Ionic-Liquid-Modified Electrocatalysts: From Surface Science to Spectroelectrochemistry

离子液体改性电催化剂：从表面科学到光谱电化学

• 批准号: 322419553
• 负责人: Professor Dr. Jörg Libuda
• 金额: --
• 依托单位: Lehrstuhl für Katalytische Grenzflächenforschung
• 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 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/322419553?language=en
• 关键词: Ionic; Liquid; Modified; Electrocatalysts; Surface

The unique physicochemical properties of ionic liquids (ILs) have inspired the development of new concepts in catalysis, such as the Solid Catalyst with Ionic Liquid Layer (SCILL). In this approach the IL is employed as a designer modifier to enhance the selectivity. The concept is successfully applied in heterogeneous catalysis and, recently, was transferred to electro¬catalysis. In spite of the great potential of electrochemical SCILLs the mechanism of IL-induced selectivity enhancement has remained unexplored up to date. This project aims at an in-depth understanding of IL-modified electrocatalysis at the molecular level. We will follow a unique approach that couples surface science in ultrahigh vacuum (UHV) to in-situ spectroelectro¬chemistry. UHV surface science and electrochemistry will be linked (i) using the same atomically-defined model surfaces, (ii) using the same model reactions, and (iii) using closely related experimental methods. In UHV we will identify the surface intermediates by infrared reflection absorption spectroscopy and the products by temperature programmed desorption/reaction in combination with molecular beam methods. Under electrochemical conditions equivalent information is obtained from electrochemical infrared reflection absorption spectroscopy and differential electrochemical mass spectrometry combined with cyclic voltammetry. Additional information will be available through a network of cooperation partners in experiment and theory. We identified three prototypic model reactions of increasing complexity: (1) the oxidation of CO, (2) the oxidation of methanol (3) the oxidation/reduction of allyl alcohol/acrolein. These model reactions, accessible in UHV studies and in electrochemistry, show pronounced structure dependencies, electronic effects and ensemble effects. They are perfect test cases to identify the molecular origins of IL-induced changes in the reaction mechanism, energetics and microkinetics. Starting from simple single crystals (Pt, Pd) we will proceed to complex model catalysts consisting of metallic nanoparticles (Pt, Pd) on ordered oxide films (Co3O4(111)/Ir(100)). Identical model surfaces will be employed in surface science and in electrochemistry. This will be possible using a new experimental system that allows UHV preparation and direct transfer to the spectroelectrochemical cell. On the model catalysts, we will deposit imidazolium based ILs by physical vapor deposition, tuning the properties of the IL by substitution (coordination strength, polarity, etc.). Taking advantage of the structural diversity of UHV-born model catalysts we will obtain mechanistic insights into electrochemical SCILLs at an unprecedented level of detail.

离子液体独特的物理化学性质激发了催化新概念的发展，如具有离子液体层的固体催化剂（SCILL）。在这种方法中，IL被用作设计者改性剂以提高选择性。该概念成功地应用于多相催化，最近被转移到电催化。尽管电化学SCILLs具有很大的潜力，但IL诱导选择性增强的机制至今仍未被探索。本项目旨在从分子水平上深入了解IL修饰的电催化。我们将遵循一种独特的方法，将超真空（UHV）中的表面科学与原位光谱电化学结合起来。特高压表面科学和电化学将（i）使用相同的原子定义的模型表面，（ii）使用相同的模型反应，以及（iii）使用密切相关的实验方法。在超高真空中，我们将通过红外反射吸收光谱法识别表面中间体，并通过程序升温脱附/反应结合分子束方法识别产物。在电化学条件下，电化学红外反射吸收光谱和差示电化学质谱结合循环伏安法可获得等效信息。将通过实验和理论合作伙伴网络提供更多信息。我们确定了三个原型模型反应的复杂性增加：（1）CO的氧化，（2）甲醇的氧化，（3）氧化/还原烯丙醇/丙烯醛。这些模型反应可用于超高真空研究和电化学，显示出明显的结构依赖性、电子效应和系综效应。它们是确定IL诱导的反应机制、能量学和微观动力学变化的分子起源的完美测试案例。从简单的单晶（Pt，Pd）开始，我们将进行复杂的模型催化剂，由金属纳米颗粒（Pt，Pd）在有序的氧化物膜（Co 3 O 4（111）/Ir（100））。相同的模型表面将用于表面科学和电化学。这将有可能使用一个新的实验系统，允许超高真空制备和直接转移到光谱电化学池。在模型催化剂上，我们将通过物理气相沉积来沉积基于存款咪唑鎓的IL，通过取代来调节IL的性质（配位强度、极性等）。利用超高压模型催化剂的结构多样性，我们将在前所未有的细节水平上获得电化学SCILLs的机理见解。

项目成果

Selective electrooxidation of 2-propanol on Pt nanoparticles supported on Co3O4: an in-situ study on atomically defined model systems

• DOI: 10.1088/1361-6463/abd9ea
• 发表时间: 2021-04
• 期刊: Journal of Physics D: Applied Physics
• 作者: Tian Yang;Maximilian Kastenmeier;Michal Ronovský;Lukáš Fusek;T. Skála;Fabian Waidhas;M. Bertram;N. Tsud;P. Matvija;K. Prince;V. Matolín;Zhi Liu;V. Johánek;J. Mysliveček;Y. Lykhach;O. Brummel;J. Libuda

Secondary Alcohols as Rechargeable Electrofuels: Electrooxidation of Isopropyl Alcohol at Pt Electrodes

仲醇作为可充电电燃料：异丙醇在铂电极上的电氧化

• DOI: 10.1021/acscatal.0c00818
• 发表时间: 2020
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: F. Waidhas;S. Haschke;P. Khanipour;L. Fromm;A. Görling;J. Bachmann;I. Katsounaros;K.J.J. Mayrhofer;O. Brummel;J. Libuda
• 通讯作者: J. Libuda

Structural Dynamics of Ultrathin Cobalt Oxide Nanoislands under Potential Control

• DOI: 10.1002/adfm.202009923
• 发表时间: 2021-01
• 期刊: Advanced Functional Materials
• 影响因子: 19
• 作者: Corinna Stumm;M. Bertram;Maximilian Kastenmeier;F. Speck;Zhaozong Sun;J. Rodrı́guez-Fernández;J. Laurits

Electrifying Oxide Model Catalysis: Complex Electrodes Based on Atomically-Defined Oxide Films

• DOI: 10.1007/s10562-019-03078-x
• 发表时间: 2020-06-01
• 期刊: CATALYSIS LETTERS
• 影响因子: 2.8
• 作者: Brummel, Olaf;Libuda, Joerg
• 通讯作者: Libuda, Joerg