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}
Pub Date : 2024-11-08DOI: 10.1016/j.susc.2024.122636
Miquel B. Salmeron, Xiao Zhao
Compared to the bulk, surfaces of materials usually exhibit unique chemical, structural and electronic properties due to their distinct interactions with the external phase, such as vacuum, gas, liquid or another solid. Breakthroughs in this field are typically driven by significant instrumental development. In this review we will highlight a few developments in surface science in the last 40 years, as well as the discoveries they brought to the scientific and engineering communities. These findings, together with relevant technical developments, enable a deeper understanding of phenomena critical to catalysis, energy conversion, and nanotechnology.
{"title":"One century of evolution of surface science, a personal perspective","authors":"Miquel B. Salmeron, Xiao Zhao","doi":"10.1016/j.susc.2024.122636","DOIUrl":"10.1016/j.susc.2024.122636","url":null,"abstract":"<div><div>Compared to the bulk, surfaces of materials usually exhibit unique chemical, structural and electronic properties due to their distinct interactions with the external phase, such as vacuum, gas, liquid or another solid. Breakthroughs in this field are typically driven by significant instrumental development. In this review we will highlight a few developments in surface science in the last 40 years, as well as the discoveries they brought to the scientific and engineering communities. These findings, together with relevant technical developments, enable a deeper understanding of phenomena critical to catalysis, energy conversion, and nanotechnology.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122636"},"PeriodicalIF":2.1,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662013","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 : 2024-11-06DOI: 10.1016/j.susc.2024.122648
Khalid Mujasam Batoo , Iman Samir Alalaq , Rekha MM , Anurag Mishra , Shilpa Sharma , G.V. Siva Prasad , Muhammad Farzik Ijaz , Salima B. Alsaadi , Ahmed Ali Mtasher , Fadeel F. Seed
Our work has reflected considerable interest in unique Pd nanocluster/MoS2 heterojunction systems due to their potential applications in materials science, chemistry and physics. We focused on exploiting Pd5/MoS2 nanocluster system, a novel heterojunction material for gas sensing applications. In addition, we exploited the electronic properties of Pd dopant on the MoS2 surface to make a comparative study. Our DFT calculations indicate that the Pd5/MoS2 heterojunction structure exhibits a higher affinity for adsorbing gas molecules such as CO, NH3, NO, and NO2, while the perfect MoS2 shows weak gas adsorption capacity. Pd5/MoS2 heterojunction exhibits semiconducting feature with a weakened and narrower band gap, making it more suitable for gas sensing due to its higher conductivity. We analyzed important factors like adsorption distance/energies, density of states, band structure and difference of electron density concerning adsorbed gases on the heterojunction surface. Based on the electron density difference maps, we can see the giant growth of charges over the adsorbed molecules, as well as between the adsorbing atoms. Based on our findings, the conductivity of the nanomaterial undergoes a remarkable change, which helps reinforce the applicability of the Pd5/MoS2 heterojunction nanosystem in sensing and adsorbing gas molecules.
