Surface Science最新文献

{"title":"Diamond surface nano-structures in an oxidizing atmosphere: A first principles study","authors":"Ke Ri Liang , Rich P. Mildren , Catherine Stampfl","doi":"10.1016/j.susc.2024.122685","DOIUrl":"10.1016/j.susc.2024.122685","url":null,"abstract":"<div><div>Diamond’s unique properties has found it numerous applications in electronics, optics and medicine. As desirable are diamond’s potential applications, it is notoriously difficult to process on the nanoscale. A new and promising mechanism involving a two-photon laser induced desorption could solve many of these problems. However, the underlying mechanism of this process is still not well understood; what is known, is that oxygen plays an important role. Therefore a detailed and consistent understanding of the fundamental behaviour of oxygen on diamond surfaces is required. In the present paper, systematic density-functional theory calculations are performed to investigate the interaction of oxygen with the low-index surfaces of diamond, taking into account the effect of pressure and temperature. This affords predictions of the surface atomic structures, including the newly discovered keto-ether structure on the <span><math><mrow><mi>C</mi><mrow><mo>(</mo><mn>110</mn><mo>)</mo></mrow></mrow></math></span> surface, and the associated properties such as the adsorption energies, work-function, surface dipole moment, electron density difference, density of states, and electronic bandstructure. By including the effect of the environment, namely, the oxygen pressure and temperature in which the surface is held, surface phase diagrams are obtained. From these results, and using the Wulff construction, the shape of oxygen-terminated nanoparticles are predicted. Further, using the calculated surface free energies, the surface populations of different structures on the <span><math><mrow><mi>C</mi><mrow><mo>(</mo><mn>100</mn><mo>)</mo></mrow></mrow></math></span>, <span><math><mrow><mi>C</mi><mrow><mo>(</mo><mn>110</mn><mo>)</mo></mrow></mrow></math></span> and <span><math><mrow><mi>C</mi><mrow><mo>(</mo><mn>111</mn><mo>)</mo></mrow></mrow></math></span> surfaces as a function of temperature, for both atmospheric pressure and ultra high vacuum conditions are evaluated. Interestingly, the results predict that although the full monolayer bridge site on <span><math><mrow><mi>C</mi><mrow><mo>(</mo><mn>100</mn><mo>)</mo></mrow></mrow></math></span> has the highest population, the top site ketone structure can be populated by as much as 20% and coexist. Regarding the half monolayer bridge structure on the reconstructed <span><math><mrow><mi>C</mi><mrow><mo>(</mo><mn>111</mn><mo>)</mo></mrow><mo>−</mo><mrow><mo>(</mo><mn>1</mn><mo>×</mo><mn>2</mn><mo>)</mo></mrow></mrow></math></span> surface, the bandstructure shows that it possesses no surface states in the band gap making it attractive for quantum sensing applications and is the most favourable structure at this coverage. Interestingly, the calculations predict another structure that is only 0.02 eV less favourable and so is likely to coexist on the surface. Overall, the present work provides a most comprehensive theoretical understanding of the interaction of oxygen with the low index diamond surfaces,","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"754 ","pages":"Article 122685"},"PeriodicalIF":2.1,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143150349","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":"Corrigendum to “Theoretical investigation of NH3 nitridation on Cl-terminated Si(100)-2 × 1 surfaces” [Surface Science 753 (2025) 122655, p2.]","authors":"Tomoya Nagahashi , Hajime Karasawa , Ryota Horiike , Kenji Shiraishi","doi":"10.1016/j.susc.2024.122681","DOIUrl":"10.1016/j.susc.2024.122681","url":null,"abstract":"","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"754 ","pages":"Article 122681"},"PeriodicalIF":2.1,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143151034","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 adsorption of oxygen on bimetallic Pd3M2 clusters (M = Ag, Au, Co, Cu, Mn, Ni, Pt, and Ru) with and without alumina support by density functional theory","authors":"Nusaiba Zaman ,&nbsp;Karima Lasri ,&nbsp;Abdelkader Kara","doi":"10.1016/j.susc.2024.122684","DOIUrl":"10.1016/j.susc.2024.122684","url":null,"abstract":"<div><div>We performed density functional theory (DFT) calculations to systematically investigate the adsorption of atomic and molecular oxygen on the bimetallic Pd₃M₂ clusters (<em>M</em> = Ag, Au, Co, Cu, Mn, Ni, Pt, and Ru) supported