Pub Date : 2024-11-28DOI: 10.1016/j.susc.2024.122668
Tinghui Li , Yun Shan , Lizhe Liu
Electrochemical conversion from nitrate to ammonia becomes a feasible technology to improve nitrate pollutants and realize room-temperature ammonia synthesis, but which is limited by multiple competing reaction and low energy conversion efficiency. Herein, we suggest dense and well-defined magnetic metal sites on the M(CN)3 (M = Fe, Co, Ni) surface with spontaneous hydroxyl decoration, which leads to electronic rearrangement at half-filled 3d orbitals due to its tailored coordination environment that optimizes nitrate adsorption and dissociation. The comprehensive calculations associated with density functional theory disclose that the rate-limiting potential barrier effectively reduces and finally leads to a higher nitrogen conversion ability, because the bonding interaction and electron transfer between metal sites and reactants is optimized by decorating hydroxyls. This work provides a new insight into understanding the reaction kinetics for nitrate reduction.
{"title":"Electronic reconfiguration induced by dynamic hydroxyl decoration facilitates electrochemical nitrate reduction to ammonia","authors":"Tinghui Li , Yun Shan , Lizhe Liu","doi":"10.1016/j.susc.2024.122668","DOIUrl":"10.1016/j.susc.2024.122668","url":null,"abstract":"<div><div>Electrochemical conversion from nitrate to ammonia becomes a feasible technology to improve nitrate pollutants and realize room-temperature ammonia synthesis, but which is limited by multiple competing reaction and low energy conversion efficiency. Herein, we suggest dense and well-defined magnetic metal sites on the M(CN)<sub>3</sub> (M = Fe, Co, Ni) surface with spontaneous hydroxyl decoration, which leads to electronic rearrangement at half-filled 3d orbitals due to its tailored coordination environment that optimizes nitrate adsorption and dissociation. The comprehensive calculations associated with density functional theory disclose that the rate-limiting potential barrier effectively reduces and finally leads to a higher nitrogen conversion ability, because the bonding interaction and electron transfer between metal sites and reactants is optimized by decorating hydroxyls. This work provides a new insight into understanding the reaction kinetics for nitrate reduction.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"753 ","pages":"Article 122668"},"PeriodicalIF":2.1,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142748420","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}
Pub Date : 2024-11-23DOI: 10.1016/j.susc.2024.122654
Felipe Marinho Fernandes , Neubi Francisco Xavier Jr , Glauco Favilla Bauerfeldt , Márcio Soares Pereira , Clarissa Oliveira da Silva
The search for alternative energy sources with sustained economic viability and minimal pollution is imperative, making hydrogen a promising candidate as a fuel. This work provides important findings on the Oxygen Evolution Reactions (OER) on TiO2, with a focus on elucidating the reaction mechanisms. Density Functional Theory calculations were applied on both the (101) and (100) surfaces of the catalyst. The application of overpotentials was evaluated, with 2.85 and 2.32 eV required for (101) and (100) surface, respectively, for all reaction steps to be exergonic. The 0.53 eV difference suggests a potentially favorable pathway for the OER on the (100) surface. When evaluating the kinetics, an additional barrier of 2.84 eV under the V condition on the (100) surface is found for the formation of the OOH intermediate, suggesting the kinetics preference for the oxygen evolution process on the (101) surface.
