Surface Science最新文献

{"title":"Comparing phase sensitive detection and Fourier analysis of modulation excitation spectroscopy data exemplified by Ambient Pressure X-ray Photoelectron Spectroscopy","authors":"Ulrike Küst ,&nbsp;Julia Prumbs ,&nbsp;Calley Eads ,&nbsp;Weijia Wang ,&nbsp;Virginia Boix ,&nbsp;Alexander Klyushin ,&nbsp;Mattia Scardamaglia ,&nbsp;Robert Temperton ,&nbsp;Andrey Shavorskiy ,&nbsp;Jan Knudsen","doi":"10.1016/j.susc.2024.122612","DOIUrl":"10.1016/j.susc.2024.122612","url":null,"abstract":"<div><div>Dynamic processes in catalysis are gaining increased attention and could very well be one of the next frontiers in surface science. One way to study such processes is to induce chemical changes on the surface for example by periodically adjusting the (electro)chemical potential in situ and identify the resulting spectral changes. Often this is referred to as Modulation Excitation Spectroscopy (MES). Using Ambient Pressure Photoelectron Spectroscopy data, we here discuss and compare the analysis of MES data using both Phase Sensitive Detection (PSD) and Fourier analysis. We discuss that PSD determines the component magnitude at a user-defined phase value while Fourier analysis provides the maximum oscillation amplitude and respective phase value of oscillating spectral features. We discuss advantages and disadvantages of the different analysis schemes and explore how the full time-evolution can be obtained.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"751 ","pages":"Article 122612"},"PeriodicalIF":2.1,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142421413","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The surface chemistry of cuprous oxide","authors":"Tianhao Hu ,&nbsp;Burcu Karagoz ,&nbsp;Fang Xu ,&nbsp;Ashley R. Head ,&nbsp;Jonas Weissenrieder ,&nbsp;Dario Stacchiola","doi":"10.1016/j.susc.2024.122622","DOIUrl":"10.1016/j.susc.2024.122622","url":null,"abstract":"<div><div>The chemical and electronic properties of copper combined with its large natural abundance lend this material to impact a wide range of technological applications, including heterogeneous catalysis. The reactivity of copper in its Cu¹⁺oxidation state makes this specific configuration relevant in various chemical reactions, but the facile redox properties of copper make the isolation of individual states for fundamental studies difficult. Here we review three Cu₂O model systems used to study the interaction of Cu¹⁺ with small molecules making use of surface science techniques: Cu₂O/Cu(111), thin polycrystalline Cu₂O films on Cu foil, and bulk Cu₂O crystals. Advantages and disadvantages of each system are discussed and exemplified through case studies of chemical adsorption and reactivity studies.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"751 ","pages":"Article 122622"},"PeriodicalIF":2.1,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142421414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"CO oxidation on IrO2(110) surfaces","authors":"Connor Pope ,&nbsp;Jungwon Yun ,&nbsp;Rishikishore Reddy ,&nbsp;Jovenal Jamir ,&nbsp;Minkyu Kim ,&nbsp;Aravind Asthagiri ,&nbsp;Jason F. Weaver","doi":"10.1016/j.susc.2024.122619","DOIUrl":"10.1016/j.susc.2024.122619","url":null,"abstract":"<div><div>We investigated the oxidation of CO on stoichiometric and O-rich IrO₂(110) surfaces using temperature programmed reaction spectroscopy (TPRS), density functional theory (DFT) calculations and microkinetic simulations. Adsorbed CO on the s-IrO₂(110) surface generates CO and CO₂ peaks near 545 K during TPRS, and only about 38 % of the CO oxidized to CO₂ when the initial CO layer was saturated. Pre-adsorbed O-atoms, so-called on-top oxygen (O_t), promote the oxidation of CO adsorbed on IrO₂(110). On the O_t-covered surface, CO oxidation by O_t atoms produces a CO₂ TPRS peak at ∼370 K, and all of the initially adsorbed CO oxidizes to CO₂ when the initial O_t coverage is greater than the CO coverage. In agreement with the TPRS results, DFT calculations predict that the barrier is about 100 kJ/mol lower for CO oxidation by an O_t atom than a lattice O-atom of IrO₂(110). A microkinetic model, parameterized with energy barriers computed using DFT, accurately reproduces the CO and CO₂ TPRS traces only after CO binding energies are lowered to values determined using a hybrid exchange-correlation functional and the barrier for CO molecules to fill bridging O-vacancies is lowered. The simulations predict that O-vacancies play an important role in mediating the CO oxidation kinetics on s-IrO₂(110), and thereby demonstrate the importance of future spectroscopic studies aimed at characterizing the nature of the surface CO and O species involved in reaction. This study provides new insights for understanding CO oxidation on IrO₂(110), and provides evidence that several elementary steps can be involved in governing this chemistry.