on hydroxylated alumina. The interaction between the atomic and molecular oxygen with unsupported Pd₃M₂ clusters was also computed for comparison. It was found that oxygen molecule dissociates spontaneously upon adsorption on Pd₃Co₂, Pd₃Mn₂, and Pd₃Ru₂ for both unsupported and hydroxylated alumina-supported situations. For all other cases, the bond length of molecular oxygen is activated to a superoxo state upon adsorption. Bader charge analysis revealed that when the charge transfer to the antibonding π orbital of the oxygen molecule was greater than -1.3 electrons, the oxygen molecule dissociated spontaneously. The study of the adsorption of atomic oxygen on the hydroxylated alumina-supported clusters showed that the adsorbed oxygen atom spontaneously picks up H-atom from the substrate for all cases forming OH and representing a reverse H-spillover except for the Pd₃Ru₂ cluster. Water molecule is formed when atomic oxygen is adsorbed on hydroxylated alumina-supported Pd₃Mn₂ cluster due to the spontaneous pick up of two H-atoms from the substrate by the adsorbed atomic oxygen.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"754 ","pages":"Article 122684"},"PeriodicalIF":2.1,"publicationDate":"2024-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143151029","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":"Destruction of surface oxide on (100)W in high-temperature atomic carbon deposition","authors":"E.V. Rut'kov,&nbsp;E.Y. Afanas'eva,&nbsp;N.R. Gall","doi":"10.1016/j.susc.2024.122689","DOIUrl":"10.1016/j.susc.2024.122689","url":null,"abstract":"<div><div>Sequential adsorption of oxygen and carbon on the (100)W surface was studied in a wide temperature range at <em>T</em> = 900–2100 K. Surface tungsten oxide WO is formed upon oxygen adsorption at <em>T</em> = 300 K. Carbon deposition with atomic flux on surface oxide at <em>T</em> = 900–1100 K results in the replacement of the surface oxide by surface tungsten carbide, and this process requires a double carbon dose compared to that required to create the surface carbide on the atomically clean tungsten surface. Oxygen leaves the surface, apparently, due to the formation of CO molecules, which thermally desorb at this temperature, and carry away not only oxygen, but also half of the deposited carbon. The oxygen-free adsorption centers are simultaneously filled with newly arriving carbon atoms, which build the surface carbide WC.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"754 ","pages":"Article 122689"},"PeriodicalIF":2.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143151033","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":"Support-dependent modulation of Pt33 nanoparticles: Insights into oxygen interaction, stability, electronic properties, and geometric structure","authors":"David S․ Rivera Rocabado ,&nbsp;Michihisa Koyama","doi":"10.1016/j.susc.2024.122686","DOIUrl":"10.1016/j.susc.2024.122686","url":null,"abstract":"<div><div>Understanding how support materials influence the properties of Pt nanoparticles is crucial for advancing catalyst development. Using density functional theory calculations, we examine the effects of graphene, MgO(100), α-Al₂O₃(0001), and SnO₂(110) supports on O atom adsorption and the stability, electronic, and geometric properties of Pt₃₃ nanoparticles. Our findings reveal that all supports significantly enhance O atom adsorption at the Pt₃₃/support interface, with varying implications for Pt atom detachment and nanoparticle stability. The strength of Pt–support interactions follows the order: graphene &lt; MgO(100) &lt; α-Al₂O₃(0001) &lt; SnO₂(110). Bond order analysis indicates that supports stabilize the Pt–Pt interactions in the supported Pt₃₃ and their outer shell atoms. Electronic equilibrium between Pt₃₃ and the support induces electron transfer from graphene, MgO(100), and α-Al₂O₃(0001) to Pt₃₃, and from Pt₃₃ to SnO₂(110), shifting the <em>d</em>-band center and influencing catalytic properties. Strain analysis reveals compressive and tensile effects on Pt–Pt distances, correlating with the Pt₃₃ adsorption energies and indicating a link between geometric changes and nanoparticle stability. These insights elucidate the role of supports in O atom adsorption mechanisms and the tuning of Pt nanoparticle properties, providing valuable guidance for designing advanced catalysts with enhanced efficiency and stability for applications in fuel cells, sensors, and environmental remediation.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"754 ","pages":"Article 122686"},"PeriodicalIF":2.