Surface Science最新文献

{"title":"The effect of NO and CO on the Rh(100) surface at room temperature and atmospheric pressure","authors":"Dajo Boden,&nbsp;Jörg Meyer,&nbsp;Irene M.N. Groot","doi":"10.1016/j.susc.2024.122679","DOIUrl":"10.1016/j.susc.2024.122679","url":null,"abstract":"<div><div>Rhodium is used in automotive catalysis to reduce NO and CO emission by catalyzing the reduction of NO to N<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span> and the oxidation of CO to CO<span><math><msub><mrow></mrow><mrow><mn>2</mn></mrow></msub></math></span>. Rhodium nanoparticles in the catalyst are exposed to high pressures of NO and CO, which leads to disintegration and sintering of the catalyst. To design more stable catalysts, the effects of high pressures of NO and CO on rhodium must be understood. Therefore, we studied the Rh(100) surface, which is most active for NO reduction by CO, at atmospheric pressures of NO and CO with scanning tunneling microscopy. Atomistic thermodynamics, low-energy electron diffraction, and Auger electron spectroscopy were used to understand the behavior of adsorbates on the surface. We observe the formation of rhodium islands and roughening of the step edges at high CO pressures. Roughening does not occur at the same pressures of NO, and is also less severe when co-dosing NO and CO, even at identical CO partial pressures. Atomistic thermodynamics shows that NO likely inhibits CO adsorption by blocking adsorption sites, preventing carbonyl formation, and decreasing surface roughening.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"754 ","pages":"Article 122679"},"PeriodicalIF":2.1,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143151027","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":"Impact of Ni doping on the catalytic activity and stability of RuO2 electrocatalyst for the oxygen evolution reaction in acidic media","authors":"Hyunwoo Jang,&nbsp;Seungwon Shim,&nbsp;Youngho Kang","doi":"10.1016/j.susc.2024.122691","DOIUrl":"10.1016/j.susc.2024.122691","url":null,"abstract":"<div><div>Doping with transition metals (TMs) has been recognized as an effective strategy to improve the material stability of RuO₂ electrocatalysts for the oxygen evolution reaction (OER). However, the detailed mechanisms of material degradation and the impact of TM doping remain unclear. In this work, using density functional theory (DFT) calculations, we demonstrate that the experimental conditions under which OER proceeds can also trigger the degradation of RuO₂ through Ru dissolution, and that Ni doping can suppress this dissolution process. Specifically, the formation of RuO₄(<em>aq</em>), a product of the dissolution reaction, becomes thermodynamically favorable at a bias comparable to OER overpotentials. Ni doping makes RuO₄ formation less favorable without significantly altering the OER pathway. Furthermore, the Ru-O bond near a Ni dopant becomes stronger, making the reaction pathway for Ru dissolution more difficult to proceed. By expanding the atomistic understanding of the role of Ni doping on OER and material stability, this work paves the way for the development of high-performance and sustainable electrocatalysts for water splitting.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"754 ","pages":"Article 122691"},"PeriodicalIF":2.1,"publicationDate":"2024-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143150350","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":"Diamond surface nano-structures in an oxidizing atmosphere: A first principles study","authors":"Ke Ri Liang ,&nbsp;Rich P. Mildren ,&nbsp;Catherine Stampfl","doi":"10.1016/j.susc.2024.122685","DOIUrl":"10.1016/j.susc.2024.122685","url":null,"abstract":"&lt;div&gt;&lt;div&gt;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 &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mi&gt;C&lt;/mi&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mn&gt;110&lt;/mn&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; 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 &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mi&gt;C&lt;/mi&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mn&gt;100&lt;/mn&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt;, &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mi&gt;C&lt;/mi&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mn&gt;110&lt;/mn&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; and &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mi&gt;C&lt;/mi&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mn&gt;111&lt;/mn&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; 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 &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mi&gt;C&lt;/mi&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mn&gt;100&lt;/mn&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; 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 &lt;span&gt;&lt;math&gt;&lt;mrow&gt;&lt;mi&gt;C&lt;/mi&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mn&gt;111&lt;/mn&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;mo&gt;−&lt;/mo&gt;&lt;mrow&gt;&lt;mo&gt;(&lt;/mo&gt;&lt;mn&gt;1&lt;/mn&gt;&lt;mo&gt;×&lt;/mo&gt;&lt;mn&gt;2&lt;/mn&gt;&lt;mo&gt;)&lt;/mo&gt;&lt;/mrow&gt;&lt;/mrow&gt;&lt;/math&gt;&lt;/span&gt; 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 ,&nbsp;Hajime Karasawa ,&nbsp;Ryota Horiike ,&nbsp;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}