Surface Science最新文献

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X-ray and photoelectron spectroscopy of surface chemistry; from bonding via femtosecond to operando 表面化学的 X 射线和光电子能谱学；从飞秒成键到运算量

IF 2.1 4区化学 Q3 CHEMISTRY, PHYSICAL

Surface Science

Pub Date : 2024-10-29 DOI: 10.1016/j.susc.2024.122637

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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引用次数: 0

Adsorption and sensing performances of transition metal doped ZnO monolayer for CO and NO: A DFT study 掺杂过渡金属的氧化锌单层对 CO 和 NO 的吸附和传感性能：DFT 研究

IF 2.1 4区化学 Q3 CHEMISTRY, PHYSICAL

Surface Science

Pub Date : 2024-10-28 DOI: 10.1016/j.susc.2024.122635

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。

引用次数: 0

Fabrication of B-C-N nanosheets on Rh(111) from benzene – borazine mixtures 利用苯-硼嗪混合物在 Rh(111) 上制备 B-C-N 纳米薄片

IF 2.1 4区化学 Q3 CHEMISTRY, PHYSICAL

Surface Science

Pub Date : 2024-10-24 DOI: 10.1016/j.susc.2024.122633

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.

20 世纪 70 年代中期，当我们在塞格德的研究小组开始在超高真空（UHV）下对固体表面进行原子级研究时，已经过去了 15-20 年。在此之前，已经开发出了几种非常重要的方法，如超高真空技术、商用电子和光电子能谱技术等。对金属和半导体（氧化物）表面的特征及其吸附特性的研究已经非常广泛。无论如何，在过去的 40-50 年间，我们也见证了许多重大发现和令人振奋的新技术。仅考虑到与我们研究小组主要关注的异相催化相关的活动，就出现了新的突破性方法，如 HREELS、RAIRS、SPM、NAPXPS、EXAFS 和 NEXAFS。沿着这条道路，出现了新的实验和理论方法，如平面模型催化剂和反催化剂、原子级研究和理解表面扩散控制现象（颗粒生长和破坏、强金属-支撑相互作用（SMSI）、装饰、溢出）、活性位点的原子级识别、自组织纳米系统、表面合金和纳米模板。能够参与这项神奇的活动已有 50 多年，我感到非常高兴。在过去的二十年里，无论是在国际上还是在塞格德本地，表面科学都为诸如半金属石墨烯和绝缘体六方氮化硼等二维材料打开了广阔的世界。然而，由于相分离的主要趋势，C、B 和 N 混合层的形成被证明是一项艰巨的任务。在本研究中，我们报告了一种以苯/硼嗪混合物为前驱体在 Rh(111) 上制备蜂窝状 "BCN "材料的方法。结果表明，通过适当选择生长参数，可以避免形成大的、分离的石墨烯和 h-BN 岛。

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引用次数: 0

Growth and electronic structure of the nodal line semimetal in monolayer Cu2Si on Cu(111) 单层 Cu2Si 在 Cu(111) 上的生长和节点线半金属的电子结构

IF 2.1 4区化学 Q3 CHEMISTRY, PHYSICAL

Surface Science

Pub Date : 2024-10-22 DOI: 10.1016/j.susc.2024.122632

Cu₂Si, a single-layer two-dimensional material with a honeycomb structure, has been proposed to have Dirac nodal line fermions. In this study, the synchrotron radiation X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and angle-resolved photoemission spectroscopy (SR-XPS, SR-UPS, and SR-ARPES) techniques were used to investigate the dynamic process of in situ deposition of single-layer Cu₂Si on a Cu(111) crystal surface via molecular beam epitaxy (MBE). Cu₂Si existed as a monolayer (ML) alloy, and there were competing mechanisms of distinct chemical states of silicon in different growth periods, according to a detailed examination of the experimental SR-XPS and SR-UPS spectra. Additionally, a weak interaction between the Cu₂Si ML and Cu(111) was demonstrated via SR-ARPES and first-principles computations. The unique electronic structure of the Cu₂Si ML was not destroyed by either this weak interaction or the disordered silicon produced on the surface during the growth process. The study of the Cu₂Si growth kinetics provides a guarantee and a basis for the future exploration of the exotic properties of Cu₂Si.