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"751 ","pages":"Article 122619"},"PeriodicalIF":2.1,"publicationDate":"2024-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142420979","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stability and dissolution of single-crystalline iron oxide thin films in electrochemical environments","authors":"Peter Seidel,&nbsp;Sascha Pomp,&nbsp;Florian Schwarz,&nbsp;Martin Sterrer","doi":"10.1016/j.susc.2024.122621","DOIUrl":"10.1016/j.susc.2024.122621","url":null,"abstract":"<div><div>The stability of single-crystalline monolayer FeO(111) and 10 nm thin Fe₃O₄(111) films on Pt(111) upon exposure to environments of increasing chemical complexity has been studied with X-ray photoelectron spectroscopy, temperature-programmed desorption, in-situ scanning tunneling microscopy, and cyclic voltammetry. The well-defined oxide films, which were prepared under ultrahigh-vacuum conditions, were exposed to aqueous solutions of different pH and electrochemical cycling in pure and catechol-containing electrolyte. The films are stable in neutral (pH 7) and alkaline (pH 13) solutions both at open circuit conditions and during electrochemical cycling within the limits of hydrogen and oxygen evolution potentials. Also in strongly acidic (pH 1) perchlorate solution the films remain intact under open circuit conditions, but they quickly dissolve on application of electrochemical potential. Especially for the ultrathin FeO(111) films, catechol enhances the dissolution at neutral pH during electrochemical cycling. A comparison of Pt(111), FeO(111) and Fe₃O₄(111) substrates in the electrochemical catechol oxidation reaction reveals enhanced and sustained activity of FeO in alkaline environment, while strong deactivation occurs on Pt(111) and Fe₃O₄(111). This is explained by the weaker interaction between catechol and FeO(111) compared to the other substrates, which hampers the formation of a barrier layer on the electrode surface.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"751 ","pages":"Article 122621"},"PeriodicalIF":2.1,"publicationDate":"2024-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142421411","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydroxylation of an ultrathin Co3O4(111) film on Ir(100) studied by in situ ambient pressure XPS and DFT","authors":"Thomas Haunold ,&nbsp;Krešimir Anić ,&nbsp;Alexander Genest ,&nbsp;Christoph Rameshan ,&nbsp;Matteo Roiaz ,&nbsp;Hao Li ,&nbsp;Thomas Wicht ,&nbsp;Jan Knudsen ,&nbsp;Günther Rupprechter","doi":"10.1016/j.susc.2024.122618","DOIUrl":"10.1016/j.susc.2024.122618","url":null,"abstract":"<div><div>In the present work, we have studied the interaction of water with spinel cobalt oxide (Co₃O₄), an effect which has been considered a major cause of its catalytic deactivation. Employing a Co₃O₄(111) model thin film grown on Ir(100) in (ultra)high vacuum, and ambient pressure X-ray photoelectron spectroscopy (APXPS), hydroxylation in 0.5 mbar H₂O vapor at room temperature was monitored in real time. The surface hydroxyl (OH) coverage was determined <em>via</em> two different models based (i) on the termination of a pristine and OH-covered Co₃O₄(111) surface as derived from density functional theory (DFT) calculations, and (ii) on a homogeneous cobalt oxyhydroxide (CoO(OH)) overlayer. Langmuir pseudo-second-order kinetics were applied to characterize the OH evolution with time, suggesting two regimes of chemisorption at the mosaic-like Co₃O₄(111) film: (i) plateaus, which were quickly saturated by OH, followed by (ii) slow hydroxylation in the “cracks” of the thin film. H₂O dissociation and OH formation, blocking exposed Co²⁺ ions and additionally consuming surface lattice oxygen, respectively, may thus account for catalyst deactivation by H₂O traces in reactive feeds.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"751 ","pages":"Article 122618"},"PeriodicalIF":2.1,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142421412","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Interfacial effect investigation of lithium perchlorate-interacted oxygen-containing carbon paper","authors":"Yibing Xie ,&nbsp;Chen Yao","doi":"10.1016/j.susc.2024.122615","DOIUrl":"10.1016/j.susc.2024.122615","url":null,"abstract":"<div><div>The lithium perchlorate-interacted oxygen-containing carbon paper (LiClO4-OCP) is designed to act as electroactive supercapacitor electrode substrates for the energy storage application. The OCP is fabricated through hydrothermal activation treatment of carbon paper in H₂O₂ reaction medium. The OCP is composed of graphite pitches with ultra-thin graphene