{"title":"Thermodynamic and kinetic analysis of the oxygen evolution reaction on TiO2 (100) and (101) surfaces: A DFT study","authors":"Felipe Marinho Fernandes , Neubi Francisco Xavier Jr , Glauco Favilla Bauerfeldt , Márcio Soares Pereira , Clarissa Oliveira da Silva","doi":"10.1016/j.susc.2024.122654","DOIUrl":"10.1016/j.susc.2024.122654","url":null,"abstract":"<div><div>The search for alternative energy sources with sustained economic viability and minimal pollution is imperative, making hydrogen a promising candidate as a fuel. This work provides important findings on the Oxygen Evolution Reactions (OER) on TiO<sub>2</sub>, with a focus on elucidating the reaction mechanisms. Density Functional Theory calculations were applied on both the (101) and (100) surfaces of the catalyst. The application of overpotentials was evaluated, with 2.85 and 2.32 eV required for (101) and (100) surface, respectively, for all reaction steps to be exergonic. The 0.53 eV difference suggests a potentially favorable pathway for the OER on the (100) surface. When evaluating the kinetics, an additional barrier of 2.84 eV under the <span><math><mrow><mi>U</mi><mo>=</mo><mn>0</mn><mo>.</mo><mn>00</mn></mrow></math></span> V condition on the (100) surface is found for the formation of the OOH intermediate, suggesting the kinetics preference for the oxygen evolution process on the (101) surface.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"753 ","pages":"Article 122654"},"PeriodicalIF":2.1,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142748419","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}
Pub Date : 2024-11-21DOI: 10.1016/j.susc.2024.122657
Hiroshi Kondoh
This minireview provides an overview of recent advancements in in situ/operando soft X-ray surface spectroscopy, particularly focusing on the development and application of techniques such as near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and soft X-ray absorption spectroscopy (SXAS) conducted at the Photon Factory. These techniques enable us to observe catalytic surfaces under working conditions, which provides new insights into catalytic mechanisms by probing the chemical states of reactive species as well as catalytic surfaces. The review highlights three case studies: the reduction of nitrogen oxide (NO) on rhodium (Rh) catalysts, ethylene epoxidation on silver (Ag) catalysts, and water-splitting photocatalysis using SrTiO3 with co-catalysts. Each study shows how these techniques reveal critical aspects about surface reactions, structures of intermediate species, and photoinduced processes, which contributes to a deeper understanding of reactive species and reaction pathways. I also discuss about the challenges in operando kinetic analyses, structure analyses and extension of applicable catalytic phenomena and suggest future improvements in operando spectroscopy to enhance the capability of these analyses.
本微型视图概述了原位/操作软 X 射线表面光谱学的最新进展，尤其侧重于光子工厂开展的近环境压力 X 射线光电子能谱（NAP-XPS）和软 X 射线吸收光谱（SXAS）等技术的开发和应用。这些技术使我们能够观察工作条件下的催化表面，通过探测反应物和催化表面的化学状态，为催化机制提供新的见解。综述重点介绍了三个案例研究：铑（Rh）催化剂的氧化氮（NO）还原、银（Ag）催化剂的乙烯环氧化以及使用 SrTiO3 与助催化剂的水分离光催化。每项研究都展示了这些技术如何揭示表面反应、中间物种结构和光诱导过程的关键方面，从而有助于加深对反应物种和反应途径的理解。我还讨论了在操作动力学分析、结构分析和适用催化现象的扩展方面所面临的挑战，并提出了操作光谱学的未来改进建议，以提高这些分析的能力。
{"title":"Surface science study on catalytic surfaces under working conditions with soft-X-ray surface spectroscopy at the Photon Factory","authors":"Hiroshi Kondoh","doi":"10.1016/j.susc.2024.122657","DOIUrl":"10.1016/j.susc.2024.122657","url":null,"abstract":"<div><div>This minireview provides an overview of recent advancements in <em>in situ/operando</em> soft X-ray surface spectroscopy, particularly focusing on the development and application of techniques such as near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and soft X-ray absorption spectroscopy (SXAS) conducted at the Photon Factory. These techniques enable us to observe catalytic surfaces under working conditions, which provides new insights into catalytic mechanisms by probing the chemical states of reactive species as well as catalytic surfaces. The review highlights three case studies: the reduction of nitrogen oxide (NO) on rhodium (Rh) catalysts, ethylene epoxidation on silver (Ag) catalysts, and water-splitting photocatalysis using SrTiO<sub>3</sub> with co-catalysts. Each study shows how these techniques reveal critical aspects about surface reactions, structures of intermediate species, and photoinduced processes, which contributes to a deeper understanding of reactive species and reaction pathways. I also discuss about the challenges in <em>operando</em> kinetic analyses, structure analyses and extension of applicable catalytic phenomena and suggest future improvements in <em>operando</em> spectroscopy to enhance the capability of these analyses.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"753 ","pages":"Article 122657"},"PeriodicalIF":2.1,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142722420","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}
Pub Date : 2024-11-20DOI: 10.1016/j.susc.2024.122656
Rosemary Jones , Esko Kokkonen , Calley Eads , Ulrike K. Küst , Julia Prumbs , Jan Knudsen , Joachim Schnadt