Cu2Si 是一种具有蜂巢结构的单层二维材料，被认为具有狄拉克结线费米子。本研究采用同步辐射 X 射线光电子能谱、紫外光电子能谱和角分辨光发射光谱（SR-XPS、SR-UPS 和 SR-ARPES）技术，研究了通过分子束外延（MBE）在铜（111）晶体表面原位沉积单层 Cu2Si 的动态过程。根据对 SR-XPS 和 SR-UPS 实验光谱的详细研究，Cu2Si 以单层 (ML) 合金的形式存在，并且在不同的生长时期存在硅的不同化学状态的竞争机制。此外，通过 SR-ARPES 和第一原理计算，证明了 Cu2Si ML 与 Cu(111) 之间存在微弱的相互作用。Cu2Si ML 的独特电子结构既没有被这种弱相互作用破坏，也没有被生长过程中表面产生的无序硅破坏。对 Cu2Si 生长动力学的研究为今后探索 Cu2Si 的奇异特性提供了保证和基础。

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引用次数: 0

Step-by-step silicon carbide graphitisation process study in terms of time and temperature parameters 根据时间和温度参数逐步研究碳化硅石墨化过程

IF 2.1 4区化学 Q3 CHEMISTRY, PHYSICAL

Surface Science

Pub Date : 2024-10-18 DOI: 10.1016/j.susc.2024.122630

This work investigates the temperature and time as key parameters for graphene formation on the silicon carbide surface during the high thermal decomposition process. Measurements were performed using various experimental techniques under ultra-high vacuum conditions. The graphitisation process was divided into various stages, after which the surface chemical composition and atomic structures were analysed in detail. It has been shown that despite the known theory of graphitisation mechanism and initial condition for occurrence of this process, the application of different temperatures and heating times affect the quality and quantity of formed graphene layers. Applying a temperature too low or annealing the sample for a too short time led to an inefficient silicon sublimation process. On the other hand, too high temperature during flashing modifies the visibility of surface structures, which may be crucial for other investigations and potential applications of such systems.

这项研究将温度和时间作为高热分解过程中碳化硅表面石墨烯形成的关键参数。测量是在超高真空条件下使用各种实验技术进行的。石墨化过程分为多个阶段，之后对表面化学成分和原子结构进行了详细分析。实验结果表明，尽管石墨化机理和发生这一过程的初始条件的理论是已知的，但应用不同的温度和加热时间会影响所形成的石墨烯层的质量和数量。温度过低或样品退火时间过短会导致硅升华过程效率低下。另一方面，闪蒸过程中温度过高会改变表面结构的可见度，这可能对此类系统的其他研究和潜在应用至关重要。

引用次数: 0

Imaging on surfaces with vibrational sum frequency generation microscopy 利用振动和频发生显微镜进行表面成像

IF 2.1 4区化学 Q3 CHEMISTRY, PHYSICAL

Surface Science

Pub Date : 2024-10-17 DOI: 10.1016/j.susc.2024.122627

Nonlinear spectroscopy has been a valuable technique for probing surfaces for many decades. Still, in the recent past, nonlinear spectroscopy has become a useful tool for imaging monolayers on surfaces. This technique of nonlinear microscopy, more specifically sum frequency generation microscopy, provides both spectral and spatial information with varying resolution, allowing for the surface activity to be monitored and imaged. The following paper highlights the history, theory, and range of experimental advantages sum frequency generation imaging provides, focusing on specific experiments that put those advantages on display.

几十年来，非线性光谱学一直是探测表面的重要技术。近来，非线性光谱学又成为表面单层成像的有用工具。这种非线性显微镜技术，更具体地说是和频发生显微镜技术，可提供不同分辨率的光谱和空间信息，从而对表面活性进行监测和成像。以下论文重点介绍了和频发生成像的历史、理论和一系列实验优势，并着重介绍了展示这些优势的具体实验。

引用次数: 0

In air STM observation of Au(111) surface disturbance including Au magic fingers as modified by solvent choice 空气中 STM 观察金（111）表面扰动，包括溶剂选择改变的金魔指

IF 2.1 4区化学 Q3 CHEMISTRY, PHYSICAL

Surface Science

Pub Date : 2024-10-17 DOI: 10.1016/j.susc.2024.122629

A widely studied surface phenomena on Au(111) is the formation of Au magic fingers, which were first discovered nearly 20 years ago. A variety of experimental conditions have been used to observe the formation of Au magic fingers with a slight preference to ultra-high vacuum and low temperature studies. With the advances in scanning probe techniques, it is possible to study these unique structures under more relevant conditions including in air and at room temperature. After exposure to a 0.1 M solvent solution, Au(111) displayed three types of surface disturbances, including the formation of Au magic fingers, based on the identity of the solvent. The type of disturbance was dependent on the solvent molecule's characteristics, specifically its total charge and its electrolytic behavior in aqueous environments. The mechanism of disturbance relied on a strong tip-surface interaction and the mass transport of Au atoms, which was modified by the solvent selected. Overall, the ability to form organized nanostructures, like Au magic fingers, in a repeated way in environments outside of UHV and without a protective liquid layer increases the utility of these structures into a wider array of fields and applied areas.