structure of top layer, showing the improved graphitization degree. The LiClO4-OCP with the polarized electrostatic force-induced interfacial adsorption reveals much more intensive interaction than LiClO4-CP with van der Waals force-induced interfacial adsorption, contributing to promoting interfacial charge transfer of LiClO4-OCP. LiClO4-OCP reveals more effective interface charge transfer and more feasible electrolyte diffusion than LiClO4-CP, contributing to higher electrochemical double-layer capacitance. LiClO4-OCP with oxygen-containing groups conducts reversible redox process to supply additional Faradaic capacitance. Mean response current is increased from 0.10 ∼ 1.34 mA cm^-2 for LiClO4-CP to 0.19 ∼ 2.31 mA cm^-2 for LiClO4-OCP at scan rates of 5∼100 mV s^-1, indicating the improved electrochemical activity of LiClO4-OCP. The cyclic voltammetry-based capacitance increases from 19.91 ∼ 13.01 mF cm^-2 mF g-1 for LiClO4-CP to 37.76 ∼ 23.06 mF cm^-2 for LiClO4-OCP. The galvanostatic charge/discharge-based capacitance decreases from 13.84 ∼ 3.97 mF cm^-2 for LiClO4-CP to 29.71 ∼ 12.92 mF cm^-2 for LiClO4-OCP. Density-functional theory-based simulation calculation proves LiClO4-OCP with such a short molecular distance is allowed to occur strong electrostatic interaction which is caused by the perchlorate ion-induced polarization of oxygen-containing groups. The LiClO4-OCP has lower interfacial energy, lower band gap and higher density of states at Fermi energy level than LiClO4-CP, indicating the improved interfacial interaction and electrical conductivity of LiClO4-OCP. The experimental measurement and theoretical calculation achieve the consistent results of higher electrochemical activity of LiClO4-OCP electrode substrate to present its superior capacitance performance.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"751 ","pages":"Article 122615"},"PeriodicalIF":2.1,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142315542","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The evolution of model Rh/Fe3O4(001) catalysts in hydrogen environments","authors":"Mausumi Mahapatra ,&nbsp;Marcus A. Sharp ,&nbsp;Christopher J. Lee ,&nbsp;Yifeng Zhu ,&nbsp;Oliver Y. Gutiérrez ,&nbsp;Bruce D. Kay ,&nbsp;Zdenek Dohnálek","doi":"10.1016/j.susc.2024.122617","DOIUrl":"10.1016/j.susc.2024.122617","url":null,"abstract":"<div><div>Single metal atoms dispersed on oxides are a new emerging class of catalysts owing to their unique electronic and chemical properties. In this study, we have prepared a series of model single-atom catalysts possessing well-characterized Rh sites that include Rh adatoms (Rh_ad), mixed surface layers with octahedrally-coordinated Rh (Rh_oct), as well as metallic Rh clusters and nanoparticles (Rh_met) on Fe₃O₄(001). Using X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM), we investigated the activity of such model systems towards H₂ and their stability in reducing environments. Our results show that the atomically dispersed Rh_ad and Rh_oct species do not activate H_2, which would result in the formation of surface hydroxyls on Fe₃O₄(001). In contrast, the presence of Rh_met in H₂ results in the formation of hydroxyls and subsequent etching of the Fe₃O₄(001) at higher temperatures (≥ 500 K) due to water formation via the Mars−van Krevelen mechanism. Additionally, such surface etching leads to the release of the Rh_oct from the surface lattice and their sintering to Rh_met. To bridge the material gap between the surface science models and high surface area catalysts, we perform parallel studies on powder Rh/Fe₃O₄ catalysts. The XPS characterization shows remarkable similarities between these systems. Further, our surface science studies provide an atomistic picture of the behavior of high surface area catalysts in the H₂ atmosphere.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"751 ","pages":"Article 122617"},"PeriodicalIF":2.1,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142323806","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Evolution of the surface morphology of GaSb epitaxial layers deposited by molecular beam epitaxy (MBE) on GaAs (100) substrates","authors":"Dawid Jarosz ,&nbsp;Ewa Bobko ,&nbsp;Marcin Stachowicz ,&nbsp;Ewa Przeździecka ,&nbsp;Piotr Krzemiński ,&nbsp;Marta Ruszała ,&nbsp;Anna Juś ,&nbsp;Małgorzata Trzyna-Sowa ,&nbsp;Kinga Maś ,&nbsp;Renata Wojnarowska-Nowak ,&nbsp;Oskar Nowak ,&nbsp;Daria Gudyka ,&nbsp;Brajan Tabor ,&nbsp;Michał Marchewka","doi":"10.1016/j.susc.2024.122607","DOIUrl":"10.1016/j.susc.2024.122607","url":null,"abstract":"<div><p>This study presents a demonstration of the surface morphology behavior of gallium antimonide (GaSb) layers deposited on gallium arsenide (GaAs) (100) substrates using three different