Applied Surface Science最新文献

{"title":"Nature-Derived corrosion inhibition of steel in HCl by Pančić spruce essential Oil: Insights from experimental and Computational Approaches","authors":"Anđela R. Simović ,&nbsp;Jelica Novaković ,&nbsp;Branislav Milovanović ,&nbsp;Mihajlo Etinski ,&nbsp;Peđa Janaćković ,&nbsp;Jelena B. Bajat","doi":"10.1016/j.apsusc.2025.163048","DOIUrl":"10.1016/j.apsusc.2025.163048","url":null,"abstract":"<div><div>This study examines the potential of essential oil extracted from the needles of Pančić spruce as an innovative, eco-friendly corrosion inhibitor for carbon steel in a 1 M HCl solution. Analysis by GC/MS and FTIR revealed that the essential oil is rich in active organic compounds. Impedance measurements showed a significant increase in charge transfer resistance values for steel samples treated with the oil, achieving a maximum inhibition efficiency of 93 % at a concentration of 200 ppm after 4 h. Polarization measurements indicated that the oil acts as a mixed-type inhibitor. SEM demonstrated that the oil significantly altered the surface morphology of carbon steel. Adsorption studies followed the Langmuir isotherm, while thermodynamic analysis suggested that the organic components of the oil adsorb onto the metal surface through a combination of physisorption and chemisorption. XPS confirmed the presence of a protective film consisting of Fe oxides/hydroxides and phytochemicals from the essential oil. Theoretical methods (DFTB-MD) supported the experimental data, predicting strong interactions between key phytochemicals and the Fe surface.</div><div>This study opens the door for further exploration of conifer essential oils as sustainable corrosion inhibitors, contributing to the global shift towards green chemistry and reducing the environmental footprint in industrial applications.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"698 ","pages":"Article 163048"},"PeriodicalIF":6.3,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703290","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational and experimental insights into Single-Atom catalysts supported on g-C3N4: Unraveling the superior stability and catalytic activity of Rh in hydroformylation reactions","authors":"Roger Monreal-Corona, Lole Jurado, Hiroya Ishikawa, Martí Gimferrer, Albert Poater, Luis F. Bobadilla, M. Rosa Axet, Sergio Posada-Pérez","doi":"10.1016/j.apsusc.2025.163050","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.163050","url":null,"abstract":"Single-atom catalysts (SACs) have emerged as a promising class of materials, leveraging the benefits of both homogeneous and heterogeneous catalysis to enhance efficiency and selectivity. We investigated the catalytic performance of SACs supported on graphitic carbon nitride (g-C₃N₄) for hydroformylation reactions. A systematic evaluation of nine transition metal SACs (Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt) anchored on g-C₃N₄ was conducted using a combination of Density Functional Theory (DFT) calculations and experimental validation. Computational results indicate that at higher metal loadings, most metal atoms tend to migrate into the interlayers of g-C₃N₄, reducing their accessibility to reactant species and limiting their involvement in the catalytic process. However, Ru, Os, Ir, and Co single atoms remain stabilized on the heptazine rings, residing on the outermost layer and preserving active sites, albeit with lower predicted catalytic activity compared to Rh, while Fe, Ni, Pd, and Pt preferentially localize within the interlayers. Ru, Rh, and Co SACs anchored on g-C₃N₄ were experimentally synthesized and characterized using Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), and in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), along with catalytic testing, confirming the single-atom nature of the catalysts and corroborating the theoretical findings.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"35 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703291","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mild photochemical surface modification of fluoropolymer by aliphatic amine under UV irradiation","authors":"Wangfeng Du,&nbsp;Chuan Li,&nbsp;Changwen Zhao,&nbsp;Wantai Yang","doi":"10.1016/j.apsusc.2025.163071","DOIUrl":"10.1016/j.apsusc.2025.163071","url":null,"abstract":"<div><div>Developing a simple and mild strategy for surface modification of chemically inert polytetrafluoroethylene (PTFE) remains highly desirable for applications involving adhesion and surface bioactivity. In this work, we successfully surface-functionalized PTFE using a solution of commonly used aliphatic amine under UV irradiation. The water contact angle (WCA) of PTFE film decreased from 122° to 42° after 9 min of UV irradiation in the presence of a solution of triethylenetetramine in dimethylformamide. Attenuated total reflectance Fourier transform infrared spectra