Today, atomic layer deposition (ALD) has become a firm corner stone of thin film deposition technology. The microelectronics industry, an early adopter of ALD, imposes stringent requirements on ALD to produce films with highly defined physical and chemical properties, which becomes even more important as device and component dimensions decrease. This, in turn, means that our understanding of the chemical processes underlying ALD needs to increase exponentially. Here, we show that one can use synchrotron-based time-resolved ambient pressure x-ray photoelectron spectroscopy (APXPS) to obtain highly detailed operando information on the surface chemistry of ALD, not only, as proven earlier, during the initial ALD cycles, but also for the steady-growth regime reached during the later stages of deposition. Using event averaging and Fourier-transform methods, we show that the ALD of TiO2 from titanium tetraisopropoxide (TTIP) and water precursors in the steady-growth regime follows the suggested ligand-exchange reaction mechanism, with no sign of oxygen transport between the deposited layers and the bulk of the film, as has been observed for other materials systems. Hence, the TiO2 ALD from TTIP and water constitutes a textbook example of metal oxide ALD, as expected for this well-known ALD process. The detailed insight is made possible by computerised control of the precursor pulses that enable the recording of long data sets, which comprise many ALD cycles at highly regular intervals, in combination with an advanced data analysis that allows us to pick out signals undetectable in the raw data. The analysis method also allows to separate oscillating contributions to the signals induced by the ALD pulsing from the overwhelming bulk signal.
{"title":"Time-resolved ambient pressure x-ray photoelectron spectroscopy: Advancing the operando study of ALD chemistry","authors":"Rosemary Jones , Esko Kokkonen , Calley Eads , Ulrike K. Küst , Julia Prumbs , Jan Knudsen , Joachim Schnadt","doi":"10.1016/j.susc.2024.122656","DOIUrl":"10.1016/j.susc.2024.122656","url":null,"abstract":"<div><div>Today, atomic layer deposition (ALD) has become a firm corner stone of thin film deposition technology. The microelectronics industry, an early adopter of ALD, imposes stringent requirements on ALD to produce films with highly defined physical and chemical properties, which becomes even more important as device and component dimensions decrease. This, in turn, means that our understanding of the chemical processes underlying ALD needs to increase exponentially. Here, we show that one can use synchrotron-based time-resolved ambient pressure x-ray photoelectron spectroscopy (APXPS) to obtain highly detailed <em>operando</em> information on the surface chemistry of ALD, not only, as proven earlier, during the initial ALD cycles, but also for the steady-growth regime reached during the later stages of deposition. Using event averaging and Fourier-transform methods, we show that the ALD of TiO<sub>2</sub> from titanium tetraisopropoxide (TTIP) and water precursors in the steady-growth regime follows the suggested ligand-exchange reaction mechanism, with no sign of oxygen transport between the deposited layers and the bulk of the film, as has been observed for other materials systems. Hence, the TiO<sub>2</sub> ALD from TTIP and water constitutes a textbook example of metal oxide ALD, as expected for this well-known ALD process. The detailed insight is made possible by computerised control of the precursor pulses that enable the recording of long data sets, which comprise many ALD cycles at highly regular intervals, in combination with an advanced data analysis that allows us to pick out signals undetectable in the raw data. The analysis method also allows to separate oscillating contributions to the signals induced by the ALD pulsing from the overwhelming bulk signal.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"753 ","pages":"Article 122656"},"PeriodicalIF":2.1,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142748421","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}
Enhancing SiN deposition, particularly using NH₃ in atomic layer and chemical vapor deposition, is crucial for improving the performance of Si-based devices. However, while NH₃ nitridation on clean Si surfaces is well understood, its behavior on Cl-terminated Si surfaces remains largely unexplored. In this study, the mechanism of NH3 nitridation on Cl-terminated Si(100)-2 × 1 surfaces is investigated using first-principles calculations and thermodynamic analysis. NH3 reacts with Si–Cl on the surface with low reaction barriers, generating Si–NH2 and gaseous HCl. Subsequently, Si–NH2 forms a Si–NH–Si structure via NH2 insertion into the Si–Si dimer bond and H migration onto the Si-dangling bond. Si–NH–Si formation is more favorable on the Si–Si dimer bond than on the Si–Si back bond. Thermodynamic analyses indicate that NH3 nitridation leads to the Si–NH–Si structure, as Si–NH–Si formation is more thermodynamically stable than Si–NH2 formation. Moreover, it is confirmed that the Si–NH–Si formation reaction is more favorable at higher temperatures and NH3 partial pressures. These findings could potentially be used to improve SiN deposition processes and enhance the performance of Si-based devices.