{"title":"A novel MoS2/Pd5 nanocluster heterojunction system with improved surface reactivity for efficient gas sensing: A DFT study","authors":"Khalid Mujasam Batoo , Iman Samir Alalaq , Rekha MM , Anurag Mishra , Shilpa Sharma , G.V. Siva Prasad , Muhammad Farzik Ijaz , Salima B. Alsaadi , Ahmed Ali Mtasher , Fadeel F. Seed","doi":"10.1016/j.susc.2024.122648","DOIUrl":"10.1016/j.susc.2024.122648","url":null,"abstract":"<div><div>Our work has reflected considerable interest in unique Pd nanocluster/MoS<sub>2</sub> heterojunction systems due to their potential applications in materials science, chemistry and physics. We focused on exploiting Pd<sub>5</sub>/MoS<sub>2</sub> nanocluster system, a novel heterojunction material for gas sensing applications. In addition, we exploited the electronic properties of Pd dopant on the MoS<sub>2</sub> surface to make a comparative study. Our DFT calculations indicate that the Pd<sub>5</sub>/MoS<sub>2</sub> heterojunction structure exhibits a higher affinity for adsorbing gas molecules such as CO, NH<sub>3</sub>, NO, and NO<sub>2</sub>, while the perfect MoS<sub>2</sub> shows weak gas adsorption capacity. Pd<sub>5</sub>/MoS<sub>2</sub> heterojunction exhibits semiconducting feature with a weakened and narrower band gap, making it more suitable for gas sensing due to its higher conductivity. We analyzed important factors like adsorption distance/energies, density of states, band structure and difference of electron density concerning adsorbed gases on the heterojunction surface. Based on the electron density difference maps, we can see the giant growth of charges over the adsorbed molecules, as well as between the adsorbing atoms. Based on our findings, the conductivity of the nanomaterial undergoes a remarkable change, which helps reinforce the applicability of the Pd<sub>5</sub>/MoS<sub>2</sub> heterojunction nanosystem in sensing and adsorbing gas molecules.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122648"},"PeriodicalIF":2.1,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662011","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 : 2024-11-03DOI: 10.1016/j.susc.2024.122647
Eun Mi Kim, Junseok Kim, Kristen A. Fichthorn
We used ab initio grand-canonical Monte Carlo (AIGCMC) simulations based on plane-wave density-functional theory to probe the structures and surface energies of Pt(100) and Pt(111) with adsorbed chlorine. For Pt(100), we considered both the (1 × 1) surface and a (5 × 1) reconstruction, as a model for the experimentally observed “hex” reconstruction of Pt(100). We constructed phase diagrams of the surface energies as function of the Cl chemical potential and identified the most relevant surfaces. For Pt(100), we find the hex reconstruction is favored at low Cl chemical potentials and that Cl adsorption lifts the reconstruction. The progression of ordered structures predicted for this surface is: bare (5 × 1) Pt(100), Θ = 1/2 (1 × 1) Pt(100), and Θ = 2/3 (1 × 1) Pt(100), where Θ is the fractional surface coverage of Cl. All these structures are seen experimentally. We also observe a structure with Θ = 3/4 and intermixing between Pt and Cl on Pt(100) that is related to the structure at Θ = 2/3. For Pt(111), we find a progression of (3 × 3) unit cells at Θ = 1/9, 1/3, 4/9, 5/9, and 2/3. The structures at Θ = 1/3 and 4/9 have been proposed experimentally and most experiments predict a series of (3 × 3) unit cells with increasing Cl coverage. If intermixing between Cl and Pt does not occur in experiment, then we find a (4 × 2) Cl structure at Θ = 1/2 is energetically favored, as is observed in experiment. A strength of AIGCMC is the capability to identify relevant structures, including disordered structures, without predefined input. This increases the chance of having high fidelity to experiment and identifying relevant substrates for applications.