suggested the introduction of aliphatic C–H, –NH₂, –OH and C = C groups on the modified PTFE. X-ray photoelectron spectroscopy and time-of-flight secondary-ion mass spectrometry tests further verified the occurrence of defluorination and introduction of oxygen and nitrogen species. Patterned modification of PTFE can be achieved by using a photomask and regionally selective immobilization of protein on patterned substrate demonstrated the reactivity of modified surface. The peel strength for modified PTFE/stainless steel is 12 times higher than that of the pristine film. This strategy is also applicable to other perfluoropolymers such as poly(tetrafluoroethylene-co-hexafluoropropylene), for which the F content was reduced to 0.7 % and the WCA was reduced to about 10° after photochemical modification.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"698 ","pages":"Article 163071"},"PeriodicalIF":6.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695303","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An oxygen vacancies-enriched dual-phase bismuth oxide heterostructure derived from metal-organic framework enabling advanced nickel bismuth batteries","authors":"Kun Yang,&nbsp;Haoxian Zhu,&nbsp;Lei Zhang,&nbsp;Wei Li,&nbsp;Li Sun,&nbsp;Yihe Zhang","doi":"10.1016/j.apsusc.2025.163070","DOIUrl":"10.1016/j.apsusc.2025.163070","url":null,"abstract":"<div><div>In this work, an oxygen vacancies (O_v)-enriched heterostructure was prepared, consisting of a monoclinic (mcl) Bi₂O₃ and a tetragonal (tetr) Bi₂O₃ both derived from Bi-metal–organic framework (MOF). At the same time, the first-principle calculation based on density function theory (DFT) was utilized to prove the advantages of the mcl/tetr-Bi₂O₃ heterostructure. The O_v can narrow the band gap and increase the conductivity, carbon skeleton is able to retard the volumetric expansion and the heterostructure can facilitate the interfacial charge transfer. Therefore, mcl/tetr-Bi₂O₃ electrode delivers a high specific capacity of 1446F g⁻¹ (3.0F cm⁻²) at 1 A/g. Nickel-bismuth (Ni//Bi) batteries were prepared using NiCoLDH as positive electrodes. Its aqueous Ni//Bi battery exhibits a high specific capacity as well. The assembled all-solid-state Ni//Bi battery shows high power density and energy density. In particular, the flexible Ni//Bi battery can accommodate bending, unfolding enormous potential for application.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"698 ","pages":"Article 163070"},"PeriodicalIF":6.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Atomic-level mechanisms of methane absorption in silica-based porous materials with non-uniform faults: Enhancing adsorption via surface faults","authors":"Mingyang Yang ,&nbsp;Bo Yang ,&nbsp;Xiaojing Meng ,&nbsp;Qiang Sheng ,&nbsp;Lin Guo ,&nbsp;Cheng Bi ,&nbsp;Mu Du","doi":"10.1016/j.apsusc.2025.163069","DOIUrl":"10.1016/j.apsusc.2025.163069","url":null,"abstract":"<div><div>Natural gas is a promising clean energy source, but its storage and transport remain challenging. This work demonstrates that a novel silica-based porous structure with non-uniform faults can significantly enhance methane absorption, as revealed through large-time molecular dynamics (MD) simulations of 1500 ns. Silica nanoparticles with random faults were constructed under methane conditions (5 atm), and a validated method was developed to identify absorbed methane molecules, showing good agreement with experimental data. Our findings reveal that optimizing fault density results in a 111 % increase in methane absorption compared to fault-free structures. Absorbed methane molecules form three layers: an absorption layer, a Knudsen layer, and a bulk layer. Faults enhance solid–gas interactions in the absorption layer and gas–gas interactions in the Knudsen layer. However, increasing temperature significantly reduces methane absorption, for which we propose a temperature-absorption relationship. These insights provide a foundation for designing nanostructures optimized for methane storage and selective absorption applications.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"698 ","pages":"Article 163069"},"PeriodicalIF":6.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695378","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Highly efficient grafting of silazanes to the inner surface of the vials under mild conditions by surface engineering to improve the chemical durability","authors":"Ruolin Zhou,&nbsp;Shengyao Tan,&nbsp;Fangrui Xie,&nbsp;Jing Dong,&nbsp;Jianping Zhu,&nbsp;Linxuan Fang,&nbsp;Lianbin Wu","doi":"10.1016/j.apsusc.2025.163059","DOIUrl":"10.1016/j.apsusc.2025.163059","url":null,"abstract":"<div><div>As the composition of drugs has become more complex, the chemical durability of glass has been challenged. In this study, two silazanes, n-n-butyl-azido-2,2-dimethoxysilazane (BADMACP) and hexamethyldisilazane (HMDS) were used separately to efficiently modify