methods: metamorphic, interfacial misfit (IMF) matrix, and a method based on a Polish patent application number P.443805. The first two methods are commonly used, while the third differs in the sequence of successive steps and the presence of Be doping at the initial growth stage. By comparing GaSb layers made by these methods for the same growth parameters, the most favorable procedure for forming a GaSb buffer layer is selected. Using GaAs substrates with a GaSb buffer layer is a cheaper alternative to using GaSb substrates in infrared detector structures based on II-type superlattices T2SL, such as InAs/GaSb. The quality of the GaSb buffer layer determines the quality of the subsequent layers that form the entire T2SL and affects factors such as dark current in terms of application.</p></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"751 ","pages":"Article 122607"},"PeriodicalIF":2.1,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0039602824001584/pdfft?md5=8c36a3bf254391ffeefbcb9b455b7662&pid=1-s2.0-S0039602824001584-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142271535","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"First principles study on photocatalytic water decomposition of ZnO/WS2 heterojunctions","authors":"Junyi Fan ,&nbsp;Haixia Chen ,&nbsp;Jijun Ding ,&nbsp;Haiwei Fu ,&nbsp;Jianhong Peng","doi":"10.1016/j.susc.2024.122616","DOIUrl":"10.1016/j.susc.2024.122616","url":null,"abstract":"<div><p>The generation of clean energy hydrogen through solar-driven water decomposition is an effective solution to the current global energy shortage and environmental pollution. In this paper, ZnO/WS₂ heterojunction is constructed based on first-principles. The effect of uniaxial strain and vacancy defects (V_Zn, V_O, V_S, V_2S) on electronic and optical properties of ZnO/WS₂ heterojunction are calculated. The results indicate that the bandgap of the heterojunction is decreased and the visible absorption range is expanding. Additionally, the built-in electric field of the heterojunction is determined to be oriented from ZnO to WS₂, which enhances the efficiency of carrier separation. Band-edge position analysis indicates that ZnO/WS₂ heterojunctions exhibit good redox water properties under an applied compressive strain of −2 %. Finally, the visible light absorption range of the heterostructures is also expanded by introducing V_S and V_2S vacancy defects. However, it exhibits a superior ability to oxidize and reduce water only under V_Zn defects. The corresponding photocatalytic mechanism of ZnO/WS₂ heterojunctions is discussed.</p></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"751 ","pages":"Article 122616"},"PeriodicalIF":2.1,"publicationDate":"2024-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142271534","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic insight into the synergistic effect of O2 and SO2 for improving removal of arsenic over Mn-modified Fe2O3-based sorbent","authors":"Yuyu Huang ,&nbsp;Jindong An ,&nbsp;Guoqing Huang ,&nbsp;Ruikun Wang ,&nbsp;Huimin Liu ,&nbsp;Ping Xiao ,&nbsp;Shiqing Wang ,&nbsp;Yue Zhang","doi":"10.1016/j.susc.2024.122614","DOIUrl":"10.1016/j.susc.2024.122614","url":null,"abstract":"<div><p>Iron-based materials are promising sorbents for controlling arsenic emissions. However, the effects of SO₂, especially the synergistic mechanism of As₂O₃ adsorption under the combined effects of O₂ and SO₂, remain inadequately explored. This study investigated for the first time the impact of the newly formed surface resulting from the adsorption and dissociation of O₂ and SO₂ on the adsorption of As₂O₃. The results showed that Mn_3f and Fe_3f sites were the active sites for the adsorption of O₂ and SO₂, which competed with As₂O₃ and hindered its adsorption. Conversely, dissociation created more reactive sites, which promoted the process. Selectivity analysis revealed that As₂O₃ preferentially adsorbed on the dissociated surface, highlighting the dominance of the promotion effect. Finally, starting from the adsorption sequence of O₂ and SO₂, the impact of arsenic adsorption and oxidation was examined on sorbents created through the sequential adsorption of O₂ and SO₂. Regardless of the adsorption sequence, active O atoms with catalytic effects were exposed, supporting the enhanced removal of arsenic under the synergistic effect of O₂ and SO₂. Building upon this analysis, a theoretical framework for efficiently removing As₂O₃ from O₂ and SO₂ flue gases using Mn-modified Fe₂O₃-based materials was developed.</p></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"751 ","pages":"Article 122614"},"PeriodicalIF":2.1,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142271327","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}