{"title":"A study of Cl adsorption on Pt(111) and Pt(100) using Ab Initio Grand-canonical Monte Carlo","authors":"Eun Mi Kim, Junseok Kim, Kristen A. Fichthorn","doi":"10.1016/j.susc.2024.122647","DOIUrl":"10.1016/j.susc.2024.122647","url":null,"abstract":"<div><div>We used <em>ab initio</em> grand-canonical Monte Carlo (AIGCMC) simulations based on plane-wave density-functional theory to probe the structures and surface energies of Pt(100) and Pt(111) with adsorbed chlorine. For Pt(100), we considered both the (1 × 1) surface and a (5 × 1) reconstruction, as a model for the experimentally observed “hex” reconstruction of Pt(100). We constructed phase diagrams of the surface energies as function of the Cl chemical potential and identified the most relevant surfaces. For Pt(100), we find the hex reconstruction is favored at low Cl chemical potentials and that Cl adsorption lifts the reconstruction. The progression of ordered structures predicted for this surface is: bare (5 × 1) Pt(100), Θ = 1/2 (1 × 1) Pt(100), and Θ = 2/3 (1 × 1) Pt(100), where Θ is the fractional surface coverage of Cl. All these structures are seen experimentally. We also observe a structure with Θ = 3/4 and intermixing between Pt and Cl on Pt(100) that is related to the structure at Θ = 2/3. For Pt(111), we find a progression of (3 × 3) unit cells at Θ = 1/9, 1/3, 4/9, 5/9, and 2/3. The structures at Θ = 1/3 and 4/9 have been proposed experimentally and most experiments predict a series of (3 × 3) unit cells with increasing Cl coverage. If intermixing between Cl and Pt does not occur in experiment, then we find a (4 × 2) Cl structure at Θ = 1/2 is energetically favored, as is observed in experiment. A strength of AIGCMC is the capability to identify relevant structures, including disordered structures, without predefined input. This increases the chance of having high fidelity to experiment and identifying relevant substrates for applications.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122647"},"PeriodicalIF":2.1,"publicationDate":"2024-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662012","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 : 2024-11-01DOI: 10.1016/j.susc.2024.122646
Rui Yang, Xiao-Huan Lv, Ke-Xin Hou, Xing-Qiang Shi, Jiang-Long Wang
The graphene/MoS2 heterostructures (Gr/MoS2) exhibit excellent performance for ion batteries, such as superior stability and cyclicity for ion battery storage, and have great potentials for other applications. Lithium (Li) adsorption on/in Gr/MoS2 heterostructures exhibits advanced properties and interesting phenomena, as well as the phase engineering of MoS2. However, unified understanding for the different adsorption behaviors remains lacking, although fully understanding to the adsorption behaviors is of vital importance for their applications. In the current work, the Li adsorptions on the Gr surface of Gr/dT(H)-MoS2 heterostructures are systematically analyzed based on density functional theory calculations, and highlight the differences between Gr/H-MoS2 and Gr/dT-MoS2 for Li adsorption. To fully understand the adsorption behaviors, we perform detailed analyses from four interrelated aspects: 1) Electrostatic interactions from detailed Bader charge analysis, 2) charge density difference Δρ(z), 3) energy-level alignment between Li and the band edges of Gr, dT-, and H-MoS2, and 4) the resulted interface dipoles. We find that partial electrons in Li can pass through Gr to H-MoS2 and the origin is attributed to the weak electronic-shielding of Gr (even weaker than H-MoS2). All of the above extended analysis not only enables us to understand the abnormal adsorption of Li on the Gr surface of Gr/dT(H)-MoS2 heterostructures, but also helps guide the selection of ion battery materials. Moreover, we extend the discussion of Li adsorption to other alkali metal atoms with smaller work functions (such as: Na and K). Our work not only provides understanding to the abnormal adsorption of Li on the Gr surface of Gr/dT(H)-MoS2 heterostructures, but also helps guide the selection of ion battery materials. So, the insights from this study are important for their related applications. This paper reveals and explains an interesting abnormal adsorption phenomenon of lithium on van der Waals heterostructures of graphene and different phases of MoS2.The conclusion and insights from this work is not limited to Li (applicable at least to Na and K, also), and hence our work is helpful for establishing the surface-adsorption mechanisms of ion batteries.