the inner surfaces of vials under mild conditions. These two silazanes were reacted with the –OH groups on the inner surface of the vials through Si-N bonds, and grafted by O-Si bonds to form a functional hydrolysis-resistant surface with excellent stability. The success of the chemical modification was confirmed by colorimetric staining experiments, Fourier transform infrared spectra, water contact angle and the morphology of the inner surface of the vials before and after modification. The water contact angle was increased from unmodified 65° to more than 100°, and improved the hydrolytic resistance of the glass by modifying the hydrophobicity of the inner surface of the glass vial. Hydrothermal aging tests were performed before and after modification defined by the pharmacopeias, and the volume of 0.01 M HCl consumed during titration decreased by 88 % and 86 %, indicating that metal ion precipitation is greatly reduced, effectively reducing the risk of glass delamination. It is worth mentioning that the surface modification engineering of the inner surface of the vials with HMDS and BADMSCP can significantly improve the barrier properties of the inner surface of the vials without affecting the appearance and the transmittance of the vials.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"697 ","pages":"Article 163059"},"PeriodicalIF":6.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677985","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Activation of g-C3N4 by oxidative treatment for enhanced photocatalytic H2 evolution","authors":"Sofiya Kharina ,&nbsp;Anna Kurenkova ,&nbsp;Egor Aydakov ,&nbsp;Denis Mishchenko ,&nbsp;Evgeny Gerasimov ,&nbsp;Andrey Saraev ,&nbsp;Angelina Zhurenok ,&nbsp;Viktoria Lomakina ,&nbsp;Ekaterina Kozlova","doi":"10.1016/j.apsusc.2025.163074","DOIUrl":"10.1016/j.apsusc.2025.163074","url":null,"abstract":"<div><div>Graphitic carbon nitride g-C₃N₄ has attracted a scientific interest as a visible light active non-metallic photocatalyst for a H₂ evolution. Recently, the techniques aimed at oxidizing g-C₃N₄ surface have been investigated in order to improve its photocatalytic properties. The present study is devoted to the modification of g-C₃N₄ via hydrothermal treatment in aqueous H₂O₂ solution. The treatment led to partial structural decomposition and functionalization of the g-C₃N₄ surface with −C=O and –COOH groups, thereby affecting the structural, textural, and electronic properties. The platinum deposited on the surface of the pretreated g-C₃N₄ was in a special configuration with metal particles surrounded by single atoms. The platinized g-C₃N₄ treated in H₂O₂ solution at 140 °C was shown to be active in H₂ evolution from glucose aqueous solution with a reaction rate of 344 μmol H₂·h⁻¹·(g_cat)⁻¹ (λ_max = 440 nm), while Pt/g-C₃N₄ without hydrothermal treatment demonstrated no activity. Moreover, the activity of platinized g-C₃N₄ after hydrothermal treatment was improved by a factor of 9.5 and 4.3 in ethanol and triethanolamine aqueous solutions, respectively. The study presents a novel simple avenue for the synthesis of g-C₃N₄-based photocatalyst for H₂ generation from different substrates, including plant biomass components, thus expanding the scope of g-C₃N₄ applications.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"698 ","pages":"Article 163074"},"PeriodicalIF":6.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695300","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sensitivity of phosphorus introduction stage to the catalytic activity of CeO2/TiO2 catalysts for selective catalytic reduction of NOx with NH3","authors":"Shibo Yu ,&nbsp;Yiqing Zeng ,&nbsp;Mengna Zhan ,&nbsp;Shule Zhang ,&nbsp;Zhaoxiang Zhong","doi":"10.1016/j.apsusc.2025.163075","DOIUrl":"10.1016/j.apsusc.2025.163075","url":null,"abstract":"<div><div>The influence of phosphorus (P) on ammonia selective catalytic reduction (NH₃-SCR) catalysts has been the subject of considerable scrutiny. Nevertheless, the precise mechanism of its influence remains a matter of contention. Furthermore, the impact of introducing P at varying stages during catalyst preparation process and its different sites within the catalyst structure on performance is frequently disregarded, significantly hindering practical guidance for designing effective modified catalysts. In this study, a series of P-modified CeO₂/TiO₂ catalysts were synthesized by introducing P at different preparation stages, and various of characterization and comparison experiments were conducted to elucidate the effect of introducing P at different stages on NH₃-SCR performance of NO<em>_x</em>. Results show that introducing P before loading CeO₂ boosts catalyst activity, whereas delaying the introduction of P results in decreased activity and a progressive decline in catalyst performance as the sequence of P introduction is postponed. P introduced earlier tends to be distributed on the