金（111）表面现象中被广泛研究的一种是金魔指的形成，这种现象在近 20 年前首次被发现。观测金魔指形成的实验条件多种多样，但人们更倾向于超高真空和低温研究。随着扫描探针技术的发展，我们有可能在包括空气和室温在内的更多相关条件下研究这些独特的结构。在暴露于 0.1 M 溶剂溶液后，Au(111) 显示出三种类型的表面扰动，包括根据溶剂特性形成的金魔指。扰动类型取决于溶剂分子的特性，特别是其总电荷及其在水环境中的电解行为。扰动机理依赖于针尖与表面的强烈相互作用以及金原子的质量传输，而所选溶剂则改变了这一机理。总之，能够在超高真空以外的环境中以重复的方式形成有组织的纳米结构（如金魔指），并且不需要保护液层，这提高了这些结构在更广泛领域和应用领域的实用性。

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引用次数: 0

Computational insight into the selectivity of γ-valerolactone hydrodeoxygenation over Rh(111) and Ru(0001) 通过计算深入了解 Rh(111) 和 Ru(0001) 上 γ-戊内酯加氢脱氧的选择性

IF 2.1 4区化学 Q3 CHEMISTRY, PHYSICAL

Surface Science

Pub Date : 2024-10-16 DOI: 10.1016/j.susc.2024.122624

The observed difference in the selectivity towards alkane, ketone, and alcohol hydrodeoxygenation products over Ru and Rh catalysts is explored using a combination of density functional theory and microkinetics. Using

γ

-valerolactone as a model compound, we investigate the reaction mechanism in order to identify selectivity determining species. The effect of the coadsorbed water molecule as well as the higher adsorbate surface coverage on reaction barriers and energies is explored as well. The performed calculations suggest that the desired alkane product is formed from a ketone intermediate on Ru, and through both ketone and alcohol on Rh, although the selectivity towards alkane on Rh is much lower than on Ru.

我们结合密度泛函理论和微动力学，探讨了在 Ru 和 Rh 催化剂上观察到的对烷烃、酮类和醇类加氢脱氧产物的选择性差异。我们以 γ-戊内酯为模型化合物，研究了反应机理，以确定决定选择性的物种。我们还探讨了共吸附水分子以及较高吸附剂表面覆盖率对反应壁垒和能量的影响。计算结果表明，所需的烷烃产物在 Ru 上是由酮中间体形成的，而在 Rh 上则是通过酮和醇形成的，不过在 Rh 上对烷烃的选择性要比在 Ru 上低得多。

引用次数: 0

Surface science studies on electron-induced reactions of NH3 and their perspectives for enhancing nanofabrication processes 有关 NH3 电子诱导反应的表面科学研究及其在改进纳米制造工艺方面的前景

IF 2.1 4区化学 Q3 CHEMISTRY, PHYSICAL

Surface Science

Pub Date : 2024-10-14 DOI: 10.1016/j.susc.2024.122628

Ammonia (NH₃) dissociates efficiently when it interacts with an electron beam. This applies not only to single electron-NH₃ collisions in the gas phase but also to electron irradiation of NH₃ adsorbed on surfaces. The dissociation products include atomic hydrogen which can act as a reducing agent or NH₂ radicals that can bind to suitable surfaces or to adsorbed molecules. This chemistry can be exploited in nanofabrication processes that use electron beams for deposition, etching, or modification of materials. This review describes the current state of insight regarding electron-induced reactions of NH₃ adsorbed on surfaces and outlines approaches to the use of these reactions for enhancing electron beam induced nanofabrication processes. First, an overview of surface science studies on electron-induced reactions of NH₃ adsorbed on single crystal surfaces is given. This is followed by a summary of studies on the use of NH₃ for improving the purity of deposits prepared by electron beam induced deposition (EBID) and on the prospects of NH₃ to suppress unwanted thermal surface chemistry during EBID. Finally, we discuss electron-induced reactions of NH₃ that are fundamental to the modification of carbonaceous nanomaterials as well as potential application scenarios such as the functionalization of self-assembled monolayers and humidity sensing.