石墨烯/MoS2 异质结构（Gr/MoS2）在离子电池方面表现出卓越的性能，例如在离子电池存储方面具有超强的稳定性和循环性，在其他应用方面也具有巨大的潜力。锂（Li）在 Gr/MoS2 异质结构上的吸附表现出先进的性能和有趣的现象，以及 MoS2 的相工程。然而，尽管充分了解吸附行为对其应用至关重要，但对不同吸附行为仍缺乏统一的认识。在目前的工作中，基于密度泛函理论计算，系统分析了 Gr/dT(H)-MoS2 异质结构的 Gr 表面对锂的吸附，并强调了 Gr/H-MoS2 和 Gr/dT-MoS2 对锂吸附的差异。为了充分理解吸附行为，我们从四个相互关联的方面进行了详细分析：1) 通过详细的 Bader 电荷分析得出的静电相互作用；2) 电荷密度差 Δρ(z)；3) Li 与 Gr、dT- 和 H-MoS2 带边之间的能级排列；以及 4) 由此产生的界面偶极子。我们发现，Li 中的部分电子可以穿过 Gr 到达 H-MoS2，其原因在于 Gr 的弱电子屏蔽（甚至比 H-MoS2 更弱）。上述所有扩展分析不仅使我们能够理解锂在 Gr/dT(H)-MoS2 异质结构的 Gr 表面的异常吸附，而且有助于指导离子电池材料的选择。此外，我们还将锂吸附的讨论扩展到了功函数较小的其他碱金属原子（如 Na 和 K）。我们的工作不仅有助于理解锂在 Gr/dT(H)-MoS2 异质结构的 Gr 表面的异常吸附，还有助于指导离子电池材料的选择。因此，本研究的见解对其相关应用具有重要意义。本文揭示并解释了锂在石墨烯和不同相 MoS2 的范德华异质结构上的一种有趣的异常吸附现象。这项工作的结论和见解不仅限于锂（至少也适用于 Na 和 K），因此我们的工作有助于建立离子电池的表面吸附机制。
{"title":"Abnormal adsorption of lithium on the graphene surface of graphene/dT(H)-MoS2 heterostructures","authors":"Rui Yang, Xiao-Huan Lv, Ke-Xin Hou, Xing-Qiang Shi, Jiang-Long Wang","doi":"10.1016/j.susc.2024.122646","DOIUrl":"10.1016/j.susc.2024.122646","url":null,"abstract":"<div><div>The graphene/MoS<sub>2</sub> heterostructures (Gr/MoS<sub>2</sub>) exhibit excellent performance for ion batteries, such as superior stability and cyclicity for ion battery storage, and have great potentials for other applications. Lithium (Li) adsorption on/in Gr/MoS<sub>2</sub> heterostructures exhibits advanced properties and interesting phenomena, as well as the phase engineering of MoS<sub>2</sub>. However, unified understanding for the different adsorption behaviors remains lacking, although fully understanding to the adsorption behaviors is of vital importance for their applications. In the current work, the Li adsorptions on the Gr surface of Gr/dT(H)-MoS<sub>2</sub> heterostructures are systematically analyzed based on density functional theory calculations, and highlight the differences between Gr/H-MoS<sub>2</sub> and Gr/dT-MoS<sub>2</sub> for Li adsorption. To fully understand the adsorption behaviors, we perform detailed analyses from four interrelated aspects: 1) Electrostatic interactions from detailed Bader charge analysis, 2) charge density difference Δρ(<em>z</em>), 3) energy-level alignment between Li and the band edges of Gr, dT-, and H-MoS<sub>2</sub>, and 4) the resulted interface dipoles. We find that partial electrons in Li can pass through Gr to H-MoS<sub>2</sub> and the origin is attributed to the weak electronic-shielding of Gr (even weaker than H-MoS<sub>2</sub>). All of the above extended analysis not only enables us to understand the abnormal adsorption of Li on the Gr surface of Gr/dT(H)-MoS<sub>2</sub> heterostructures, but also helps guide the selection of ion battery materials. Moreover, we extend the discussion of Li adsorption to other alkali metal atoms with smaller work functions (such as: Na and K). Our work not only provides understanding to the abnormal adsorption of Li on the Gr surface of Gr/dT(H)-MoS<sub>2</sub> heterostructures, but also helps guide the selection of ion battery materials. So, the insights from this study are important for their related applications. This paper reveals and explains an interesting abnormal adsorption phenomenon of lithium on van der Waals heterostructures of graphene and different phases of MoS<sub>2</sub>.The conclusion and insights from this work is not limited to Li (applicable at least to Na and K, also), and hence our work is helpful for establishing the surface-adsorption mechanisms of ion batteries.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122646"},"PeriodicalIF":2.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142592995","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 : 2024-10-29DOI: 10.1016/j.susc.2024.122637