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143150990","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":"Chemical interaction and molecular growth of a highly dipolar merocyanine molecule on metal surfaces: A photoelectron spectroscopy study","authors":"Baris Öcal,&nbsp;Philipp Weitkamp,&nbsp;Klaus Meerholz,&nbsp;Selina Olthof","doi":"10.1016/j.susc.2024.122690","DOIUrl":"10.1016/j.susc.2024.122690","url":null,"abstract":"<div><div>The growth and ordering of molecules on surfaces is an intriguing research topic as insights gained here can be of significant relevance for organic electronic devices. While often simple, rigid molecules are employed as model systems, we show results for a highly dipolar merocyanine which is studied on top of Au(100), Ag(100) and Cu(100) metal single crystals. Film thicknesses ranging from sub-monolayer to multilayer regimes are analyzed using UV (UPS) and X-ray photoelectron spectroscopy (XPS). For the monolayer regime, there is strong indication of face-on orientation, with both of the molecules’ sulfur atoms bonding to the metal surfaces. Here, on Ag and Au(100) the sulfur atoms lose some or all of their intrinsic charges due to a charge transfer with the substrate, while on Cu(100) a strong metal-sulfur bond forms. The interaction between the substrate and the molecules can also be seen in the intensity and width of the highest occupied molecular orbital features in UPS. Upon multilayer deposition, a gradual lowering in ionization energy is observed, likely due to the formation of antiparallel dimers followed by an increased charge carrier delocalization due to the formation of an extended molecular aggregate for thicker layers. Interestingly, on Cu(100) the aggregated phase is already observed for much lower deposition, showing the importance of substrate-molecule interaction on the subsequent film growth. Therefore, this study offers a detailed understanding of the interface formation and electronic structure evolution for merocyanine films on different metal surfaces.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"754 ","pages":"Article 122690"},"PeriodicalIF":2.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143151036","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":"“Single-atom” catalysis: An opportunity for surface science","authors":"Gareth S. Parkinson","doi":"10.1016/j.susc.2024.122687","DOIUrl":"10.1016/j.susc.2024.122687","url":null,"abstract":"<div><div>Over the past decade, extensive research into ``single-atom'' catalysts (SACs) has revealed that the catalytic behavior of metal adatoms is highly dependent on how they interact with their support. A strong dependence on the local coordination environment has led to comparisons with metal-organic complexes, and there is growing excitement about the potential to fine-tune SACs by controlling the adsorption geometry. The rise of computational screening to identify the optimal support/metal combinations underscores the need for rigorous benchmarking of theoretical methods, to validate realistic geometries, mechanisms, and the impact of adsorption on stability and catalytic activity. The surface science approach is particularly well-suited for this task because it allows to precisely determine the geometry of the metal atom and interpret its catalytic behavior. Moreover, the effects of temperature and molecular adsorption on the model catalysts stability can be studied in isolation, and conclusions drawn from UHV studies tested in increasingly common near-ambient pressure and electrochemical setups. This perspective highlights recent breakthroughs and specific systems—including metal oxides, metal-organic frameworks, and carbon nitrides—where insights from surface science experiments can significantly advance understanding in this rapidly evolving field.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"754 ","pages":"Article 122687"},"PeriodicalIF":2.