/10.1021/acs.langmuir.4c04353","url":null,"abstract":"","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"41 12","pages":"7926–7927 7926–7927"},"PeriodicalIF":3.7,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737626","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":"Spontaneous Formation of Core–Shell Microdroplets during Conventional Coacervate Phase Separation","authors":"Chelsea E. R. Edwards, Hongyi Zhang, Ginny Wang, Matthew E. Helgeson","doi":"10.1021/acs.langmuir.4c04201","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04201","url":null,"abstract":"We report the single-step formation and stability of protocell-like, core-shell coacervate droplets comprising a polyelectrolyte-rich shell and a solvent-rich vacuole core from the poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) system. These double emulsion (DE) coacervate droplets coexist with single emulsion (SE) droplets, suggesting a kinetic mechanism of formation. We use high-throughput microscopy and machine learning to classify droplet morphologies across various final compositions (polyelectrolyte ratios and salt concentrations) and processing routes (mixing rate and thermodynamic path). We find that DE droplets form preferentially over SE droplets at a wide range of compositions using a slow injection mixing rate. DE droplet formation is enhanced at lower salt (NaCl) levels and near 1:1 charge stoichiometry, showing a preference for polycation excess. DE droplets are stable to the micron scale and retain their core-shell structure even after coalescence. Nevertheless, they are metastable; direct observations of various coarsening phenomena suggest that they are primarily stabilized by the viscoelasticity and high viscosity of the polymer-rich shell. Overall, the scalable, simple mixing process used herein offers a novel mechanism to produce multiphase coacervate droplets that is orthogonal to existing routes, which require either dropwise synthesis or thermodynamic tuning.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"18 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703630","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":"Nitrogen Pyrolysis-Induced Enhancement of Active Sites in an Algae Residue for an Electrochemical Dopamine Biosensor","authors":"Hao Wu, Xiaoteng Ding, Wenfeng Li, Hui Liu, Meilin Duan, Yu Lei, Gang Wei, Lei Guo","doi":"10.1021/acs.langmuir.5c00187","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c00187","url":null,"abstract":"As a kind of biomass, the seaweed residue will cause resource waste and environmental pollution if it is discharged as waste at will. As a cheap and easy biomass residue, its reuse has attracted more and more attention, and it has tapped the unexplored potential of renewable biological resources. In this study, we synthesize a carbon aerogel (CA) derived from an algae residue, which is utilized as an electrocatalyst for constructing an electrochemical dopamine (DA) biosensor. Utilizing the heightened disorder of carbon within CAs that was achieved through high-temperature pyrolysis and the augmentation of active sites, CAs show excellent electrocatalytic performance in the detection of DA and can selectively detect DA with a detection limit of 0.033 μM. Furthermore, the DA electrochemical biosensor is also employed to detect real samples with satisfactory reproducibility and stability. This study not only confirms the feasibility of introducing active defects to improve catalytic performance but also extends the application of the algae residue in electrochemical sensors for monitoring various biomolecules.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"183 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695343","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":"Interrogating the Surface Interactions of Resilin-Like Peptides on h-BN and Graphene","authors":"Sradha M. Thomas, Tiffany R. Walsh, Marc R. Knecht","doi":"10.1021/acs.langmuir.4c05252","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c05252","url":null,"abstract":"Resilin protein-based elastomers could provide pathways to synthetic materials with increased mechanical resilience; however, it remains challenging to replicate their properties when they are made in the lab. This is because Tyr-based cross-linking is necessary, which may require preorganized configurations of resilin in its natural environment. In previous work, the P1 graphene-binding peptide was conjugated with resilin-like peptides (RLPs) to produce P1/RLP conjugates. The binding of these peptides to the graphene surface was studied using QCM analysis and atomic force microscopy as an initial step toward preorganization for eventual cross-linking. Herein, the adsorption studies of RLPs (R1 and R2) and their conjugates with the P1 graphene-binding peptide are studied on hexagonal boron nitride (<i>h</i>-BN) using QCM analysis and molecular modeling. The results are compared with those of previous work based on the graphene surface. The binding affinity of P1/RLPs to <i>h</i>-BN is found to be similar to that of graphene, with notable changes that can be attributed to the variations in the surface composition. In addition, molecular simulations of the surface-adsorbed P1/RLP structures on <i>h</i>-BN indicate substantial differences compared to those on the graphene surface, with the RLP domain dominating the binding on <i>h</i>-BN. Moreover, the parent RLP peptides demonstrated increased binding to <i>h</i>-BN, which was not observed with graphene, thus indicating that <i>h</i>-BN is likely to be a poorer surface for peptide preorganization for eventual cross-linking for the controlled preparation of resilient elastomers.