Anders Nilsson
For the 60th anniversary of Surface Science, I present here a personal account of some of the most significant contributions I have made to the field over the past three decades. The utilisation of X-rays serves as the foundation for these studies, encompassing X-ray spectroscopy for the mapping of surface chemical bonds, probing of surface reactions on ultrafast timescales, and X-ray photoelectron spectroscopy under operando conditions. The direct projection of electronic states onto the adsorbed atom allowed the detection of bonding and anti-bonding states within the d-band model. The selective probing of orbitals of different symmetries on the two atoms in adsorbed N2 provided a fundamental understanding of the nature of diatomic bonding to surfaces. Ultrafast optical pumping and X-ray laser techniques allowed the study of CO undergoing desorption leading to the observation of the precursor state. Pump-probed studies of co-adsorbed CO and O on Ru enabled the means to detect transition state species during catalytic CO oxidation. The use of operando X-ray photoelectron spectroscopy at near-atmospheric pressures opened the door to probe the surface chemistry and gain insight into the reaction mechanism during hydrogenation reactions to produce ammonia, hydrocarbons, methanol and ethanol. By inserting an electrochemical cell into the spectroscopic chamber, both fuel cell and water splitting electrocatalysis could be studied giving insight about the reaction mechanism.
值此《表面科学》杂志创刊 60 周年之际，我在此以个人名义介绍了过去三十年来我在该领域做出的一些最重要的贡献。X 射线的利用是这些研究的基础，其中包括用于绘制表面化学键的 X 射线光谱、超快时间尺度的表面反应探测以及操作条件下的 X 射线光电子能谱。通过将电子状态直接投射到吸附原子上，可以探测到 d 带模型中的成键和反键状态。通过对吸附 N2 的两个原子上不同对称性轨道的选择性探测，可以从根本上了解硅原子与表面成键的性质。通过超快光学泵浦和 X 射线激光技术，可以研究 CO 的解吸过程，从而观察到前驱体状态。通过对 Ru 上共吸附的 CO 和 O 的泵探研究，可以检测催化 CO 氧化过程中的过渡态物种。在接近大气压的条件下使用操作型 X 射线光电子能谱，为探测表面化学性质和深入了解氢化反应过程中产生氨、碳氢化合物、甲醇和乙醇的反应机制打开了大门。通过在光谱室中插入一个电化学电池，可以对燃料电池和水分离电催化进行研究，从而深入了解反应机理。
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Pub Date : 2024-10-28DOI: 10.1016/j.susc.2024.122635
Hongliang Tang , Ying Duan , Xu Yang , Jing Wang , Yuyang Wang
In this study, theoretically, density functional theory was employed to explore the adsorption behavior of CO and NO prevalent hazardouss gases, on transition metal (TM = Fe, Co, Ni, and Cu) doped ZnO monolayer. The multifaceted analysis encompasses an array of critical aspects, including the adsorption structure, adsorption energy, density of states (DOS) and electron transfer to unravel the adsorption behavior. Our calculations show that TM atom doped ZnO monolayer exhibit high stability. TM doped can significantly enhance the interaction between the gas molecules (CO and NO) and the ZnO monolayer. Analysis of the recovery time and electrical conductivity of the adsorbed systems suggests that the Co-ZnO could be a suitable material for CO sensing,while the Cu-ZnO and Ni-ZnO can be used for NO sensing. These results suggest that transition metal doped can be a promising sensor candidate for toxic gas molecules adsorption and detection.