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143151028","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":"X-ray photoelectron diffraction as one efficient tool for surface structure determination of corrugated 2D materials","authors":"Luis Henrique de Lima ,&nbsp;Abner de Siervo","doi":"10.1016/j.susc.2024.122683","DOIUrl":"10.1016/j.susc.2024.122683","url":null,"abstract":"<div><div>This brief review discusses the application of X-ray photoelectron diffraction (XPD) as an effective experimental tool for determining the surface structure of two-dimensional (2D) corrugated materials, such as graphene and hexagonal boron nitride. XPD stands out for its ability to provide precise atomic positions, interlayer distances, bond lengths, and bond angles. Such detailed experimental data are essential for refining theoretical models and complement the findings obtained through other techniques, like scanning probe microscopy (SPM). This brief review includes examples of surface structure studies on sp<span><math><msup><mrow></mrow><mrow><mn>2</mn></mrow></msup></math></span>-hybridized corrugated monolayers, such as graphene on Ir(111), Fe-intercalated graphene on Ir(111), <span><math><mi>h</mi></math></span>BN on Rh(111), and graphene on SiC(0001). XPD has uncovered significant structural details, such as corrugation amplitude and adsorption distances to the substrate, contributing to an enhanced understanding of the electronic, mechanical, optical, magnetic, and physicochemical properties of 2D materials.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"754 ","pages":"Article 122683"},"PeriodicalIF":2.1,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143151030","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":"Measurement of surface segregation via He+ ion scattering in CuxAgyAu1-x-y composition spread thin films","authors":"Zhitao Guo ,&nbsp;Robert A. Burnley ,&nbsp;Andrew J. Gellman","doi":"10.1016/j.susc.2024.122682","DOIUrl":"10.1016/j.susc.2024.122682","url":null,"abstract":"<div><div>Surface segregation under UHV conditions was mapped out across Cu<em>_x</em>Ag<em>_y</em>Au_1-<em>_x</em>_-<em>_y</em> (<em>x</em> = 0→1,<em>y</em> = 0→1‐x) composition space and over a temperature range of 500 – 800 K. E-beam deposition of Composition Spread Alloy Films (CSAFs), high-throughput SEM-EDX, XPS and LEIS experiments were performed to study the relationship between the alloy surface composition and bulk alloy composition. Strong depletion of Cu was observed across all alloy compositions, with &lt;1 % surface Cu detected in alloys containing &gt;20 % bulk Ag or &gt;60 % bulk Au. The majority of the composition space is represented by AgAu surface alloys, showing weak Ag enrichment in alloys with low bulk Cu compositions (&lt;25 % Ag enrichment) and significant Ag enrichment in alloys with higher Cu content (∼75 % Ag enrichment). Surface enrichment of Au in Cu was only observed in alloys with &lt;5 % bulk Ag. These observations are quantitatively consistent with prior studies of the relevant binary alloys and qualitatively consistent with surface segregation driven by differences in surface energies. Alloys with surface Cu greater than 1 % were found to have temperature dependent segregation, varying by as much as 15 % surface Cu over the temperature range 500 – 800 K, while all other alloys showed negligible differences.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"754 ","pages":"Article 122682"},"PeriodicalIF":2.1,"publicationDate":"2024-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143151723","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":"A first-principles study of hydrazine adsorption and decomposition on Pt(111) surface: The effect of partially dissociative H2O on decomposition process","authors":"Yaolin Zhao ,&nbsp;Dayin Tong ,&nbsp;Zhongcun Chen ,&nbsp;Songtao Xiao","doi":"10.1016/j.susc.2024.122680","DOIUrl":"10.1016/j.susc.2024.122680","url":null,"abstract":"<div><div>Density functional theory with dispersion correction (DFT-D3) is used to investigate the adsorption and decomposition of hydrazine (N₂H₄) on Pt(111) surface, and the effect of water on decomposition process is considered. The stable adsorption configurations and adsorption energies are obtained for hydrazine, water and intermediate species. The hydrazine decomposition is investigated in three kinds of pathways including intramolecular dehydrogenation and intermolecular dehydrogenation via H atom or OH group assistance. It is shown that the adsorption of water in partially dissociative conformation (H and OH radicals) is the most stable on Pt(111) surface for its largest adsorption energy. The OH group can greatly promote the decomposition of hydrazine by drastically decreasing the energy barriers of dehydrogenation reactions, which are closely related to the overall PDOS distribution shifts of their transition states. From thermodynamics and kinetics points of view, the favorable decomposition pathway of hydrazine may be N₂H₄+OH→N₂H₃+OH→NHNH+OH→NNH+OH→N₂.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"754 ","pages":"Article 122680"},"PeriodicalIF":2.1,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143150991","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}