DFG-RSF: Doped-graphene for electrochemical energy storage and conversion: Impact of the electronic structure on electrocatalytic activity in oxygen redox reactions

DFG-RSF：用于电化学能量存储和转换的掺杂石墨烯：电子结构对氧氧化还原反应中电催化活性的影响

• 批准号: 310366325
• 负责人: Professor Dr. Clemens Laubschat
• 金额: --
• 依托单位: Lomonosov Moscow State University (MSU)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2021-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/310366325?language=en
• 关键词: DFG; RSF; Doped; graphene; electrochemical

Storing energy in chemical bonds enables power supply from sub-W to tens of MW. Electrochemical systems that convert energy of chemical bonds directly to electric power can store GWh of energy and utilize a huge variety of chemical systems. Being easily accessible in ambient atmosphere and nearly inexhausable, molecular oxygen is an excellent component for electrochemical energy conversion and storage systems, so that oxygen redox reactions are of decisive importance for many electrochemical devices such as fuel cells or metal-air batteries. In such systems, heterogeneous electron transfer to/from oxygen occurs at the surface of an electrode. Carbon electrodes, being light-weight, cheap and well conductive, are the materials of choice in the most cases. The surface of carbon electrodes consists of a graphene-like domains, various carbons, however, reveal different efficiency for oxygen redox processes. It was recently demonstrated that doping of carbons with light elements like N, B or S enhances the kinetics of electron transfer to/from oxygen remarkably and leads to an electrocatalytic activity comparable to that of noble metals. However, the underlying physics has yet not been fully understood. A number of studies devoted to this topic suffer from high complexity of real carbon electrodes, i.e. individual effects of electronic structure, impurities, microstructure, etc. can be hardly distinguished.We propose to use epitaxial graphene as a model system to elucidate the role of electronic structure and impurities in doped carbons in heterogeneous electron transfer to and from oxygen. We will start from epitaxial graphene as purely chemical model system and are planning to develop functional electrochemical cells with increasing complexity using transferred graphene as electrode.To realize the chemical model systems monolayers of doped graphene will be grown in situ by chemical vapor deposition on Ni(111) and Co(0001) surfaces. The electronic properties of N-, B- and S-graphene will be explored experimentally and theoretically employing angle resolved photoemission spectroscopy (ARPES) and DFT-based calculations. Chemisorption of hydrogen and alkali metals on doped graphene layers will be used to control the Fermi level position under ultra-high vacuum conditions. The evolution of the system during oxygen exposure will then be traced using ARPES, XPS and near ambient pressure XPS (NAP XPS).A similar methodology will be applied to operating electrochemical cells utilizing doped graphene as an electrode. Graphene will be grown on metallic foils and then transferred onto solid electrolytes or onto Si3N4 grids with liquid electrolyte supplied from the back side. The electron transfer between graphene and oxygen as well as the formation of new oxygen-containing species will be followed using photoelectron spectroscopy and X-ray absorption spectroscopy (NEXAFS) under operando conditions.

在化学键中存储能量可以使电源从低于W到数十MW。将化学键的能量转换为电力的电化学系统可以存储能源的GWH，并利用各种化学系统。在环境大气中很容易获得分子氧，这是电化学转化和储存系统的绝佳组成部分，因此对于许多电化学设备（例如燃料电池或金属式电池）而言，氧氧化还原反应具有决定性的重要性。在这样的系统中，异质电子转移到氧气中发生在电极的表面。在大多数情况下，碳电极轻巧，便宜且导电良好，是首选的材料。碳电极的表面由一个石墨烯状结构域组成，但是，各种碳均显示出不同的氧气氧化还原过程效率。最近证明，具有N，B或S之类的光元素的碳掺杂可以增强电子转移的动力学，从而显着从氧气转移，并导致与贵金属相当的电催化活性。但是，尚未完全理解基础物理学。许多专门针对该主题的研究遭受了真实碳电极的高复杂性，即电子结构，杂质，微观结构等的个别效应。我们建议使用外延石墨烯作为模型系统来阐明异质电子转移和从氧气转移的掺杂碳中的电子结构和杂质。我们将从外在石墨烯作为纯化学模型系统开始，并计划使用转移的石墨烯作为电极以增加复杂性来开发功能性电化学细胞。 111）和CO（0001）表面。 N-，B-和S-石膏的电子性能将在实验和理论上采用角度分辨光发射光谱（ARPE）和基于DFT的计算进行探索。掺杂石墨烯层上氢和碱金属的化学吸收将用于控制超高真空条件下的费米水平位置。然后，将使用ARPE，XPS和近环境压力XP（NAP XPS）来追踪系统在氧气暴露期间的演变。将使用类似的方法应用于使用掺杂石墨烯作为电极的运行电化学细胞。石墨烯将在金属箔上生长，然后将其转移到固体电解质上，或在Si3n4网格上，并带有从后侧提供的液体电解质。在操作系统条件下，将使用光电子光谱和X射线吸收光谱（NEXAFS）进行石墨烯和氧之间的电子转移以及新的含氧物种的形成。

项目成果

Electron-phonon coupling in graphene placed between magnetic Li and Si layers on cobalt

• DOI: 10.1103/physrevb.97.085132
• 发表时间: 2018-02
• 期刊: Physical Review B
• 影响因子: 3.7
• 作者: D. Usachov;A. Fedorov;O. Vilkov;I. Ogorodnikov;M. Kuznetsov;A. Grüneis;C. Laubschat;D. Vyalikh

Raman Spectroscopy of Lattice-Matched Graphene on Strongly Interacting Metal Surfaces.

• DOI: 10.1021/acsnano.7b02686
• 发表时间: 2017-05
• 期刊: ACS nano
• 影响因子: 17.1
• 作者: D. Usachov;V. Davydov;V. Levitskii;V. O. Shevelev;D. Marchenko;B. Senkovskiy;O. Vilkov;A. Rybkin;L. Yashina;E. Chulkov;I. Sklyadneva;R. Heid;K. Bohnen;C. Laubschat;D. Vyalikh

Laterally Selective Oxidation of Large-Scale Graphene with Atomic Oxygen

• DOI: 10.1021/acs.jpcc.7b07840
• 发表时间: 2017-12-21
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY C
• 影响因子: 3.7
• 作者: Kapitanova, Olesya O.;Kataev, Elmar Yu.;Yashina, Lada V.
• 通讯作者: Yashina, Lada V.

Photoelectron Diffraction and Holography Studies of 2D Materials and Interfaces

二维材料和界面的光电子衍射和全息研究

• DOI: 10.7566/jpsj.87.061005
• 发表时间: 2018
• 期刊: Journal of the Physical Society of Japan
• 影响因子: 1.7
• 作者: M. Kuznetsov;I.I.Ogorodnikov;D.Yu.Usachov;C. Laubschat;D.V.Vyalikh;L.V.Yashina
• 通讯作者: L.V.Yashina

Oxygen reduction by lithiated graphene and graphene-based materials.

• DOI: 10.1021/nn5052103
• 发表时间: 2015-01
• 期刊: ACS nano
• 影响因子: 17.1
• 作者: E. Kataev;D. Itkis;A. Fedorov;Boris Senkovsky;D. Usachov;N. Verbitskiy;A. Grüneis;A. Barinov;D. Tsukanova;A. Volykhov;K. Mironovich;V. Krivchenko;Maksim G. Rybin;E. Obraztsova;C. Laubschat;D. Vyalikh;L. Yashina