本研究采用密度泛函理论从理论上探讨了一氧化碳和一氧化氮这两种常见有害气体在掺杂过渡金属（TM = 铁、钴、镍和铜）的氧化锌单层上的吸附行为。多方面的分析涵盖了一系列关键方面，包括吸附结构、吸附能、状态密度（DOS）和电子转移，从而揭示了吸附行为。我们的计算表明，掺杂 TM 原子的氧化锌单层具有很高的稳定性。掺杂 TM 能显著增强气体分子（CO 和 NO）与氧化锌单层之间的相互作用。对吸附体系的恢复时间和电导率的分析表明，Co-ZnO 是一种适用于 CO 传感的材料，而 Cu-ZnO 和 Ni-ZnO 则可用于 NO 传感。这些结果表明，掺杂过渡金属可以成为吸附和检测有毒气体分子的理想传感器候选材料。
{"title":"Adsorption and sensing performances of transition metal doped ZnO monolayer for CO and NO: A DFT study","authors":"Hongliang Tang , Ying Duan , Xu Yang , Jing Wang , Yuyang Wang","doi":"10.1016/j.susc.2024.122635","DOIUrl":"10.1016/j.susc.2024.122635","url":null,"abstract":"<div><div>In this study, theoretically, density functional theory was employed to explore the adsorption behavior of CO and NO prevalent hazardouss gases, on transition metal (TM = Fe, Co, Ni, and Cu) doped ZnO monolayer. The multifaceted analysis encompasses an array of critical aspects, including the adsorption structure, adsorption energy, density of states (DOS) and electron transfer to unravel the adsorption behavior. Our calculations show that TM atom doped ZnO monolayer exhibit high stability. TM doped can significantly enhance the interaction between the gas molecules (CO and NO) and the ZnO monolayer. Analysis of the recovery time and electrical conductivity of the adsorbed systems suggests that the Co-ZnO could be a suitable material for CO sensing,while the Cu-ZnO and Ni-ZnO can be used for NO sensing. These results suggest that transition metal doped can be a promising sensor candidate for toxic gas molecules adsorption and detection.</div></div>","PeriodicalId":22100,"journal":{"name":"Surface Science","volume":"752 ","pages":"Article 122635"},"PeriodicalIF":2.1,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142553518","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 : 2024-10-24DOI: 10.1016/j.susc.2024.122633
László Óvári , Gábor Vári , Máté Farkas , Gyula Halasi , Nikolett Oláh , Csaba Vass , Arnold P. Farkas , András Berkó , János Kiss , Zoltán Kónya
Atomic level studies of solid state surfaces performed in ultra-high vacuum (UHV) had already an energetic 15–20 years past when our research group in Szeged started working in this field in mid 1970s. Till then several very important methods had been developed, like UHV technology, commercially available electron and photoelectron spectroscopy techniques, etc. Characterization of metal and semiconductor (oxide) surfaces and their adsorption properties had already been widely studied. In any case, the last 40–50 years also witnessed great discoveries and exciting new techniques. Considering only the activity related to heterogeneous catalysis, the main focus of our research group, new breakthrough methods emerged like HREELS, RAIRS, SPM, NAPXPS, EXAFS, NEXAFS. Along this path, new experimental and theoretical approaches appeared like planar model catalysts and inverse catalysts, atomic level investigation and understanding of surface diffusion-controlled phenomena (particle growth and disruption, strong metal-support interaction (SMSI), decoration, spillover), atomic level identification of active sites, self-organized nano-systems, surface alloys and nanotemplates. It was great to participate in this magical activity for more than 50 years. Both internationally and locally in Szeged, in the last two decades, surface science has opened to the wide world of 2D materials like the semimetal graphene and the insulator hexagonal boron nitride. However, the formation of a mixed layer of C, B and N proved to be a difficult task due to the primary tendency for phase separation. In the present work, we report on a preparation method of honeycomb “BCN” materials on Rh(111) by using benzene/borazine mixtures as precursors. It was demonstrated that by a suitable choice of the growth parameters, the formation of large, separated graphene and h-BN islands can be avoided.
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