当氨气（NH3）与电子束发生作用时，它能有效地解离。这不仅适用于气相中的单电子-NH3 碰撞，也适用于电子辐照吸附在表面上的 NH3。解离产物包括可作为还原剂的原子氢或可与适当表面或吸附分子结合的 NH2 自由基。在使用电子束对材料进行沉积、蚀刻或改性的纳米制造工艺中，可以利用这种化学反应。本综述介绍了有关表面吸附的 NH3 电子诱导反应的最新研究成果，并概述了利用这些反应增强电子束诱导的纳米制造工艺的方法。首先，概述了关于单晶表面吸附 NH3 的电子诱导反应的表面科学研究。随后，概述了利用 NH3 提高电子束诱导沉积 (EBID) 制备的沉积物纯度的研究，以及 NH3 在 EBID 过程中抑制不必要的热表面化学反应的前景。最后，我们讨论了 NH3 的电子诱导反应，这些反应对于碳质纳米材料的改性以及自组装单层的功能化和湿度传感等潜在应用场景至关重要。

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引用次数: 0

Electrochemical surface science: Self-assembly of Porphyrin molecules at single crystal metal electrodes 电化学表面科学：单晶金属电极上卟啉分子的自组装

IF 2.1 4区化学 Q3 CHEMISTRY, PHYSICAL

Surface Science

Pub Date : 2024-10-12 DOI: 10.1016/j.susc.2024.122626

A detailed understanding of properties and processes at surfaces and interfaces requires at least two types of most basic information, chemical composition and –distribution as well as structure. While surface science in ultrahigh vacuum is blessed with a plethora of high sensitivity and highest spatial and temporal resolution due to the free accessibility of the surfaces by any kind of probe beams, investigations of solid surfaces under ambient conditions, i.e. in contact with gases or liquids, were for a long time restricted to the use of integral photon-based reflection-, absorption-, emission-, and diffraction methods. This “methodological gap” between UHV surface science and environmental interface research became immediately, at least partially, closed after the realization of the scanning tunneling microscope (STM) and following variants of proximity probes (SPM). The full applicability of this class of methods also under ambient conditions opened the door to structure information of solid-liquid interfaces of comparable resolution as in UHV at room temperature, a “quantum leap” for the understanding of e.g. interfacial electrochemistry. This, in turn, highlighted the need of reliable determination of the chemical composition and distribution at solid-liquid interfaces and pushed the development of in situ X-ray photoelectron spectroscopy (XPS).

The availability of both techniques, in situ SPM and in situ XPS closes the former methodological gap between the research in UHV and under ambient conditions. In particular, interfacial electrochemistry, being primarily interested in chemical processes at electrode/electrolyte interfaces benefits decisively of this development.

In this article, as an example, we present systematic in situ STM measurements and results on the interactions and self-assembly of porphyrins at anion modified metal/electrolyte interfaces, an important class of molecules for the functionalization of surfaces for various applications. Atomically and sub-molecularly resolved potentiostatic and potentiodynamic in situ STM images of such molecular layers are nowadays standard and wait for an in-depth theoretical analysis.

要详细了解表面和界面的特性和过程，至少需要两类最基本的信息：化学成分和分布以及结构。超高真空条件下的表面科学具有得天独厚的高灵敏度和最高的空间和时间分辨率，因为任何类型的探针光束都可以自由进入表面，但在环境条件下，即与气体或液体接触时，对固体表面的研究长期以来仅限于使用基于积分光子的反射、吸收、发射和衍射方法。在扫描隧道显微镜（STM）及其后的近距离探针（SPM）变体问世后，超高真空表面科学与环境界面研究之间的这一 "方法论鸿沟 "立即（至少是部分）得以弥合。这类方法在环境条件下的完全适用性为获得固液界面结构信息打开了大门，其分辨率可与室温下的超高真空相媲美，这对于理解界面电化学等问题来说是一次 "质的飞跃"。这反过来又突出了可靠测定固液界面化学成分和分布的需要，推动了原位 X 射线光电子能谱（XPS）的发展。在本文中，我们将以阴离子修饰的金属/电解质界面上卟啉的相互作用和自组装为例，介绍系统的原位 STM 测量和结果。这类分子层的原子和亚分子分辨电位静力学和电位动力学原位 STM 图像如今已成为标准图像，有待深入的理论分析。

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