{"title":"Theoretical investigation of NH3 nitridation on Cl-terminated Si(100)-2 × 1 surfaces","authors":"Tomoya Nagahashi , Hajime Karasawa , Ryota Horiike , Kenji Shiraishi","doi":"10.1016/j.susc.2024.122655","DOIUrl":"10.1016/j.susc.2024.122655","url":null,"abstract":"<div><div>Enhancing SiN deposition, particularly using NH₃ in atomic layer and chemical vapor deposition, is crucial for improving the performance of Si-based devices. However, while NH₃ nitridation on clean Si surfaces is well understood, its behavior on Cl-terminated Si surfaces remains largely unexplored. In this study, the mechanism of NH<sub>3</sub> nitridation on Cl-terminated Si(100)-2 × 1 surfaces is investigated using first-principles calculations and thermodynamic analysis. NH<sub>3</sub> reacts with Si–Cl on the surface with low reaction barriers, generating Si–NH<sub>2</sub> and gaseous HCl. Subsequently, Si–NH<sub>2</sub> forms a Si–NH–Si structure via NH<sub>2</sub> insertion into the Si–Si dimer bond and H migration onto the Si-dangling bond. Si–NH–Si formation is more favorable on the Si–Si dimer bond than on the Si–Si back bond. Thermodynamic analyses indicate that NH<sub>3</sub> nitridation leads to the Si–NH–Si structure, as Si–NH–Si formation is more thermodynamically stable than Si–NH<sub>2</sub> formation. Moreover, it is confirmed that the Si–NH–Si formation reaction is more favorable at higher temperatures and NH<sub>3</sub> partial pressures. These findings could potentially be used to improve SiN deposition processes and enhance the performance of Si-based devices.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"753 ","pages":"Article 122655"},"PeriodicalIF":2.1,"publicationDate":"2024-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142721968","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}
Pub Date : 2024-11-18DOI: 10.1016/j.susc.2024.122653
Alexandre Pancotti , Diogo Duarte dos Reis , Jerzy T. Sadowski , Alex Sandre Kilian , John Boeckl , Patrick Soukiassian , Christophe Lubin , Ludovic Douillard , Nick Barrett , Tyson Back
We have studied the surface structure of a single crystal β-Ga2O3(010) using quantitative Low Energy Electron Diffraction (LEED) and X-ray photoelectron spectroscopy (XPS). The XPS measurements show spectra typical of stoichiometric Ga2O3 with a clean surface. LEED consistently shows a p(1×1) pattern, free of surface reconstruction. Quantitative LEED I(V) curves are acquired for 41 distinct diffraction spots. The experimental I(V) curves are compared to simulations over the first five layers. The best fits to the experimental LEED I(V) curves acquired at all diffraction spots are then used to calculate the interplanar relaxation and atomic rumpling. Significant atomic rumpling and interplanar relaxation are found over the first 5 atomic layers. As a result of rumpling a polarization of ∼ 2 µC/cm2 develops in the topmost surface layer. The structural results are in good agreement with previous density functional theory calculations and experimental X-ray photoelectron diffraction.