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"96 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695341","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":"Fabrication of a TiO2 Inverse Opal Film-Modified Photocatalytic Microreactor for Highly Efficient Degradation of Dyes","authors":"Zewei Huang, Yingjie Wang, Meiying Ye, Heyong Cheng","doi":"10.1021/acs.langmuir.4c04934","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04934","url":null,"abstract":"Two TiO₂ inverse opal films (F-TiO₂-IOF and CO-TiO₂-IOF) were synthesized on glass substrates by a limited planar rapid evaporation method, which was time- and reagent-saving, and it was easy to control their shape. The CO-TiO₂-IOF displayed a smoother mophology and better photocatalytic efficiency and stability than F-TiO₂-IOF. Over 95% of 5 mg L^–1 rhodamine B (RhB) was degraded within 120 s in the IOF-modified microreactors. A higher photocatalytic efficiency could be achieved with the synergistic catalysis of H₂O₂ and CO-TiO₂-IOF, based on which the online monitoring of RhB was realized within 2 min in the IOF-modified photocatalytic microreactor integrated with the flow cell of a UV–vis spectrophotometer. Other nitrogen-containing dyes like tartrazine and indigo carmine were also degraded in CO-TiO₂-IOF-modified microreactors with degradation rates of 83–95%.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"94 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677981","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":"A Platform Approach for Designing Sustainable Indole Thiosemicarbazone Corrosion Inhibitors with Enhanced Adsorption Properties","authors":"A. K. S. Koushik, Demetrius Finley, Nadia N. Intan, Lucas J. Showman, Kyle Podolak, Zachery Crandall, Theresa L. Windus, Jim Pfaendtner, Siegfried R. Waldvogel, George A. Kraus, Jean-Philippe Tessonnier","doi":"10.1021/acs.langmuir.5c00183","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c00183","url":null,"abstract":"With an estimated global cost of $2.5 trillion per year, metal corrosion represents a major challenge across all industrial sectors. Numerous inorganic and organic corrosion inhibitors have been developed, but there are growing concerns about their toxicity and impact on the environment. Here, superior organic corrosion inhibitors based on indole-3-carboxaldehyde, a compound commonly found in the digestive system, and thiosemicarbazones, a safe class of ligands, were designed and studied for mild steel in pH 1 sulfuric acid solutions. Electroanalytical techniques and gravimetric tests revealed inhibition efficiencies as high as 98.9% at 30 °C. Models using Langmuir isotherms gave adsorption equilibrium constants <i>K</i>_ads of 2 to 9 × 10⁴ M^–1 and corresponding Gibbs free energies of adsorption (Δ<i>G</i>_ads) as high as −41.44 kJ mol^–1, indicating their chemisorption. SEM images confirmed the efficacy of these corrosion inhibitors, as surface features showed limited to no changes after tests. Surface analysis by XPS and LC-MS revealed inhibitor concentrations on the order of 0.7 to 1.8 μg cm^–2 for the best compounds, further underlining their performance at low concentrations. Mapping of the surface by MALDI-MS further confirmed the homogeneous coating of the steel surface, with no visible fluctuations in concentrations. As all inhibitors shared the same indole thiosemicarbazone platform, unique structure–performance relationships were drawn from theoretical calculations. Notably, DFT and AIMD explained the differences in performance, highlighting the role of side groups in the distribution of the molecular orbitals and the role of water molecules in enhancing the electronic properties of the organic corrosion inhibitors and promoting their chemisorption.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"183 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677982","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":"Fabrication of a TiO2 Inverse Opal Film-Modified Photocatalytic Microreactor for Highly Efficient Degradation of Dyes","authors":"Zewei Huang,&nbsp;Yingjie Wang,&nbsp;Meiying Ye* and Heyong Cheng,&nbsp;","doi":"10.1021/acs.langmuir.4c0493410.1021/acs.langmuir.4c04934","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04934https://doi.org/10.1021/acs.langmuir.4c04934","url":null,"abstract":"<p >Two TiO₂ inverse opal films (F-TiO₂-IOF and CO-TiO₂-IOF) were synthesized on glass substrates by a limited planar rapid evaporation method, which was time- and reagent-saving, and it was easy to control their shape. The CO-TiO₂-IOF displayed a smoother mophology and better photocatalytic efficiency and stability than F-TiO₂-IOF. Over 95% of 5 mg L^–1 rhodamine B (RhB) was degraded within 120 s in the IOF-modified microreactors. A higher photocatalytic efficiency could be achieved with the synergistic catalysis of H₂O₂ and CO-TiO₂-IOF, based on which the online monitoring of RhB was realized within 2 min in the IOF-modified photocatalytic microreactor integrated with the flow cell of a UV–vis spectrophotometer. Other nitrogen-containing dyes like tartrazine and indigo carmine were also degraded in CO-TiO₂-IOF-modified microreactors with degradation rates of 83–95%.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"41 12","pages":"8138–8143 8138–8143"},"PeriodicalIF":3.7,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143737624","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}