Photoelectron Emission at Diamond-Liquid Interfaces

金刚石-液体界面处的光电子发射

• 批准号: 1507432
• 负责人: Robert Hamers
• 金额: $ 47.38万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-08-01 至 2018-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1507432&HistoricalAwards=false
• 关键词: Photoelectron; Emission; Diamond; Liquid; Interfaces

Non-technical AbstractDiamond surfaces, including inexpensive thin-films and industrial-grade diamond powders, have the usual ability to emit electrons directly in to water and other liquids when illuminated with ultraviolet light. Electrons in water are a potent chemical reducing agent, able to induce very difficult chemical transformations such as the conversion of dinitrogen to ammonia and the reduction of carbon dioxide, but they have not been well studied because of the absence of convenient and efficient methods of preparation. The ability to directly emit electrons into water using inexpensive, reusable industrial-grade diamond provides a number of opportunities for inducing novel chemical transformations not accessible with conventional photochemical or electrochemical methods. With support of the Solid State and Materials Chemistry program in the Division of Materials Research, the objectives of this project are to understand the fundamental materials properties that influence electron emission from diamond into water, to use this understanding to create photoelectron emitters that function with good stability in water and other non-vacuum environments, and to identify whether diamond can be modified to allow it to easily emit electrons using visible light. If successful, the ability to easily produce electrons in water using visible or near-ultraviolet light would enable new, energy-efficient chemical transformation pathways not currently possible. Graduate students are being trained in state-of-the-art electrochemical methods and receive extensive professional development opportunities. The principal investigator and students are also mentoring undergraduate students and high school students on summer research projects as part of a broader effort to increase the number of students who have the opportunity to engage in state-of-the-art scientific research. The principal investigator and students are actively participating in several programs targeted specifically toward enhancing the diversity of the scientific workforce. Technical AbstractThis renewal project is an outgrowth of research from the principal investigator demonstrating that diamond surfaces are able to emit electrons into water when illuminated with ultraviolet light, thereby allowing inexpensive diamond thin films and even industrial powders to be used as solid-state sources of electrons in liquids. While electron emission into vacuum has been studied previously, little is known about electron emission into water and other liquids. The primary goal of is project is to investigate the factors that control the photoemission of electrons from diamond into adjacent liquids, and to use this information to create photoelectron emitters that function with good stability and efficiency in non-vacuum environments. The project has three primary components. One is to understand how the electronic structure of the diamond-liquid interface influences the emission of electrons into adjacent liquids, by characterizing how variables such as the surface terminating layers, solution-phase ions, and externally applied potentials influence electron emission. A second is to determine whether metal-semiconductor junctions and plasmonic structures are able to increase the optical absorption of diamond and/or provide alternative pathways to exciting electrons to the conduction band. A third is to determine whether mid-gap states introduced by substitutional nitrogen or other dopants can provide a pathway to achieving electron emission using visible light. A wide range of experimental methods are being employed. X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopies are being used to characterize the chemical composition and electronic structure of diamond surfaces. Electrochemical methods including Mott-Schottky Analysis and Electrochemical Impedance Spectroscopy are being used to characterize the interfacial electronic structure and band alignments in aqueous media. Solvated electrons are being directly characterized using transient absorption spectroscopy and via chemical probes. Together, these methods are providing a comprehensive understanding of electron emission into liquids and providing insights into how to design interfaces that are most effective in enabling diamond to be used as a solid-state source of electrons in non-vacuum environments.

非技术摘要金刚石表面，包括廉价的薄膜和工业级金刚石粉末，在紫外线照射下通常具有直接向水和其他液体发射电子的能力。水中的电子是一种有效的化学还原剂，能够引发非常困难的化学转化，例如氮转化为氨和二氧化碳的还原，但由于缺乏方便有效的制备方法，它们尚未得到充分研究。使用廉价、可重复使用的工业级金刚石直接将电子发射到水中的能力为诱导传统光化学或电化学方法无法实现的新型化学转化提供了许多机会。在材料研究部固态和材料化学项目的支持下，该项目的目标是了解影响从金刚石到水中的电子发射的基本材料特性，利用这种理解来创建在水和其他非真空环境中具有良好稳定性的光电子发射器，并确定是否可以对金刚石进行改性以使其能够使用可见光轻松发射电子。如果成功，利用可见光或近紫外光在水中轻松产生电子的能力将实现目前不可能的新的、节能的化学转化途径。研究生正在接受最先进的电化学方法的培训，并获得广泛的专业发展机会。 首席研究员和学生还指导本科生和高中生进行暑期研究项目，作为增加有机会参与最先进科学研究的学生数量的更广泛努力的一部分。 首席研究员和学生正在积极参与多个专门旨在增强科学劳动力多样性的项目。技术摘要这个更新项目是主要研究人员研究的成果，证明金刚石表面在紫外线照射下能够将电子发射到水中，从而允许廉价的金刚石薄膜甚至工业粉末用作液体中的固态电子源。 虽然之前已经研究了向真空中的电子发射，但对于向水和其他液体中的电子发射知之甚少。该项目的主要目标是研究控制电子从金刚石光发射到邻近液体的因素，并利用这些信息来创建在非真空环境中具有良好稳定性和效率的光电子发射器。 该项目由三个主要组成部分组成。一是通过表征表面终止层、溶液相离子和外部施加电势等变量如何影响电子发射，了解金刚石-液体界面的电子结构如何影响电子发射到相邻液体中。 第二个是确定金属-半导体结和等离子体结构是否能够增加金刚石的光学吸收和/或提供将电子激发到导带的替代途径。 第三个是确定由替代氮或其他掺杂剂引入的中间带隙态是否可以提供利用可见光实现电子发射的途径。 正在采用多种实验方法。 X 射线光电子能谱和紫外光电子能谱用于表征金刚石表面的化学成分和电子结构。 包括莫特肖特基分析和电化学阻抗谱在内的电化学方法可用于表征水介质中的界面电子结构和能带排列。 使用瞬态吸收光谱和化学探针直接表征溶剂化电子。 这些方法共同提供了对液体电子发射的全面理解，并提供了关于如何设计最有效地使金刚石在非真空环境中用作固态电子源的界面的见解。