{"title":"Surface structure of Sn doped β-Ga2O3(010) p(1×1) studied by quantitative low energy electron diffraction","authors":"Alexandre Pancotti , Diogo Duarte dos Reis , Jerzy T. Sadowski , Alex Sandre Kilian , John Boeckl , Patrick Soukiassian , Christophe Lubin , Ludovic Douillard , Nick Barrett , Tyson Back","doi":"10.1016/j.susc.2024.122653","DOIUrl":"10.1016/j.susc.2024.122653","url":null,"abstract":"<div><div>We have studied the surface structure of a single crystal β-Ga<sub>2</sub>O<sub>3</sub>(010) using quantitative Low Energy Electron Diffraction (LEED) and X-ray photoelectron spectroscopy (XPS). The XPS measurements show spectra typical of stoichiometric Ga<sub>2</sub>O<sub>3</sub> with a clean surface. LEED consistently shows a p(1×1) pattern, free of surface reconstruction. Quantitative LEED I(V) curves are acquired for 41 distinct diffraction spots. The experimental I(V) curves are compared to simulations over the first five layers. The best fits to the experimental LEED I(V) curves acquired at all diffraction spots are then used to calculate the interplanar relaxation and atomic rumpling. Significant atomic rumpling and interplanar relaxation are found over the first 5 atomic layers. As a result of rumpling a polarization of ∼ 2 µC/cm<sup>2</sup> develops in the topmost surface layer. The structural results are in good agreement with previous density functional theory calculations and experimental X-ray photoelectron diffraction.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"753 ","pages":"Article 122653"},"PeriodicalIF":2.1,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142748418","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}
Pub Date : 2024-11-13DOI: 10.1016/j.susc.2024.122652
Cristina Africh , Maria Peressi , Giovanni Comelli
We present a short review of the work we have performed over the last decade in the framework of a scientific program dedicated to characterizing the structure, formation and functionalization of graphene layers grown on Ni surfaces. To this aim, several surface science experimental tools were complemented by numerical simulations mainly based on ab initio methods. In a step-by-step process, both the details and the general trends characterizing the investigated systems became progressively clearer, delineating a unique and consistent story.
All together the outcome of this intense effort can be regarded as a good example of the level of understanding of a complex problem it is possible to reach through a persistent and systematic approach in which state-of-the-art methods are employed.
我们简要回顾了过去十年来在一项科学计划框架内开展的工作，该计划致力于表征生长在镍表面的石墨烯层的结构、形成和功能化。为此，我们使用了多种表面科学实验工具，并辅以主要基于 ab initio 方法的数值模拟。在这个循序渐进的过程中，所研究系统的细节和总体趋势都逐渐清晰起来，勾勒出了一个独特而一致的故事。
{"title":"Graphene on Ni surfaces: A personal journey","authors":"Cristina Africh , Maria Peressi , Giovanni Comelli","doi":"10.1016/j.susc.2024.122652","DOIUrl":"10.1016/j.susc.2024.122652","url":null,"abstract":"<div><div>We present a short review of the work we have performed over the last decade in the framework of a scientific program dedicated to characterizing the structure, formation and functionalization of graphene layers grown on Ni surfaces. To this aim, several surface science experimental tools were complemented by numerical simulations mainly based on <em>ab initio</em> methods. In a step-by-step process, both the details and the general trends characterizing the investigated systems became progressively clearer, delineating a unique and consistent story.</div><div>All together the outcome of this intense effort can be regarded as a good example of the level of understanding of a complex problem it is possible to reach through a persistent and systematic approach in which state-of-the-art methods are employed.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"753 ","pages":"Article 122652"},"PeriodicalIF":2.1,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142722422","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}
Sodium-sulfur batteries have garnered significant attention recently due to their high energy density. Nevertheless, the dissolution of sodium polysulfides in the electrolyte results in the shuttle effect, severely impacting the cycling efficiency of these batteries and limiting their widespread application. In this study, a novel two-dimensional VS2/ graphene heterostructure was designed. This material is used as an anchoring material for the anode of sodium-sulfur battery to suppress the shuttle effect. This van der Waals heterostructure is composed of graphene and VS2 stacked, and retains their inherent electronic structures. Graphene not only enhances the conductivity of sulfur cathode, but also improves the polarity of VS2 thin film. Adsorption simulations of sodium polysulfide showed that the VS2/graphene heterostructures possessed suitable adsorption energies in the range of 1.63 ∼ 3.47 eV, which were able to effectively anchor the polysulfide. In addition, the lower Na2S decomposition energy barriers and sodium ion migration energy barriers show the potential of the heterostructures in catalyzing the reaction kinetics. Therefore, the VS2/graphene heterostructure is anticipated to be an optimal anchoring material for sodium-sulfur batteries.