surface of the TiO₂ support, which contributes to the dispersion and anchoring of Ce species. In contrast, when the introduction of P was delayed, it tended to be distributed on the surface of the active species, which led to pore plugging and active sites being covered. Secondly, the variation in loading sites resulting from alterations in the stage of P introduction significantly affected on the chemical environment of Ce species, leading to notable differences in the redox capacity of the catalysts. This is the primary reason for the considerable discrepancy in the SCR performance of the catalysts. This study revealed the sensitivity of the stage of P introduction to CeO₂/TiO₂ catalysts, providing new insights for designing modified CeO₂/TiO₂ catalysts.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"698 ","pages":"Article 163075"},"PeriodicalIF":6.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695305","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Suppression of side reactions on Zn metal anode by Bi-coated zincophilic three-dimensional Cu host for aqueous Zn-ion batteries","authors":"Hyeok Jae Lee,&nbsp;Chul Hyun Jun,&nbsp;Chandan Chandru Gudal,&nbsp;Seong Soo Kim,&nbsp;Pil J. Yoo,&nbsp;Jung Kyu Kim,&nbsp;Chan-Hwa Chung","doi":"10.1016/j.apsusc.2025.163072","DOIUrl":"10.1016/j.apsusc.2025.163072","url":null,"abstract":"<div><div>Rechargeable aqueous Zn-ion batteries have garnered significant interest due to their inherent safety and high power density. However, the long-term cycling performance of the Zn metal anode is impeded by several challenges, including the formation of Zn dendrites, undesirable side-reactions such as the hydrogen evolution reaction (HER), and corrosion. Herein, a three-dimensional (3D) host with a surface coating was employed for the Zn metal anode. A 3D Cu foam was formed using an H₂ bubble template, followed by a galvanic displacement reaction with a [BiCl₆]^3- complex to exploit the chemical properties of Bi, such as its strong affinity for Zn and inertness toward the HER. The resulting 3D Bi-Cu foam synthesized through this method effectively alleviates dendrite growth and inhibits side-reactions, enhancing the lifespan of the battery. In half cell, the 3D Bi-Cu foam exhibited an ultralow nucleation overpotential of 4 mV (vs. Zn²⁺/Zn) at 1 mA cm⁻². In addition, it showed stable cycling for 1000 cycles with an average Coulombic efficiency of 99.5 % at 10 mA cm⁻², indicating that a highly reversible redox reaction occurs during cycling. Moreover, the enhanced performance in symmetric cell and full cell with δ-MnO₂ cathode further highlights the advantages of the 3D Bi-Cu foam.</div></div>","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"698 ","pages":"Article 163072"},"PeriodicalIF":6.3,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695302","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unveiling the effect of the polymerization degree of graphitic carbon nitride on the surface functionalization by low-temperature plasma: Insights from XPS and DFT study","authors":"F. Zažímal, D. Plašienka, S. Atri, L. Vrána, O. Monfort, P. Stavárek, P. Klusoň, M. Šob, T. Homola","doi":"10.1016/j.apsusc.2025.163073","DOIUrl":"https://doi.org/10.1016/j.apsusc.2025.163073","url":null,"abstract":"This study investigates the electronic structure and surface chemistry of graphitic carbon nitride (gCN) with distinct degrees of polymerization. We compare gCN materials prepared via conventional pyrolysis of melamine (M−gCN) and pyrolysis of a melamine-cyanuric acid complex (CM-gCN). Using.X-ray photoelectron spectroscopy (XPS) and Density functional theory (DFT) calculations, we provide unique comparison of melon and fully-heptazine based gCN structures, enabling precise identification of core-level XPS components and resolving common discrepancies in the literature. To introduce carboxyl (COOH), amide (CONH₂), and amine (NH₂) groups on the surface of gCN, both materials.(M−gCN−PT and CM-gCN-PT) were treated by low-temperature air plasma and the presence of these groups was confirmed by XPS and DFT analysis. We demonstrate that the polymerization degree of gCN influences the concentration and orientation of surface functional groups, with differences observed in the amide group binding depending on the gCN structure. We also discuss influence of surface functional groups on the band structure of the materials experimentally by valence band XPS spectra and DFT simulations by comparing calculated projected density of states (PDOS). This work highlights the critical role of polymerization in optimizing the functionalization efficiency of gCN, providing valuable insights for enhancing its performance in practical applications.","PeriodicalId":247,"journal":{"name":"Applied Surface Science","volume":"21 1","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143695304","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}