{"title":"VS2/graphene heterostructures as cathode materials for sodium-sulfur batteries: A first-principles study","authors":"Jihong Li , Chengdong Wei , Jian Xu , Hongtao Xue , Fuling Tang","doi":"10.1016/j.susc.2024.122650","DOIUrl":"10.1016/j.susc.2024.122650","url":null,"abstract":"<div><div>Sodium-sulfur batteries have garnered significant attention recently due to their high energy density. Nevertheless, the dissolution of sodium polysulfides in the electrolyte results in the shuttle effect, severely impacting the cycling efficiency of these batteries and limiting their widespread application. In this study, a novel two-dimensional VS<sub>2</sub>/ graphene heterostructure was designed. This material is used as an anchoring material for the anode of sodium-sulfur battery to suppress the shuttle effect. This van der Waals heterostructure is composed of graphene and VS<sub>2</sub> stacked, and retains their inherent electronic structures. Graphene not only enhances the conductivity of sulfur cathode, but also improves the polarity of VS<sub>2</sub> thin film. Adsorption simulations of sodium polysulfide showed that the VS<sub>2</sub>/graphene heterostructures possessed suitable adsorption energies in the range of 1.63 ∼ 3.47 eV, which were able to effectively anchor the polysulfide. In addition, the lower Na<sub>2</sub>S decomposition energy barriers and sodium ion migration energy barriers show the potential of the heterostructures in catalyzing the reaction kinetics. Therefore, the VS<sub>2</sub>/graphene heterostructure is anticipated to be an optimal anchoring material for sodium-sulfur batteries.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122650"},"PeriodicalIF":2.1,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662014","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}
Pub Date : 2024-11-09DOI: 10.1016/j.susc.2024.122649
Qing Liu , Wenchao Jin , Fugong Qi , Shuaiqi Hua , Jinfeng Wang , Jiyu Zhou , Pengjie Wang , Xiangguang Kong , Haimin Ding
The addition of trace alloying elements to metal matrix composites has an important effect on their interfacial bonding properties and strength. In this study, the electronic structure, interfacial stability, and bonding properties of Cu/Ni2Si interfaces with doping alloying elements are systematically investigated on the atomic scale. It was found that the addition of alloying elements to the Cu side of the Cu(100)/Ni2Si(101)-Ni interface improved the interfacial stability, where Ti, Zn, Zr, and Al increased the interfacial work of adhesion from 2.53 J/m2 to 3.04 J/m2, 2.65 J/m2, 3.20 J/m2, and 2.82 J/m2, respectively. When alloying elements were doped in the sub-interfacial and third interfacial layers, only Zr enhances interfacial stability significantly. Analyses of interfacial and electronic structures show that Ti and Zr stabilize the Cu(100)/Ni2Si(101) interface through strong chemical bonds, while Zn and Al reduce interface distortion energy. The thermodynamic stability of the interface increases with higher doping rates. Moreover, increased adhesion tends to enhance the wettability of heterogeneous interfaces. At a 16.6% doping rate of the interfacial layer, Ti and Zr have the most significant effect on the contact angle, reducing it from 98.8° to 89.1° and 86.2°, respectively, thus promoting the wetting process.
{"title":"Effect of alloying elements (Ti, Zn, Zr, Al) on the interfacial properties of Cu/Ni2Si: A DFT study","authors":"Qing Liu , Wenchao Jin , Fugong Qi , Shuaiqi Hua , Jinfeng Wang , Jiyu Zhou , Pengjie Wang , Xiangguang Kong , Haimin Ding","doi":"10.1016/j.susc.2024.122649","DOIUrl":"10.1016/j.susc.2024.122649","url":null,"abstract":"<div><div>The addition of trace alloying elements to metal matrix composites has an important effect on their interfacial bonding properties and strength. In this study, the electronic structure, interfacial stability, and bonding properties of Cu/Ni<sub>2</sub>Si interfaces with doping alloying elements are systematically investigated on the atomic scale. It was found that the addition of alloying elements to the Cu side of the Cu(100)/Ni<sub>2</sub>Si(101)-Ni interface improved the interfacial stability, where Ti, Zn, Zr, and Al increased the interfacial work of adhesion from 2.53 J/m<sup>2</sup> to 3.04 J/m<sup>2</sup>, 2.65 J/m<sup>2</sup>, 3.20 J/m<sup>2</sup>, and 2.82 J/m<sup>2</sup>, respectively. When alloying elements were doped in the sub-interfacial and third interfacial layers, only Zr enhances interfacial stability significantly. Analyses of interfacial and electronic structures show that Ti and Zr stabilize the Cu(100)/Ni<sub>2</sub>Si(101) interface through strong chemical bonds, while Zn and Al reduce interface distortion energy. The thermodynamic stability of the interface increases with higher doping rates. Moreover, increased adhesion tends to enhance the wettability of heterogeneous interfaces. At a 16.6% doping rate of the interfacial layer, Ti and Zr have the most significant effect on the contact angle, reducing it from 98.8° to 89.1° and 86.2°, respectively, thus promoting the wetting process.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122649"},"PeriodicalIF":2.1,"publicationDate":"2024-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662015","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}
Pub Date : 2024-11-08DOI: 10.1016/j.susc.2024.122651
Bogdana Bahrim, Aaron Martinez, Jonah Watts
The H− ion survival probabilities following on-top collisions with Na adsorbates deposited on Ag(111) at low coverage, are investigated for a wide range of exit angles from 20° to 90° measured from surface, and for various incident ion energies. A wave packet propagation approach is used in these calculations. The survival probabilities exhibit a series of well-defined peaks located at certain exit angles, that are indicative of avoided crossings between the various energy levels involved in the projectile/adsorbate/surface interaction. Both image states and the back-and-forth electronic motion between the ion projectile and the adsorbate/surface system contribute to the electronic population recaptured during the exit trajectory. For ion-surface collisions away from the on-top configuration, but in the close vicinity of adsorbates, a model is proposed to describe the variation of the H− projectile's distance of closest approach to the adsorbate-covered Ag(111) surface in terms of the ion's impact point on surface, e.g., starting from the on-top collision with a single adsorbate and gradually moving away, towards the “clean” surface. The distance of closest approach is a key factor in calculating correctly the ion survival probabilities in the close region around the adsorbate, where the scattered ion fractions are affected the most. Results are shown for H− in interaction with K/Ag(111).
针对从表面测量的 20° 至 90° 的大范围出口角以及各种入射离子能量，研究了与沉积在 Ag(111) 上的低覆盖率 Na 吸附物发生顶面碰撞后 H 离子的存活概率。这些计算采用了波包传播方法。存活概率在特定出射角处显示出一系列明确的峰值，这些峰值表明射弹/吸附剂/表面相互作用所涉及的各种能级之间避免了交叉。离子射弹和吸附剂/表面系统之间的图像状态和来回电子运动都有助于在出轨过程中重新捕获电子群。对于远离顶部构型但靠近吸附剂的离子-表面碰撞，提出了一个模型来描述 H-射弹与吸附剂覆盖的 Ag(111) 表面的最近接近距离的变化，该模型以离子在表面上的撞击点为基础，例如，从与单一吸附剂的顶部碰撞开始，逐渐远离，直至 "干净 "的表面。最近接近距离是正确计算离子在吸附剂周围近距离区域存活概率的关键因素，在该区域散射离子分数受到的影响最大。结果显示了 H- 与 K/Ag(111) 的相互作用。
{"title":"Adsorbate-induced effects on the H− ion collisions with Na/Ag(111) and K/Ag(111) surfaces","authors":"Bogdana Bahrim, Aaron Martinez, Jonah Watts","doi":"10.1016/j.susc.2024.122651","DOIUrl":"10.1016/j.susc.2024.122651","url":null,"abstract":"<div><div>The <em>H</em><sup>−</sup> ion survival probabilities following on-top collisions with Na adsorbates deposited on Ag(111) at low coverage, are investigated for a wide range of exit angles from 20° to 90° measured from surface, and for various incident ion energies. A wave packet propagation approach is used in these calculations. The survival probabilities exhibit a series of well-defined peaks located at certain exit angles, that are indicative of avoided crossings between the various energy levels involved in the projectile/adsorbate/surface interaction. Both image states and the back-and-forth electronic motion between the ion projectile and the adsorbate/surface system contribute to the electronic population recaptured during the exit trajectory. For ion-surface collisions away from the on-top configuration, but in the close vicinity of adsorbates, a model is proposed to describe the variation of the <em>H</em><sup>−</sup> projectile's distance of closest approach to the adsorbate-covered Ag(111) surface in terms of the ion's impact point on surface, e.g., starting from the on-top collision with a single adsorbate and gradually moving away, towards the “clean” surface. The distance of closest approach is a key factor in calculating correctly the ion survival probabilities in the close region around the adsorbate, where the scattered ion fractions are affected the most. Results are shown for <em>H</em><sup>−</sup> in interaction with K/Ag(111).</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122651"},"PeriodicalIF":2.1,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662010","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}
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